EP4355452A2 - Method for purifying an extraction liquid - Google Patents

Method for purifying an extraction liquid

Info

Publication number
EP4355452A2
EP4355452A2 EP22735109.5A EP22735109A EP4355452A2 EP 4355452 A2 EP4355452 A2 EP 4355452A2 EP 22735109 A EP22735109 A EP 22735109A EP 4355452 A2 EP4355452 A2 EP 4355452A2
Authority
EP
European Patent Office
Prior art keywords
liquid
extraction
distillation
phase
stage
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.)
Pending
Application number
EP22735109.5A
Other languages
German (de)
French (fr)
Inventor
Lukas ALMHOFER
Robert BISCHOF
Martin MADERA
Klaus SCHLACKL
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.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Publication of EP4355452A2 publication Critical patent/EP4355452A2/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0488—Flow sheets

Definitions

  • This invention relates to a method for the purification of a depleted organic extraction liquid from a production process, said method comprising the following steps in the given sequence: a. intensive mixing the depleted organic extraction liquid with an amine-containing liquid in a first liquid-liquid extraction step, b. phase separation of the two liquids of step a., c. washing of the organic extraction liquid phase of step b. with an aqueous liquid in a second liquid-liquid extraction step, d. phase separation of the two liquids of step c., and e. recycling of the purified organic extraction liquid into the production process, wherein the enriched amine-containing phase of step b. and the enriched aqueous phase of step d. are purified and recycled into steps a. resp. step c..
  • Extraction is a well-known separation operation for many applications, in particular in the chemical process engineering, pharmaceutical industry etc..
  • Commonly used devices for extraction are among others batch wise single stage extractions and multistage countercurrent continuous processes, e.g. continuous batteries of mixer-settlers, packed columns, stirred columns or centrifugal extractors.
  • EP 36406 A1 discloses a method for extracting solutes like acetic acid, formic acid, optionally furfural and the like from an aqueous solution of hydrolysis products of biomasses, e.g. from the hydrolysis of comminuted wood in a pulp cooking process.
  • aqueous solutions may be the condensates of waste liquors formed during the cooking process.
  • the acetic acid, furfural and the like may be interesting by-products of the pulp production in a biorefinery.
  • the extraction according to EP 36406 A1 uses as a solvent a mixture of
  • the depleted extraction solvent still contains some residues, in particular lipophilic compounds with low vapor pressure, like long-chain fatty acids, resin acids, sterols, lignans, etc.) and condensation products of furan derivatives, so called humins, which would be accumulated during repeated recycling cycles. Due to the long residence time, they may form solid particles that can cause significant fouling in the pipes, heat exchangers and other parts of the plant. This requires frequent cleaning or exchange of such parts and causes high operating costs.
  • a further disadvantage of these unwanted residues is that they may act similar to surfactants and thereby may have a negative effect on the phase separation. In a worst case, they may lead to the formation of emulsions, making phase separation impossible.
  • the problem to be solved consisted in preventing fouling of extraction process equipment caused by residues in the depleted extraction solvent, and in particular in removing the unwanted residues from the depleted extraction solvent and the extraction plant itself in an economic way without creating too much waste material in order to keep cost for disposal as low as possible.
  • a further problem to be solved consisted in improving the economy of the process.
  • the amine-containing liquid favourably is not miscible with the organic extraction liquid.
  • the aqueous liquid may be either recovered water from a distillation or fresh water. In a preferred embodiment of the invention it may be an aqueous phase coming from an evaporation plant as the vapour condensate and contains a small amount of acetic acid, i.e. being slightly acidic. The acidic pH may improve the extraction of the amine.
  • the purification of the enriched amine-containing phase 5 of step b. and the enriched aqueous phase 6 of step d. is done by combining both phases and subjecting them to a fractionated distillation 7 and the residue 8 of the fractionated distillation is removed separately.
  • Some amine may get lost during operation of the process of the invention and has to be replaced by fresh amine.
  • the fresh amine can be introduced at a suitable location within the process; one possible location is an inlet into the pipeline of stream 9.
  • the fractionated distillation is a 2-stage distillation consisting of a conventional distillation column 7 for the first stage and an evaporator 12 for the second stage, wherein the sump 11 of the first stage is further distilled in order to increase the amine recovery rate.
  • the fractionated distillation is a 2-stage distillation consisting of a conventional distillation column 7 for the first stage and an evaporator 12 for the second stage, wherein the sump 11 of the first stage is further distilled in order to increase the amine recovery rate.
  • there may be higher efforts needed for cleaning the devices as the evaporator has to be operated at higher temperatures than the distillation column and therefore more residues will occur there.
  • the evaporator has to be bigger than in the second stage, hence needs more cleaning efforts.
  • the distillation 7 in the first stage is controlled in a way to recover as much amine as possible, but to prevent the residues from coagulation and depositing in the first distillation column 7.
  • the concentrated sump 11 is forwarded to a second distillation stage consisting of a kind of evaporator 12 that is designed to process high-viscosity media and that is easier to clean, i.e. to remove the coagulated residues.
  • a thin WO 2022/175564 3 L0766-WO PCT/EP2022/066278 film evaporator is suitable.
  • the separated residues 8 finally are disposed of, e.g. by incineration.
  • the distillation is a 1 -stage distillation consisting of a conventional distillation column.
  • the sump of the distillation stage is removed, the residues in the sump are coagulated by adding an acid and subsequently separated mechanically and the remaining liquid is deprotonated, in particular by adding calcium hydroxide, and recycled into the extraction process.
  • the acid is sulfuric acid.
  • the calcium sulfate formed during neutralization can be separated mechanically, e.g. by filtration, centrifugation or other suitable operations.
  • this whole distillation step may be replaced by simply coagulating the residues by an acid, however this would require more acid, sufficient to neutralize the whole quantity of amine, as well as more calcium hydroxide for deprotonation.
  • the separated residues finally are disposed of, e.g. by incineration.
  • the distillation is a 1 -stage distillation consisting of a conventional distillation column and the sump of the distillation stage is treated with salts of earth alkali metals (oxides, hydroxides, chlorides, etc.) to precipitate fatty acids and hum in particles.
  • the precipitate may be removed separately, e.g. by filtration, flotation or the like.
  • the amine-containing liquid contains one or more alkanolamines of the group containing N- Methylethanolamine (NMEA), 2-(Dimethylamino)ethan-1-ol (DMAE) and N- Methyldiethanolamine.
  • NMEA N-Methylethanolamine
  • NMEA is especially preferred as it can be recovered very well by the process according to the invention. In particular, it shows the best distillation properties in the process according to the invention.
  • amines are forming azeotropes with water and hence cannot be simply distilled.
  • Such amines may either be converted to the corresponding salts by adding an acid, e.g. H2SO4 before entering the distillation column and later WO 2022/175564 3 L0766-WO PCT/EP2022/066278 can be concentrated in the sump of the distillation column.
  • the concentrated ammonium salt can be converted back to the corresponding free amine via neutralization with a base, e.g. NaOH.
  • the free amine may then be separated from the inorganic salt in a distillation step.
  • azeotropic mixtures of these amines may be concentrated to the desired concentration by membrane separation procedures like reverse osmosis. In both cases the separated amines can then be recovered back into the process of the invention.
  • liquid-liquid extraction steps of step a. (2) and/or step c. (3) are continuous extraction steps.
  • Batch extraction steps are in principle possible as well.
  • continuous extraction is generally preferred. Typical devices for such continuous extraction are packed columns, rotating disc contactors, mixer-settler arrangements, etc..
  • liquid-liquid extraction step of step a. is a discontinuous extraction step and step c. is a continuous extraction step.
  • step a. is done in a stirred vessel.
  • the steps a. to e., and, as the case may be, all steps in between are performed at a temperature of between 50 and 100°C, more preferably between 55 and 90°C.
  • the production process may be a process for obtaining by-products from a biomaterial.
  • the biomaterial is wood.
  • the by-products may be acetic acid, furfural and/or other by-products obtainable from a wood pulp manufacturing process, for example in a so-called “biorefinery”.
  • the invention may be applicable also for other production processes wherein biomasses and hydrophobic solvents with low vapor pressure occur, such as, but not limited to reactive extractions with trioctylamine, deep eutectic solvents or recycling of ionic liquids, e.g. in the manufacture of man-made cellulosic fibers.
  • the production process contains a vapor condensate extraction stage and the organic extraction liquid was used to extract the by-products acetic acid and furfural from the vapor condensate and was subjected to a stripping step to deplete the by-products before being subjected to the purification method according to the invention.
  • the quantity of this partial flow may depend on the content of impurities in the organic extraction liquid and may be smaller if less impurities are contained in the liquid. It may be between 0.1 and 100% (weight/weight) of the total organic extraction liquid coming from the vapour condensate extraction stage. In case of a smaller content of impurities the partial flow may be only between 0.1 and 50% (weight/weight), preferably between 0.1 and 20% (weight/weight) or even more preferred between 0.1 and 5% (weight/weight) in case of a very small impurity content.
  • a second washing of the organic extraction liquid phase of step d. with an aqueous liquid 15 in a third liquid-liquid extraction step 14 and subsequently a phase separation of the two liquids of this second washing step are performed.
  • the aqueous liquid 15 may be either recovered water from a distillation or fresh water.
  • the aqueous liquid 15 may be an aqueous phase coming from an evaporation plant as the vapour condensate and contains a small amount of acetic acid, i.e. being slightly acidic. The acidic pH may improve the extraction of the amine.
  • the enriched aqueous phase 16 of this second washing step may be either combined with the enriched aqueous phase 6 of step d. before distillation 7 or forwarded to a wastewater treatment plant with a treatment stage able to remove the amine.
  • a second washing of the organic extraction liquid phase of step d. with an aqueous liquid 15 in a third liquid- liquid extraction step 14 and subsequently a phase separation of the two liquids of this second washing step are performed.
  • the aqueous liquid 16 may be either recovered water from a distillation or fresh water.
  • the aqueous liquid 15 may be an aqueous phase coming from an evaporation plant as the vapour condensate and contains a small amount of acetic acid, i.e. being slightly acidic.
  • the acidic pH may improve the extraction of the amine.
  • the enriched aqueous phase 16 of this second washing step may be either combined with the enriched aqueous phase 6 of step d. before distillation 7 or forwarded to a wastewater treatment plant with a treatment stage able to remove the amine.
  • the fractionated distillation is a 2- stage distillation consisting of a conventional distillation column 7 for the first stage and an evaporator 12 for the second stage, wherein the sump 11 of the first stage is further distilled in order to increase the amine recovery rate.
  • another possible location for the introduction of fresh amine is the container 13.
  • Example 1 Removal of palmitic acid from a depleted organic extraction liquid a) A depleted organic extraction liquid obtained from a commercial biorefinery containing 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for palmitic acid (by GC) and solid particles (by gravimetry) and found to contain 22.2 g L ⁇ 1 palmitic acid and 0.49%w/w solid particles. The liquid further contains other extractives, water, acetic acid and other residues. A zeta potential of - 44.0 mV for the solid particles was determined using electrophoretic light scattering (20 °C, 1 mg mL 1 in H2O).
  • Example 1 demonstrates (see also Fig. 5) that increasing the amine concentration and/or increasing the temperature may improve the removal of the unwanted residues like palmitic acid from a depleted organic liquid as e.g. coming from a vapor condensate extraction.
  • Example 2 Removal of the amine from the purified organic extraction liquid a) 150 ml_ of the depleted organic extraction solvent described in example 1 was mixed with 150 mL of an aqueous solution of 357 g L 1 2- (dimethylamino)ethan-l-ol at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. 5 mL sample were withdrawn from the organic phase and analyzed for 2-(dimethylamino)ethan-1-ol. b) 51 g of the extracted organic phase obtained in step a) was stirred with an equal mass of demineralized water at 60 °C and 200 rpm in a double walled glass apparatus.
  • Example 2 demonstrates (see also Fig. 6) that a slightly acidic washing water may improve the amine removal.
  • Example 3 Purification of a depleted organic extraction liquid a) A depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) WO 2022/175564 3 L0766-WO PCT/EP2022/066278 and wood extractives (by GC) and found to contain 0.49%w/w solid particles and 52.6 g L 1 wood extractives.
  • Fig. 7 shows gas chromatograms of the solutions of example 3.
  • Example 3 demonstrates that most of the wood extractives and by the additional washing step nearly all of the amine is removed from the organic extraction liquid.
  • Example 4 Distillation of a 2-(dimethylamino)ethan-1-ol solution loaded with palmitic acid a) To 99.8 g of a 357 g L 1 aqueous solution of 2-(dimethylamino)ethan-1 - ol were added 3.0 g of palmitic acid. The resulting solution was charged to a 250 ml_ round bottom flask connected to a condenser equipped with a thermometer and a receiving flask.
  • Example 4 shows that by the distillation in principle palmitic acid successfully can be removed from the amine in a model system.
  • Example 5 Distillation of a loaded solution of 2-(dimethylamino)ethan-1-ol a) A depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) and wood extractives (by GC) and found to contain 0.49%w/w solid particles and 52.6 g L 1 wood extractives.
  • Example 5 demonstrates that by the distillation the unwanted residues in a commercially relevant solution successfully can be removed from an aqueous solution of 2 (dimethylamino) ethan-1-ol.
  • Example 6 Precipitation of impurities from the loaded amine phase usinq
  • H2SO4 a depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) and wood extractives (by GC) and found to contain 0.49%w/w solid particles and 52.6 g L 1 wood extractives.
  • Example 6 demonstrates that by adding acid the wood extractives can be removed by precipitation. At pH 2.0 other, presently unidentified compounds precipitated, too.
  • Example 7 Purification of a depleted organic extraction liquid using N- Methylethanolamine a) A depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) and wood extractives (by GC) and found to contain 1.00%w/w solid particles and 47.8 g L 1 wood extractives. b) 4743 g of this liquid were stirred with 5964 g of an aqueous solution of 325 g L 1 N-Methylethanolamine at 60 °C and 170 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate c) 1400 g of the loaded amine phase were charged to a 2.5 L round bottom flask and the flask was connected to a rotary evaporator.
  • Example 7 demonstrates that in a single extraction step using N-Methylethanolamine most of the wood extractives and by a single washing step a large amount of amine is removed from the organic extraction liquid. By distilling the loaded aqueous solution from the first extraction, 98.6% of N-Methylethanolamine can be recovered.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

This invention relates to a method for the purification of a depleted organic extraction liquid from a production process, said method comprising the following steps in the given sequence: a. intensive mixing the depleted organic extraction liquid with an amine-containing liquid in a first liquid-liquid extraction step, b. phase separation of the two liquids of step a., c. washing of the organic extraction liquid phase of step b. with an aqueous liquid in a second liquid-liquid extraction step, d. phase separation of the two liquids of step c., and e. recycling of the purified organic extraction liquid into the production process, wherein the enriched amine-containing phase of step b. and the enriched aqueous phase of step d. are purified and recycled into steps a. resp. step c..

Description

WO 2022/1755643 L0766-WO PCT/EP2022/066278
Method for purifying an extraction liquid
This invention relates to a method for the purification of a depleted organic extraction liquid from a production process, said method comprising the following steps in the given sequence: a. intensive mixing the depleted organic extraction liquid with an amine-containing liquid in a first liquid-liquid extraction step, b. phase separation of the two liquids of step a., c. washing of the organic extraction liquid phase of step b. with an aqueous liquid in a second liquid-liquid extraction step, d. phase separation of the two liquids of step c., and e. recycling of the purified organic extraction liquid into the production process, wherein the enriched amine-containing phase of step b. and the enriched aqueous phase of step d. are purified and recycled into steps a. resp. step c..
Prior Art
Extraction is a well-known separation operation for many applications, in particular in the chemical process engineering, pharmaceutical industry etc.. Commonly used devices for extraction are among others batch wise single stage extractions and multistage countercurrent continuous processes, e.g. continuous batteries of mixer-settlers, packed columns, stirred columns or centrifugal extractors.
EP 36406 A1 discloses a method for extracting solutes like acetic acid, formic acid, optionally furfural and the like from an aqueous solution of hydrolysis products of biomasses, e.g. from the hydrolysis of comminuted wood in a pulp cooking process. Such aqueous solutions may be the condensates of waste liquors formed during the cooking process. The acetic acid, furfural and the like may be interesting by-products of the pulp production in a biorefinery. The extraction according to EP 36406 A1 uses as a solvent a mixture of
Trioctylphosphine oxide (preferably between 30 and 40 weight-%) and n- Undecan (preferably between 60 and 70 weight-%). According to EP 36406 A1 after removing of the solutes (e.g. by stripping) the depleted extraction solvent can be re-used in the extraction without further purification. WO 2022/1755643 L0766-WO PCT/EP2022/066278
However, it was found that during the commercial-scale operation of such a process, the depleted extraction solvent still contains some residues, in particular lipophilic compounds with low vapor pressure, like long-chain fatty acids, resin acids, sterols, lignans, etc.) and condensation products of furan derivatives, so called humins, which would be accumulated during repeated recycling cycles. Due to the long residence time, they may form solid particles that can cause significant fouling in the pipes, heat exchangers and other parts of the plant. This requires frequent cleaning or exchange of such parts and causes high operating costs.
The presence of these unwanted residues furthermore reduces the capacity of the extraction solvent for the valuable compounds, i.e. acetic acid and furfural. Additionally, the residues remaining in the cycles would have to be heated up together with the extraction solvent and therefore consume additional energy, without contributing to the extraction itself. Both effects reduce the efficiency of the whole process.
A further disadvantage of these unwanted residues is that they may act similar to surfactants and thereby may have a negative effect on the phase separation. In a worst case, they may lead to the formation of emulsions, making phase separation impossible.
Therefore, it appeared to be necessary to remove these lipophilic compounds continuously, before they accumulate and cause the aforementioned problems. Mechanical separation methods like filtration or centrifugation are not applicable as they work only for solid impurities. One possible approach is called “overliming” and applies lime milk or magnesium hydroxide to the depleted extraction solvent, to remove acidic compounds in situ by precipitation. However, this creates significant amounts of solid waste inside the plant, which aggravates the fouling, only partly consists of the unwanted residues, but contains much lime or magnesium hydroxide that could better be used otherwise, instead. Alternatively, active carbon may be used to adsorb the unwanted residues. However this creates significant amounts of solid waste, as well, and furthermore consumes a significant amount of the WO 2022/1755643 L0766-WO PCT/EP2022/066278 extraction solvent. Extraction with aqueous inorganic alkali (like sodium hydroxide or potassium hydroxide) does not work well, due to unfavorable distribution ratios and poor solubility of the resulting fatty acid salts.
Furthermore stable emulsions are formed, which are hard to break.
Problem
In view of this prior art the problem to be solved consisted in preventing fouling of extraction process equipment caused by residues in the depleted extraction solvent, and in particular in removing the unwanted residues from the depleted extraction solvent and the extraction plant itself in an economic way without creating too much waste material in order to keep cost for disposal as low as possible. A further problem to be solved consisted in improving the economy of the process.
Description
It is an object of the present invention to provide a method for the purification of a depleted organic extraction liquid 1 coming from a production process, said method comprising the following steps in the given sequence: a) Intensively mixing the depleted organic extraction liquid 1 with an amine-containing liquid 9 in a first liquid-liquid extraction step 2, b) Phase separation of the two liquids of step a., thereby forming an enriched amine-containing phase 5 and an organic extraction liquid phase, c) Washing of the organic extraction liquid phase of step b in order to recover the amine with an aqueous liquid in a second liquid-liquid extraction step 3, d) Phase separation of the two liquids of step c., thereby forming an enriched aqueous phase 6 and a purified organic extraction liquid 4 e) Recycling of the purified organic extraction liquid 4 into the production process, wherein the enriched amine-containing phase 5 of step b. and the enriched aqueous phase 6 of step d. are purified and recycled into steps a. resp. step c.. WO 2022/1755643 L0766-WO PCT/EP2022/066278
The amine-containing liquid favourably is not miscible with the organic extraction liquid. The aqueous liquid may be either recovered water from a distillation or fresh water. In a preferred embodiment of the invention it may be an aqueous phase coming from an evaporation plant as the vapour condensate and contains a small amount of acetic acid, i.e. being slightly acidic. The acidic pH may improve the extraction of the amine.
According to a preferred embodiment of the invention, as shown in Fig. 1 , the purification of the enriched amine-containing phase 5 of step b. and the enriched aqueous phase 6 of step d. is done by combining both phases and subjecting them to a fractionated distillation 7 and the residue 8 of the fractionated distillation is removed separately. Some amine may get lost during operation of the process of the invention and has to be replaced by fresh amine. The fresh amine can be introduced at a suitable location within the process; one possible location is an inlet into the pipeline of stream 9.
According to a preferred embodiment of the invention, as shown in Fig. 2, the fractionated distillation is a 2-stage distillation consisting of a conventional distillation column 7 for the first stage and an evaporator 12 for the second stage, wherein the sump 11 of the first stage is further distilled in order to increase the amine recovery rate. In principle it is also possible to use an evaporator in the first stage and a distillation column in the second stage. However in that embodiment there may be higher efforts needed for cleaning the devices as the evaporator has to be operated at higher temperatures than the distillation column and therefore more residues will occur there. In the first stage the evaporator has to be bigger than in the second stage, hence needs more cleaning efforts.
The distillation 7 in the first stage is controlled in a way to recover as much amine as possible, but to prevent the residues from coagulation and depositing in the first distillation column 7. The concentrated sump 11 is forwarded to a second distillation stage consisting of a kind of evaporator 12 that is designed to process high-viscosity media and that is easier to clean, i.e. to remove the coagulated residues. For this purpose among others, a thin WO 2022/1755643 L0766-WO PCT/EP2022/066278 film evaporator is suitable. The separated residues 8 finally are disposed of, e.g. by incineration.
According to another preferred embodiment of the invention the distillation is a 1 -stage distillation consisting of a conventional distillation column. The sump of the distillation stage is removed, the residues in the sump are coagulated by adding an acid and subsequently separated mechanically and the remaining liquid is deprotonated, in particular by adding calcium hydroxide, and recycled into the extraction process. Preferably, the acid is sulfuric acid. The calcium sulfate formed during neutralization can be separated mechanically, e.g. by filtration, centrifugation or other suitable operations. Alternatively, this whole distillation step may be replaced by simply coagulating the residues by an acid, however this would require more acid, sufficient to neutralize the whole quantity of amine, as well as more calcium hydroxide for deprotonation. The separated residues finally are disposed of, e.g. by incineration.
According to yet another preferred embodiment of the invention the distillation is a 1 -stage distillation consisting of a conventional distillation column and the sump of the distillation stage is treated with salts of earth alkali metals (oxides, hydroxides, chlorides, etc.) to precipitate fatty acids and hum in particles. The precipitate may be removed separately, e.g. by filtration, flotation or the like.
According to a preferred embodiment of the invention the amine-containing liquid contains one or more alkanolamines of the group containing N- Methylethanolamine (NMEA), 2-(Dimethylamino)ethan-1-ol (DMAE) and N- Methyldiethanolamine. N-Methylethanolamine (NMEA) is especially preferred as it can be recovered very well by the process according to the invention. In particular, it shows the best distillation properties in the process according to the invention.
Some amines are forming azeotropes with water and hence cannot be simply distilled. Such amines may either be converted to the corresponding salts by adding an acid, e.g. H2SO4 before entering the distillation column and later WO 2022/1755643 L0766-WO PCT/EP2022/066278 can be concentrated in the sump of the distillation column. The concentrated ammonium salt can be converted back to the corresponding free amine via neutralization with a base, e.g. NaOH. The free amine may then be separated from the inorganic salt in a distillation step. Alternatively azeotropic mixtures of these amines may be concentrated to the desired concentration by membrane separation procedures like reverse osmosis. In both cases the separated amines can then be recovered back into the process of the invention. These embodiments are not shown in the figures but could easily be realized by someone skilled in the art once this person has learned about the invention described herein.
Preferably the liquid-liquid extraction steps of step a. (2) and/or step c. (3) are continuous extraction steps. Batch extraction steps are in principle possible as well. However, in a commercial scale plant, continuous extraction is generally preferred. Typical devices for such continuous extraction are packed columns, rotating disc contactors, mixer-settler arrangements, etc..
However, in another preferred embodiment the liquid-liquid extraction step of step a. is a discontinuous extraction step and step c. is a continuous extraction step. Preferably in this embodiment of the invention the discontinuous extraction step a. is done in a stirred vessel.
Preferably the steps a. to e., and, as the case may be, all steps in between, are performed at a temperature of between 50 and 100°C, more preferably between 55 and 90°C.
In the method according to the invention the production process may be a process for obtaining by-products from a biomaterial. Preferably, the biomaterial is wood. The by-products may be acetic acid, furfural and/or other by-products obtainable from a wood pulp manufacturing process, for example in a so-called “biorefinery”. However, the invention may be applicable also for other production processes wherein biomasses and hydrophobic solvents with low vapor pressure occur, such as, but not limited to reactive extractions with trioctylamine, deep eutectic solvents or recycling of ionic liquids, e.g. in the manufacture of man-made cellulosic fibers. WO 2022/1755643 L0766-WO PCT/EP2022/066278
According to a preferred embodiment of the invention, the production process contains a vapor condensate extraction stage and the organic extraction liquid was used to extract the by-products acetic acid and furfural from the vapor condensate and was subjected to a stripping step to deplete the by-products before being subjected to the purification method according to the invention.
According to a preferred embodiment of the invention, only a part of the organic extraction liquid coming from the vapour condensate extraction stage is purified according to the invention. The quantity of this partial flow may depend on the content of impurities in the organic extraction liquid and may be smaller if less impurities are contained in the liquid. It may be between 0.1 and 100% (weight/weight) of the total organic extraction liquid coming from the vapour condensate extraction stage. In case of a smaller content of impurities the partial flow may be only between 0.1 and 50% (weight/weight), preferably between 0.1 and 20% (weight/weight) or even more preferred between 0.1 and 5% (weight/weight) in case of a very small impurity content.
According to another preferred embodiment of the invention, shown in Fig. 3, between step d. and step e. a second washing of the organic extraction liquid phase of step d. with an aqueous liquid 15 in a third liquid-liquid extraction step 14 and subsequently a phase separation of the two liquids of this second washing step are performed. The aqueous liquid 15 may be either recovered water from a distillation or fresh water. In a particularly preferred embodiment of the invention, the aqueous liquid 15 may be an aqueous phase coming from an evaporation plant as the vapour condensate and contains a small amount of acetic acid, i.e. being slightly acidic. The acidic pH may improve the extraction of the amine. The enriched aqueous phase 16 of this second washing step may be either combined with the enriched aqueous phase 6 of step d. before distillation 7 or forwarded to a wastewater treatment plant with a treatment stage able to remove the amine.
According to yet another preferred embodiment of the invention, shown in Fig. 4, the features of the two embodiments shown in Fig. 2 and in Fig. 3 are WO 2022/1755643 L0766-WO PCT/EP2022/066278 combined. Between step d. and step e. a second washing of the organic extraction liquid phase of step d. with an aqueous liquid 15 in a third liquid- liquid extraction step 14 and subsequently a phase separation of the two liquids of this second washing step are performed. The aqueous liquid 16 may be either recovered water from a distillation or fresh water. In a particularly preferred embodiment of the invention the aqueous liquid 15 may be an aqueous phase coming from an evaporation plant as the vapour condensate and contains a small amount of acetic acid, i.e. being slightly acidic. The acidic pH may improve the extraction of the amine. The enriched aqueous phase 16 of this second washing step may be either combined with the enriched aqueous phase 6 of step d. before distillation 7 or forwarded to a wastewater treatment plant with a treatment stage able to remove the amine. Furthermore, in this preferred embodiment the fractionated distillation is a 2- stage distillation consisting of a conventional distillation column 7 for the first stage and an evaporator 12 for the second stage, wherein the sump 11 of the first stage is further distilled in order to increase the amine recovery rate. In this embodiment another possible location for the introduction of fresh amine is the container 13.
In the figures the reference numbers have the following meaning:
1 depleted organic extraction liquid coming from a production process
2 first liquid-liquid extraction step, including phase separation
3 second liquid-liquid extraction step, including phase separation
4 purified organic extraction liquid going back into the production process
5 enriched amine-containing phase of step b.
6 enriched aqueous phase of step d.
7 fractionated distillation
8 residue (sump) of the distillation, going to disposal
9 recovered aqueous amine solution, coming from recovery unit
(distillation + evaporation)
10 depleted aqueous liquid, coming from distillation 7
11 sump coming from the distillation stage 7
12 evaporator for the second recovery stage
13 container for purified amine coming from second distillation stage 12 WO 2022/1755643 L0766-WO PCT/EP2022/066278
14 third liquid-liquid extraction step, including phase separation
15 aqueous liquid, going to the third liquid-liquid extraction step 15
16 enriched aqueous liquid phase of third liquid-liquid extraction step 15
The invention will now be illustrated by examples. These examples are not limiting the scope of the invention in any way. The invention includes also any other embodiments which are based on the same inventive concept.
Examples
Example 1 : Removal of palmitic acid from a depleted organic extraction liquid a) A depleted organic extraction liquid obtained from a commercial biorefinery containing 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for palmitic acid (by GC) and solid particles (by gravimetry) and found to contain 22.2 g L·1 palmitic acid and 0.49%w/w solid particles. The liquid further contains other extractives, water, acetic acid and other residues. A zeta potential of - 44.0 mV for the solid particles was determined using electrophoretic light scattering (20 °C, 1 mg mL 1 in H2O). b) 100 mL of this liquid were stirred with 100 mL of an aqueous solution of 175 g L 1 2-(dimethylamino)ethan-1-ol (Aldrich, 99.5%) at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes, the stirring was stopped and the phases were allowed to separate. 5 mL samples were withdrawn from each phase and the process was repeated 4 times with the same organic liquid and an equal quantity of fresh aqueous amine solution. In all extraction steps, it was observed that some of the aqueous phase was emulsified in the organic phase. The samples from the organic phases after each extraction step were analyzed for palmitic acid and 2-(dimethylamino)ethan-1-ol (by CE) and the following results were found (Table 1.a). In the 5th step the amine content again decreased due to forming of an emulsion. WO 2022/1755643 L0766-WO PCT/EP2022/066278 Table 1.a: c) Higher amine concentration: 100 ml_ of the depleted organic extraction liquid as in a) above were stirred with 100 ml_ of an aqueous solution of 360 g L 1 2-(dimethylamino)ethan-1-ol at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes, the stirring was stopped and the phases were allowed to separate. 5 ml_ samples were withdrawn from each phase and the process was repeated 4 times with the same organic liquid and an equal quantity of fresh aqueous amine solution. No formation of emulsions was observed. The samples from the organic phases after each extraction step were analyzed for particles, palmitic acid and 2-(dimethylamino)ethan-1-ol and the following results were found (Table 1.b).
WO 2022/1755643 L0766-WO PCT/EP2022/066278 Table 1.b: d) Higher temperature: 100 ml_ of the depleted organic extraction liquid of a) above were stirred with lOOrriL of an aqueous solution of 360 g L 1 2-(dimethylamino)ethan-1-ol at 80 °C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. 5 ml_ samples were withdrawn from each phase and the process was repeated 4 times with the same organic liquid and an equal quantity of fresh aqueous amine solution. No formation of emulsions was observed. The samples from the organic phases after each extraction step were analyzed for palmitic acid and 2-(dimethylamino)ethan-1-ol and the following results were found (Table 1.c).
WO 2022/1755643 L0766-WO PCT/EP2022/066278
Table 1.c:
Example 1 demonstrates (see also Fig. 5) that increasing the amine concentration and/or increasing the temperature may improve the removal of the unwanted residues like palmitic acid from a depleted organic liquid as e.g. coming from a vapor condensate extraction.
Example 2: Removal of the amine from the purified organic extraction liquid a) 150 ml_ of the depleted organic extraction solvent described in example 1 was mixed with 150 mL of an aqueous solution of 357 g L 1 2- (dimethylamino)ethan-l-ol at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. 5 mL sample were withdrawn from the organic phase and analyzed for 2-(dimethylamino)ethan-1-ol. b) 51 g of the extracted organic phase obtained in step a) was stirred with an equal mass of demineralized water at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. 5 mL samples were withdrawn from each phase and the process was repeated two times with the same organic liquid and an equal quantity of fresh demineralized water. The samples from the organic phases after each extraction step were analyzed for 2-(dimethylamino)ethan-1-ol and the following results were found (Table 2. a). WO 2022/1755643 L0766-WO PCT/EP2022/066278
Table 2. a: c) 57 g of the extracted organic phase obtained in step a) was mixed with an equal mass of an aqueous solution of 20 g L 1 acetic acid at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. 5 ml_ samples were withdrawn from each phase and the process was repeated two times with the same organic liquid and an equal quantity of fresh aqueous solution of 20 g L1 acetic acid. The samples from the organic phases after each extraction step were analyzed for 2- (dimethylamino)ethan-l-ol and the following results were found (Table 2.b).
Table 2.b:
Example 2 demonstrates (see also Fig. 6) that a slightly acidic washing water may improve the amine removal.
Example 3: Purification of a depleted organic extraction liquid a) A depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) WO 2022/1755643 L0766-WO PCT/EP2022/066278 and wood extractives (by GC) and found to contain 0.49%w/w solid particles and 52.6 g L 1 wood extractives. b) 100 mL of this liquid were stirred with 100 mL of an aqueous solution of 351 g L 1 2-(dimethylamino)ethan-1-ol at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. The aqueous phase was discarded and the process was repeated 4 times with the same organic liquid and an equal quantity of fresh aqueous amine solution. c) To remove the amine from the purified organic phase resulting from b) above it was stirred with an equal mass of demineralized water at 60
°C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. The aqueous phase was discharged and the process was repeated 2 times with the same organic liquid and an equal quantity of fresh demineralized water. The obtained washed organic extraction liquid was analyzed for wood extractives, particles and 2- (dimethylamino)ethan-l-ol and the following results were found (Table 3):
Table 3: Fig. 7 shows gas chromatograms of the solutions of example 3.
Example 3 demonstrates that most of the wood extractives and by the additional washing step nearly all of the amine is removed from the organic extraction liquid. WO 2022/1755643 L0766-WO PCT/EP2022/066278 Example 4: Distillation of a 2-(dimethylamino)ethan-1-ol solution loaded with palmitic acid a) To 99.8 g of a 357 g L 1 aqueous solution of 2-(dimethylamino)ethan-1 - ol were added 3.0 g of palmitic acid. The resulting solution was charged to a 250 ml_ round bottom flask connected to a condenser equipped with a thermometer and a receiving flask. The loaded amine solution was heated with a hotplate via a silicone oil bath and the distillation was done under reduced pressure. Several distillate fractions were collected and analyzed for 2-(dimethylamino)ethan-1-ol and palmitic acid. The distillation sump remained liquid throughout the whole distillation but solidified upon cooling. Only 0.3%w/w of 2-(dimethylamino)ethan-1-ol remained in the distillation residue. The following compositions of the different fractions were found (Table 4):
Table 4:
Example 4 shows that by the distillation in principle palmitic acid successfully can be removed from the amine in a model system. WO 2022/1755643 L0766-WO PCT/EP2022/066278 Example 5: Distillation of a loaded solution of 2-(dimethylamino)ethan-1-ol a) A depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) and wood extractives (by GC) and found to contain 0.49%w/w solid particles and 52.6 g L 1 wood extractives. b) 101 g of this liquid were stirred with 101 g of an aqueous solution of 357 g L·1 2-(dimethylamino)ethan-1-ol at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. The organic phase was discarded and 105 g of the loaded amine phase were charged to a 250 ml_ round bottom flask. c) The flask was connected to a condenser equipped with a thermometer and a receiving flask and was heated with a hotplate via a silicone oil bath. The distillation was done under reduced pressure and several distillate fractions were collected and analyzed for 2-(dimethylamino)ethan-1-ol and palmitic acid. Finally the pressure was reduced down to 25mbar. The distillation sump remained liquid throughout the whole distillation and 76%w/w of 2-(dimethylamino)ethan-1-ol were recovered in the distillate. The following compositions of the different fractions were found (Table 5):
WO 2022/1755643 L0766-WO PCT/EP2022/066278
Table 5:
Example 5 demonstrates that by the distillation the unwanted residues in a commercially relevant solution successfully can be removed from an aqueous solution of 2 (dimethylamino) ethan-1-ol. Example 6: Precipitation of impurities from the loaded amine phase usinq
H2SO4 a) A depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) and wood extractives (by GC) and found to contain 0.49%w/w solid particles and 52.6 g L 1 wood extractives. b) 100 g of this liquid were stirred with 100 g of an aqueous solution of 357 g L 1 2-(dimethylamino)ethan-1-ol at 60 °C and 200 rpm in a double walled glass apparatus. After 15 minutes, the stirring was stopped and the phases were allowed to separate. c) Certain amounts of the loaded amine phase were titrated with 0.25 M sulfuric acid to reach a certain pH value. The formed solids WO 2022/1755643 L0766-WO PCT/EP2022/066278 were filtered, dried at 40 °C and 200 mbar and weighted. The results of the precipitations are given in the following table (Table 6):
Table 6: Example 6 demonstrates that by adding acid the wood extractives can be removed by precipitation. At pH 2.0 other, presently unidentified compounds precipitated, too.
Example 7: Purification of a depleted organic extraction liquid using N- Methylethanolamine a) A depleted organic extraction liquid obtained from a commercial biorefinery consisting of 52.6%w/w undecane and 32.4%w/w trioctylphosphine oxide was analyzed for solid particles (by gravimetry) and wood extractives (by GC) and found to contain 1.00%w/w solid particles and 47.8 g L1 wood extractives. b) 4743 g of this liquid were stirred with 5964 g of an aqueous solution of 325 g L 1 N-Methylethanolamine at 60 °C and 170 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate c) 1400 g of the loaded amine phase were charged to a 2.5 L round bottom flask and the flask was connected to a rotary evaporator.
Distillation was done under reduced pressure and several distillate WO 2022/1755643 L0766-WO PCT/EP2022/066278 fractions were collected and analyzed for N-Methylethanolamine and palmitic acid. Finally the pressure was reduced down to 50mbar. The distillation sump remained liquid throughout the whole distillation and 98.6%w/w of N-Methylethanolamine were recovered in the distillate. The compositions of the different fractions are given in Table 7 d) To remove the amine from the purified organic phase resulting from b) above it was stirred with an equal mass of demineralized water at 60 °C and 170 rpm in a double walled glass apparatus. After 15 minutes the stirring was stopped and the phases were allowed to separate. The obtained washed organic extraction liquid was analyzed for wood extractives, particles and N-Methylethanolamine and the results are given in Table 8
Table 7: WO 2022/1755643 L0766-WO PCT/EP2022/066278 Table 8:
Example 7 demonstrates that in a single extraction step using N-Methylethanolamine most of the wood extractives and by a single washing step a large amount of amine is removed from the organic extraction liquid. By distilling the loaded aqueous solution from the first extraction, 98.6% of N-Methylethanolamine can be recovered.

Claims

WO 2022/1755643 L0766-WO PCT/EP2022/066278 Claims
1. A method for the purification of a depleted organic extraction liquid from a production process, said production process comprising an extraction step using an organic extraction liquid and a step to deplete the organic extraction liquid, said method comprising the following steps in the given sequence: a. Intensively mixing the depleted organic extraction liquid with an amine-containing liquid in a first liquid-liquid extraction step, b. Phase separation of the two liquids of step a., c. Washing of the organic extraction liquid phase of step b. with an aqueous liquid in a second liquid-liquid extraction step, d. Phase separation of the two liquids of step c., e. Recycling of the purified organic extraction liquid into the production process, wherein the enriched amine-containing phase of step b. and the enriched aqueous phase of step d. are purified and recycled into steps a. resp. step c..
2. A method according to claim 1 , wherein the purification of the enriched amine-containing phase of step b. and the enriched aqueous phase of step d. is done by combining both phases and subjecting them to a fractionated distillation and the residue of the fractionated distillation is removed separately.
3. A method according to claim 2, wherein the distillation is a 2-stage distillation consisting of a conventional distillation column for the first stage and an evaporator for the second stage, wherein the sump of the first stage is further distilled in order to increase the amine recovery.
4. A method according to claim 2, wherein the distillation is a 1 -stage distillation consisting of a conventional distillation column and the sump of the distillation stage is removed, the residues in the sump are coagulated by adding an acid and separated mechanically and the remaining liquid is deprotonated, in particular by adding calcium hydroxide, and recycled into the extraction process. WO 2022/1755643 L0766-WO PCT/EP2022/066278
5. A method according to claim 2, wherein the distillation is a 1 -stage distillation consisting of a conventional distillation column and the sump of the distillation stage is treated with salts of earth alkali metals to precipitate fatty acids and hum in particles.
6. A method according to claim 1, wherein the amine-containing liquid contains one or more alkanolamines of the group containing N- Methylethanolamine, 2-(Dimethylamino)ethan-1-ol and N- Methyldiethanolamine.
7. A method according to claim 1 , wherein the liquid-liquid extraction step of step a. is a discontinuous extraction step and step c. is a continuous extraction step.
8. A method according to claim 1 , wherein the liquid-liquid extraction steps of step a. and/or step c. are continuous extraction steps.
9. A method according to claim 1 , wherein the phase separation step b. is performed in a centrifuge.
10. A method according to claim 1, wherein the steps a. to e. are performed at a temperature of between 50 and 100°C, preferably between 55 and 90°C.
11. A method according to claim 1, wherein the production process is a process for obtaining by-products from a biomaterial.
12. A method according to claim 11 , wherein the biomaterial is wood.
13. A method according to claim 11, wherein the production process contains a vapor condensate extraction stage and the organic extraction liquid was used to extract the by-products from the vapor condensate and was subjected to a stripping step to deplete the by-products before being subjected to the purification method.
14. A method according to claim 1, wherein between step d. and step e. a second washing of the organic extraction liquid phase of step d. with an aqueous liquid in a third liquid-liquid extraction step and subsequently a phase separation of the two liquids of this second washing step are performed.
EP22735109.5A 2021-06-18 2022-06-15 Method for purifying an extraction liquid Pending EP4355452A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21180315.0A EP4104913A1 (en) 2021-06-18 2021-06-18 Method for purifying an extraction liquid
PCT/EP2022/066278 WO2022175564A2 (en) 2021-06-18 2022-06-15 Method for purifying an extraction liquid

Publications (1)

Publication Number Publication Date
EP4355452A2 true EP4355452A2 (en) 2024-04-24

Family

ID=76532051

Family Applications (2)

Application Number Title Priority Date Filing Date
EP21180315.0A Withdrawn EP4104913A1 (en) 2021-06-18 2021-06-18 Method for purifying an extraction liquid
EP22735109.5A Pending EP4355452A2 (en) 2021-06-18 2022-06-15 Method for purifying an extraction liquid

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP21180315.0A Withdrawn EP4104913A1 (en) 2021-06-18 2021-06-18 Method for purifying an extraction liquid

Country Status (2)

Country Link
EP (2) EP4104913A1 (en)
WO (1) WO2022175564A2 (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT365080B (en) 1980-03-14 1981-12-10 Kanzler Walter METHOD FOR THE EXTRACTION OF ACETIC ACID, ANTIC ACID, OR, IF NECESSARY, FURFUROL
KR100738507B1 (en) * 2006-01-24 2007-07-11 대일개발 주식회사 The method for separating and collecting each acid from waste acids of etching process in IT industry
JP2011517445A (en) * 2008-03-20 2011-06-09 テート アンド ライル テクノロジー リミテッド Removal of acids from tertiary amide solvents
US20130211138A1 (en) * 2010-04-29 2013-08-15 University Of Maine System Board Of Trustees Removal of Contaminants from Liquid-Liquid Extraction Solvent
FI126351B (en) * 2011-11-04 2016-10-14 Taminco Finland Oy Method and apparatus for separating at least one carboxylic acid and furfural from a dilute aqueous solution

Also Published As

Publication number Publication date
EP4104913A1 (en) 2022-12-21
WO2022175564A2 (en) 2022-08-25
WO2022175564A3 (en) 2022-10-20

Similar Documents

Publication Publication Date Title
JP4233121B2 (en) Recovery of fermented salts from dilute aqueous solutions.
CN102015611B (en) A process for preparation of formate salt
CN104619951B (en) The processing of output aqueous concentrate
BR122014002952B1 (en) process for the recovery of 1,3-propanediol from a fermentation broth
CN104619950B (en) Use the processing for the output water for adding crystal seed evaporator
CN105016360A (en) Methods and apparatus for purifying solid salt compositions
US10132145B2 (en) Produced water treatment and solids precipitation from thermal treatment blowdown
US4374283A (en) Purification of aqueous effluent streams containing BPA and phenol
US4400553A (en) Recovery of BPA and phenol from aqueous effluent streams
US3940334A (en) Method for separating oil from water
EP4355452A2 (en) Method for purifying an extraction liquid
CN107381911B (en) Comprehensive treatment method of aminoacetic acid wastewater
CN1216043C (en) Method for separating hydroxymethylthiobutyric acid
CN110387279B (en) Recovery method of hydrophilic ionic liquid for removing sulfur in coal
WO2005082831A1 (en) Method of processing methacrylic-ester-containing solution
JPH02102703A (en) Treatment of inorganic salt contamination with organic compound
JP2004043434A (en) Method for refining high-purity dimethyl sulfoxide and mixture of dimethyl sulfoxide with amines
CN112481490A (en) Method for continuously removing impurities and purifying ferrous chloride solution
CN113912236A (en) Method for recovering glycolic acid from CMC wastewater
JP2660820B2 (en) Method for recovering carboxylic acid from aqueous solution
CN114477098A (en) Purification process of byproduct sulfur in HPF (high pressure fluidized bed) desulfurization
CN110586615A (en) Continuous preparation process of saturated brine
JPS60135493A (en) Method for recovering oil from high-viscosity alkali cleaning waste oil
JPH0495899A (en) Extraction and separation of spent solution generated from nuclear fuel cycle
JPH06122892A (en) Production of crude wax

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240118

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR