EP1606238A1 - Elimination d'impuretes formees lors de la production de 1,3-propanediol - Google Patents

Elimination d'impuretes formees lors de la production de 1,3-propanediol

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Publication number
EP1606238A1
EP1606238A1 EP03781563A EP03781563A EP1606238A1 EP 1606238 A1 EP1606238 A1 EP 1606238A1 EP 03781563 A EP03781563 A EP 03781563A EP 03781563 A EP03781563 A EP 03781563A EP 1606238 A1 EP1606238 A1 EP 1606238A1
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EP
European Patent Office
Prior art keywords
propanediol
crude
acetal
pdo
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03781563A
Other languages
German (de)
English (en)
Inventor
Robert Lawrence Blackbourn
Stephen Edward Brewer
Zaida Diaz
Glenn Charles Komplin
Joseph Broun Powell
Paul Richard Weider
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication date
Priority claimed from US10/676,796 external-priority patent/US6972346B2/en
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP1606238A1 publication Critical patent/EP1606238A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound

Definitions

  • This invention relates to a process for the production of 1,3-propanediol (PDO) wherein an aqueous solution of 3-hydroxypropanal (HPA) is formed, and the neutralized HPA is hydrogenated to produce a PDO mixture that is distilled to produce purified PDO.
  • PDO 1,3-propanediol
  • ethylene oxide is reacted with synthesis gas (syngas), a mixture of carbon monoxide and hydrogen, which may be obtained by steam reforming of natural gas or partial oxidation of hydrocarbons.
  • syngas synthesis gas
  • carbon monoxide a mixture of carbon monoxide and hydrogen
  • U.S. Patents 4,873,378, 4,873,379, and 5,053,562 from Hoechst Celanese describe a single step reaction using 2:1 (molar) syngas at 110 to 120°C and about 1000 psig (6900 kPa) to give 65 to 78 mole percent yield of PDO and precursors thereof.
  • the catalyst system used consisted of rhodium, various phosphines, and various acids and water as promoters.
  • the present invention provides such a chemical method.
  • the present invention is an improvement upon the process for the production of 1 ,3-propanediol (PDO) wherein an aqueous solution of 3-hydroxypropanal (HPA) is formed, and the HPA is subjected to hydrogenation to produce a crude PDO mixture comprising PDO, water, MW176 acetal (so called because it is an acetal and has a molecular weight of about 176), and high and low volatility materials, wherein the crude PDO mixture is dried, usually by distillation, to produce a first overhead stream comprising water and some high volatility materials, such as ethanol and/or process solvents, and a dried crude PDO mixture as a first distillate bottoms stream comprising PDO, MW176 acetal, and low volatility materials, and wherein the dried crude PDO mixture is distilled to produce a second overhead stream comprising some high volatility materials, a middle stream comprising PDO and MW176 acetal, and a second distillate bottoms stream comprising PDO and low volatility materials.
  • PDO 1
  • the major part of the recoverable PDO is in the middle stream which is as much as 99.9 %wt PDO.
  • the second distillate bottoms stream may contain up to 50 %wt of PDO but this PDO is difficult to separate from the low volatility materials. There may be trace amounts of MW176 acetal in the bottoms stream.
  • the improvement comprises contacting 1) the crude PDO . mixture prior to drying and/or 2) the dried crude PDO mixture prior to distillation and/or 3) the middle stream (with this third embodiment, another distillation would be required to remove the more volatile MW176 acetal reaction products from the PDO) with an acidic zeolite (for example a mordenite clay) at 40 to 150°C to convert the MW176 cyclic acetal to alternate chemical species which can be more easily separated from PDO by distillation, in a process where the production of other color producing impurities and oligomers of PDO is minimized.
  • an acidic zeolite for example a mordenite clay
  • 1) and/or 2) and/or 3) are contacted with an acid form cation exchange resin, typically of the sulfonic acid type, at temperatures between ambient and 150°C.
  • soluble acids such as H2SO4 are used to treat the streams, preferably in a column which is resistant to corrosion, at a temperature of 20 to 100°C.
  • the contacting of the crude PDO mixture with the solid acid purifier is done as a continuous process, or batchwise, using standard methods and practice for contacting a liquid stream with a solid catalyst or adsorbent. In this manner, difficult to separate impurities such as the MW176 acetal are largely eliminated, such that PDO may be distilled to high purity with high recovery efficiencies.
  • this invention provides a process for producing 1,3- propanediol comprising the steps of: a) forming an aqueous solution of 3-hydroxypropanal, b) hydrogenating the 3-hydroxypropanal to form a first crude 1,3-propanediol mixture comprising 1,3-propanediol, water, and MW132 cyclic acetal, c) distilling the first crude 1 ,3-propanediol mixture to remove water and low boiling impurities and form a second crude 1,3-propanediol mixture, d) contacting the second crude 1,3-propanediol mixture with an acid form cationic exchange resin at a temperature of from 50 to 150°C to convert the MW132 cyclic acetal to more volatile cyclic acetals and/or other degradation products, and e) separating the more volatile cyclic acetals and/or other degradation products from the 1,3-propanediol by distillation or gas stripping
  • steps d) and e) are carried out together (such as in the same vessel or column) such that the volatile cyclic acetals and/or other degradation products are separated from the 1,3-propanediol as they are formed.
  • an acidic zeolite can be used in place of the cationic acid exchange resin.
  • the temperature preferably is from
  • FIG. 1 is very simple schematic representation of an example of a simplified distillation scheme. Detailed Description of the Invention
  • the 3-hydroxypropanal (HPA) aqueous solution which is the starting material of the present invention, can be produced by a number of different processes.
  • HPA can also be produced by hydration of acrolein in the presence of acidic catalysts. Processes for accomplishing this result are described in U.S. Patents 5,426,249, .
  • Ethylene oxide (EO) is hydroformylated in a reactor such as a bubble column or agitated tank at 200 to 5000 psi (1380 to 34,500 kPa) of syngas having a ratio of hydrogen to carbon monoxide of 1 :5 to 25:1 at 50 to 110°C in the presence of a hydroformylation catalyst at a concentration of 0.05 to 15 weight percent, more preferably 0.05 to 1 percent.
  • a reactor such as a bubble column or agitated tank at 200 to 5000 psi (1380 to 34,500 kPa) of syngas having a ratio of hydrogen to carbon monoxide of 1 :5 to 25:1 at 50 to 110°C in the presence of a hydroformylation catalyst at a concentration of 0.05 to 15 weight percent, more preferably 0.05 to 1 percent.
  • the hydroformylation reaction effluent is preferably extracted with a small amount of water at water-solvent ratios ranging from 2:1 to 1 :20 at 5 to 55°C under an atmosphere of greater than 50 psi (350 kPa) carbon monoxide.
  • the solvent layer containing more than 90 percent of the catalyst in active form is recycled back to the hydroformylation reactor.
  • the HPA is extracted in the water layer at a concentration of 10 to 45 weight percent.
  • the catalyst may be removed from this aqueous solution of HPA by any known means including first oxidizing the catalyst and then removing it utilizing an acid ion exchange resin.
  • the ion exchange resin may be a weak or strong acid ion exchange resin.
  • AMBERLYST 15, 35, and XN-1010 AMBERLITE IR-118, IRC76, A1200, DOWEX 50 x 2-100 and 5 x 8-100, XL-383 and -386, plus BIO RAD AG50W-X2 and AMBERSEP 252H resins, or other strong (sulfonic) acid or weak (carboxylic) acid resins (AMBERLYST, AMBERLITE, DOWEX, BIO RAD and AMBERSEP are trademarks).
  • the aqueous solution is hydrogenated. This may be carried out by hydrogenation over a fixed bed of hydrogenation catalyst at typically 100 to 2000 psi (690 to 13,800 kPa) of hydrogen.
  • the hydrogenation catalyst can be any of those described in U.S. 5,786,524, which is herein inco ⁇ orated by reference, including catalysts of a group VIII metal such as nickel, cobalt, ruthenium, platinum, or palladium.
  • Initial hydrogenation is preferably conducted at 40 to 80°C and the temperature is preferably increased to 120 to 175°C to encourage the reaction of reactive components such as cyclic acetals to revert back to PDO.
  • water and , entrained light (low boiling) solvent and highly volatile (low boiling) impurities. are distilled (overhead stream) from the crude PDO and the lower volatility components are also separated during distillation as the bottoms stream.
  • the dried crude product stream (of the distillation), containing MW132 acetal and PDO is treated as described below to recover PDO in high yield and high purity.
  • Crude PDO as described above can exhibit high levels of MW132 cyclic acetal impurity. This impurity is undesirable and limits PDO recovery efficiencies during subsequent distillation. It can form by reaction of PDO with HPA. Reaction #1
  • the dried crude PDO stream containing the undesirable MW132 cyclic acetal is contacted with an acid form cationic exchange resin or an acidic zeolite under conditions which favor the reaction scheme shown above for the conversion of MW132 acetal to EDCA.
  • This step is combined with removal of the EDCA via concerted distillation or via use of a stripping gas such as nitrogen or steam.
  • Concerted distillation and reaction where distillation and reaction are combined in the same processing unit to separate reactants from products as they are formed, may employ any of the well known methods for conducting a "reactive distillation.”
  • an inert gas such as nitrogen may be used to strip the reaction mixtures (concerted stripping and reaction) of the more volatile degradation product of MW132 acetal (EDCA), and thus prevent reformation of MW132 via chemical equilibrium.
  • Use of water vapor (steam) is a common commercial practice for providing process heat and an inert stripping gas.
  • the stripping is again conducted in the same processing unit as the reaction of MW132 acetal.
  • the reaction products are removed as formed in order to drive the chemical equilibrium to eliminate or reduce the presence of MW132 acetal.
  • the combination of acid-catalyzed reaction plus stripping in the same processing step effects reactant-product separation in the same manner as the "reactive distillation” combination of acid-catalyzed reaction and distillation.
  • water was found to suppress the reversion of and removal of MW132 acetal.
  • small amounts of water are generally present due to incomplete removal, so ⁇ tion in the solid catalyst, or due to the dehydration reaction itself (#1 above) and may al ⁇ a portion of the MW132 removal to proceed via the reversal of reaction # 1.
  • HPA if formed in this manner, may then be further dehydrated to highly volatile acrolein, which is readily stripped or distilled from the reaction mixture.
  • concerted acid- catalyzed reaction with separation (distillation or stripping) of volatile reaction products results in a reduction in the MW132 impurity of the product PDO.
  • Concerted distillation or inert gas stripping is required to drive the chemical equilibrium away from the thermodynamically favored MW132 cyclic acetal.
  • An acid formed zeolite can also be used during the procedure described above to catalyze the degradation of the MW132 acetal.
  • the reaction is preferably carried out at a temperature of from 50 to 150°C, more preferably at from 80 to 120°C.
  • Contacting with the resin catalyst is either conducted batchwise, or in a continuous column, using well known reactor design methods to insure virtually complete conversion of the MW132 acetal. Batchwise contacting at 80 to 120°C may be conducted for 1 to 5 hours with 10 weight percent of acid resin, for example, to effect complete conversion.
  • the contacting may be effected in a continuous reaction vessel, preferably a column, with a "weight hourly space velocity" (weight of impure PDO feed per weight of acid resin per hour — "WHSV") of 0.1 to 1 per hour.
  • WHSV weight hourly space velocity
  • the reaction with acidic zeolite is preferably carried out at a temperature of from 70 to 250°C, more preferably at from 90 to 170°C, via batch or continuous contacting. Similar contacting times or weight hourly space velocities could be used.
  • the preferred catalysts are ion exchange resins with strongly acidic cation exchange (acid form cationic exchange resins). These include the gel type or macroreficular (macroporous) ion exchange resins with sulfonic acid functional groups wherein the sulfonic acid function is bonded directly or indirectly to an organic polymer backbone. Examples include Rohm and Haas AMBERLITE or
  • Another example of cation exchange resins is NAFION acidified perfluorinated polymer of sulphonic acid (SYBRON, PUROLITE, RESINTECH and NAFION are trademarks).
  • the suitable zeolite catalysts contain one or more modified zeolites preferably in the acidic form. These zeolites should contain pore dimensions large enough to admit the entry of the acyclic or aliphatic compounds.
  • the preferred zeolites include, for example, zeolites of the structural types MFI (e.g., ZSM-5), MEL (e.g., ZSM-11), FER (e.g., ferrierite and ZSM-35), FAU (e.g., zeolite Y), BEA (e.g., beta) ,MFS (e.g., ZSM-57), NES (e.g. NU-87), MOR (e.g.
  • MFI e.g., ZSM-5
  • MEL e.g., ZSM-11
  • FER e.g., ferrierite and ZSM-35
  • FAU e.g., zeolite Y
  • BEA e.g., beta
  • MFS e.
  • zeolites of the mixed crystalline phases such as, for example, zeolite PSH-3.
  • the structural types and references to the synthesis of the various zeolites can be found in the "Atlas of Zeolite Structure Types" (published on behalf of the Structure Commission of the International Zeolite Association), by W.M. Meier, D.H. Olson and Ch. Baerlocher, published by Butterworth-Heinemann, fourth revised edition, 1996. Structural types and references to the zeolites mentioned above are available on the World Wide Web at www.iza-structure.org Such zeolites are commercially available from Zeolyst International, Inc. and ExxonMobil Co ⁇ oration. Additional examples of suitable zeolite catalysts can be found in U.S. Patent Nos. 5,762,777; 5,808,167; 5,110,995;
  • the aqueous PDO containing MW176 acetal flows into drying distillation column 2. Water and some high volatility materials are removed in the overhead stream 3 and the dried PDO with M 176 acetal from the distillate bottoms stream flows into distillation column 5. More high volatility materials are separated and leave through overhead stream 6 and the distillate bottoms stream 8 contains low volatility materials and some PDO as well as trace amounts of MW176 acetal. The recoverable PDO exits in the middle stream. Vessels 1, 4, and 7 are optional (although at least one is required in the system shown in the figure) acid treatment vessels.
  • the acid catalyst treatment may take place before drying in vessel 1 or it may take place after drying in vessel 4 but before distillation or it may take place after distillation in vessel 7.
  • an additional distillation is required to separate the more volatile MW176 acetal reaction products from the PDO.
  • the MW102 acetal formed upon acid catalyzed decomposition of MW176 acetal is known to be much more volatile than PDO and hence can be readily separated from PDO with high efficiency. This result was expected basis the absence of hydroxyl groups in MW102 due to condensation elimination. While we do not wish to be bound by a specific mechanism, the following reactions may explain the degradation of MW176 acetal and formation of MW102 acetal (that can be readily separated from the PDO by distillation) and also the formation of MW132 acetal as observed in the experiments.
  • De-ethoxylation is known to occur under acidic conditions. Aldehydes readily condense with PDO under acidic conditions to form thermodynamically - favored cyclic acetals, in this case, MW102 acetal.
  • An acid form cation exchange resin or an acidic zeolite also facilitates the removal of MW132 acetal via conversion to 2-ethylene- 1, 3 -dioxane cyclic acetal (EDCA) which is a substantially higher volatility material.
  • EDCA 2-ethylene- 1, 3 -dioxane cyclic acetal
  • the crude PDO stream containing the undesirable MW176 acetal is treated with an acid form cation exchange resin or an acidic zeolite or soluble acid under conditions which favor the reaction schemes shown above.
  • Batch or continuous flow processes may be used in any manner providing intimate contacting of the liquid stream with the solid acid purifier or the soluble acid.
  • continuous contacting in a fixed, fluidized, or expanded bed will be preferred commercially, in either downflow or upflow operation or via a horizontal contactor. While the optimal size of the bed will depend upon the particle size and nature of the solid acid purifier employed, a typical design will entail a "weight hourly space velocity" (WHSV) from 0.1 to 10, with WHSV expressed as the mass flowrate of crude PDO per mass of solid acid purifier per hour.
  • the optimal bed size and operating temperature are selected to effect a high level of conversion of MW 176 acetal, while minimizing the oligomerization of PDO to other heavy ends components.
  • the preferred zeolite catalysts contain one or more modified zeolites preferably in the acidic form. These zeolites should contain pore dimensions large enough to admit the entry of the acyclic or aliphatic compounds.
  • the preferred zeolites include, for example, zeolites of the structural types MFI (e.g., ZSM-5), MEL(e.gi, ZSM-11), ' FER (e.g., ferrierite and ZSM-35), FAU (e.g., zeolite Y), BEA (e.g., beta) ,MFS , :. (e.g., ZSM-57), NES (e.g. NU-87), MOR (e.g.
  • MFI e.g., ZSM-5
  • MEL e.gi, ZSM-11
  • ' FER e.g., ferrierite and ZSM-35
  • FAU e.g., zeolite Y
  • BEA e.g.
  • MTT e.g., ZSM-23
  • MWW e.g., MCM-22 and SSZ-25
  • EUO e.g. EU-1; ZSM- 50, and TPZ-3
  • OFF e.g., offretite
  • MTW e.g., ZSM-12
  • zeolites of the mixed crystalline phases such as, for example, zeolite PSH-3.
  • the structural types and references to the synthesis of the various zeolites can be found in the "Atlas of Zeolite Structure Types" (published on behalf of the Structure Commission of the International Zeolite Association), by W.M. Meier, D.H. Olson and Ch. Baerlocher, published by Butterworth-Heinemann, fourth revised edition, 1996. Structural types and references to the zeolites mentioned above are available on the World Wide Web at www.iza-structure.org Such zeolites are commercially available from Zeolyst International, Inc. and ExxonMobil Co ⁇ oration. Additional examples of suitable zeolite catalysts can be found in U.S. Patent Nos. 5,762,777; 5,808,167; 5,110,995;
  • Suitable catalysts include acid form cation exchange resins. These include the gel type or macroreticular (macroporous) ion exchange resins with sulfonic acid functional groups in acid form, wherein the sulfonic acid function is bonded directly or indirectly to an organic polymer backbone. Examples include: Rohm and Haas AMBERLITE or AMBERLYST A200, A252, IR-118, IR120, A15,
  • Another example of these cation exchange resins is NAFION acidified perfluorinated polymer of sulphonic acid.
  • Soluble acids which can be used include H2SO4, H3PO4, HC1, and soluble sulfonic acids such as para-toluene sulfonic acid, benzene sulfonic acid, and methane sulfonic acid, etc.
  • H2SO4 and soluble sulfonic acids are preferred. If these soluble acids are used, corrosion-resistant columns are highly preferred.
  • the acid is removed with the heaviest components (heavy ends).
  • the concentration of the acid is preferably 0.1 to 1.0 wt%! ' :
  • Example 176-1 The results in Table 2 show that ambient temperature treatment of a PDO sample contaminated with MW176 acetal with acid-form USY-type zeolite was ineffective in reverting MW176 acetal. Room temperature reversion using strong acid resin A15 (Rohm and Haas AMBERLYST 15) was demonstrated. High temperature treatment with the zeolite at 150°C overnight resulted in elimination of MW176 with formation of 2-methyl -1,3-dioxane. However, formation of poly PDO
  • a mordenite sample was inadvertently first tested in sodium form overnight at 150°C, giving copious amounts of new heavy ends byproducts, presumably via degradation of PDO.
  • a sample of the acid-form mordenite heated with the same PDO overnight at 60°C showed, however, essentially complete elimination of the MW176 acetal, with formation of the same 2-methyl-l,3-dioxane (MW102 acetal) and MW132 acetal impurities as observed with the USY type zeolite. The reversion was selective as no additional byproducts were observed. The performance of the acid-form mordenite was thus comparable with that of the USY acid-form zeolite.
  • H-mordenite LR23768-128 (1/28/2000)
  • MW176 acetal impurity with a strong cation acid ion exchange resin (Rohm and Haas AMBERLYST A35) at room temperature.
  • the results shown in Table 3 indicate degradation of MW176 acetal, with formation of MW102 acetal, MW18 (H 2 O), and MW132 acetal.
  • Solid acid treatment of PDO tainted with MW176 acetal can degrade this impurity into lighter components (MW102 nonhydroxylated acetal) which are readily separable via distillation.
  • Strong cation acid ion exchange resins can revert the MW176 acetal at room temperature.
  • Acidic zeolites can also revert the MW176 acetal at a higher temperature.
  • PDO is condensed by the acidic zeolites to poly 1,3-propylene glycols, leading to yield loss and lower purity.
  • This experiment entailed treatment of 1500 grams of crude PDO following water removal, via distillation, with 43.5 grams dry A15 (Amberlyst A15 resin) strong acid form cationic exchange resin under a nitrogen atmosphere for 3 hours at
  • MW 132 acetal was reduced only from 3.2 wt% to 2.6 wt%.
  • the treated material was distilled and successive distillation cuts showed reduction in MW 132 acetal from
  • MW 132 cyclic acetal 1.38 wt% MW 132 cyclic acetal from which a majority of the water had been removed by distillation. The sample was heated via a metal block heater to 100°C with vigorous nitrogen stripping (concerted stripping) as evidenced by an expansion of the liquid by about 10 volume percent. MW 132 acetal was readily eliminated with formation of significant quantities of di- and tri-PDO via direct PDO self condensation.
  • a twice distilled PDO product sample exhibiting a visible light yellow color upon testing for color body precursors was contacted with 5 wt% dry A15 strong acid form cationic exchange resin with nitrogen stripping for 4 hours at 105°C.
  • MW 132 acetal was virtually eliminated while 1.7 wt% di-PDO was formed (Table 7), giving a gc (gas chromatographic) purity of 97.9 wt%.
  • the treated sample was redistilled at 9 mm Hg (1.3 kPa) in a small 2-ft (0.6 meter) concentric tube column with a bottoms temperature of 121 to 123°C. Distillation showed ready separation of di-PDO from the PDO distillate. Distillate cuts were substantially reduced in MW 132 acetal with the gc purity approaching 99.9%.
  • the color test now gave only slightly yellow tint, indicating a reduction in the amount of color body precursors.
  • Inorganic solid acids such as silica-aluminas or zeolites are more amenable to commercial use in a nitrogen or steam stripper.
  • their activity in dehydrating beta-hydroxy cyclic acetals such as MW 132 is poorer than the activity strong acid ion exchange resins under comparable conditions (Table 9).
  • the highly active resins make more di- and tri-PDO as byproducts.
  • These oligomers are not believed to be color precursors, however, and are more readily separated by distillation than the original MW132 acetal.
  • Temperatures and reaction (contacting) times preferably are optimally adjusted for the acid form cationic exchange resin vs. the acidic zeolite to maximize MW132 acetal reversion to PDO while minimizing the formation of other heavy impurities.

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

Abstract

Cette invention concerne des améliorations sur un procédé de production de 1,3-propanediol (PDO) dans lequel une solution aqueuse de 3-hydroxypropanal (HPA) est formée, le HPA étant soumis à une hydrogénation afin de produire un mélange brut de PDO. Une amélioration de ce procédé consiste à traiter le mélange brut de PDO avec une zéolithe acide, une résine d'échange cationique sous forme acide, ou un acide soluble afin de convertir l'acétal cyclique MW176 en matériaux plus volatils pouvant facilement être séparés du PDO par distillation. Une autre amélioration consiste à éliminer l'eau du mélange brut de 1,3-propanediol, à contacter le mélange résultant avec un purificateur solide acide à une température allant d'environ 50 à environ 250 °C afin de convertir l'acétal cyclique MW 132 en acétals cycliques plus volatils, et à séparer les acétals cycliques plus volatils du 1,3-propanediol par distillation ou par extraction liquide de gaz.
EP03781563A 2002-11-01 2003-10-30 Elimination d'impuretes formees lors de la production de 1,3-propanediol Withdrawn EP1606238A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US676796 2000-09-29
US42314002P 2002-11-01 2002-11-01
US42309702P 2002-11-01 2002-11-01
US423097P 2002-11-01
US423140P 2002-11-01
US10/676,796 US6972346B2 (en) 2002-11-01 2003-10-01 Solid acid catalyzed reactive stripping of impurities formed during the production of 1, 3-propanediol
PCT/US2003/034581 WO2004041759A1 (fr) 2002-11-01 2003-10-30 Elimination d'impuretes formees lors de la production de 1,3-propanediol

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US8809596B2 (en) 2009-01-21 2014-08-19 Basf Se Method for producing deodorized 1,2-propanediol
KR101448210B1 (ko) * 2012-09-28 2014-10-08 한국생명공학연구원 미생물 배양액으로부터 ２,３-부탄디올을 제거하는 방법
CN111068588B (zh) * 2018-10-22 2022-02-08 中国石油化工股份有限公司 一种柴油超深度脱硫装置及柴油加氢反应系统
CN112441882B (zh) * 2019-09-02 2023-04-07 中国石油化工股份有限公司 用于乙二醇精制的稳定剂及其制备方法
CN115215730B (zh) * 2022-06-17 2023-10-31 宁波大学 一种醇类中醛类杂质的高效脱除方法

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CA2504378A1 (fr) 2004-05-21
MXPA05004560A (es) 2005-07-26
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