USRE45240E1 - Process for preparing pure triethanolamine (TEOA) - Google Patents

Process for preparing pure triethanolamine (TEOA) Download PDF

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USRE45240E1
USRE45240E1 US14/085,964 US200914085964A USRE45240E US RE45240 E1 USRE45240 E1 US RE45240E1 US 200914085964 A US200914085964 A US 200914085964A US RE45240 E USRE45240 E US RE45240E
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teoa
column
deoa
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weight
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Johann-Peter Melder
Gunther Van Cauwenberge
Tom Fremau
Jürgen Moors
Thilo Hahn
Bernd Stein
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/10—Separation; Purification; Stabilisation; Use of additives

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  • the invention relates to a process for preparing pure TEOA by continuously distillatively separating an ethanolamine mixture comprising TEOA and diethanolamine (DEOA), by distilling off DEOA in a distillation column (DEOA column) and supplying the resulting bottom stream comprising TEOA to a downstream column (TEOA column) in which the pure TEOA is withdrawn as a side draw stream.
  • DEOA column distillation column
  • TEOA column downstream column
  • a method of assessing the color quality of pure TEOA which has been found to be useful, in addition to the time-consuming storage tests in which the APHA color number (to DIN-ISO 6271) of the TEOA is measured as a function of the storage time, is the so-called acid neutralization test.
  • This acid neutralization test allows the assessment of the color stability in the course of storage of freshly prepared TEOA within a few minutes.
  • test is described in Japanese documents JP 62 019 558 A (Derwent abstract No. 87-067647/10) and JP 62 005 939 A (Derwent abstract No. 87-047397/07), according to which the TEOA is treated (neutralized) with acetic acid, citric acid, sulfuric acid, hydrochloric acid or phosphoric acid, and then the absorbance of the absorption bands is measured at 420 nm and 530 nm.
  • the TEOA is color-stable in the course of storage, i.e. remains colorless over a period of several months,
  • the literature describes various methods of preparing pure and colorless to low-color TEOA.
  • EP 4015 A (BASF AG) states that ethanolamines with relatively low discoloration are obtained by adding phosphorous acid or hypophosphorous acid during the preparation of the ethanolamines and/or the distillative workup.
  • EP 36 152 A and EP 4015 A (both BASF AG) explain the influence of the materials used in processes for preparing alkanolamines on the color quality of the process products and recommend nickel-free or low-nickel steels.
  • U.S. Pat. No. 3,819,710 discloses a process for improving the color quality of ethanolamines by hydrogenating the crude ethanolamines in the presence of selected catalysts.
  • the process is technically complex and does not lead to a TEOA product which remains colorless over several months.
  • U.S. Pat. No. 3,207,790 describes a process for improving the color quality of alkanolamines by adding a borohydride of an alkali metal.
  • U.S. Pat. No. 3,742,059 and DE 22 25 015 A describe the improvement of the color quality of alkanolamines by the addition of an alkanolamine ester of boric acid or alkali metal/alkaline earth metal borates.
  • GB 1 062 730 A describes a process for purifying ethanolamines by purifying distillation in the presence of silicates or aluminates.
  • JP 62 019 558 A (Derwent abstract No. 87-067647/10) reports the preparation of qualitatively good TEOA by treatment of crude TEOA with inorganic oxides at 170 to 250° C. and subsequent distillation in the absence of oxygen.
  • SU 326 178 A (Derwent abstract No. 63384T-AE) describes the preparation of TEOA with good color quality by gentle reaction of anhydrous monoethanolamine (MEOA) or diethanolamine (DEOA) or mixtures of the two substances with ethylene oxide at temperatures less than 50° C.
  • MEOA monoethanolamine
  • DEOA diethanolamine
  • WO 2001/53250 A1 relates to a continuous process for the manufacture of TEOA comprising (i) a step of synthesizing the TEOA by continuously bringing ammonia into contact with ethylene oxide, under conditions allowing the formation of a reaction mixture comprising mono-, di- and triethanolamines, (ii) a step of continuously separating the ammonia that has not reacted from the reaction mixture, and (iii) a step of continuously separating the TEOA from the mixture resulting from step (ii), which process is characterized in that, in the last step, the monoethanelamine and some of the diethanolamine are separated from the mixture resulting from step (ii), a specific mixture of alkanolamines comprising TEOA and from 0.5 to 50% by weight of at least one secondary dialkanolamine is prepared or isolated, and in that the TEOA is separated and isolated with a degree of purity of ⁇ 99.2% by weight by continuous distillation of the specific mixture of alkanol
  • WO 2005/035481 A2 (BASF AG) describes the distillative removal of triethanolamine, in which the substance mixture is distilled in two stages. In the first stage, the low boiler fraction and the high boiler fraction are withdrawn and discharged, and, in the second stage, the medium boiler fraction with a triethanolamine content of >99.4% by weight and a diethanolamine content of ⁇ 0.2% by weight is distilled.
  • the substance mixture is distilled preferably in a first column and a second column connected thereto, or in a dividing wall column.
  • a high purity and color quality i.e. reduction of discoloration and/or improvement in color stability, especially in the course of storage, should be achieved.
  • the preparation process should additionally be particularly simple and economically viable.
  • TEOA pure triethanolamine
  • DEOA column distillation column
  • TEOA column downstream column
  • the invention is based on the recognition that the color quality, i.e. reduction of discoloration and/or improvement in color stability, especially in the course of storage, of the triethanolamine can be influenced positively by reducing the residence time of the ethanolamine mixture comprising di- and triethanolamine in the column bottom during the removal of the diethanolamine from this mixture.
  • FIG. 1 demonstrates the defnition of the residence time in a column.
  • the invention preferably uses a substance mixture which is obtained as follows. First, for example according to EP 673 920 A (BASF AG), by the reaction of aqueous ammonia with ethylene oxide in the liquid phase under elevated pressure and elevated temperature in a suitable reactor, an ethanolamine mixture is prepared, comprising the main components monoethanolamine (MEOA), diethanolamine (DEOA) and triethanolamine (TEOA).
  • MEOA monoethanolamine
  • DEOA diethanolamine
  • TEOA triethanolamine
  • the reaction temperatures here are especially 110 to 180° C., preferably 120 to 150° C., and the pressures are especially 50 to 150 bar (5 to 15 MPa), preferably 75 to 120 bar (7.5 to 12 MPa).
  • the molar ratio of ammonia to ethylene oxide is especially 1:1 to 100:1, preferably 3:1 to 50:1, more preferably 4:1 to 15:1, and the ammonia is used particularly as a 60 to 99.99% by weight, preferably 70 to 95% by weight, aqueous solution.
  • the ethylene oxide used can be added as the entire amount at once or in 2 to 10, preferably 2 to 6, portions of in each case 1 to 99% by weight, preferably 5 to 95% by weight, for example 10 to 70% by weight (based in each case on the total amount of EO).
  • a typical crude mixture comprises, for example, 50 to 80% by weight of DEOA and 20 to 50% by weight of TEOA.
  • the residence time of the ethanolamine mixture in the bottom of the MEOA column is preferably ⁇ 35 minutes, for example in the range from 3 to 30 min, preferably ⁇ 15 minutes, for example in the range from 2 to 10 min, more preferably ⁇ 7 minutes, for example in the range from 1 to 5 min.
  • the MEOA column is adjusted so as to result in a reflux ratio in the range from especially 0 to 0.9, preferably from 0.1 to 0.4.
  • composition of this crude product may vary according to the originally used molar ratio of ammonia to ethylene oxide.
  • the resulting ethanolamine mixture comprising predominantly DEOA and TEOA can be subjected directly to a fractional distillation, in which pure DEOA and TEOA are obtained in succession.
  • this crude product comprising predominantly DEOA and TEOA, which has a water content of preferably less than 0.3% by weight, especially less than 0.1% by weight, and an ammonia content of preferably less than 0.1% by weight, especially less than 0.01% by weight, is reacted with 0.6 to 1.2 mol, preferably 0.8 to 1.1 mol, of ethylene oxide (EO) per gram atom of hydrogen bonded to nitrogen in the crude product at temperatures of 110 to 180° C., preferably 120 to 180° C., in the liquid phase.
  • EO ethylene oxide
  • the ethanolamine mixture comprising DEOA and TEOA, preferably comprising predominantly DEOA and TEOA, used in the process according to the invention more preferably has DEOA and TEOA contents as follows:
  • DEOA 50 to 80% by weight, especially 60 to 75% by weight.
  • TEOA 20 to 50% by weight, especially 25 to 40% by weight.
  • the ethanolamine mixture comprising DEOA and TEOA is continuously separated by distillation.
  • Suitable apparatus for this purpose is customary distillation apparatus. Such apparatus is known to a person skilled in the art.
  • a DEOA column is used to remove a predominant amount of DEOA from the mixture.
  • a downstream TEOA column is used. It is possible with preference to use distillation columns with at least one transverse or longitudinal division, embodied in the form of a tray, of a dividing wall, of structureD packings or of random packings, as described, for example, in WO 2005/035481 A2 (BASF AG).
  • the so-called DEOA column in which the diethanolamine is first separated from the triethanolamine, is operated at a temperature in the bottom in the range from preferably 170° C. to 200° C.
  • the absolute pressure selected varies preferably at values in the range from 10 mbar to 20 mbar.
  • Pressure data for distillation columns in this document are always based on the absolute pressure in the top of the column.
  • the column is adjusted so as to result in a reflux ratio in the range of especially 0 to 0.6, preferably of 0.25 to 0.4.
  • the ethanolamine mixture comprising DEOA and TEOA is preferably fed into the DEOA column at the side, particularly into the side of the middle column region.
  • the residence time of the ethanolamine mixture in the bottom of the DEOA column is ⁇ 20 minutes, for example in the range from 1 to 18 min, preferably ⁇ 15 minutes, for example in the range from 2 to 13 min, more preferably ⁇ 12 minutes, for example in the range from 3 to 11 min.
  • the residence time in the bottom of the DEOA column is understood to mean the time which is calculated when the actual liquid volumes of column bottom, pipelines and pump in the bottoms circuit and holdup in the evaporator/heat exchanger are added up and divided by the volume flow which is withdrawn from this bottoms circuit.
  • the drawing of FIG. 1 serves for further explanation on this subject.
  • the diethanolamine is isolated from the DEOA column preferably as a side draw stream and preferably has a purity of z 99.3% by weight.
  • the bottoms of the DEOA column which are conducted to the downstream TEOA column, comprise particularly in the range from 15 to 33% by weight of DEOA, 65 to 83% by weight of TEOA and 0.1 to 2% by weight of other secondary components.
  • the TEOA column in which the triethanolamine is isolated is operated at a temperature in the bottom of preferably in the range from 170° C. to 200° C.
  • the absolute pressure selected varies preferably from values of 1 mbar to 10 mbar.
  • the column is adjusted so as to result in a reflux ratio in the range from especially 0 to 0.6, preferably from 0.1 to 0.4.
  • the ethanolamine mixture comprising DEOA and TEOA for separation is preferably fed into the TEOA column at the side, particularly into the side of the middle column region.
  • a low boiler fraction comprising a mixture of diethanolamine (60 to 100% by weight, particularly 70 to 95% by weight) and triethanolamine (0 to 40% by weight, particularly 5 to 30% by weight) is removed at the top of the column and, if appropriate, fed back into the DEOA column.
  • the high boiler fraction consists of triethanolamine (50 to 100% by weight, particularly 80 to 98% by weight, of TEOA) and secondary components, and is withdrawn and discharged at the bottom of the column.
  • the remaining medium boiler fraction with a triethanolamine content of ⁇ 99.3% by weight, particularly ⁇ 99.4% by weight, is isolated as a side draw stream, preferably in the middle portion of the TEOA column.
  • the TEOA column Owing to the thermal sensitivity of the ethanolamine mixture, it is advantageous to operate the TEOA column with an evaporator which has a low wall temperature and a small liquid capacity. Overall, it has been found to be particularly favorable to use a falling film evaporator.
  • the column bottom and the evaporator bottom are configured such that the residence time of the high boiler fraction in the bottom of the TEOA column is in the range from 10 to 180 min, preferably 30 to 150 min. At these residence times, an optimum of the removal of the medium boiler fraction and the prevention of formation of undesired by-products is achieved.
  • the TEOA obtained in the side draw in the TEOA column, for further purification and/or improvement in the color quality is distilled in a further downstream column and removed there via the top, especially as described in WO 2005/035481 A2 (BASF AG).
  • the high boilers obtained in the bottom of the downstream column are preferably recycled into the middle region of the TEOA column.
  • the reflux ratio in the downstream column is preferably in the range from 0.2 to 0.7.
  • the TEOA column and the downstream column are preferably operated with equal or approximately equal temperature profiles.
  • the TEOA column is a dividing wall column, especially as described in WO 2005/035481 A2 (BASF AG).
  • a dividing wall column is in principle an apparatus simplification of two thermally coupled distillation columns. It generally comprises a vertical dividing wall which extends above and below the feed point, which divides the column into a feed section and a withdrawal section.
  • the dividing wall column may be configured as a packed column comprising random packings or structured packings, or as a tray column. The substance mixture is fed into the column in the middle region of the dividing wall.
  • the first distillation stage is carried out in the feed section of the column, and the medium boiler fraction which remains after withdrawal of the low boiler fraction at the top of the column and high boiler fraction at the bottom of the column is distilled in the withdrawal section of the column, pure triethanolamine (TEOA) being discharged via a side draw in the middle region of the dividing wall (opposite the introduction point), and the high boilers which form in the second distillation stage likewise being discharged in the bottom of the column.
  • TEOA triethanolamine
  • a plurality of DEOA columns and TEOA columns (in each case, for example, 2 or 3) can be operated and connected as desired.
  • the discharge from the DEOA column can either be conducted directly into the TEOA column or else stored intermediately first.
  • the process according to the invention affords TEOA particularly in a purity of ⁇ 99.3% by weight, more particularly ⁇ 99.4% by weight, especially ⁇ 99.8% by weight.
  • the APHA color number of TEOA obtained in accordance with the invention is particularly ⁇ 100, more particularly ⁇ 90, and is very particularly in the range from 30 to 80.
  • TEOA in particularly good color quality, particularly with an APHA color number of ⁇ 20, and high color stability is obtained when, as described especially in EP 4015 A and EP 1 132 371 A, an effective amount of phosphorous acid or hypophosphorous acid or a derivative of one of these acids (e.g. a salt, e.g. sodium salt) is added before or during the ethanolamine synthesis from ethylene oxide and ammonia and/or in the course of the distillative separation of the resulting ethanolamine mixture. It is preferably not added until before the TEOA purifying distillation in the TEOA column.
  • an effective amount of phosphorous acid or hypophosphorous acid or a derivative of one of these acids e.g. a salt, e.g. sodium salt
  • the amount metered in is preferably in the range from 0.005 to 2% by weight based on the sum of the ethanolamines (MEOA, DEOA, TEOA), in the feed to the column in question.
  • the APHA color number of TEOA obtained in accordance with the invention in this way is particularly ⁇ 20, more particularly ⁇ 15, and is very particularly in the range from 1 to 10.
  • the APHA color number is determined to DIN-ISO 6271.
  • An ethanolamine mixture comprising the main components monoethanolamine (MEOA), diethanolamine (DEOA) and triethanolamine (TEOA) was prepared by the reaction of aqueous ammonia with ethylene oxide in the liquid phase under elevated pressure and elevated temperature in a suitable reactor. After removal of NH 3 , water and MEOA, the resulting ethanolamine mixture was conducted into a DEOA column in order to isolate DEOA.
  • the feed to the DEOA column comprised 1.6% by weight of MEOA, 70.2% by weight of DEOA and 28.2% by weight of TEOA.
  • the DEOA column was operated at an absolute pressure of 14 mbar and with a top temperature of 135° C. and with a bottom temperature of 189° C.; the reflux ratio was 0.33.
  • the residence time of the mixture in the bottom of the DEOA column was set to 18 minutes.
  • the top product obtained was DEOA with a purity of 99.5% by weight.
  • the bottom product (23% by weight of DEOA, 76% by weight of TEOA, 1% by weight of secondary components) was then conducted into the TEOA column which was operated at an absolute pressure of 1.3 mbar and with a top temperature of 71° C. and with a bottom temperature of 185° C.
  • the reflux ratio was 0.22.
  • phosphorous acid (0.12% by weight based on the feed to the column) was added.
  • the top product of the TEOA column was recycled into the DEOA column.
  • the side effluent was conducted into a further downstream column.
  • TEOA was isolated with a purity of 99.52% by weight and a color number of 20 APHA.
  • TEOA was obtained with a purity of 99.62% by weight and a color number of 6 APHA.
  • the residence time was in each case calculated as described above.
  • the examples show that reduction of the residence time of the bottoms mixture in the DEOA column and hence a reduction in the thermal stress on the TEOA during the removal of the different ethanolamines achieves a positive effect on the color quality, especially the color number, of the triethanolamine.
  • the residence time in the bottom of the DEOA column is reduced, especially to ⁇ 20 minutes, more preferably ⁇ 12 minutes, a significantly less colored triethanolamine is obtained.
  • the bottom product of a DEOA column was analyzed: 17.0% by weight of DEOA, 81.4% by weight of TEOA, 1.6% by weight of secondary components, color number (APHA) 17. This mixture was heated at 190° C. under nitrogen for 1 h. The proportion of secondary components rose to 4.0% by weight and the color number (APHA) increased to 120.
  • a TEOA column with a side draw column according to WO 2005/035481 A was charged with a mixture of DEOA, TEOA and secondary components according to the list below (feed 1 and 2 ). These feeds were bottom products of a DEOA distillation which had been obtained at different residence times in the bottom of the DEOA column. The residence time was in each case calculated as described above.
  • Feed 1 24% by weight of DEOA, 72% by weight of TEOA, 4% by weight of secondary components, obtained from a DEOA distillation at approx. 180° C. with residence time >30 min and ⁇ 70 min in the bottom of the column.
  • Feed 2 17% by weight of DEOA, 79% by weight of TEOA, 4% by weight of secondary components, obtained from a DEOA distillation at bottom temperature 175 to 180° C. with residence time 5 to 10 min in the bottom of the column.
  • the TEOA column was operated at top pressure 4 mbar (abs.), bottom temperature 195° C., top temperature 160° C. and a reflux ratio at the top of the column (reflux ratio here only defined as follows: amount of reflux (liters)/total amount of top effluent (liters)) of 0.1 with metered addition of 0.05% by weight of phosphorous acid (based on the column feed).
  • TEOA was isolated in the top of a downstream column (side draw column).
  • TEOA TEOA was obtained with a purity of 98.7% by weight and a color number (APHA) of 17.
  • TEOA was obtained with a purity of 99.4% by weight and a color number (APHA) of 3.
  • the example shows: a long residence time in the bottom of the DEOA column has an adverse effect on the downstream TEOA distillation, and leads to a TEOA quality with lower purity and worse color number.

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EP08172435 2008-12-19
EP08172435 2008-12-19
US14/085,964 USRE45240E1 (en) 2008-12-19 2009-12-10 Process for preparing pure triethanolamine (TEOA)
US13/141,016 US8466323B2 (en) 2008-12-19 2009-12-10 Process for preparing pure triethanolamine (TEOA)
PCT/EP2009/066839 WO2010069856A1 (de) 2008-12-19 2009-12-10 Verfahren zur herstellung von reinem triethanolamin (teoa)

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EP (1) EP2379488B1 (de)
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BR (1) BRPI0922984B1 (de)
EA (1) EA020158B9 (de)
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EP2379488B1 (de) * 2008-12-19 2013-02-20 Basf Se Verfahren zur herstellung von reinem triethanolamin (teoa)
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EP2855443B1 (de) 2012-06-01 2016-03-30 Basf Se Verfahren zur herstellung eines mono-n-alkyl-piperazins
US8884015B2 (en) 2012-06-01 2014-11-11 Basf Se Process for the preparation of a mono-N-alkypiperazine
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EP3129349A1 (de) 2014-04-08 2017-02-15 SABIC Global Technologies B.V. Minimierung des wassergehalts in ethanolaminproduktströmen
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WO2015181751A1 (en) * 2014-05-30 2015-12-03 Sabic Global Technologies B.V. Improved quality and color of ethanolamine product streams by reduced temperature at the triethanolamine column
ES2971101T3 (es) 2015-12-11 2024-06-03 Sabic Global Technologies Bv Métodos para reducir el color en composiciones de alcanolamina
EP3397612B1 (de) 2015-12-29 2022-06-29 SABIC Global Technologies B.V. Verfahren zur farbreduktion in alkanolaminzusammensetzungen und dadurch hergestellte zusammensetzungen
JP6916366B1 (ja) 2020-11-16 2021-08-11 株式会社日本触媒 ジオールの製造方法
CN113549045A (zh) * 2021-06-03 2021-10-26 南通百川新材料有限公司 一种降低环状三羟甲基丙烷缩甲醛色号的处理方法

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