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WO2012130316A1 - Procédé pour purifier mpg (monopropylèneglycol) à partir d'un bouillon de fermentation - Google Patents

Procédé pour purifier mpg (monopropylèneglycol) à partir d'un bouillon de fermentation Download PDF

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Publication number
WO2012130316A1
WO2012130316A1 PCT/EP2011/055034 EP2011055034W WO2012130316A1 WO 2012130316 A1 WO2012130316 A1 WO 2012130316A1 EP 2011055034 W EP2011055034 W EP 2011055034W WO 2012130316 A1 WO2012130316 A1 WO 2012130316A1
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Prior art keywords
mpg
fermentation broth
phase
aqueous feed
purifying
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Inventor
Pascal Rousseaux
Frédéric OLLIVIER
Claire Ethgen
Thomas David
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Metabolic Explorer SA
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Metabolic Explorer SA
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    • 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
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • 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

Definitions

  • the present invention relates to the purification of monopropylene glycol (MPG) or 1 ,2-propanediol from a fermentation broth.
  • MPG monopropylene glycol
  • MPG is a widely-used chemical. It is a component of unsaturated polyester resins, liquid detergents, coolants, anti-freeze and de-icing fluids for aircrafts. Propylene glycol has been increasingly used since 1993-1994 as a replacement for ethylene derivatives, which are recognised as being more toxic than propylene derivatives.
  • MPG has mainly been produced and purified from petrochemical sources. MPG is currently produced by chemical processes using a propylene oxide hydration process that consumes large amounts of water. Propylene oxide can be produced by either of two processes, one using epichlorhydrin, and the other hydroperoxide. Both routes use highly toxic substances. In addition, the hydroperoxide route generates by-products such as tert- butanol and 1 -phenyl ethanol. For the production of propylene to be profitable, a use must be found for these by-products.
  • the chemical route generally produces racemic 1 ,2- propanediol, whereas each of the two stereoisomers (R) 1 ,2-propanediol and (S) 1 ,2- propanediol are of interest for certain applications (e.g. chiral starting materials for specialty chemicals and pharmaceutical products).
  • MPG may be produced by fermentation of microorganisms using sugars such as glucose or sucrose.
  • sugars such as glucose or sucrose.
  • the production of MPG by fermentation from biological products has numerous advantages including a significant reduction in production costs compared to chemical synthesis using petroleum products.
  • the development of the industrial production of MPG by fermentation now requires efficient methods to purify the MPG from the fermentation broth.
  • the production of alcohols by fermentation is commonly accompanied by the production of organic acids.
  • the production of MPG by microbial fermentation is usually associated with co-production of other products or by-products and the fermentation broth also contains impurities or unwanted by-products such as water, organic impurities, mineral salts and organic salts.
  • an essential step in the production of MPG by fermentation of biological products is the purification of the MPG from the fermentation broth.
  • salts are typically sodium chlorides and calcium chlorides but also include ammonium, potassium, magnesium, sulphate and phosphate salts. If these mineral salts are not eliminated during purification, they precipitate during the process and the overall efficiency of the purification method is significantly reduced. Precipitation of salts during the purification process notably leads to fouling of ion exchange resins, adsorbents and distillation columns.
  • Impurities and unwanted by-products also may include hydroxyacetones, acetones, acetates, ethanol, succinates, citrates and glycerol.
  • Another major challenge is therefore the elimination of heavy impurities including organic molecules such as organic acids which are less volatile i.e. have a higher boiling point than MPG. These impurities tend to precipitate or to stick to the distillation columns and/or heat exchanger walls used for purification of MPG resulting in a sharp decrease of productivity.
  • the present invention in particular addresses the purification of MPG obtained by fermentation with glucose and/or sucrose as the carbon source for 1,2-propanediol production.
  • impurities may include glucose and/or sucrose and acetates.
  • MPG is produced and purified from petrochemical sources
  • purification methods are directed to separation of MPG from other alcohols and organic molecules. Further, most methods are related to the purification of alcohols from mixtures comprising other alcohols and organic molecules. The purification of MPG from a mostly aqueous phase comprising mineral and organic salts is not addressed.
  • WO 2008/057317 describes processes for isolating propylene glycol or ethylene glycol from mixtures containing other polyols such as butanediols. These processes comprise the addition of a polar solvent and extractive distillation.
  • WO 2010/012604 describes the development of microorganisms that produce 1,2- propanediol from glycerol. Extraction of 1,2-propanediol from the clarified broth may be accomplished by a variety of methods including evaporation/distillation, membrane technology, extraction by organic solvent and adsorption. Suitable solvents include alcohols such as tert-amyl alcohol, cyclopentanol, octanol, propanol, methanol and ethanol. Extraction of the 1,2-propanediol with other solvents is not described.
  • 1,2-propanediol is obtained from glycerol as the carbon source for the production of 1,2-propanediol.
  • the impurities present in the fermentation broth which have to be separated from the 1,2-propanediol differ from the impurities obtained when 1,2- propanediol is produced from sucrose and/or glucose.
  • WO 2004/101479 is related to the purification of biologically-produced 1,3- propanediol.
  • the purification process comprises filtration, ion exchange purification and a distillation procedure comprising at least two distillation columns. Salts are removed at the start of the process using ion exchange resins.
  • a major problem is the fouling of the ion exchange resins, which is due to the heavy impurities of the filtrated fermentation broth. Ion exchange is an efficient technique but it leads to very high operation costs due to the need for regeneration of the resin, when the technique is applied to solutions having a high salt content. Fouling of the ion exchange resin due to the heavy impurities and quick saturation due to high salts content both lead to elevated operation costs because regeneration and/or replacement of the resin are frequently required.
  • WO 2006/025697 describes isolation of 1,3-propanediol or of mixtures of 1,3- propanediol and MPG from a biological culture medium. These methods include extraction with a solvent selected from ethyl acetate, methyl ethyl ketone and mixtures thereof, followed by low pressure liquid chromatography. The efficiency of the extraction step is however insufficient.
  • CN1880290 describes a method for separation and refinement of 1,3-propanediol from a microbial fermentation broth.
  • a diluent selected from n-pentanol, isopentanol, n- butanol or n-haexanol is added to the fermentation broth and water is removed by distillation. This steps leads to the precipitation of salts and other impurities including nucleic acids and proteins from the mixture followed by a separation of the solid impurities which have precipitated. This separation is typically carried out by filtration.
  • the methods described in CN1880290 do not comprise a liquid-liquid extraction step.
  • US 7,056,439 describes a process for recovery of 1,3-propanediol from an aqueous feed stream including extraction with a solvent. Purification of MPG is not described and elimination of salts is not specifically addressed.
  • WO 2009/068110 describes a method for purifying an alcohol from a fermentation broth.
  • the addition of glycerol to the concentrated fermentation broth prevents crystallization of salts at the bottom of distillation columns.
  • the addition of glycerol retains salts in the liquid phase until the end of the purification process.
  • a drawback of this process is that the amount of glycerol required to dissolve salts may be high, leading to high purification costs.
  • the present invention proposes a novel method for purifying MPG from a fermentation broth.
  • the methods of the present invention include extraction of the MPG with a solvent. After addition of the solvent to the fermentation broth, the aqueous and organic phases are separated. The MPG is recovered in the organic phase whereas most of the mineral salts and some of the heavy impurities are recovered in the aqueous phase.
  • mixing and separation of the organic and aqueous phases is performed in a mechanically-agitated liquid/liquid extraction column.
  • Specific solvents have been selected for the liquid-liquid extraction of MPG in the methods of the present invention.
  • the solvents provide for a good yield of MPG in the organic phase whereas the heavy impurities and mineral salts remain mostly in the aqueous phase.
  • liquid- liquid solvent extraction step may be further improved by combining the liquid- liquid solvent extraction step with a first distillation step to remove both the solvent and light impurities and a second distillation step to remove heavy impurities.
  • This second distillation is configured to yield pure MPG and a residue containing MPG and heavy impurities. This residue is recycled in the process.
  • the specific combination of these three steps is economically advantageous while providing highly purified MPG.
  • a distillation step has been added in which part of the MPG containing heavy impurities is recycled in the process.
  • the methods of the present invention provide both efficient desalinisation of the fermentation broth prior to further purification and efficient elimination of organic impurities and in particular of heavy impurities and light impurities.
  • the methods of the present invention prevent degradation of MPG during the purification steps.
  • the methods according to the present invention provide for efficient elimination of salts and impurities during the purification of MPG from a fermentation broth using a simple, cheap and easily scalable process.
  • the present invention is related to methods for purifying MPG (monopropylene glycol) from a fermentation broth comprising the following steps:
  • step b) removing water from the aqueous feed containing the MPG obtained in step a) to obtain a concentrated aqueous feed, wherein the concentrated aqueous feed contains water, mineral salts, at least one heavy impurity, at least one light impurity and MPG,
  • the concentrated aqueous feed in step b) comprises at least one heavy impurity selected from glycerol, succinic acid, hexanoic acid fructose, glucose and sucrose and the weight ratio of at least one of said heavy impurities to MPG is lower in the first phase than in the concentrated aqueous feed.
  • the concentrated aqueous feed in step b) comprises at least one light impurity selected from ethanol, acetone, acetic acid, hydro xyacetone, propionic acid and methylglyoxal and the weight ratio of at least one of said light impurities to MPG is lower in the first bottom product than in the first phase.
  • the concentrated aqueous feed in step b) comprises at least one mineral salt selected from sodium chlorides, calcium chlorides, potassium chlorides, ammonium, sulfates and phosphate salts and the weight ratio of at least one of said mineral salts to MPG is lower in the first bottom product than in the first phase.
  • the methods of the present invention comprise further purification of MPG from the first bottom product by distillation.
  • MPG further purification of MPG is performed by ion exchange and/or adsorption.
  • the present invention is also directed to a method for purifying MPG
  • step b) distilling the first bottom product to obtain a second distillate product comprising MPG and a second bottom product containing heavy impurities and MPG, i) recycling the second bottom product to the concentrated aqueous feed obtained in step b),
  • the first bottom product contains MPG and at least one heavy impurity selected from glycerol, succinic acid, hexanoic acid, fructose, glucose and sucrose and the weight ratio of at least one of said heavy impurities to MPG is lower in the second distillate product than in the first bottom product.
  • distilling the first bottom product is performed at a pressure comprised between 10 mbar and atmospheric pressure.
  • distilling the first bottom product is performed at a pressure of 60mbar.
  • distilling the first bottom product is performed in a distillation column configured to obtain a second bottom product containing heavy impurities and MPG in a weight ratio MPG/heavy impurities comprised between 0.1-10 wherein the weight of the heavy impurities is the weight of the dry solids in the second bottom product.
  • the weight ratio MPG/heavy impurities in the second bottom product is comprised between 0.5-3, particularly between 1 and 2.5.
  • the weight ratio MPG/heavy impurities is equal to about 1.2.
  • the weight of the heavy impurities is the weight of the dry solids in the second bottom product as determined on a thermobalance at 105°C until the weight variation is lower than lmg/20 seconds.
  • removing water from the aqueous feed containing MPG is preferably performed by evaporation.
  • the solvent further comprises ethanol.
  • the solvent is added to reach a proportion of solvent comprised between 50% and 90%> per weight of the concentrated aqueous feed.
  • separating the biphasic mixture into a first phase and a second phase is performed in a mechanically-agitated liquid- liquid extraction column.
  • distilling the first phase is performed by reduced pressure evaporation which is preferably performed at a pressure comprised between 10 mbar and atmospheric pressure, particularly between 50 and 500 mbar.
  • recovering MPG from the second distillate product comprises preferably further purification of the MPG by distillation.
  • recovering MPG from the second distillate product comprises further purification of the MPG by ion exchange and/or adsorption.
  • Another object of the present invention is a method for producing MPG comprising the following steps:
  • the present invention is also directed to a method for purifying MPG (monopropylene glycol) from a fermentation broth comprising the following steps:
  • step b) removing water from the aqueous solution containing the MPG obtained in step a) wherein a concentrated solution is obtained;
  • step c) adding solvent to the concentrated solution obtained in the previous step to reach a proportion of solvent comprised between 10%> and 90%> per weight, wherein the solvent is selected in the group consisting of 1-pentanol, 1-butanol, heptanol hexanol and mixtures thereof, and wherein a biphasic mixture is obtained; d) separating the mixture of step c) into an organic phase and an aqueous phase wherein the organic phase comprises a majority of the solvent and a product of the MPG from the fermentation broth;
  • Clarification of the fermentation broth in step a) is preferably carried out by filtration.
  • filtration comprises a 0.1 ⁇ cut off micro filtration step.
  • step b) removing water from the aqueous solution containing the MPG is performed by evaporation.
  • the solvent may further comprise ethanol.
  • step c) solvent is added to reach a proportion of solvent comprised between 50% and 90% per weight.
  • step d) separating the mixture into an organic phase and an aqueous phase is performed in a mechanically-agitated liquid-liquid extraction column.
  • step e) evaporating solvent and water from the organic phase is performed by reduced pressure evaporation.
  • step f) recovering the MPG comprises further purification of the MPG by distillation.
  • step f) recovering the MPG comprises further purification of the MPG by ion exchange and/or adsorption.
  • the invention thus relates to the purification of MPG from a fermentation broth.
  • MPG may, for example, be produced by the fermentation of various carbon sources e.g. glucose, sucrose or glycerol.
  • the fermentation broth obtained after fermentation contains typically water, MPG, residual carbon source, mineral and organic salts mainly of the carboxylate type.
  • MPG produced by fermentation contains a high concentration of organic and mineral salts.
  • salt means any mineral or organic salt present in the fermentation broth
  • mineral salts include ions such as Na , K , CI " , S0 4 and P0 4 Mg , Ca , NH 4 .
  • Organic impurities and by-products may include citrate, glucose, sucrose, succinate, acetate, pyruvate, glycerol, hexanoic acid hydroxyacetone and methylglyoxal.
  • the present invention relates to a method for removing mineral salts from a fermentation broth after fermentative production of MPG.
  • the methods of the present invention also relate to further purification of the MPG after removal of the majority of mineral salts.
  • Another object of the present invention is the efficient purification of MPG from an aqueous solution or a concentrated aqueous feed containing mineral and/or organic salts.
  • the methods of the present invention provide purification of MPG from a fermentation broth comprising mineral salts, heavy impurities and light impurities.
  • an object of the present invention is the separation of the MPG from mineral salts including sodium chlorides, calcium chlorides, potassium chlorides, ammonium, sulfates and phosphate salts.
  • Another object of the present invention is the separation of MPG from heavy impurities present in the fermentation broth including organic molecules such as organic acids which are less volatile i.e. have a higher boiling point than MPG.
  • the heavy impurities are typically selected from glycerol, succinic acid, hexanoic acid fructose, glucose and sucrose. At least one of these heavy impurities is removed by the purification methods of the present invention.
  • heavy impurities refers to impurities which are less volatile than MPG, heavy impurities found in fermentation broth include for example glycerol, succinic acid, hexanoic acid, fructose, glucose and sucrose and other organic acids.
  • Another object of the present invention is the separation of MPG from light impurities present in the fermentation broth including ethanol, acetone, acetic acid, hydroxyacetone, propionic acid and methylglyoxal.
  • light impurities refers to impurities which are more volatile than MPG i.e. have a lower boiling point than MPG
  • light impurities found in fermentation broth include for example ethanol, acetone, acetic acid, propionic acid, hydroxyacetone, propionic acid and methylglyoxal.
  • the light impurities are typically selected from ethanol, acetone, acetic acid, hydroxyacetone, propionic acid and methylglyoxal. At least on of these light impurities is removed by the purification methods of the present invention.
  • a first embodiment of the present invention is a method for purifying MPG (monopropylene glycol) from a fermentation broth comprising the following steps:
  • step b) removing water from the aqueous feed containing the MPG obtained in step a) to obtain a concentrated aqueous feed, wherein the concentrated aqueous feed contains water, mineral salts, at least one heavy impurity, at least one light impurity and MPG,
  • the biphasic mixture into a first phase comprising solvent, at least one light impurity and at least a fraction of the MPG and a second phase comprising water, at least some of the mineral salts and at least some of the heavy impurities from the concentrated aqueous feed, wherein the weight ratio mineral salts/MPG is lower in the first phase than in the concentrated aqueous feed and the weight ratio heavy impurities/MPG is lower in the first phase than in the concentrated aqueous feed,
  • Fermentation may optionally be stopped by addition of a base to the fermentation broth.
  • a base is added, for example, in the form of soda, potash or ammonia with the purpose of stopping bacterial activity.
  • the pH achieved is between 7.5 and 14.
  • the first step of the 1,2-propanediol purification method consists in clarification of the fermentation broth to eliminate insoluble elements, most notably large molecules, biomass, proteins and all suspended particles.
  • Clarification of the fermentation broth may be carried out by any appropriate method including filtration, centrifugation or fiocculation. In preferred embodiments, all molecules having a size over 0.1 um are eliminated by filtration. In other embodiments, all molecules having a molecular weight over 200 Da are eliminated by clarification.
  • clarification of the fermentation broth is carried out by filtration. "Filtration" refers to a membrane separation method.
  • filtration consists successively of micro filtration, ultrafiltration and nano filtration steps.
  • the clarification step consists of micro filtration and ultrafiltration.
  • the clarification step consists of micro filtration.
  • micro filtration is a 0.1 ⁇ cutoff microfiltration. Filtration may be carried out on a filter press or a rotary filter. In preferred embodiments, clarification of the fermentation broth is performed by tangential flow filtration on hollow fiber membranes.
  • clarification of the fermentation broth is carried out by centrifugation.
  • water is removed prior to further purification of the MPG. Any appropriate method may be applied to remove water from the aqueous feed, e.g; but not limited to evaporation, crystallization or reverse osmosis. Removal of water leads to a concentrated aqueous feed containing the MPG from the fermentation broth.
  • water is removed by evaporation.
  • Evaporation may be carried out in a thermosyphon-type evaporator or in any suitable evaporator.
  • evaporation is carried out under reduced pressure comprised between 5 and 1500mbar, more preferably between 100 mbar and atmospheric pressure, even more preferably between 100 and 900 mbar.
  • this first step consisting in the concentration of the clarified fermentation broth (aqueous feed), between 10% and 95 % of the aqueous feed is evaporated; preferably at least 60%, 70%> or at least 80%> of the aqueous feed is evaporated. Typically between 80%) and 90%> of the aqueous feed is evaporated.
  • a concentrated aqueous feed enriched in MPG is recovered after this water removal step.
  • this concentrated aqueous feed comprises at least 15%, 20%>, 25% 30%> or at least 35% of MPG.
  • purification of MPG from an aqueous feed containing a significant amount of mineral and organic salts comprises a liquid-liquid extraction step of MPG with a solvent.
  • MPG is extracted with an organic solvent or a mixture of organic solvents.
  • MPG is thereby recovered in the organic phase (first phase) whereas most of the salts and heavy impurities remain in the aqueous phase (second phase).
  • Solvents have been selected providing a good partition coefficient and an efficient recovery of the MPG in the resulting organic phase (first phase).
  • solvents used in the present invention provide for efficient separation of MPG and mineral salts and/or of MPG and heavy impurities.
  • the solvent is an alcohol comprising more than four carbon atoms preferably selected in the group consisting of 1-butanol, 1-pentanol, hexanol, heptanol and mixtures thereof.
  • the solvent comprises a solvent selected in the group consisting of 1-butanol, 1-pentanol, hexanol, heptanol and mixtures thereof.
  • the solvent consists of 1-butanol, 1-pentanol, hexanol or heptanol.
  • the solvent comprises a mixture of at least two solvents selected in the group consisting of 1-butanol, 1-pentanol, hexanol and heptanol.
  • the solvent may further comprise some ethanol in a ratio comprised between 1% and 100% by weight and more preferably comprised between 1% and 20%) by weight of the solvent.
  • the solvent comprises a mixture of 1-butanol with ethanol in a ratio comprised between 1% and 100% by weight and more preferably comprised between 1% and 20%> by weight.
  • the solvent comprises a mixture of 1-pentanol with ethanol in a ratio comprised between 1% and 100% by weight and more preferably comprised between 1% and 20%> by weight.
  • the solvent is added to reach a proportion of solvent comprised between 2% and 98%) per weight, preferably comprised between 10% and 95% per weight and even more preferably, between 50% and 95% per weight.
  • the amount of solvent added is sufficient to promote the extraction of the MPG from the concentrated aqueous feed.
  • a biphasic mixture comprising the MPG from the fermentation broth is obtained.
  • the solvent provides for extraction of the MPG from the concentrated aqueous feed containing the majority of salts and other impurities.
  • the biphasic mixture is separated into an organic phase (first phase) and an aqueous phase (second phase) wherein the organic phase comprises the majority of the solvent and at least a fraction of the MPG. Separation of the two phases is performed by any suitable method, in preferred embodiments separation is carried out by mixing and settling. It has been found that it is advantageous to perform mixing of the solvent with the concentrated aqueous feed containing the MPG and separation of the biphasic mixture in a mechanically-agitated liquid-liquid extraction column.
  • This step is typically carried out at a temperature comprised between 10 and 90 °C, preferably between 20 and 70 °C and most preferably at between 20 and 40°C.
  • the temperature is advantageously kept constant during the whole separation procedure.
  • the MPG obtained in the organic phase (first phase) contains fewer mineral salts and heavy impurities than the concentrated aqueous feed.
  • the concentrated aqueous feed comprises at least one heavy impurity selected from glycerol, succinic acid, hexanoic acid, fructose, glucose and sucrose and the weight ratio of at least one of said heavy impurities to MPG is lower in the first phase obtained after the liquid- liquid solvent extraction step than in the concentrated aqueous feed.
  • the concentrated aqueous feed comprises mineral salts and the weight ratio of the mineral salts to MPG is lower in the first phase obtained after the liquid-liquid solvent extraction step than in the concentrated aqueous feed.
  • the first phase containing a fraction of the MPG from the fermentation broth is recovered.
  • the first phase comprises the majority of the MPG.
  • the first phase comprises at least 70%, 80%>, 85% or at least 90%> of the MPG from the fermentation broth.
  • the first phase comprises the majority of the solvent, at least one light impurity and at least a fraction of the MPG.
  • the second phase comprises a majority of the water, at least some heavy impurities from the concentrated aqueous feed and a majority of the mineral salts from the concentrated aqueous feed.
  • solvent, light impurities and/or water are removed from the first phase containing the MPG. Removal of solvent, light impurities and water is carried out by any suitable method.
  • a preferred method is distillation.
  • solvent, light impurities and water are removed by evaporation of solvent and water from the first phase. Evaporation of solvent, light impurities and water from the organic phase is performed according to any suitable method known to the skilled person.
  • evaporation is carried at a pressure comprised between 50 mbar and atmospheric pressure.
  • distilling the first phase is performed at a pressure of about 200 mbar.
  • This distillation or evaporation step produces a first distillate product comprising a majority of the solvent and at least one light impurity and a first bottom product containing MPG, wherein the weight ratio light impurities/MPG is lower in the first bottom product than in the first phase
  • the concentrated aqueous feed comprises at least one light impurity selected from ethanol, acetone, acetic acid, hexanoic acid, hydroxyacetone, propionic acid and methylglyoxal and the weight ratio of at least one of said light impurities to MPG is lower in the first bottom product than in the first phase.
  • the first distillate containing the majority of the solvent may be recycled in the process.
  • the solvent may be saturated with water.
  • a solvent filler may be required in continuous MPG purification methods.
  • the first bottom product containing the majority of the MPG is recovered.
  • the MPG may be further purified according to any known alcohol-purification technique, in particular by distillation ion exchange and/or adsorption.
  • the present invention is related to methods for purifying MPG (monopropylene glycol) from a fermentation broth comprising the following steps: a) clarifying the fermentation broth in order to obtain an aqueous feed containing MPG,
  • step b) removing water from the aqueous feed containing the MPG obtained in step a) to obtain a concentrated aqueous feed, wherein the concentrated aqueous feed contains water, mineral salts, at least one heavy impurity, at least one light impurity and MPG,
  • the biphasic mixture into a first phase comprising solvent, at least one light impurity and at least a fraction of the MPG and a second phase comprising water, at least some of the mineral salts and at least some of the heavy impurities from the concentrated aqueous feed, wherein the weight ratio mineral salts/MPG is lower in the first phase than in the concentrated aqueous feed and the weight ratio heavy impurities/MPG is lower in the first phase than in the concentrated aqueous feed,
  • step b) distilling the first bottom product to obtain a second distillate product comprising MPG and a second bottom product containing the majority of the heavy impurities and MPG, i) recycling the second bottom product to the concentrated aqueous feed obtained in step b),
  • the first bottom product contains MPG and at least one heavy impurity selected from glycerol, succinic acid, fructose, glucose and sucrose and the weight ratio of at least one of said heavy impurities to MPG is lower in the second distillate product than in the first bottom product.
  • This second distillation step allows for removal of any remaining heavy impurities from the MPG.
  • the second distillate product comprises at least 95%, 98%, 99%, 99,5% or at least
  • distillation step some of the MPG is left at the bottom of the second distillation column and recycled with the heavy impurities to the concentrated aqueous feed.
  • This specific configuration of the distillation column combined with the recycling step of a fraction of the MPG of the first bottom product provides for a cost efficient purification method yielding highly purified MPG.
  • This configuration of the distillation column also advantageously avoids fouling of the distillation column with heavy impurities which tend to form a solid residue at the bottom of the column.
  • the amount of MPG left at the bottom of the second distillation column is below 50% per weight, advantageously below 25% per weight of the total MPG of the first bottom product.
  • the MPG left at the bottom of the second distillation column amounts 20 to 25% of the total MPG of the first bottom product.
  • the person skilled in the art may decide to left less than 20% of the total MPG depending on the type of distillation column being used and other operating conditions.
  • the methods for purifying MPG according to the present invention are performed continuously.
  • continuous purification of MPG according to the methods of the present invention some of the second bottom product containing MPG and heavy impurities is purged to avoid accumulation of high impurities in the continuous process.
  • distilling the first bottom product is performed at a pressure comprised between 10 mbar and atmospheric pressure.
  • distilling the first bottom product is performed at a pressure comprised between 50 and lOOmbar, more preferably between 50 and 150 mbar and most preferably, distilling the first bottom product is performed at a pressure of 60 mbar.
  • Ant appropriate distillation column may be used in the methods of the present invention, preferably distillation is performed in a forced circulation evaporator.
  • distilling the first bottom product is performed in a distillation column configured to obtain a second bottom product containing the majority of heavy impurities and MPG in a weight ratio MPG/heavy impurities comprised between 0.1-10, wherein the weight of the heavy impurities is defined as the weight of the dry solids in the second bottom product.
  • the weight ratio MPG/heavy impurities in the second bottom product is comprised between 0.5-3.
  • the weight ratio MPG/heavy impurities is equal to 1.2.
  • the weight of the heavy impurities in the second bottom product is the weight of the dry solids in the second bottom product as determined on a thermobalance at 105°C until the weight variation is lower than lmg/20 seconds.
  • recovering MPG from the second distillate product comprises further purification of the MPG by distillation.
  • recovering MPG from the second distillate product comprises further purification of the MPG by ion exchange and/or adsorption.
  • the MPG can be further purified according to any known alcohol- purification technique, in particular by distillation.
  • MPG of the first bottom product or of the second distillate product may be further purified to obtain highly purified MPG.
  • topping and stripping may be performed.
  • an ion exchange step and/or adsorption step may also be included in the distillation sequence, as a polishing step, to maximize final product quality.
  • Another optional step of the method of the present invention is adjusting the pH to a pH>7 during purification. By raising the pH, acids can be separated and eliminated as ions.
  • the method according to the present invention also comprises further removal of water leading to concentration of the evaporated product containing the MPG.
  • Water can be eliminated by various techniques known to persons skilled in the art.
  • water is removed by evaporation.
  • further purification of the MPG is performed by distillation techniques.
  • Elimination by distillation of products with a boiling point lower than that of the MPG to be purified and products with a boiling point higher than that of the MPG to be purified is carried out according to conventional techniques known to persons skilled in the art.
  • an ion exchange step and/or adsorption may be performed in between the different distillation steps or after the final distillation step. These techniques are used as a final polishing step, in order to maximize product quality.
  • ion exchange is an efficient technique for the removal of salts from various solutions.
  • the removal of high salt concentration requires frequent regeneration or renewal of ion exchange resins and is linked to high operation costs.
  • the majority of organic and mineral salts are removed beforehand.
  • Ion exchange may be used primarily to remove residual ionic impurities. Fouling of the resin is thus reduced, avoiding frequent regeneration and/or replacement of the ion exchange resins and preventing high operation costs.
  • so-called ion exchange resins may further be used for the removal of other impurities.
  • ion exchange resins may be used for adsorption of various organic impurities.
  • Ion exchange is a well-known technique and may be carried out with any suitable resin.
  • ion exchange resins are selected from strong anion exchange resins, weak anion exchange resins, strong cation exchange resins and weak cation exchange resins, or mixtures thereof, e.g. well known mixed-bed type ion exchange resins.
  • the ion exchange step may consist in a treatment on any combination of the above-mentioned ion exchange resins.
  • Further purification of the MPG may further comprise adsorption of impurities on adsorbent solids.
  • adsorption refers to the capture of impurities onto the surface of an adsorbent solid. This adsorption step allows removal of impurities, which are bound to the adsorbent solid by chemical or physical attraction.
  • activated charcoal or other solid adsorbents are used to remove impurities from the purified MPG.
  • ion exchange resins may also be used for to remove such impurities.
  • adsorption and/or ion exchange are performed after distillation, thus reducing fouling of the solid adsorbent and minimizing costs.
  • an ion exchange step and/or adsorption step is performed at the end of the distillation sequence, to produce pure MPG from distilled MPG.
  • addition of water to the distilled MPG may be needed to prevent degradation of the resin or adsorbent solid degradation and/or to decrease viscosity, thus increasing mass transfer coefficients and adsorption efficiency.
  • water may have to be added in proportions ranging from 1 and 100%, more preferably from 10 and 20%.
  • the invention is also related to methods for producing MPG comprising the following steps:
  • Figure 1 Method for purifying MPG by adding a solvent to eliminate salts and heavy impurities
  • Figure 2 Method for purification of MPG comprising a liquid- liquid extraction, recycling of pentanol and recycling of a fraction of the MPG containing heavy impurities.
  • the micro filtrate is concentrated 6 to 7 times during a distillation stage conducted between 200 mbar and 1013 mbar.
  • the product from the foot of this initial distillation stage (1) is mixed with the recycling line (6) (foot of (D3), constituted by heavy compounds and MPG) to give the mixture (2).
  • the liquid-liquid extraction column is fed by the liquid (2) and the solvent (pentanol saturated in water) (9).
  • the MPG contained in the liquid (2) is extracted by the organic phase in the extraction column (Dl).
  • the organic phase (3) rich in pentanol and MPG which leaves the extraction column is sent to column (D2).
  • Column (D2) is a distillation column which operates at 200 mbar and separates pentanol and water from MPG.
  • the flow (5) comprises pentanol, water and light compounds (acids, ester).
  • the flow (4) comprises MPG and heavy compounds. Water and pentanol form a heteroazeotrope in the column (D2).
  • the flow (5) comprises two liquid phases, and is sent to a decanter to separate the organic phase (pentanol) (8) and the aqueous phase (7).
  • the flow (4) is sent to the distillation column (D3) which operates at 60 mbar to separate MPG (18) from the heavy compounds (6).
  • the flow (6) contains MPG and the heavy compounds and is recycled to the extraction column Dl .
  • the flow (6') is a purge. The flow (6') eliminates the heavy compounds which accumulate in the process.
  • the aqueous phase (10) which leaves the extraction column (Dl) is sent to the regeneration column (D4) which operates at atmospheric pressure to recover the fraction of pentanol moved to the aqueous phase in the column (Dl).
  • the aqueous phase rich in heavy compounds and in salts (13) is recovered at the foot of column (D4).
  • the flow (13) is an effluent of the process. Water and pentanol form a heteroazeotrope in (D4).
  • the flow (12) comprises two liquid phases, and is sent to a decanter for separation of the organic phase (pentanol) (14) and aqueous phase (15).
  • the flow (8) and (14) are mixed for recycling of the pentanol.
  • the resulting flow (16) is sent to the extraction column (Dl).
  • the flow (7) and (15) are mixed for recycling of the aqueous phase.
  • the resulting flow (17) is mixed with the flow (10).
  • the resulting flow (11) feeds the column (D4).
  • the flow (19) represents the pentanol filler.
  • 1-pentanol 80.6 g was then added to 100 g of (Al) mixture.
  • 1-Pentanol was purchased from Sigma- Aldrich® (99% vol. purity), and used without further purification.
  • This liquid- liquid mixture (Bl) was introduced into a thermostatic cell. Temperature was kept constant at 30°C throughout the test. The (Bl) mixture was mixed for three hours. Then, mixing was stopped to allow settling of the mixture for eight hours. Thus, equilibrium was reached between the organic (CI) and aqueous (Dl) phases.
  • a mixture (A2) of 1,2-propanediol (10%) and water (90%) was used as a starting material for the following experiments.
  • 1,2-propanediol was purchased from Sigma- Aldrich® (99.0% vol. purity).
  • This liquid-liquid mixture (B2) was introduced into a thermostatic cell. Temperature was kept constant at 30°C throughout the test. The (B2) mixture was mixed during three hours. Then, mixing was stopped to allow settling of the mixture during eight hours.
  • a mixture (A3) of 1,2-propanediol (10%) and water (90%) was used as a starting material for the following experiments.
  • 1,2-propanediol was purchased from Sigma- Aldrich® (99.0% vol. purity).
  • Ethyl acetate 88.5 g was then added to 100.8 g of (A3) mixture.
  • Ethyl acetate was purchased from Fluka® (>99.5% vol. purity), and used without further purification.
  • This liquid-liquid mixture (B3) was introduced into a thermostatic cell. Temperature was kept constant at 30°C throughout the test. The (B3) mixture was mixed during three hours. Then, mixing was stopped to allow settling of the mixture during eight hours.
  • a mixture (A4) of 1,2-propanediol (10%) and water (90%) was used as a starting material for the following experiments.
  • 1,2-propanediol was purchased from Sigma- Aldrich® (99.0% vol. purity).
  • This liquid-liquid mixture (B4) was introduced into a thermostatic cell.
  • a filtered fermentation broth containing 1,2-propanediol (MPG) (A5) was used as a starting material for the following experiments.
  • Filtration of the fermentation broth consisted in a 0.65 ⁇ cutoff microfiltration.
  • the (A5) filtered fermentation broth was first concentrated by evaporation.
  • (A5) Filtered fermentation broth (49.8 kg) was loaded into a thermosyphon-type evaporator. Operating top pressure was between 100 and 150 mbar. 85.6 wt% of the solution was evaporated. 7.1 kg of a MPG-rich mixture (B4) was recovered. Filtered fermentation broth (A5) and concentrate mixture (B5) was analyzed by HPLC and results are reported in Table 5.
  • This liquid-liquid mixture (C5) was introduced into a thermostatic cell. Temperature was kept constant at 30°C throughout the test. The (C5) mixture was mixed during three hours. Then, mixing was stopped to allow settling of the mixture during eight hours.
  • the concentrated fermentation broth containing 1,2-propanediol (MPG) (B5) was used as a starting material for the following experiments.
  • (B6) MPG-rich mixture was fed to the bottom of a batch distillation column.
  • the operating pressure was set to 5 mbar.
  • the top operating temperature was about 95°C.
  • One sample of MPG was produced with a purity higher than 99.5%) (surface value measured by GC/MS), without any trace of the impurities reported in Table 5.
  • a filtered fermentation broth containing 1,2-propanediol (MPG) (A5) was used as a starting material for the following experiments.
  • This liquid-liquid mixture (C5) was introduced into a thermostatic cell. Temperature was kept constant at 30°C throughout the test. The (C5) mixture was mixed during three hours. Then, mixing was stopped to allow settling of the mixture during two hours.
  • a filtered fermentation broth containing 1,2-propanediol (MPG) (A6) was used as a starting material for the following experiments. Filtration of the fermentation broth consisted in a 0.1 ⁇ cutoff micro filtration.
  • the (A6) filtered fermentation broth was first concentrated by evaporation.
  • (A6) Filtered fermentation broth (95.8 kg) was loaded into a thermosyphon-type evaporator. Operating top pressure was between 100 and 150 mbar. 86.6 wt% of the solution was evaporated. 10.1 kg of a MPG-rich mixture (B6) was recovered. Filtered fermentation broth (A6) and concentrate mixture (B6) was analyzed by HPLC and results are reported in Table 11 and 12.
  • Dry solids are measured with a themobalance. Dry solids are composed of salt, sugar and heavy compounds (glycerol, succinate)
  • the organic phase (D6) is extracted at the top of the column and the aqueous phase (E6) is extracted at the bottom of the column.
  • Table 15 Quantity and composition of organic (D6) and aqueous (E6) phases.
  • the yield of dry solids in aqueous phase is 66.5%.
  • Dry solids are measured with a thermobalance. Dry solids are composed of salt, sugar and heavy compounds (glycerol, succinate)
  • (A7) feeds a distillation column.
  • the distillation column is packed with 1.2 m of Propack.
  • the distillate (B7) is composed in majority of pentanol
  • the residue (C7) is composed in majority of 1.2 propanediol and dry solids.
  • the residue is composed of 59.6%> wt of 1.2 propanediol and 40.4%> wt of dry solids. With this composition the residue is still liquid with a viscosity of 1 Pa.s at 25°C. This residue can be recycled in the extraction column REFERENCES

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Abstract

La présente invention concerne un procédé pour purifier MPG à partir d'un bouillon de fermentation comprenant l'extraction de MPG avec un solvant comprenant le 1-butanol, le 1-pentanol, l'heptanol et/ou l'hexanol.
PCT/EP2011/055034 2011-03-31 2011-03-31 Procédé pour purifier mpg (monopropylèneglycol) à partir d'un bouillon de fermentation Ceased WO2012130316A1 (fr)

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WO2013148505A1 (fr) * 2012-03-27 2013-10-03 Eastman Chemical Company Procédé de séparation et de purification d'un flux de diols mélangés
US8703999B2 (en) 2012-03-27 2014-04-22 Eastman Chemical Company Hydrocarboxylation of methylene dipropionate in the presence of propionic acid and a heterogeneous catalyst
US8709376B2 (en) 2010-09-23 2014-04-29 Eastman Chemical Company Process for recovering and recycling an acid catalyst
US8765999B2 (en) 2012-03-27 2014-07-01 Eastman Chemical Company Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and a homogeneous catalyst
US8779214B2 (en) 2010-08-18 2014-07-15 Eastman Chemical Company Methods for recovery and recycle of ruthenium homogenous catalysts
US8785686B2 (en) 2010-09-23 2014-07-22 Eastman Chemical Company Process for recovering and recycling an acid catalyst
US8829248B2 (en) 2010-08-18 2014-09-09 Eastman Chemical Company Method for recovery and recycle of ruthenium homogeneous catalysts
WO2014191516A1 (fr) * 2013-05-31 2014-12-04 Shell Internationale Research Maatschappij B.V. Procédé de séparation d'alcools
US8927766B2 (en) 2012-03-27 2015-01-06 Eastman Chemical Company Hydrocarboxylation of methylene dipropionate in the presence of a propionic acid and a homogeneous catalyst
US9227896B2 (en) 2010-08-18 2016-01-05 Eastman Chemical Company Process for the separation and purification of a mixed diol stream
WO2017042602A1 (fr) 2015-09-10 2017-03-16 Metabolic Explorer Nouvelles lactaldéhydes réductases pour la production de 1,2-propanédiol
US9718752B2 (en) 2013-05-31 2017-08-01 Shell Oil Company Process for the separation of an alkylene glycol
US9932284B2 (en) 2013-05-31 2018-04-03 Shell Oil Company Process for the separation of 1,4-butanediol and co-products
EP3342873A1 (fr) 2016-12-29 2018-07-04 Metabolic Explorer Conversion de méthylglyoxale en hydroxyacétone utilisant des enzymes et applications associées
US10099980B2 (en) 2013-05-31 2018-10-16 Shell Oil Company Glycol recovery with solvent extraction
WO2019011976A1 (fr) * 2017-07-11 2019-01-17 Stichting Wageningen Research Procédé d'extraction de sel à partir d'une composition qui comprend une matière organique
US10221116B2 (en) 2014-04-02 2019-03-05 Shell Oil Company Process for the separation of monoethylene glycol and 1,2-butanediol
US10265641B2 (en) 2014-05-01 2019-04-23 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Simultaneous recovery of organic compounds and extractants
WO2019092495A1 (fr) * 2017-11-09 2019-05-16 Braskem S.A. Procédé de récupération de cétones et de glycols de la fermentation

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US9227896B2 (en) 2010-08-18 2016-01-05 Eastman Chemical Company Process for the separation and purification of a mixed diol stream
US8779214B2 (en) 2010-08-18 2014-07-15 Eastman Chemical Company Methods for recovery and recycle of ruthenium homogenous catalysts
US8829248B2 (en) 2010-08-18 2014-09-09 Eastman Chemical Company Method for recovery and recycle of ruthenium homogeneous catalysts
US10329230B2 (en) 2010-08-18 2019-06-25 Eastman Chemical Company Process for the separation and purification of a mixed diol stream
US8709376B2 (en) 2010-09-23 2014-04-29 Eastman Chemical Company Process for recovering and recycling an acid catalyst
US8785686B2 (en) 2010-09-23 2014-07-22 Eastman Chemical Company Process for recovering and recycling an acid catalyst
US8703999B2 (en) 2012-03-27 2014-04-22 Eastman Chemical Company Hydrocarboxylation of methylene dipropionate in the presence of propionic acid and a heterogeneous catalyst
US8765999B2 (en) 2012-03-27 2014-07-01 Eastman Chemical Company Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and a homogeneous catalyst
US8927766B2 (en) 2012-03-27 2015-01-06 Eastman Chemical Company Hydrocarboxylation of methylene dipropionate in the presence of a propionic acid and a homogeneous catalyst
WO2013148505A1 (fr) * 2012-03-27 2013-10-03 Eastman Chemical Company Procédé de séparation et de purification d'un flux de diols mélangés
CN105189427B (zh) * 2013-05-31 2018-07-03 国际壳牌研究有限公司 用于分离醇的方法
US9718752B2 (en) 2013-05-31 2017-08-01 Shell Oil Company Process for the separation of an alkylene glycol
US9932284B2 (en) 2013-05-31 2018-04-03 Shell Oil Company Process for the separation of 1,4-butanediol and co-products
CN105189427A (zh) * 2013-05-31 2015-12-23 国际壳牌研究有限公司 用于分离醇的方法
WO2014191516A1 (fr) * 2013-05-31 2014-12-04 Shell Internationale Research Maatschappij B.V. Procédé de séparation d'alcools
US10099980B2 (en) 2013-05-31 2018-10-16 Shell Oil Company Glycol recovery with solvent extraction
US10221116B2 (en) 2014-04-02 2019-03-05 Shell Oil Company Process for the separation of monoethylene glycol and 1,2-butanediol
US10265641B2 (en) 2014-05-01 2019-04-23 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Simultaneous recovery of organic compounds and extractants
WO2017042602A1 (fr) 2015-09-10 2017-03-16 Metabolic Explorer Nouvelles lactaldéhydes réductases pour la production de 1,2-propanédiol
EP3342873A1 (fr) 2016-12-29 2018-07-04 Metabolic Explorer Conversion de méthylglyoxale en hydroxyacétone utilisant des enzymes et applications associées
WO2018122388A1 (fr) 2016-12-29 2018-07-05 Metabolic Explorer Conversion du méthylglyoxal en hydroxyacétone à l'aide de nouvelles enzymes et applications associées
NL2019228B1 (en) * 2017-07-11 2019-01-25 Stichting Wageningen Res Method for extracting salt from a composition comprising organic matter
WO2019011976A1 (fr) * 2017-07-11 2019-01-17 Stichting Wageningen Research Procédé d'extraction de sel à partir d'une composition qui comprend une matière organique
WO2019092495A1 (fr) * 2017-11-09 2019-05-16 Braskem S.A. Procédé de récupération de cétones et de glycols de la fermentation
US10710950B2 (en) 2017-11-09 2020-07-14 Braskem S.A. Process for the recovery of ketones and glycols from fermentation
JP2021502088A (ja) * 2017-11-09 2021-01-28 ブラスケム・エス・エー 発酵からケトン及びグリコールを回収する方法
US10988428B2 (en) * 2017-11-09 2021-04-27 Braskem S.A. Process for the recovery of ketones and glycols from fermentation
JP7124075B2 (ja) 2017-11-09 2022-08-23 ブラスケム・エス・エー 発酵からケトン及びグリコールを回収する方法

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