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
  • C07C209/82—Purification; Separation; Stabilisation; Use of additives
  • C07C209/84—Purification
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

• the present invention relates to a process for the preparation of 3-dimethylaminopropropylamine (DMAPA). Furthermore, the present invention relates to mixtures of DMAPN and 2- (dimethylaminomethyl) -glutaronitrile (DGN) with a low DGN content.
• DMAPA 3-dimethylaminopropropylamine
• DGN 2- (dimethylaminomethyl) -glutaronitrile
• DMAPA 3-Dimethylaminopropylamine
• DMAPA is usually made by a two-step process.
• ACN acrylonitrile
• DMA dimethylamine
• DMAPN 3-dimethylaminopropionitrile
• DMAPN is then generally reduced to DMAPA in a further step.
• an integral manufacturing method or an integral device is used for the production of DMAPA.
• the product stream initially obtained, which has DMAPN is used directly or after purification in order to be converted into DMAPA in a further step.
• the quality of the DM APN product stream from the first reaction (DMA and ACN) is of decisive importance for the reduction reaction of DMAPN to DMAPA, in particular for the consumption of the catalyst used in the reduction.
• WO 2007/128803 therefore teaches a process for the preparation of DMAPN by reacting DMA with ACN in a continuous mode, wherein first DMA and then ACN are fed continuously and the reaction of the reaction takes place in a first reaction region and at least partially in a second reaction region.
• the resulting DMAPN is then reduced without further workup in a further reaction area with hydrogen directly to DMAPA.
• the service life of the hydrogenation catalyst can be prolonged if a DMAPN is used in the DMAPN hydrogenation which, according to the teaching of WO 2007/128803, is prepared in two separate reaction spaces.
• the object of the present invention over the prior art was to further improve the service life of the catalysts used in the hydrogenation of DMAPN.
• unwanted side reactions such as the exothermic Decomposition of the nitrile, the cleavage of DMAPN to ACN and DMA or the formation of secondary amines by condensation of DMAPA can be kept low during use of the catalyst without having to reduce the catalyst load.
• a low content of DMAPN in the product is advantageous because DMAPN is difficult to separate from DMAPA and leads to undesirable properties such as odor and discoloration in the subsequent applications.
• DMAPA 3-dimethylaminopropylamine
• DMAPN 3-dimethylaminoprionitrile
• DGN 2- (dimethylaminomethyl) glutaronitrile
• WO 2007/128803 discloses that the quality of the DMAPN used in the hydrogenation can be decisive for the quality of the DMAPA obtained by hydrogenation of DMAPN, there is no indication as to which parameters of the DMAPN influence the hydrogenation reaction. Farther does not directly and immediately disclose a DMAPN having a DGN content of 300 ppm and less by the method disclosed in WO 2007/128803.
• a DMAPN with a content of 300 ppm or less of DGN, based on the DMAPN used, is used in the process according to the invention. Preference is given to using in the process according to the invention a DMAPN having a content of DGN of 250 ppm and less, more preferably 150 ppm and less and particularly preferably 50 ppm and less.
• DMAPN may be prepared at a level of 300 ppm DGN or less by continuous reaction of ACN with DMA and subsequent distillation.
• the production of DMAPN can in principle be carried out analogously to the teaching of WO 2007/128803 or the teaching of WO 2007/051786, the contents of which are expressly incorporated by reference.
• the reaction of ACN with DMA in this preferred embodiment takes place in a reactor cascade, wherein preferably 2 to 10, particularly preferably 2 to 8 and very particularly preferably 3 to 7 reactors are connected in series.
• the reaction of DMA with ACN in a reactor cascade allows the setting of different reaction conditions. This allows a more complete reaction of ACN while reducing the proportion of by-products in the reaction stream can be achieved.
• the reactors of the reactor cascade may be, for example, stirred tank reactors, external pump circulation reactors (loop reactors) or tubular reactors, it being preferred that the first or first reactors of the reactor cascade are stirred tank reactors and the last or last reactors of the reactor cascade are tube reactors.
• the reaction temperature in the reactors is in the range of 20 ° C to 120 ° C. More preferably, the range is 40 ° C to 90 ° C, and it is further preferred that the temperature in the last reactor or in the last reactor of the reactor cascade has a lower reaction temperature than in the first and the first reactors of the reactor cascade.
• reaction of ACN and DMA is preferably carried out in a pressure range of 1 bar to 20 bar, preferably 2 to 15 bar and more preferably 3 to 8 bar, the pressure usually by the autogenous pressure of the DMA used in the respective Reaction conditions is determined.
• reaction of ACN with DMA takes place in the presence of water.
• the proportion of water based on the sum of the ACNs and DMAs used, in the range of 0.5 to 10 wt .-%, particularly preferably in the range of 1 to 8% by weight and very particularly Preferably in the range of 3 to 7 wt .-% is.
• the molar ratio of DMA to ACN is then preferably from 1, 00: 1 to 1, 10: 1, preferably 1, 01: 1 to 1, 08: 1 and particularly preferably 1, 02: 1 to 1, 06: 1.
• the molar ratio of DMA to ACN is then preferably more than 1, 02: 1, particularly preferably 1, 04: 1 to 1, 35: 1 and more preferably 1, 06: 1 to 1, 25: 1.
• the supply of ACN and DMA and optionally water may be taken together or separately.
• the supply of DMA and ACN is preferably carried out separately.
• the feed is particularly preferably carried out in such a way that DMA is first introduced into a circulating stream which already contains DMAPN and the addition of ACN preferably takes place after the combination of DMA and DMAPN.
• the water can reach the reaction stream, for example in the form of an additional feed.
• at least partially DMA in the form of an aqueous solution is fed to the reaction stream. This can be done for example in the form of a 30 to 70 wt .-% aqueous DMA solution.
• the ACN used may contain water.
• DMA and ACN are supplied in liquid form. This allows a higher conversion with better space / time yield compared to processes in which DMA is supplied in the gaseous state to the reaction mixture. Therefore, the supply of ACN and DMA has a suitable temperature and pressure to ensure that these starting materials are in liquid form to produce DMAPN.
• the continuous reaction of ACN with DMA a DMAPN-containing reaction mixture is obtained as a reaction, in addition to DMAPN usually unreacted DMA, DGN and other organic compounds, and optionally water and optionally unreacted ACN can.
• a portion of the DMAPN may be recycled to the process as a recycle stream or recycle stream, with recycle preferably occurring after the first reactor.
• the DMAPN reaction mixture obtained in this preferred embodiment is then introduced into a thermal separation sequence in which volatile as well as high-boiling minor components of DMAPN are separated.
• the separation of the low and high boilers can be carried out in a column, low boilers being obtained overhead, high boilers via bottom and DMAPN via a gas or vapor side draw.
• the separation of the low and high boilers can be carried out in a column with a partition in the middle part, are obtained in the low boilers overhead, high boilers on the bottom and DMAPN on the opposite side of the inlet of the partition.
• Low-boiling components (LS) such as DMA, ACN, optionally water and other low-boiling secondary components are obtained at the top of the column or the reinforcing part.
• High boilers (SS) with respect to DMAPN are DGN and possibly other minor components with lower vapor pressure. These are separated off via the bottoms discharge of the stripping section or the stripping column.
• the exact operating conditions of the distillation sequence can be determined according to the separation efficiency of the column internals used by the skilled person from measured or estimated vapor pressures and vapor-liquid phase equilibria (VLE) of the components introduced into the distillation sequence according to conventional calculation methods.
• VLE vapor-liquid phase equilibria
• the distillation sequence preferably has internals for increasing the separation efficiency.
• the distillative internals can be present for example as soils, packed beds or ordered packing.
• ordered packings are preferably used for a dividing wall column.
• Advantageous in the use of ordered packages is the low pressure loss and low specific liquid hold-up compared to soils such as e.g. Valve trays.
• the installations can be in one or more beds.
• the reaction product from the DMAPN preparation is preferably fed in a spatial range between 25% and 75% of the theoretical plates of the distillation column (counted from below).
• the supply may be slightly below the center of the theoretical plates.
• the optimum feed point can be determined by the skilled person with the usual calculation tools.
• the number of theoretical plates for separating off the low boilers, the so-called reinforcing part, is generally in the range from 10 to 50, preferably 10 to 30.
• the number of theoretical plates for separation of the high boiler, the so-called drive part is generally in the range from 10 to 50, preferably 10 to 30.
• the top pressure of the distillation column (s) is particularly preferably 0.1 to 10 bar, more preferably 0.5 to 5 bar. Most preferably, the distillation column (s) is operated at atmospheric pressure.
• a temperature in the bottom of the low-boiling column is set, but above the evaporation temperature of water is below the vaporization temperature of DMAPN.
• a temperature in the bottom of the high-boiling column is set which is above the vaporization temperature of DMAPN but below the vaporization temperature of DGN.
• a column bottom temperature of 170 to 200 ° C is set in the stripping column at a column top pressure of 1 bar (abs.).
• a column bottom temperature of 170 to 200 ° C particularly preferably from 180 to 195 ° C can be set.
• the condenser of the low-boiling column is generally operated at a temperature in which the majority of the DMA or water at the corresponding top pressure kon- is being densified.
• the operating temperature of the capacitor is in the range of 25 to 100 ° C, preferably 25 to 50 ° C.
• the condensate obtained at the condenser is recycled to more than 30%, preferably to more than 50% by weight, into the top of the low-boiling column.
• the energy required for evaporation is usually introduced through an internal or external evaporator in the column bottom.
• a condensate is obtained, which contains predominantly DMA and optionally water and optionally other low-boiling organic secondary components. This condensate can be recycled as a starting material in the reaction for the synthesis of DMAPN.
• DMAPN is obtained as the bottom product with DGN and, if appropriate, other sparingly volatile secondary components.
• DGN is obtained as bottoms product and, if appropriate, other sparingly volatile secondary components (DGN separation).
• DMAPN is recovered at the top of the stripping column.
• a temperature in the bottom of the column which is above the evaporation temperature of DMAPN but below the evaporation temperature of DGN is preferably set.
• a column bottom temperature of 170 to 200 ° C, particularly preferably from 180 to 195 ° C can be set.
• the condenser of the distillation column is usually operated at a temperature in which the majority of the DMA or water is condensed at the corresponding top pressure.
• the operating temperature of the capacitor is in the range of 25 to 100 ° C, preferably 25 to 50 ° C.
• the condensate obtained at the condenser is recycled to more than 30%, preferably to more than 50% by weight, in the top of the distillation column.
• the energy required for evaporation is usually introduced through an internal or external evaporator in the column bottom.
• the condensate is condensate, which contains predominantly DMA and optionally water and possibly other low-boiling organic secondary components.
• This condensate can be recycled as a starting material in the reaction for the synthesis of DMAPN.
• DGN is obtained as bottoms product and, if appropriate, other sparingly volatile secondary components (DGN separation).
• DMAPN is obtained via a liquid or vapor side take-off or on the side of the dividing wall opposite the feed.
• the DMAPN obtained as the product of the separation sequence usually has a content of more than 95% by weight of DMAPN, preferably more than 98% by weight of DMAPN and particularly preferably more than 99% by weight of DMAPN.
• the DMAPN obtained in this preferred embodiment preferably has a DGN content of 300 ppm or less based on DMAPN, more preferably a content of 250 ppm or less based on DMAPN, most preferably a content of 150 ppm or less based on DMAPN and more preferably, it has a content of 50 ppm or less based on DMAPN.
• the reaction of dimethylamine and acrylonitrile is carried out in the presence of water in a reactor cascade in a temperature range of 50 to 80 ° C and a pressure range of 3 to 8 bar, wherein the molar ratio of DMA to ACN in the range is from 1, 02: 1 to 1, 10: 1 and the proportion of water in the range of 1 to 8 wt .-%, based on the sum of the ACN and DMA used. If these reaction conditions are met, distillative work-up of the reaction effluent from the DMAPN preparation is generally not required in order to obtain a DMAPN having a content of DGN of 300 ppm or less.
• the weight ratio of DMAPN to DGN in the DMAPN thus obtained is preferably in the range of 1 000 000: 1 to 1 000 000: 300, more preferably in the range of 1 000 000: 5 to 1 000 000: 250, most preferably in the range of 1 000 000: 8 to 1 000 000: 150, and more preferably in the range of 1 000 000: 10 to 1 000 000: 100.
• the present invention also relates to a mixture of DMAPN and DGN, characterized in that the weight ratio of DMAPN to DGN is in the range of 1 000 000: 5 to 1 000 000: 250.
• the content of DGN in DMAPN can easily be determined by the analysis method known to those skilled in the art, for example by gas chromatography.
• Hydrogen is also used in the process according to the invention for the preparation of DMAPA.
• hydrogen or a hydrogen-containing gas may be used.
• the hydrogen is generally used technically pure.
• the hydrogen can also be used in the form of a gas containing hydrogen, ie in admixture with other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide.
• inert gases such as nitrogen, helium, neon, argon or carbon dioxide.
• reformer effluents, refinery gases, etc. can be used as the hydrogen-containing gases, if and insofar as these gases do not contain any contact poisons for the hydrogenation catalysts used, for example CO.
• pure hydrogen or essentially pure hydrogen in the process, for example hydrogen having a content of more than 99% by weight of hydrogen, preferably more than 99.9% by weight of hydrogen, particularly preferably more than 99.99 Wt .-% hydrogen, in particular more than 99.999 wt .-% hydrogen.
• the reaction of DMAPN with a DGN content of 300 ppm or less and hydrogen can be carried out in the presence of ammonia.
• Pure ammonia is preferably used in the process, preferably ammonia with a content of more than 99% by weight of ammonia and particularly preferably more than 99.9% by weight of ammonia.
• ammonia is generally used in molar ratios to the nitrile group in the ratio of 0.5: 1 to 100: 1, preferably 2: 1 to 20: 1.
• Another preferred embodiment is a method in which no ammonia is added. The reaction of DMAPN with a DGN content of 300 ppm or less with hydrogen takes place in the presence of a catalyst.
• catalysts for the hydrogenation of the nitrile function to the amine in particular 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), preferably Fe, Co, Ni, Ru or Rh, particularly preferably Co or Ni.
• the catalysts may additionally contain one or more promoters.
• Raney nickel catalysts or Raney cobalt catalysts are used.
• the catalysts can be used as unsupported catalysts or supported.
• the preferred carriers are metal oxides such as Al 2 O 3, SiO 2, ZrO 2, Z 2, mixtures of metal oxides or carbon (activated carbon, carbon black, graphite).
• the oxide 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. Before using the passivated catalysts in the reaction, these are usually reactivated with hydrogen-containing gas at elevated temperature.
• Particularly preferred fixed bed catalysts are the full cobalt contacts disclosed in EP-A 0 742 045 and EP-A-0 636 409, doped with Mn, P and alkali metal (Li, Na, K, Rb, Cs).
• the catalytically active composition of these catalysts before reduction with hydrogen consists of 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 the oxide.
• catalysts disclosed in EP-A-1306365 comprising cobalt and optionally additionally nickel and at least one further doping metal on a particulate carrier material, characterized in that the cobalt and optionally the nickel have an average particle size of 3 to 30 nm in the active Catalyst have.
• the process according to the invention for the preparation of DMAPA preferably takes place in a continuous procedure. This enables a particularly efficient conversion combined with a high space / time yield.
• the preparation of DMAPA can also be carried out batchwise or semicontinuously.
• Typical reactors in which the hydrogenation can be carried out are, for example, high-pressure stirred tank reactors, loop reactors, autoclaves or fixed bed reactors.
• the process according to the invention is preferably carried out in a high-pressure stirred tank reactor or fixed bed reactor. Most preferably, the hydrogenation is carried out in a fixed bed reactor.
• the fixed bed reactor can be flowed through from top to bottom (trickle down) or bottom to top (bottom up). Hydrogen, DMAPN and optionally ammonia may be added together to the reaction zone of the reactor, for example as a premixed reactant stream, or separately.
• the hydrogenation is generally carried out at a pressure of 1 to 500 bar, preferably 10 to 400 bar, more preferably at a pressure of 20 to 300 bar and most preferably 30 to 200 bar.
• the pressure maintenance or pressure control is usually done via the dosage of hydrogen.
• the hydrogenation is generally carried out at temperatures of 20 to 400 ° C, preferably 40 to 250 ° C, more preferably 50 to 180 ° C and most preferably 70 to 150 ° C.
• the reaction product from the hydrogenation reactor is preferably passed through a heat exchanger. After passing through the heat exchanger, the temperature of the hydrogenation is preferably in the range of 20 to 80 ° C.
• the hydrogenation is adiabatic.
• the hydrogenation is usually worked up after the hydrogenation.
• hydrogen and ammonia are separated from the hydrogenation and can be returned to the process after separation.
• the hydrogenation effluent is preferably passed into a separator in which liquid crude product of gaseous components, such as hydrogen, DMA and ammonia, is separated off and can be carried out via an outlet.
• the crude product can be recycled at least partially to the reaction stream in a recycle mode.
• the resulting mixture of hydrogen, DMA and ammonia can be carried out via a further outlet from the phase separator and also preferably recycled into the process or optionally after separation into the DMAPN production.
• the present invention makes it possible to further improve the service life of the catalysts used in the hydrogenation of DMAPN over the prior art.
• the process according to the invention makes it possible to keep catalyst deactivation low during the process in order thus to extend the life of the catalyst while maintaining the catalyst's performance.
• a measure of these properties is the quotient of temperature increase and service life.
• a low quotient of temperature increase and operating time means that the catalyst can be operated at the starting temperature for as long as possible and that the required temperature increase, which may be required to compensate for catalyzer deactivation, is low, so that a critical temperature at which the secondary reactions increase increase very much, as long as possible is not achieved.
• the quotient of temperature increase and service life of the catalyst can be reduced.
• DMAPN acrylonitrile
• DMA dimethylamine
• a continuous apparatus was used which consisted of a cascade of three successive stirring autoclaves (C1 to C3).
• C1 had a volume of 80 ml
• C2 had a volume of 120 ml
• C3 had a volume of 200 ml.
• four more stirred autoclaves could be connected in series after C3: C4, 05, 06 and 07 with a volume of 270 each ml.
• volume is meant the volume filled with liquid.
• ACN, DMA and optional water were simultaneously metered into the plant before 01.
• the driving was done in a straight passage.
• the pressure in the autoclave was 5 bar.
• the DMAPN prepared in this way was fed directly into the hydrogenation stage (Examples 1 to 3) without further work-up. A portion of the crude DMAPN was separated and analyzed for minor components.
• Temperature 01 60 ° C; Temperature 02: 70 ° C; Temperature 03: 70 ° C
• the content of DGN based on the amount of DMAPN (1403 g) originally used in the distillation, was 227 ppm.
• Temperature 01 60 ° C; Temperature 02: 70 ° C; Temperature 03: 70 ° C; Temperature 04: 70 ° C; Temperature 05: 70 ° C; Temperature 06: 70 ° C; Temperature 07: 60 ° C
• Temperature C1 60 ° C; Temperature C2: 70 ° C; Temperature C3: 70 ° C; Temperature C4: 70 ° C; Temperature C5: 70 ° C; Temperature C6: 70 ° C; Temperature C7: 60 ° C
• the reactor was charged with 26 g of a cobalt catalyst whose preparation is described in EP-A-0636409 (Example Catalyst A).
• the catalyst precursor thus prepared contained 90.4% by weight of cobalt, 5.1% by weight of manganese, 0.3% by weight of sodium and 3.1% by weight of phosphorus.
• the catalyst was then reduced (H 2 , 300 ° C., 1 bar) and passivated (N 2 / O 2 , 50 ° C., 1 bar).
• the catalyst form body were installed in the tubular reactor and the laboratory system rendered inert with nitrogen.
• reaction mixture After passing through the reactor, the reaction mixture was separated at 180 bar and room temperature into gaseous and liquid components. From the liquid components, a flow of 80 g / h was returned to the inlet of the reactor with the aid of a circulation pump. Gaseous components were not recycled. The remaining part of the reaction mixture was decompressed to 20 bar and analyzed by means of an online gas chromatograph and finally collected at 1 bar in a discharge vessel.
• GC column 60 m CP Volamine / WCOT Fused Silica 0.32 mm
• the stated DMAPN values are% by weight.
• the DMAPN feed was gradually increased to 52.8 g / h in the experiments and the NH 3 feed to 43.4 g / h in parallel. After this period, the catalyst loading was thus 2.0 kg DMAPN per kg of catalyst per hour.
• the initial temperature of 120 ° C was increased in the experiments with increasing transit time to compensate for the catalyst deactivation caused by sales decline. As soon as the amount of DMAPN determined by gas chromatography exceeded about 0.3%, the temperature in the oil jacket was increased by 2 ° C. The experiments were run over a running time of at least 1500 h.
• the catalyst deactivation is quantified as follows:
• Quotient off Required temperature increase (over the runtime, starting from 120 ° C jacket temperature, to ensure a residual DMAPN content of ⁇ 0.3%) and running time. This indicates after how many hours on average the temperature must be raised by 1 ° C.
• Example 1
• the DMAPN from Example a was used, which had a content of 2- (dimethylaminomethyl) glutaronitrile (DGN) of 227 ppm.
• DGN 2- (dimethylaminomethyl) glutaronitrile
• the DMAPN from Example b) was used, which had a content of 2- (dimethylaminomethyl) glutaronitrile (DGN) of 373 ppm.
• the DMAPN from Example c) was used which had a content of 2- (dimethylaminomethyl) glutaronitrile (DGN) of 27 ppm.
• the catalyst deactivation was thus significantly below 1 ° C / 1000 h (120 ° C-120 ° C / 1700 h ⁇ 1 o C / 1000 h).
• the composition of the remaining swamp was:
• the water content was 0.02%.
• the bottom product was distilled at 100 mbar and at least 100 ° C bottom and head temperature until only a small amount of residual substance remained in the distillation still. From the distillate the following composition was determined: 99.95% DMAPN
• the addition of DMA to ACN was carried out in a continuously operated stirred tank cascade consisting of seven stirred tanks.
• the volume ratio of the seven stirred tanks was 1: 1, 5: 2, 5: 3, 4: 3, 4: 3, 4: 3, 4.
• the reaction was carried out at a pressure of 5 bar.
• the temperature in the first two stirred tanks was 60 ° C, in the third to seventh boiler 40 ° C.
• the addition was carried out at a load, calculated as the feed of acrylonitrile per unit time, based on the volume of the first stirred tank, of 0.54 kg / L / h.
• the molar feed ratio of DMA to ACN was 0.98.
• the acrylonitrile residual content was about 2 wt .-% (based on the total reaction).
• the mean residence time of the reaction mixture in the containers of the addition stage was about 16 hours.

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• 2011
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