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WO2023046330A1 - Procédé continu de séparation d'un mélange comprenant de la pyrrolidine, du bis(pyrrolidino)butane et de l'eau - Google Patents

Procédé continu de séparation d'un mélange comprenant de la pyrrolidine, du bis(pyrrolidino)butane et de l'eau Download PDF

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Publication number
WO2023046330A1
WO2023046330A1 PCT/EP2022/069876 EP2022069876W WO2023046330A1 WO 2023046330 A1 WO2023046330 A1 WO 2023046330A1 EP 2022069876 W EP2022069876 W EP 2022069876W WO 2023046330 A1 WO2023046330 A1 WO 2023046330A1
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stream
pyrrolidine
water
pressure
distillation
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Inventor
Tatjana HUBER
Joerg Pastre
Johann-Peter Melder
Thomas Krug
Kristin Schroeder
Sven FUERSTENBERG
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives

Definitions

  • the invention relates to a process for the separation of a mixture comprising pyrrolidine, bis(pyrrolidino)butane and water.
  • the process products are used, inter alia, as intermediates in the production of fuel additives (USA-3,275,554; DE-A-21 25 039 and DE-A-36 11 230), surfactants, drugs and crop protection agents, hardeners for epoxy resins, catalysts for polyurethanes (WO2015/200408 A1 and WO2014/121959 A1), intermediates for the preparation of quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile assistants, dyes, vulcanization accelerators and/or emulsifiers.
  • fuel additives USA-3,275,554; DE-A-21 25 039 and DE-A-36 11 230
  • surfactants drugs and crop protection agents
  • hardeners for epoxy resins WO2015/200408 A1 and WO2014/121959 A1
  • intermediates for the preparation of quaternary ammonium compounds plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile assistants, dyes,
  • US 2014/0018547 A1 (BASF) refers to a process for the production of pyrrolidine and also teaches a process for the separation of the resulting reaction mixture (see paragraphs [0073] to [0084]). The formation of bis(pyrrolidino)butane is taught as an unwanted by-product (see paragraph [0079]). US 2014/0018547 A1 is silent on any further purification steps to obtain pure bis(pyrrolidino)butane.
  • DE 199 57 672 A1 (BASF) refers to a process for the purification of pyrrolidine, wherein pyrrolidine and water are separated by means of distillation at a pressure below 0.95 bar.
  • DE 199 57672 A1 is silent on any further purification steps to obtain pure bis(pyrrolidino)butane.
  • the technical problem to be solved by the present invention was to find an efficient process for the separation of a mixture comprising pyrrolidine, bis(pyrrolidino)butane and water and to obtain pyrrolidine and bis(pyrrolidino)butane with high purity.
  • the technical problem was also to improve existing processes for separation of a mixture comprising pyrrolidine, bis(pyrrolidino)butane and water, and to remedy one or more disadvantages of the prior art.
  • the technical problem as specified above can be solved by a continuous process for the separation of a mixture comprising pyrrolidine, bis(pyrrolidino)butane and water, the process comprising the following steps:
  • the respective pyrrolidine or bis(pyrrolidino)butane obtained in accordance with the present invention has a high purity.
  • the pyrrolidine obtained according to the present invention has a purity of equal to or more than 95 wt.-%, preferably equal to or more than 98 wt.-%, even more preferably equal to or more than 99 wt.-%.
  • the water content is usually less than 2 wt.-%, preferably less than 1 wt.-%, even more preferably less than 0.5 wt.-%.
  • the bis(pyrrolidino)butane obtained according to the present invention has a purity of equal to or more than 90 wt.-%, preferably equal to or more than 93 wt.-%, even more preferably equal to or more than 95 wt.-%.
  • the water content is usually less than 2 wt.-%, preferably less than 1 wt.- %, even more preferably less than 0.5 wt.-%.
  • the removal of water and pyrrolidine according to step C) is achieved, by distillation or by extraction and subsequent distillation. Respective embodiments are discussed below in more detail.
  • the high-boiler stream (7) also comprises water.
  • Another aspect of the intention was also to find a preferred embodiment of the process to be performed in an efficient manner without the formation of a solid, the formation of which adversely affects the technical feasibility of the process.
  • the high-boiler stream (7) comprises equal to or less than 10% by weight of water. Any weight percentage for a certain stream refers to the total mass per hour of that stream. For example, the weight percentage of water in the high boiler stream (7) is based on total mass per hour of such stream (7). Weight percentage is denoted as “wt.-%” or “% by weight”, which are used synonymously.
  • the solid formation can be attributed to the formation of a bis(pyrrolidino)butane hydrate, the formation of which depends on the water content.
  • the melting point of a mixture of 50% by weight water and 50% by weight bis(pyrrolidino)butane is 56°C, whereas a mixture of 5% by weight water and 95% by weight bis(pyrrolidino)butane remains liquid at 21 °C.
  • a water content of equal to or less than 10% by weight therefore significantly reduces unwanted hydrate formation and thus requires less efforts with respect to proper insulation and heating tracing.
  • a smaller water content is even more preferred, for example a water content of equal to or less than 9% by weight, equal to or less than 8% by weight, equal to or less than 7% by weight, equal to or less than 6% by weight or equal to or less than 5% by weight.
  • a water content of less than 5% by weight is also possible.
  • step A) can be conducted by using a column, that provides for sufficient separation efficiency.
  • Separa- tion efficiency is mainly governed by the amount of theoretical stages and the reflux rate. I.e. the higher the amount of theoretical stages and the reflux rate, the higher is the separation efficiency.
  • the amount of mixture to be subjected to the process according to the present invention is preferably considerably high.
  • the mixture (i.e. the mixture stream (1)) being fed into the process has a flow rate of equal to or greater than 10 kg/h, preferably equal to or greater than 500 kg/h. Even more preferably the mixture being fed into the process has a flow rate in the range from 10 to 4000 kg/h or 500 to 3000 kg/h.
  • Suitable columns are for instance packed columns.
  • the internals of such packed columns may be structured packings, mesh packings or random packings. Tray columns can also be used.
  • the diameter of these columns is preferably in the range from 0.4 to 0.9 m.
  • the packed height of these columns is preferably in the range from 8 to 25 m.
  • Any distillation pressure as referenced herein refers to the absolute pressure in the head of the respective column.
  • Stream (2) resulting from step A) mainly consists of water and pyrrolidine. It may further contain small amounts of other compounds such as ammonia or tetrahydrofuran.
  • stream (2) is withdrawn overhead and stream (7) is withdrawn as a bottom stream.
  • Step A) is usually conducted in a column.
  • the number of theoretical stages is usually equal to or above 15, preferably in the range from 15 to 60. Suitable types of columns are specified above.
  • the pressure is preferably in the range from 1 to 5 bar.
  • the head temperature is preferably in the range from 92 to 141 °C and the sump temperature is preferably in the range from 131 to 194 °C.
  • the reflux ratio is preferably in the range from 0.1 to 10 or even more preferably 1 to 8.6.
  • step B the value product bis(pyrrolidino)butane is separated from the remaining water and other compounds.
  • bis(pyrrolidino)butane is withdrawn overhead or as a side stream.
  • water is withdrawn as a bottom stream.
  • the bis(pyrrolidino)butane stream (8) in step B) is preferably withdrawn as a side stream. Any compounds having a higher boiling point than bis(pyrrolidino)butane (for example 1-(4-(pyrrolidin- 1-yl)butyl)pyrrolidin-2-one) can be purged as bottom stream.
  • a distillate stream can be withdrawn overhead. Such distillate stream can be used to purge compounds having a lower boiling than bis(pyrrolidino)butane (for example water, 1,4-butanediamine, or N-aminobutylpyrrolidine). Increasing the distillate stream in general helps to increase the purity of the bis(pyrrolidino)butane.
  • the reflux ratio is in the range from 5 to 400 or even more preferably in the range from 24 to 180.
  • Step B) is usually conducted in a column.
  • the number of theoretical stages is usually equal to or above 15, preferably in the range from 15 to 60, more preferably in the range from 30 to 60. Suitable types of columns are specified above.
  • the pressure is preferably in the range from 0.01 to 0.60 bar.
  • the head temperature is preferably in the range from 103 to 179 °C and the sump temperature is preferably in the range from 142 to 248 °C. Preferred reflux ratio ranges are given above.
  • step C) may further comprise the removal of other compounds, in particular any compound that has not been removed via the high-boiler stream (7) in step A).
  • This can be for example compounds having a lower boiling point than pyrrolidine (for example tetra hydrofuran).
  • the high boiler stream (7) usually comprises 50 to 95 wt.-% of bis(pyrrolidino)butane, preferably 55 to 90 wt.-% or even 55 to 80 wt.-%.
  • bis(pyrrolidino)butane and water such stream may also comprise other compounds, in particular N-propylpyrrolidine, N-butylpyrrolidine and N- aminobutylpyrrolidine.
  • step C) the removal of water and the pyrrolidine stream (6) from the low boiler stream (2) is for instance possible by subjecting the low boiler stream to low-pressure distillation, preferably below 0.95 bar, wherein the pyrrolidine stream (6) is withdrawn overhead.
  • the pressure is below 0.5 bar.
  • the pressure is in the range from 0.2 to 0.4 bar, particularly preferred in the range from 0.25 to 0.35 bar.
  • Such low-pressure distillation is for instance taught in DE 199 57 672 A1 (BASF).
  • BASF DE 199 57 672 A1
  • the major drawback is, that pyrrolidine is obtained overhead and its liquefaction requires cooling at low temperature. If the available condensation temperature is not significantly low, the loss of pyrrolidine in the exhaust is significant.
  • step C) comprises the following steps: C1) dewatering low-boiler stream (2) to form a stream (5) comprising the bulk of the pyrrolidine; and
  • Dewatering of the low-boiler stream (2) as per step C1 can be conducted for instance by means of extraction or distillation. Preferred embodiments are detailed in connection with alternative I and II below.
  • Step C2 serves for the purification of pyrrolidine.
  • remaining water and organic impurities for example N-methyl-pyrrolidine
  • Step C2 serves for the purification of pyrrolidine.
  • Step C2 is usually conducted in a column.
  • the number of theoretical stages is usually equal to or above 15, preferably in the range from 15 to 100 or even more preferably 45 to 85. Suitable types of columns are specified above.
  • the pressure is preferably in the range from 1 to 5 bar.
  • the head temperature is preferably in the range from 86 to 146 °C and the sump temperature is preferably in the range from 96 to 159 °C.
  • the reflux ratio is preferably in the range from 0.1 to 50.
  • stream (6) can be withdrawn overhead or as a side stream.
  • the pyrrolidine stream (6) in step C2 is withdrawn overhead.
  • By means of overhead withdrawal it can be ensured, that the pyrrolidine is essentially free of respective mid- and high boilers. This is particularly preferred for alternative I (as further specified below), when a distillate stream is removed overhead in step Cl.I.b) or for alternative II (as further specified below), when distillate stream is removed overhead in step C1.II. a), since the respective distillate stream is used as a low boiler purge. In such cases, the amount of low boilers in stream (5) is already considerably low.
  • step C1 of the process according to the present invention comprises either steps Cl.I.a) to CI .I.c) according to alternative I or steps d .ll.a) to d .ll.c) according to alternative II as follows: alternative I:
  • CI .I.c optionally but preferably recycling stream (9I) to step Cl .I.a); wherein, the distillation according to step Cl.I.b) is conducted at a pressure of > 1.5 bar.
  • step Cl.I.b is conducted at a pressure of > 1.5 bar.
  • step Cl.I.b removal of the bulk of water from low-boiler stream (2) by distillation as a bottom stream to form an overhead or side stream (4); Cl.ll.b) separating stream (4II) by distillation into an overhead or side stream (9I) comprising a water/pyrrolidine azeotrope and stream (5) comprising pyrrolidine as a bottom stream; and
  • step Cl.ll.a optionally but preferably recycling stream (9) to step Cl.ll.a). wherein the distillation according to step d.ll.a) is conducted at a pressure of > 1.5 bar and the distillation according to step d .ll.b) is conducted at a pressure which is above, preferably at least 1 bar above the pressure of step d .Ila).
  • the bulk of water is removed via extraction.
  • the major advantage as compared to the low-pressure distillation as taught in DE 199 57672 A1 is, that according to step d .Lb), the bulk of the pyrrolidine can be removed as a bottom stream whereas the remaining water is removed as a water/pyrrolidine azeotrope.
  • the process is less sensitive with respect to the separation efficiency of the respective column.
  • the required condensation temperature is higher.
  • usually normal cooling water suffices. Therefore, with respect to pyrrolidine quality, particularly with respect to the requirement of a low water content, the process according to alternative I constitutes more robust alterative as compared to the low-pressure distillation.
  • the low-pressure distillation as taught in DE 199 57672 A1 is quite sensitive with respect to a not ideal operation conditions of the respective column which might for instance arise from slight deterioration of the column packing. In such case, the separation of water along the column is not sufficient, and an increased amount of water is contained in the pyrrolidine which is withdrawn at the head of the column. Thus, the risk of obtaining off-spec pyrrolidine, particularly in case of longer operation times, is quite high in case of the low-pressure distillation as taught in DE 199 57672 A1.
  • step Cl.I.a the bulk of water is usually withdrawn as a bottom stream.
  • the bottom stream is usually subjected to any kind of wastewater treatment.
  • Stream (41) is preferably withdrawn overhead. This is in particular preferable, when a distillate stream is withdrawn in step Cl .I.b).
  • an alkaline solution preferably a solution of caustic soda
  • its concentration is preferably in the range from 40 to 60 wt.-%.
  • the extraction according to step Cl.I.a) is usually conducted in a column.
  • the number of theoretical stages is usually equal to or above 1, preferably in the range from 1 to 10 or even more preferably in the range from 2 to 8 or even 3 to 5. Suitable types of columns are specified above.
  • the pressure is preferably in the range from 0.5 to 3 bar and the temperature is preferably in the range from 20 to 70 °C.
  • the distillation according to step Cl .I.b) is usually conducted in a column.
  • the number of theoretical stages is usually equal to or above 15, preferably in the range from 15 to 60 or even more pref- erably 40 to 60. Suitable types of columns are specified above.
  • the pressure is preferably in the range from 1.75 to 5 bar.
  • the head temperature is preferably in the range from 99 to 140 °C and the sump temperature is preferably in the range from 99 to 145 °C.
  • the reflux ratio is preferably in the range from 10 to 1000.
  • step CI.I.c stream (91) is recycled to step Cl.I.a). This can be achieved for example by feeding stream (2) and stream (91) into an appropriate mixing device, where both streams are mixed. The resulting stream (31) is then fed into step Cl .I.b). This is also shown in Fig. 1. Since stream (9I) also comprises pyrrolidine, the recycling increases the pyrrolidine yield.
  • step Cl.I.b it is preferred to withdraw stream (91) as a side stream.
  • step Cl.I.b it is even more preferred to withdraw stream (91) as a side stream and to withdraw a distillate stream overhead.
  • the distillate stream works as a low boiler purge (a respective low boiler is for instance N-methylpyrrolidine).
  • a respective low boiler is for instance N-methylpyrrolidine.
  • alternative II further has the advantage that water is removed by distillation.
  • the wastewater that is generated according to alternative II is the water removed from the mixture.
  • extraction requires an additional amount of water being part of the extracting agent, thus more wastewater needs to be treated.
  • the extracting agent is not only water but also contains a base, in particular caustic soda.
  • base in particular caustic soda.
  • caustic soda impacts the environment at least because of the CO2, that is generated thereby. All this will be of fundamental importance throughout the next decades because governmental provisions regarding environmental protection are becoming increasingly strict.
  • the process according to alternative II has also certain advantages as compared to the low-pressure distillation as taught in DE 199 57 672 A1. Particularly, according to step C1.IL b), the bulk of the pyrrolidine can be removed as a bottom stream whereas the remaining water is removed as a water/pyrrolidine azeotrope. Thus, the process is less sensitive with respect to the separation efficiency of the respective column. Therefore, with respect to pyrrolidine quality, particularly with respect to the requirement of a low water content, the process according to alternative II constitutes more robust alterative as compared to the low-pressure distillation as taught in DE 199 57672 A1. Moreover, because of the higher pressure under which the distillation is con- ducted, the required condensation temperature is higher. Thus, usually normal cooling water suffices.
  • step d.ll.a) low pressure azeotropic distillation
  • d.ll.b high pressure azeotropic distillation
  • the water/pyrrolidine azeotrope formed in step d.ll.a) has a higher pyrrolidine concentration that the water/pyrrolidine azeotrope formed in step d.ll.b), consequently having a lower pyrrolidine concentration.
  • the azeotropic point is overcome by feeding the low pressure azeotrope of step d.ll.a) into a high pressure distillation of step d.ll.b), where the azeotrope is lower in concentration.
  • the respective water/pyrrolidine azeotrope is a temperature-minimum azeotrope which means that both azeotropes will concentrate at the top of the column at the lower temperatures while the pure products such as water and pyrrolidine are being concentrated at the bottom of the columns. This is also explained in Example 4.2.7 for specific concentrations.
  • step d.ll.a) is conducted at a pressure in the range from
  • step d .ll.b) is conducted at a pressure in the range from 2.5 to 10 bar, wherein the pressure in step d .ll.b) is at least 1 bar, preferably at least 8.5 bar, above the pressure in step d.ll.a).
  • the distillation according to step d.ll.a) is conducted at a pressure in the range from 1.5 to 1.75 bar and the distillation according to step d .ll.b) is conducted at a pressure in the range from 6.5 to 10 bar, wherein the pressure in step d.ll.b) is at least 5 bar, preferably at least 8.25 bar, above the pressure in step d.ll.a).
  • the low-pressure distillation according to step d.ll.a) is preferably conducted in a column.
  • the number of theoretical stages is usually equal to or above 15, preferably in the range from 15 to 60 or even more preferably 40 to 60. Suitable types of columns are specified above.
  • the head temperature is preferably in the range from 80 to 113 °C and the sump temperature is preferably in the range from 106 to 152 °C.
  • the reflux ratio is preferably in the range from 500 to 3000.
  • the high-pressure distillation according to step C1 .IL b) is preferably conducted in a column.
  • the number of theoretical stages is usually equal to or above 15, preferably in the range from 15 to 60 or even more preferably 40 to 60. Suitable types of columns are specified above.
  • the head temperature is preferably in the range from 140 to 180 °C and the sump temperature is preferably in the range from 150 to 200 °C.
  • the reflux ratio is preferably in the range from 0,5 to 50.
  • stream (4II) is a side stream and a distillate stream is removed overhead.
  • Such distillate stream usually contains tetra hydrofuran. If stream (4II) is withdrawn overhead, low-boilers (in particular tetrahydrofuran) can only be removed, if stream (9II) is not recycled. However, if stream (9II) is recycled, it is advantageous to realize such distillate stream because otherwise such low boilers (in particular tetrahydrofuran) would be circulated between steps Cl.ll.a) and Cl .ll.b).
  • step Cl .ll.b stream (911) is withdrawn overhead.
  • stream (911) is withdrawn overhead.
  • a distillate stream in realized in step d .ll.a that means, low-boilers (e.g. tetrahydrofuran) have already been purged in step d .ll.a).
  • steam (411) is essentially free of low-boilers and the overhead stream (911) is not contaminated with low-boilers, accordingly.
  • the process according to the present invention is particularly suited for those mixtures that contain a certain amount of water.
  • this water is formed in the synthesis of the pyrrolidine and bis(pyrrolidino)butane, respectively. Details regarding synthesis are presented below.
  • the mixture to be purified by the process according to the present invention preferably has a composition as follows:
  • 4-amino-/4-hydroxybutylpyrrolidine or alkyl pyrrolidines are for example obtained as by-products in the reaction of 1 ,4-butanediol with ammonia and/or pyrrolidine. It is to be noted, that the composition of the mixture, including the amount and type of the compounds designated as “others” depends on how the mixtures was obtained.
  • the amount of the above specified organic components can be analyzed by means of gas chromatography.
  • the water content can be analyzed by means of Karl-Fischer titration.
  • the mixture can be obtained either from i. the reaction of 1 ,4-butanediol with pyrrolidine in the presence of hydrogen and a hydrogenation catalyst, or ii. the reaction of 1 ,4-butanediol with ammonia or a mixture of ammonia and pyrrolidine in the presence of hydrogen and a hydrogenation catalyst and subsequent removal of unreacted ammonia from the resulting crude reaction product, preferably via distillation.
  • Ammonia, pyrrolidine, or a respective mixture thereof can be used in a molar amount which is from 0.90 to 100 times that of the 1 ,4-butanediol. Preferably it is 1 to 30, particularly preferably 1.5 to 10 or even 2 to 8 times that of the 1 ,4-butanediol. For the avoidance of doubt, reference is made to the molar amount of entire 1 ,4-butanediol molecule; not the molar amount of two functional alcohol groups.
  • STP means standard conditions for temperature and pressure.
  • the reactions can be carried out at an absolute pressure in a range from 1 to 300 bar, preferably 10 to 50 bar, particularly preferably 10 to 30 bar or even 15 to 30 bar.
  • the reactions can be carried out at a temperature in a range from 80 to 300 °C, preferably 100 to 250 °C, particularly preferably 150 to 240 °C or even 170 to 230 °C.
  • the reaction can be carried out adiabatically, isothermally or quasi isothermally (i.e. isoperibolically) provided in each case that the temperature in the reactor is within the respective range as per the preceding sentence.
  • the reaction is carried out with an isoperibolic temperature profile to control the temperature of the reaction within borders of ⁇ 15 K, particularly preferably ⁇ 10 K.
  • the conversion of 1 ,4-butanediol is preferably in the range from 80 to 100 %, more preferably 99 to 100% or even 99.5 to 100%.
  • the reactions are preferably conducted continuously.
  • a fixed-bed reactor is used, in which case the liquid hourly space velocity is preferably in the range from 0.1 to 2.0 kg, preferably from 0.1 to 1.0 kg, particularly preferably from 0.2 to 0.6 kg, of 1 ,4-butanediol per litre of catalyst (bed volume) and hour.
  • the mixture preferably has a composition as follows:
  • the mixture i.e. after the removal of ammonia from the respective crude reaction product preferably has a composition as follows:
  • the reaction of 1 ,4-butanediol with ammonia is preferred.
  • a continuous production process is used, which comprises reacting 1 ,4-butanediol with ammonia in the presence of hydrogen and a heterogeneous hydrogenation catalyst in the gas phase using a recycle gas mode, wherein the temperature in the pressure separator is > 20°C.
  • the temperature in the pressure separator is > 21 °C or even > 25°C.
  • Best results with respect to pyrrolidine and bis(pyrrolidino)butane selectivity can be obtained by realizing a temperature in the pressure separator which is > 30°C.
  • the temperature in the pressure separator is in the range from 30 to 70°C, even more preferably from 30 to 60°C.
  • the removal of unreacted ammonia from the resulting crude reaction product is preferably conducted via distillation.
  • the distillation is preferably conducted in a column.
  • the number of theoretical stages is usually equal to or above 5, preferably in the range from 5 to 30 or even more preferably 9 to 30. Suitable types of columns are specified above.
  • the pressure is preferably in the range from 15 to 25 bar.
  • the head temperature is preferably in the range from 30 to 60 °C and the sump temperature is preferably in the range from 180 to 210 °C.
  • the reflux ratio is preferably in the range from 0,1 to 15.
  • a synthesis’ outlet (crude reaction product) is fed into the middle part of the ammonia removal column (C1).
  • the synthesis can be conducted in accordance with option ii. as further specified above.
  • the resulting mixture stream (1) is withdrawn from the bottom of C1 and fed into the middle part of the high boiler removal column (C2), where the mixture is separated into the low-boiler stream (2) withdrawn at the top of column C2 and the high boiler stream (7) withdrawn at the bottom of C2 (corresponding to step A)).
  • Stream (7) is fed in the middle part of BPB purification column (C6) where a bis(pyrrolidino)butane stream (8) is withdrawn as a side stream (corresponding to step B)).
  • Any high boilers may be purged in C6’s bottom draw.
  • the flow of the bottom draw can be adjusted in order to affect the specification of the BPB product.
  • the distillate stream obtained at the head of column C6 might be used as light boiler purge but also contains the desired product BPB (light boilers are for instance 4-amino-/4-hydroxybutylpyrrolidine, alkyl pyrrolidines (methyl-, propyl-, butyl-)).
  • Streams (2) and (9I) are fed into a mixer and the resulting stream (3I) is fed to the middle part of extraction column C3, where caustic soda solution is fed above stream (3I), a wastewater stream is withdrawn at the bottom and stream (4I) is withdrawn overhead (corresponding to step Cl.I.a) and step CI.I.c) for the recycling).
  • Stream (4I) is fed into a middle part of azeotropic column C4, where stream (9I) is obtained as a side stream and stream (5) is withdrawn from the bottom (corresponding to step C1 .Lb)).
  • C4 contains a distillate stream that works as low boiler purge (low boilers are for instance tetrahydrofuran and N-methylpyrrolidine). The flow of the distillate stream can be adjusted in order to adjust the product specifications or to decrease or increase pyrrolidine yield.
  • Stream (5) is fed into a middle part of pyrrolidine purification column C5, where a pyrrolidine stream (6) is withdrawn overhead (corresponding to step C2)).
  • a synthesis’ outlet is fed into the middle part of the ammonia removal column (C1).
  • the synthesis can be conducted in accordance with option ii. as further specified above.
  • the resulting mixture stream (1) is withdrawn from the bottom of C1 and fed into the middle part of the high boiler removal column (C2), where the mixture is separated into the low-boiler stream (2) withdrawn at the top of column C2 and the high boiler stream (7) withdrawn at the bottom of C2 (corresponding to step A)).
  • Stream (7) is fed in the middle part of BPB purification column (C6) where a bis(pyrrolidino)butane stream (8) is withdrawn as a side stream (corresponding to step B)).
  • Any high boilers may be purged in C6’s bottom draw.
  • the flow of the bottom draw can be adjusted in order to affect the specification of the BPB product.
  • the distillate stream obtained at the head of column C6 might be used as light boiler purge but also contains the desired product BPB (light boilers are for instance 4-amino-/4-hydroxybutylpyrrolidine, alkyl pyrrolidines (methyl-, propyl-, butyl-)).
  • Streams (2) and (9II) are fed into a mixer and the resulting stream (3II) is fed to the middle part of low-pressure azeotropic column C3, where a wastewater stream is withdrawn at the bottom and stream (4II) is withdrawn as a side stream (corresponding to step Cl .I.a) and step CI .I.c) for the recycling).
  • the distillate stream obtained at the head of column C3 might be used as light boiler purge (light boilers are for instance tetrahydrofuran and N-methylpyrrolidine)
  • Stream (411) is fed into a middle part of the high pressure azeotropic column C4, where stream (911) is obtained as an overhead stream and stream (5) is withdrawn from the bottom (corresponding to step Cl .I.b)).
  • Stream (5) is fed into a middle part of pyrrolidine purification column C5, where a pyrrolidine stream (6) is withdrawn overhead (corresponding to step C2)).
  • a pyrrolidine stream (6) is withdrawn overhead (corresponding to step C2)).
  • the following example was carried out using a copper/nickel catalyst having the composition 45% by weight of CuO and 10% by weight of NiO, the remainder up to 100% is AI2O3, as described in DE 10 2004 023 52 (after its last heat treatment and before reduction with hydrogen).
  • the shaped catalyst bodies were used in pellet form in sizes of 5x5 mm (i.e. 5 mm diameter and 5 mm height). Before commencement of the reaction, the catalyst was reduced (see below).
  • the experiment was carried out continuously in a gas phase furnace reactor through which the reactants flowed from the bottom upward in a 2.1 m long oil-heated double-walled tube which had an internal diameter of 4.8 cm and was filled from the bottom upward with 40 ml of ceramic spheres (2.5-3.5 mm), 1 liter of catalyst and 1.5 liters of inert material (ceramic spheres, 2.5- 3.5 mm).
  • the reactor was operated at 20 bar.
  • the catalyst was activated at atmospheric pressure according to the following method: 12 h at 180° C (oil circuit reactor) with 20 NL/h and 400 NL/h of N 2 , 12 hat 200° C.
  • the reactor output was cooled firstly with river water and then heated to the desired temperature of the pressure separator (49 °C) using a cryostat and was fed to a pressure separator.
  • the separation of liquid phase and gas phase occurred there.
  • the liquid phase was depressurized in a low-pressure separator maintained at 45° C from where the released gases were discharged via the offgas (in particular hydrogen and the major part of unreacted ammonia) and the liquid was conveyed into the output drum.
  • the gas phase from the pressure separator was recirculated in a defined amount via a circulating gas compressor and once again served as carrier gas for the starting materials.
  • a pressure regulator ensured that excess gas was conveyed to the muffle furnace for incineration. Conversion and selectivity of the output were determined by gas-chromatographic analysis and are reported in corrected GC area%. The water content was determined by Karl-Fischer titration. Composition of the raw product mixture:
  • a copper catalyst comprising 55% by weight of CuO and 45% of weight by AI2O3, as described in W02010/031719 A1 .
  • the shaped catalyst bodies were used in pellet form in sizes of 3x3 mm (i.e. 3 mm diameter and 3 mm height). Before commencement of the reaction, the catalyst was reduced (see below).
  • the experiments were carried out continuously in a steel reactor of 770 mm length, wall thickness 3 mm and inner diameter 12 mm with electric heating through which the reactants flowed from the bottom upward.
  • the reactor was filled from top to bottom with 3 wire mesh rings, 10 mL glass sphere (diameters: 3 mm), 70 mL catalyst and 15 mL glass spheres (diameter: 3 mm) and 3 wire mesh rings.
  • thermodynamic parameters used in the program for the individual components are based on published thermodynamic data or in-house measurements.
  • the specification and the simulation of the specified distillation columns used were performed with the customary routines included in the software.
  • the simulated results were compared with experimental results, where available, and the simulation model was aligned with the experimental results so that a good agreement between simulation and experimental data was able to be achieved.
  • the simulation is based on production of pyrrolidine and bis(pyrrolidino)butane by reacting 1,4- butanediol and ammonia (for instance in accordance with Example 1). That means the reactions product contains unreacted ammonia what requires ammonia removal.
  • ammonia removal already occurred in a low-pressure separator.
  • a respective ammonia column as shown below in Example 4 is used instead of a low-pressure separator.
  • FIG 1 A flow chart of the process according to alternative I is shown in Fig 1 .
  • ammonia separation is set up by the ammonia column (C1).
  • the liquid outlet of synthesis’ high pressure flash vessel (not shown in Fig. 1) feeds into the C1 whereas ammonia is separated from the residual product flow. This column operates at around
  • Such bottom draw (1) contains water (33.37 wt.-%), pyrrolidine (54.62 wt.-%), bis(pyrrolidino)butane (7.24 wt.-%), others (4.76 wt.-%).
  • the high boiler column (C2) aims to separate high boilers such as bis(pyrrolidino)butane (BPB) and some water from the light boiler stream (2) mainly consisting of pyrrolidine and water.
  • This column operates at about 3 barabs and a head and sump temperature of about 124 °C and 172 °C, respectively.
  • the bottom draw (7) contains water (5 wt.-%), bis(pyrrolidino)butane (67.51 wt.-%), others (27.49 wt.-%).
  • Such other components contained in stream (7) are in particular N-propylpyrrolidine, N-butylpyrrolidine and N- aminobutylpyrrolidine.
  • the distillate stream (2) contains water (36.78 wt.-%), pyrrolidine (61.19 wt.- %), others (2.03 wt.-%) .
  • the C2’s distillate stream (2) is mixed (MIX) with the water-pyrrolidine temperature-minimum azeotrope side draw (9I) of the azeotropic column (C4).
  • the resulting azeotropic mixture (3I) is then fed into the water extraction column (C3) which generates two phases, an aqueous and an organic phase, by adding 50 wt-% caustic soda (NaOH).
  • the ratio of caustic feed to organic feed is set up to 0.35 mass caustic to mass organic.
  • the organic outlet stream (4I) contains maximum 3 wt-% water. This way, the azeotrope has been dewatered via extraction.
  • This extraction column operates at about 1.1 barabs and around 55 - 60 °C.
  • the organic phase (4I) is fed to the azeotropic column (C4).
  • This column operates at about 3 barabs and a head and sump temperature of around 103 °C and 124.9 °C, respectively.
  • the side draw (9I) contains the azeotrope which is sent back in front of the water extraction column (C3).
  • the side draw’s (9I) composition is close to the highest possible azeotropic concentration of a pure binary system with pyrrolidine and water at 3 barabs with 86 wt-% pyrrolidine and 14 wt-% water. With this setting the bottom draw (5) is significant low in water concentration to ensure less than 0.20 weight-% water in the product stream (6).
  • the bottom draw (5) contains water (0.20 wt.-%) pyrrolidine (99.46 wt.-%) and others (0.35 wt.-%).
  • the purification column (C5) concentrates the light boiler pyrrolidine at the head.
  • the column operates at around 3 barabs and a head and sump temperature of about 124 °C and 135 °C, respectively. Any high boilers dragged along since the high boiler column (C2) are purged in C5’s bottom draw.
  • the product stream contains 99.6 weight-% pyrrolidine and 0.2 weight-% water.
  • the C2’s bottom draw (7) is fed to the BPB purification column (C6).
  • This column operates at about 0.04 barabs and a head and sump temperature of about 121 °C and 170 °C, respectively. Any high boilers may be purged in C6’s bottom draw.
  • the resulting product has purity of 95 wt.-% BPB.
  • FIG. 1 A flow chart of the process according to alternative II is shown in Fig 2.
  • the C2’s destillate stream (2) is mixed (MIX) with the high pressure water-pyrrolidine temperature-minimum azeotrope (9II) of the high pressure azeotropic column (C4) after the low pressure distillation column (C3).
  • This azeotropic mixture (3II) is then fed into C3 operating at about 2 barabs and a head and sump temperature of about 95 °C and 120 °C, respectively.
  • the bottom draw (WW) is significant low in pyrrolidine concentration used as high boiler purge.
  • the vapor and distillate streams are used as light boiler purges.
  • the low pressure azeotrope is drawn at the side (4II). The concentration is close to the highest possible azeotropic concentration of a pure binary system with pyrrolidine and water at 2 barabs with 91 weight-% pyrrolidine and 9 weight-% water.
  • the low pressure azeotrope (4II) is fed to the high pressure azeotropic column (C4).
  • This column operates at about 10 barabs and a head and sump temperature of around 168 °C and 180 °C, respectively.
  • the reflux rate is kept low to keep the distillate stream (9II) low.
  • the distillate stream’s (9II) composition is close to the highest possible azeotropic concentration of a pure binary system with pyrrolidine and water at 10 barabs with 76 weight-% pyrrolidine and 24 weight-% water. With this setting the bottom draw (5) is significant low in water concentration to ensure less than 0.20 weight-% water in the product stream (6).
  • the product stream contains 99.6 weight-% pyrrolidine and 0.2 weight-% water.
  • the resulting product has purity of 95 wt.-% BPB.
  • the azeotrope at 2 barabs is around 91 weight-% pyrrolidine while the azeotrope at 10 barabs is around 76 weight-% pyrrolidine.
  • the azeotropic point is overcome by feeding the low pressure azeotrope with around 91 weight-% pyrrolidine into a high pressure column where the azeotrope is lower in concentration at 76 weight-% pyrrolidine.
  • it is a temperature-minimum azeotrope which means that both azeotropes will concentrate at the top of the column at the lower temperatures while the pure products such as water and pyrrolidine are being concentrated at the bottom of the columns.

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

Abstract

L'invention concerne un procédé continu de séparation d'un mélange comprenant de la pyrrolidine, du bis(pyrrolidino)butane et de l'eau, ledit procédé comprenant les étapes suivantes consistant : A) à séparer un flux de mélange (1) par distillation en un flux à bas point d'ébullition (2) comprenant de la pyrrolidine et de l'eau et un flux à haut point d'ébullition (7) comprenant du bis(pyrrolidino)butane ; B) à éliminer du flux (7) un flux de bis(pyrrolidino)butane (8) par distillation ; et C) à éliminer l'eau du flux à bas point d'ébullition (2) afin d'obtenir un flux de pyrrolidine (6).
PCT/EP2022/069876 2021-11-22 2022-07-15 Procédé continu de séparation d'un mélange comprenant de la pyrrolidine, du bis(pyrrolidino)butane et de l'eau Ceased WO2023046330A1 (fr)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3275554A (en) 1963-08-02 1966-09-27 Shell Oil Co Polyolefin substituted polyamines and lubricants containing them
DE2125039A1 (de) 1970-05-21 1971-12-02 Shell Int Research Verfahren zur Herstellung von Aminen und deren Verwendung als Zusatzstoffe für Schmierstoffe und Kraft- bzw. Brennstoffe
DE3611230A1 (de) 1986-04-04 1987-10-08 Basf Ag Polybutyl- und polyisobutylamine, verfahren zu deren herstellung und diese enthaltende kraft- und schmierstoffzusammensetzungen
DE19957672A1 (de) 1999-11-30 2001-05-31 Basf Ag Verfahren zur Entwässerung und Reinigung von Rohpyrrolidin
US20030089592A1 (en) * 2001-10-30 2003-05-15 Andreas Wolfert Process for fractionating water-containing crude amine mixtures from amine synthesis
DE102004023520A1 (de) 2004-05-10 2005-12-08 Romeo Adaci Akustische Vorrichtung, insbesondere Aerophon
DE102004023529A1 (de) 2004-05-13 2005-12-08 Basf Ag Verfahren zur kontinuierlichen Herstellung eines Amins
WO2010031719A1 (fr) 2008-09-19 2010-03-25 Basf Se Procédé de préparation en continu d'une amine au moyen d'un catalyseur à base d'aluminium et de cuivre
US20140018547A1 (en) 2012-07-13 2014-01-16 Basf Se Process for Preparing Pyrrolidine
WO2014121959A1 (fr) 2013-02-05 2014-08-14 Evonik Industries Ag Amines, convenant pour une utilisation à la préparation de polyuréthanes
WO2015200408A1 (fr) 2014-06-27 2015-12-30 Huntsman Petrochemical Llc Catalyseurs à base de pyrrolidine destinés à être utilisés dans des matériaux de polyuréthane

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3275554A (en) 1963-08-02 1966-09-27 Shell Oil Co Polyolefin substituted polyamines and lubricants containing them
DE2125039A1 (de) 1970-05-21 1971-12-02 Shell Int Research Verfahren zur Herstellung von Aminen und deren Verwendung als Zusatzstoffe für Schmierstoffe und Kraft- bzw. Brennstoffe
DE3611230A1 (de) 1986-04-04 1987-10-08 Basf Ag Polybutyl- und polyisobutylamine, verfahren zu deren herstellung und diese enthaltende kraft- und schmierstoffzusammensetzungen
DE19957672A1 (de) 1999-11-30 2001-05-31 Basf Ag Verfahren zur Entwässerung und Reinigung von Rohpyrrolidin
US20030089592A1 (en) * 2001-10-30 2003-05-15 Andreas Wolfert Process for fractionating water-containing crude amine mixtures from amine synthesis
DE102004023520A1 (de) 2004-05-10 2005-12-08 Romeo Adaci Akustische Vorrichtung, insbesondere Aerophon
DE102004023529A1 (de) 2004-05-13 2005-12-08 Basf Ag Verfahren zur kontinuierlichen Herstellung eines Amins
WO2010031719A1 (fr) 2008-09-19 2010-03-25 Basf Se Procédé de préparation en continu d'une amine au moyen d'un catalyseur à base d'aluminium et de cuivre
US20140018547A1 (en) 2012-07-13 2014-01-16 Basf Se Process for Preparing Pyrrolidine
WO2014121959A1 (fr) 2013-02-05 2014-08-14 Evonik Industries Ag Amines, convenant pour une utilisation à la préparation de polyuréthanes
WO2015200408A1 (fr) 2014-06-27 2015-12-30 Huntsman Petrochemical Llc Catalyseurs à base de pyrrolidine destinés à être utilisés dans des matériaux de polyuréthane

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