WO2023099353A1 - Procédé de conversion de sels d'acide organique en acides organiques par électrodialyse et électrodialyse avec membranes bipolaires - Google Patents

Procédé de conversion de sels d'acide organique en acides organiques par électrodialyse et électrodialyse avec membranes bipolaires Download PDF

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WO2023099353A1
WO2023099353A1 PCT/EP2022/083326 EP2022083326W WO2023099353A1 WO 2023099353 A1 WO2023099353 A1 WO 2023099353A1 EP 2022083326 W EP2022083326 W EP 2022083326W WO 2023099353 A1 WO2023099353 A1 WO 2023099353A1
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stream
carboxylate
edbm
unit
concentrated
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PCT/EP2022/083326
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Carolina Anna Maria Christina Dirix
Hans Lammers
Cornelis Elizabeth Johannus Van Lare
Eilertdina Henderika Renkema
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Nobian Chemicals Bv
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives

Definitions

  • the present invention is directed to a process for converting organic acid salts produced in
  • Carboxylate product streams originating from a bioprocess are typically very dilute (usually with
  • the downstream process in addition to the acidification step for converting the carboxylate to the respective carboxylic acid, the downstream process also requires concentration and purification steps.
  • Electrodialysis is also a common technology used to perform the concentration step. ED converts the carboxylate product streams originating from a bioprocess into a concentrated
  • carboxylate solution that can be further acidified and a depleted carboxylate solution that can be recycled back to the bioprocess. It is known that an ED process can be more energy efficient in removing the first fraction of water compared to evaporation. The remaining water can subsequently be removed by evaporation, such as single stage evaporation, multistage evaporation, and Mechanical Vapor Recompression (MVR) evaporation.
  • MVR Mechanical Vapor Recompression
  • the acidification step can be performed by adding inorganic acids, by ion-exchange, or by using electrodialysis with bipolar membranes (EDBM).
  • Ion-exchange is commonly used due to its low cost and technological maturity.
  • ion-exchange can be sensitive to impurities, such as those contained in carboxylate product streams originating from a bioprocess.
  • bipolar membranes disassociate water into hydronium ions (acid) and hydroxyl ions (base) on application of an electrical field. These generated ions combine with cations and anions from a process stream, where the cations and anions are separated by one or more ion exchange membranes in the electrodialysis cell. The combination of the hydronium ions with the anions, and the hydroxyl ions with the cations, results in produced streams having acid and base.
  • the production of carboxylic acids from their respective carboxylate salts using EDBM is described as a more environmentally friendly alternative for extraction processes or ion exchange.
  • EDBM can be sensitive to impurities, such as those contained in carboxylate product streams originating from a bioprocess.
  • impurities such as those contained in carboxylate product streams originating from a bioprocess.
  • multivalent cations such as calcium and magnesium, can lead to precipitation of the corresponding hydroxides in the membranes.
  • Conductivity can also be improved by adding inert salts or supporting electrolytes to an EDBM process.
  • the added salts must be carefully selected in relation to the specific process and products, such that they are inert, so as not to generate additional byproducts, but give sufficient conductivity without precipitation.
  • these salts need to be added in a separate dosing step and need to be removed in an additional separation step.
  • adding supporting electrolytes to enhance conductivity presents a significant cost and complexity adding factor.
  • Another issue with EDBM is the high level of water required by the system.
  • the concentration of the produced acid and base streams is typically maximized at about 10 wt% (as operating at higher values results in highly inefficient processes with low current efficiency and shortens the life of the expensive membranes).
  • the present inventors have now found a process for converting carboxylic acid salts produced in bioprocesses into carboxylic acids, the process comprising: a) obtaining a carboxylate stream from a bioreactor, the carboxylate stream optionally comprising nutrient salt impurities, b) feeding the carboxylate stream to an electrodialysis (ED) unit and separating the carboxylate stream into a concentrated carboxylate stream and a dilute carboxylate stream, the concentrated carboxylate stream optionally comprising nutrient salt impurities, c) feeding the concentrated carboxylate stream to an acidic compartment of an electrodialysis with bipolar membranes (EDBM) unit, wherein at least a part of the dilute carboxylate stream is fed to a basic compartment of the EDBM unit and wherein at least a part of the dilute carboxylate stream is optionally returned to the bioreactor, and d) optionally purifying a product stream obtained from the acidic compartment of the EDBM unit, wherein at least a portion
  • the water balance of the conversion process can be enhanced.
  • the performance of the EDBM is not affected when using the dilute carboxylate stream instead of water in the basic compartment and that connecting these two units is therefore possible.
  • bioprocess impurities in the form of nutrient salts e.g., salts of cations like sodium, potassium and ammonium and anions like chloride, nitrate, nitrite, phosphate, phosphite and sulphate
  • nutrient salts e.g., salts of cations like sodium, potassium and ammonium and anions like chloride, nitrate, nitrite, phosphate, phosphite and sulphate
  • high conversion refers to conversion levels above 90%, for example, above 95%.
  • the water balance can be closed (i.e., minimal to no water addition required by the process due to the high level of water recycle);
  • Figure 1 is a flow diagram of preferred embodiments of the present disclosure.
  • the present invention provides a process for converting carboxylic acid salts produced in bioprocesses into carboxylic acids, the process comprising: a) obtaining a carboxylate stream from a bioreactor, the carboxylate stream optionally comprising nutrient salt impurities, b) feeding the carboxylate stream to an electrodialysis (ED) unit and separating the carboxylate stream into a concentrated carboxylate stream and a dilute carboxylate stream, the concentrated carboxylate stream optionally comprising nutrient salt impurities, c) feeding the concentrated carboxylate stream to an acidic compartment of an electrodialysis with bipolar membranes (EDBM) unit, wherein at least a part of the dilute carboxylate stream is fed to a basic compartment of the EDBM unit, and d) optionally purifying a product stream obtained from the acidic compartment of the EDBM unit.
  • EDBM electrodialysis with bipolar membranes
  • Step a) comprises obtaining a carboxylate stream from a bioreactor.
  • the bioreactor and bioprocesses are not particularly limited. Any suitable bioreactor, such as, but not limited to, a continuous stirred tank bioreactor, a bubble column bioreactor, an airlift bioreactor, a fluidized bed bioreactor, a packed bed bioreactor, photo-bioreactors, or any type of fermenter, may be used. Examples of bioprocesses to which the presently disclosed process may be applied include, but are not limited to, enzymatic, fermentative and/or photo-initiated bioprocesses. As a particular example, the presently disclosed process may be applied to a glycolate stream obtained using the bioprocess described in WO 201 1/036213 A1 or WO 2020/152342 A1 .
  • the carboxylate stream of step a) is an aqueous solution, suspension, slurry, or the like obtained from a bioreactor and comprising typically from 0.5 to 20 wt.%, more typically from 1 to 10 wt.% carboxylates (relative to the total weight of the carboxylate stream).
  • a filtration step may be incorporated between steps a) and b) so as to prevent damage to the ED unit.
  • the carboxylate stream comprises at least one, linear or branched, saturated or unsaturated, water-soluble C1-C10, preferably Ci-Cs, more preferably Ci-Ce mono- or polycarboxylate.
  • the carboxylate may be substituted, for example with at least one hydroxyl group.
  • the carboxylate is selected from lactate, glycolate, acetate, formate, succinate, citrate, butyrate, tartrate, malate, gluconate, itaconate, propionate, or mixtures thereof. More preferably, the carboxylate is selected from lactate, glycolate, acetate or mixtures thereof.
  • the counterion of the carboxylate is preferably sodium or potassium.
  • the carboxylate stream of step a) may contain nutrient salt impurities.
  • nutrient salt has its ordinary meaning, namely biological feed (i.e. , “nutrient”) salts found in the biological media used in the bioprocess (i.e., the media used to buffer and feed the biological agents, such as enzymes or cells, in the bioreactor).
  • biological feed i.e. , “nutrient”
  • Such salts include, but are not limited to, salts of cations selected from sodium, potassium and ammonium and anions selected from chloride, nitrate, nitrite, phosphate, phosphite and sulphate.
  • the cations are preferably monovalent in order to avoid precipitation in the membrane of the EDBM unit.
  • the anions originate from strong acids with a pKa value that is preferably 0.5, more preferably 0.7, and most preferably 1 unit less than the pKa value of the carboxylic acid.
  • the carboxylate stream of step a) contains a mixture of two or more nutrient salt impurities, for example, three or more nutrient salt impurities, such as a combination of sodium sulphate, sodium chloride and sodium nitrate.
  • the amount of nutrient salt impurities in the carboxylate stream of step a) is from about 0.01 to about 2 wt.%, more preferably from about 0.02 to about 1 wt.%, and most preferably from about 0.05 to about 0.5 wt.%, in each instance relative to the total weight of the carboxylate stream.
  • Step b) of the process comprises separating the carboxylate stream of step a) into a concentrated stream and a dilute stream.
  • the concentrated carboxylate stream may comprise from about 10 to about 30 wt.%, preferably from about 15 to about 25 wt.% carboxylate
  • the dilute carboxylate stream may comprise from about 0.1 to about 3 wt.%, preferably from about 0.5 to about 2 wt.% carboxylate, in each instance relative to the total weight of the respective carboxylate stream.
  • the concentrated carboxylate stream may be further concentrated, preferably to about 25-40 wt.%, by incorporating a further concentration step between the ED and EDBM process steps.
  • Step c) of the process comprises feeding the concentrated carboxylate stream of step b) (or optionally further concentrated carboxylate stream described above) to an acidic compartment of the EDBM unit. It is here that the acidification of the carboxylate salt takes place.
  • Step c) of the process further comprises feeding at least a part, and preferably all or substantially all, of the dilute carboxylate stream to a basic compartment of the EDBM unit. This gives rise to a more efficient process for the reasons set out above.
  • the dilute carboxylate stream may be returned to the bioreactor. It is further preferred if at least a part, and preferably all or substantially all, of a product stream obtained from a basic compartment of the EDBM unit is returned to the bioreactor.
  • the EDBM unit of the presently disclosed process can operate at lower than maximized base concentrations, that is, at base concentrations below 10 wt.% in the basic compartment, without upsetting the water balance and incurring the additional energy requirements associated with evaporation of surplus water when seeking to prepare more concentrated products (as is normally the case).
  • the EDBM unit is operated at a base concentration of from 1 to 8 wt.%, more preferably of from 2 to 5 wt.%, for example, at a concentration of from 1 to 8 wt.% NaOH and/or KOH.
  • a base concentration of from 1 to 8 wt.% more preferably of from 2 to 5 wt.%, for example, at a concentration of from 1 to 8 wt.% NaOH and/or KOH.
  • operating at lower base (caustic) concentrations improves the energy efficiency of the EDBM operation, thereby maximizing process efficiency whilst maintaining proper pH control of the bioreactor.
  • returning at least a part of the dilute carboxylate stream and/or at least a part, and preferably all or substantially all, of a product stream obtained from a basic compartment of the EDBM unit to the bioreactor provides the further advantage of recycling any functional nutrient salts contained in these streams to the biological media used in the bioprocess.
  • multivalent cations are removed in the ED unit using selective membranes and/or in a separate process step before step b) or c), such as ion-exchange.
  • multivalent cations such as calcium and magnesium are preferably below 5 ppm for proper operation of the EDBM to prevent precipitation of the corresponding hydroxides in the membrane.
  • the concentrated carboxylate stream of step b) contains nutrient salt impurities additional energy efficiency gains can be obtained.
  • the nutrient salts can be concentrated to the same extent.
  • the amount of nutrient salt impurities in the concentrated carboxylate stream is from about 0.05 to about 10 wt.%, more preferably from about 0.1 to about 5 wt.%, and most preferably from about 0.2 to about 2 wt.%, in each instance relative to the total weight of the carboxylate stream.
  • These amounts of nutrient salt impurities have been found to maintain conductivity in the acidic compartment of the EDBM unit at or above 10 mS/cm, while converting the carboxylates into their respective carboxylic acids.
  • the process of EDBM is known in the art. An overview of the technology can be found in M. Bailly, Desalination, 144, 157-162 (2002).
  • the EDBM unit of the presently disclosed process consists of a EDBM membrane stack and provisions (pumps, piping, vessels, sensors etc.) to allow flow of different fluids through the stack.
  • the membrane stack consists of at least one anode in the anode compartment, multiple cells of consecutive acidic and basic compartments (this is a so-called ‘2-compartment’ or ‘2C’ stack) and at least one cathode in a cathode compartment.
  • the acidic and basic compartments are separated by ion exchange membranes on either side.
  • each acidic compartment has a bipolar membrane positioned at the anode side with the anion side of the bipolar membrane facing the anode.
  • a cation exchange membrane is positioned on the cathode side of the acidic compartment.
  • the adjacent compartment of the acidic compartment is a basic compartment.
  • the end cells adjacent to the anode and the cathode compartment are separated from the electrode compartments with a cation exchange membrane, most preferably with a chemically stable (e.g. made of National® or another brand of similar (fully or partly) fluorinated type of) cation exchange membrane.
  • the acidic compartments of the EDBM stack are flushed with the concentrated carboxylate containing stream from the ED process to be acidified and the basic compartments of the EDBM stack are flushed with the dilute carboxylate stream originating from the ED process and optionally with a dilute base stream (e.g., 2-8 wt.% KOH and/or NaOH).
  • the electrode compartments are generally flushed with a dilute base stream from a separate fluid circuit. Gases produced at the electrodes are removed through the fluid circuits. Other electrolytes with suitable electrodes (e.g. NaaSC -aq with DSA® electrodes) can also be applied.
  • the membranes allow passing of cations (cation exchange membranes) and the splitting of water into acid and base (bipolar membranes) thereby converting the carboxylate in the acidic compartment into carboxylic acid and producing a base in the basic compartment.
  • Typical conditions of the EDBM process in the present invention are: electrical current density: between 300 and 1500 A/m 2 , more preferably between 500 and 1200 A/m 2 , most preferably between 700 and 1000 A/m 2 .
  • - temperature preferably as high as possible but typically a maximum of 60 °C and more preferably a maximum of 40 °C, for example, from 20 to 60 °C, preferably from 30 to 40 °C, to obtain a suitably high membrane lifetime.
  • Viscosity of the process fluids at process conditions typically, below 15 mPa.s, more preferably below 10 mPa.s, for example, from 1 to 15 mPa.s, preferably from 1 to 10 mPa.s. Viscosity should be such that sufficient flow is achieved to allow for sufficient cooling of the membrane compartments to avoid (local) overheating of membranes.
  • step d comprises sending the product stream that exits the acidic compartment of the EDBM unit to a purification section.
  • the purification includes removal of any nutrient salt impurities and water by means of generally known methods like ion exchange, membrane separation, crystallization, adsorption, evaporation and distillation.
  • the final product is the carboxylic acid, ideally pure or close to its solubility in water, and preferably containing less than 5 wt.% impurities, more preferably less than 2 wt.% impurities and most preferably less than 1 wt.% impurities, as determined by general analytical methods, such as Inductively Coupled Plasma Optical Emission Spectrometry for determining the content of (residual) cations such as sodium, potassium and other metal ions such as calcium, magnesium, iron etc., and Ion Chromatography for determining the content of anions such as glycolate, chloride, phosphate, nitrate, sulfate, acetate, etc.
  • potentiometric titration is applied using calibrated sodium hydroxide solution and a combined pH/reference electrode to determine end-point.
  • At least a part of a water-based stream (optionally containing salts), extracted from the product stream in the purification section is returned to an earlier stage in the process, e.g., returned to the bioreactor and/or the EDBM unit.
  • the extracted water is returned to the basic compartment of the EDBM unit.
  • F is a feed stream (comprising a carbon containing source)
  • A is a bioreactor
  • B is an ED unit
  • C is an EDBM unit
  • D is a purification section.
  • a carboxylate stream comprising nutrient salt impurities is obtained from the bioreactor A and fed, via 1 , into the ED unit B.
  • the carboxylate stream is separated into a concentrated and a dilute carboxylate stream, both streams comprising nutrient salt impurities.
  • the concentrated carboxylate stream comprising nutrient salt impurities is fed from the ED unit B into an acidic compartment of the EDBM unit C, via 2, while at least a part of the dilute carboxylate stream is fed from the ED unit B into a basic compartment of the EDBM unit C, via 4.
  • the carboxylate in the acidic compartment is converted into carboxylic acid and a base is produced in the basic compartment.
  • the carboxylic acid product stream of the acidic compartment of the EDBM unit C is fed, via 3, to the purification section D, where it is purified to a high purity carboxylic acid product stream P.
  • line 5 is the return of at least a part, preferably all or substantially all, of the base product stream obtained from the basic compartment of the EDBM unit C to the bioreactor A
  • line 5 is the return of at least a part, preferably all or substantially all, of the base product stream obtained from the basic compartment of the EDBM unit C to the bioreactor A
  • lines 7 and 8 are the return of at least a part of a water-based stream, extracted during the purification procedure, to the bioreactor A and the EDBM unit C, respectively.
  • F feed stream comprising a carbon containing source
  • the present invention provides a system for converting carboxylic acid salts produced in bioprocesses into carboxylic acid, the system comprising: a) an electrodialysis (ED) unit configured to receive a carboxylate stream optionally comprising nutrient salt impurities from a bioreactor and then separate the carboxylate stream into a concentrated carboxylate stream and a dilute carboxylate stream, the concentrated carboxylate stream optionally comprising nutrient salt impurities; and b) an electrodialysis with bipolar membranes (EDBM) unit, wherein an acidic compartment of the EDBM unit is configured to receive the concentrated carboxylate stream from the ED unit, wherein a basic compartment of the EDBM unit is configured to receive at least a part of the dilute carboxylate stream from the ED unit, and wherein the EDBM unit is optionally configured to return at least a part of a product stream from the basic compartment of the EDBM unit to the bioreactor.
  • ED electrodialysis
  • EDBM
  • the ED unit and the EDBM unit can be operated in batch, or in a ‘feed and bleed’ or continuous configuration.
  • a predetermined amount of the carboxylate stream or the concentrated carboxylate stream is fed into the ED or EDBM unit, respectively, and the processes are run until the desired product concentrations are achieved. The products are then sent for further treatment, as required.
  • a predetermined flow of the carboxylate stream or the concentrated carboxylate stream is fed into the ED or EDBM unit, respectively, in a continuous manner, and, at the same time, the excess volume is continuously discharged from the process so as to maintain constant concentrations of desired levels in the product streams.
  • the product streams are then sent for further treatment, as required.
  • the concentrate and the diluate stream of the ED unit, and/or the acid and the base stream of the EDBM unit can be operated individually in batch mode or in continuous mode or both.
  • people skilled in the art of ED or EDBM can chose the optimal configuration and conditions for their process case.
  • the ED unit is configured to return at least a part of the dilute carboxylate stream to the bioreactor.
  • the product stream obtained from the basic compartment of the EDBM unit comprises 1 to 8 wt.% caustic (being NaOH and/or KOH), preferably 2 to 5 wt.%.
  • the system further comprises a purification section configured to receive a product stream from the acidic compartment of the EDBM unit and return a water-based stream, extracted from the product stream, to the bioreactor and/or the EDBM unit.
  • the purification section is configured to return water extracted from the product stream to the basic compartment of the EDBM unit.
  • the system comprises: a. a bioreactor, b. an electrodialysis (ED) unit configured to receive a carboxylate stream optionally comprising nutrient salt impurities from a bioreactor and then separate the carboxylate stream into a concentrated carboxylate stream and a dilute carboxylate stream, the concentrated carboxylate stream optionally comprising nutrient salt impurities, wherein the ED unit is optionally configured to return at least a part of the dilute carboxylate stream to the bioreactor; c.
  • ED electrodialysis
  • an electrodialysis with bipolar membranes (EDBM) unit wherein an acidic compartment of the EDBM unit is configured to receive the concentrated carboxylate stream from the ED unit, wherein a basic compartment of the EDBM unit is configured to receive at least a part of the dilute carboxylate stream from the ED unit, and wherein the EDBM unit is optionally configured to return at least a part of a product stream from the basic compartment of the EDBM unit to the bioreactor; and d. a purification section configured to return a water-based stream, extracted from a product stream obtained from the acidic compartment of the EDBM unit to the bioreactor and/or EDBM unit, preferably to the basic compartment of the EDBM unit.
  • EDBM electrodialysis with bipolar membranes
  • Example 1 Effect of dilute sodium glycolate in the EDBM basic compartment
  • the experiments were performed in a EURODIA 2-compartment electrodialysis membrane stack containing 3 cells with a bipolar membrane area of 3 times 0.02 m 2 .
  • the stack was connected to a DC power supply and an acid, a base and an electrolyte feed vessel.
  • the acidic compartment was equipped with a pH and conductivity meter with an integrated thermometer and the basic compartment was equipped with a conductivity meter.
  • the acid, base and electrolyte solutions were recycled with the help of three pumps.
  • the electric current was kept constant at 14 Amperes (A) as long as the electrode potential difference was below a maximum value of 10 Volts (V). As soon as the potential exceeded 10 V, the current was decreased to maintain the potential at 10 V.
  • the temperature of the EDBM was kept below 40 °C by the acid and base feed solutions, which were cooled below 40 °C by means of cooling water in the double wall of the feed vessels.
  • the current and potential were monitored as well as the conductivity in the acidic and basic compartments.
  • deionized water was dosed in several portions to the base vessel to keep the conductivity, and as a consequence the base concentration, constant.
  • the electrolyte feed vessel contained the same base at the same concentration level as the basic compartment to have a good conductivity and little to non-diffusional transport between the base and the electrode compartments.
  • samples from the acidic compartment were taken and analysed on glycolic acid (GA) concentration by means of titration.
  • the sodium ion concentration in the acidic compartment samples was determined by means of radially viewed Inductively Coupled Plasma Emission Spectrometry (ICP-ES, Agilent 5110). Samples of the base were taken as well to determine the actual NaOH concentration in the basic compartment by an acid-base titration method.
  • the acid feed vessel was filled with 2500 g of a 25 wt.% sodium glycolate solution.
  • the base feed vessel was filled with 2000 g of an 8 wt.% NaOH solution.
  • 2592 g of water was dosed to the base feed vessel.
  • the acid feed vessel contained 1707 g glycolic acid solution and the base feed vessel contained 5335 g NaOH solution.
  • the acid feed vessel was filled with 2500 g of a 25 wt.% sodium glycolate solution.
  • the base feed vessel was filled with 2000 g of an 8 wt.% NaOH solution.
  • 1 wt.% of sodium glycolate was added.
  • 2637 g of water was dosed to the base feed vessel.
  • the acid feed vessel contained 1860 g glycolic acid solution and the base feed vessel contained 5420 g NaOH solution.
  • Results of experiments (A) and (B) are shown in Tables 1 A and 1 B, respectively.
  • the acid conversion is more accurately calculated from the sodium ion concentration in the acid.
  • the concentration of sodium ions is a measure for the presence of unconverted (non-protonated) carboxylate ions.
  • the current density is calculated according to: current / surface area membrane stack.
  • the energy needed per mole of acid formed in the interval between two sampling points is calculated according to: (average voltage x average current x Atime)/(Aconversion x moles glycolate in)
  • Table 1B Results of EDBM acidification with 1 wt.% glycolate added to basic compartment This example shows that the performance of the EDBM, with respect to conversion level, voltage and energy requirement, is unaffected by the presence of 1 wt.% sodium glycolate in the base solution. One can even observe a benefit in the energy requirement per mole acid formed. Therefore, it can be concluded that a dilute carboxylate salt stream, such as the dilute stream of the ED unit, can be used as feed stream for the base compartment of the EDBM.
  • Example 2 EDBM performance without nutrient salts (A) and with nutrient salts (B)
  • Example 1A the procedure described in Example 1A was followed, but nutrient salts were added to the acid solution at a concentration of 0.4 wt%.
  • the experiments were performed in a EURODIA 2-compartment electrodialysis membrane stack containing 9 cells with a bipolar membrane area of 9 times 0.02 m 2 .
  • the electric current was kept constant at 16 Amperes (A) as long as the electrode potential difference was below a maximum value of 25 Volts (V). As soon as the potential exceeded 25 V, the current was decreased to maintain the potential at 25 V.
  • the acid feed vessel was filled with 3500 g of a 25 wt.% sodium glycolate solution.
  • the base feed vessel was filled with 2000 g of a 8 wt.% NaOH solution.
  • 4371 g of water was dosed to the base feed vessel.
  • the acid feed vessel contained 2611 g glycolic acid solution and the base feed vessel contained 7237 g NaOH solution.
  • Results of experiments (A) and (B) are shown in Tables 2A and 2B, respectively.
  • the calculation of the concentration of carboxylate ions from the sodium concentration is corrected for sodium ions from the nutrient salts.
  • the conversion at levels above 90% is calculated according to: 1 - (Na concentration measured/23 [wt.%] * total weight - Na from nutrients)/(NaGlycolate concentration [wt.%]/98* weight in acid feed vessel).
  • Tables 2A and 2B also show that, in the absence of nutrient salts, the current density drops by 20-30% above a conversion level of 90% because the conductivity becomes too low when reaching a level well below 10 mS/cm. In contrast, when nutrient salts are present, the conductivity stays at or above 10 mS/cm and the current density can be maintained throughout the entire experiment.
  • the current density is a measure for the capacity of the stack.
  • the time to reach 99.5% conversion is 150 min without nutrients salts and 135 min with nutrients salts.
  • the overall capacity is over 10% larger when nutrients salts present. Therefore, it can be concluded that the overall EDBM performance, and in particular the performance at the high conversion level, is increased in case nutrient salts are present in the acid feed stream to the EDBM.
  • Example 2 the procedure described in Example 2 was followed, but nutrient salts were added to the acid solution at a concentration of 1 wt.%.
  • the acid feed vessel was filled with 2500 g of a 35 wt.% sodium glycolate solution. To this solution, 16.8 g sodium-nitrate, 7.8 g sodium-sulphate and 4.6 g sodium-chloride was added. The base feed vessel was filled with 2000 g of an 8 wt.% NaOH solution. During the experiment, 4583 g of water was dosed to the base feed vessel. At the end of the experiment, the acid feed vessel contained 1844 g glycolic acid solution and the base feed vessel contained 7159 g NaOH solution. The results are shown in Table 3.
  • Example 2 the procedure described in Example 2 was followed, but the base concentration in the basic compartment was varied.
  • the acid feed vessel was filled with 3500 g of a 25 wt.% sodium glycolate solution. To this solution, nutrient salts were added: 16.8 g sodium-nitrate, 7.8 g sodium-sulphate and 4.6 g sodium-chloride.
  • the base feed vessel was filled with 2000 g of either a 9 wt.% NaOH solution (Experiment A), 7 wt.% NaOH solution (Experiment B) or 5 wt.% NaOH solution (Experiment C).
  • the average energy needed per mole of acid formed was determined for conversion ranges of 0- 80 %, 0 - 90% and 0 - 100%. The results are shown in Table 4.
  • Example 5 Effect of dilute sodium glycolate in the EDBM basic compartment with nutrient salts present in the acidic compartment
  • Example 1 B the procedure described in Example 1 B was followed, but nutrient salts were added to the acid solution.
  • the experiments were performed in a EURODIA 2-compartment electrodialysis membrane stack containing 9 cells with a bipolar membrane area of 9 times 0.02 m 2 .
  • the electric current was kept constant at 16 Amperes (A) as long as the electrode potential difference was below a maximum value of 25 Volts (V). As soon as the potential exceeded 25 V, the current was decreased to maintain the potential at 25 V.
  • the acid feed vessel was filled with 3500 g of a 25 wt.% sodium glycolate solution. To this solution, 16.8 g sodium-nitrate, 7.8 g sodium-sulphate and 4.6 g sodium-chloride was added.
  • the base feed vessel was filled with 2000 g of an 8 wt.% NaOH solution. To the base solution, 1 wt.% of sodium glycolate was added. During the experiment, 4476 g of water was dosed to the base feed vessel. At the end of the experiment, the acid feed vessel contained 2561 g glycolic acid solution and the base feed vessel contained 7417 g NaOH solution. The results are shown in
  • Example 2 the procedure described in Example 2 was followed, but sodium lactate solution (A) or sodium acetate solution (B) was used instead of sodium glycolate solution.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de conversion de sels d'acide carboxylique produits dans des bioprocédés en acides carboxyliques, le procédé comprenant les étapes consistant à (a) obtenir un flux de carboxylate à partir d'un bioréacteur, le flux de carboxylate comprenant éventuellement des impuretés de sel de nutriment, (b) introduire le flux de carboxylate dans une unité d'électrodialyse (ED) et séparer le flux de carboxylate en un flux de carboxylate concentré et un flux de carboxylate dilué, le flux de carboxylate concentré comprenant éventuellement des impuretés de sel de nutriment, (c) introduire le flux de carboxylate concentré dans un compartiment acide d'une électrodialyse avec des membranes bipolaires (EDBM), au moins une partie du flux de carboxylate dilué étant introduite dans un compartiment de base de l'unité EDBM, et (d) purifier éventuellement un flux de produit obtenu à partir du compartiment acide de l'unité EDBM.
PCT/EP2022/083326 2021-12-02 2022-11-25 Procédé de conversion de sels d'acide organique en acides organiques par électrodialyse et électrodialyse avec membranes bipolaires WO2023099353A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011036213A2 (fr) 2009-09-25 2011-03-31 Metabolic Explorer Processus de fermentation pour la production d'acide glycolique
JP4778308B2 (ja) 2005-12-16 2011-09-21 株式会社アストム 有機酸の製造方法
WO2020152342A1 (fr) 2019-01-24 2020-07-30 Photanol B.V. Procédé de bioproduction de glycolate
US10946341B2 (en) 2015-06-11 2021-03-16 Bl Technologies, Inc. Bipolar electrodialysis methods and systems

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4778308B2 (ja) 2005-12-16 2011-09-21 株式会社アストム 有機酸の製造方法
WO2011036213A2 (fr) 2009-09-25 2011-03-31 Metabolic Explorer Processus de fermentation pour la production d'acide glycolique
US10946341B2 (en) 2015-06-11 2021-03-16 Bl Technologies, Inc. Bipolar electrodialysis methods and systems
WO2020152342A1 (fr) 2019-01-24 2020-07-30 Photanol B.V. Procédé de bioproduction de glycolate

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BAILLY M ED - HILAL NIDAL: "Production of organic acids by bipolar electrodialysis: realizations and perspectives", DESALINATION, ELSEVIER, AMSTERDAM, NL, vol. 144, no. 1-3, 10 September 2002 (2002-09-10), pages 157 - 162, XP004386212, ISSN: 0011-9164, DOI: 10.1016/S0011-9164(02)00305-3 *
FERRER J S J ET AL: "Formic acid regeneration by electromembrane processes", JOURNAL OF MEMBRANE SCIENCE, ELSEVIER BV, NL, vol. 280, no. 1-2, 1 September 2006 (2006-09-01), pages 509 - 516, XP024931990, ISSN: 0376-7388, [retrieved on 20060901], DOI: 10.1016/J.MEMSCI.2006.02.012 *
M. BAILLY, DESALINATION, vol. 144, 2002, pages 157 - 162

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