CN113924282B - Process for separating carboxylic acid from aqueous side stream - Google Patents
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- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- 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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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Abstract
A process for separating carboxylic acid from an aqueous side stream containing a metal carboxylate salt of an organic peroxide production process includes protonation of the carboxylate salt, separation of the liquid and organic phases, and removal of residual peroxide.
Description
Technical Field
The present invention relates to a process for separating carboxylic acid from an aqueous side stream (aqueous side stream) of an organic peroxide production process.
Background
Diacyl peroxides and peroxyesters can be prepared by reacting an anhydride or acid chloride with an alkaline solution of a hydroperoxide as shown below:
2R-C(＝O)-O-C(＝O)-R+Na 2 O 2 →R-C(＝O)-O-O-C(＝O)-R+2NaOC(＝O)R
R-C(＝O)-O-C(＝O)-R+ROOH+NaOH→R-C(＝O)-O-O-R+NaOC(＝O)R
2R-C(＝O)Cl+Na 2 O 2 →R-C(＝O)-O-O-C(＝O)-R+2NaCl
R-C(＝O)Cl+ROOH+NaOH→R-C(＝O)-O-O-R+NaCl。
in this reaction scheme, na 2 O 2 Not meaning the isolated product Na 2 O 2 But means to contain H 2 O 2 And NaOOH.
Acid chlorides are relatively expensive and produce a water layer containing chloride ions, which results in high salt concentrations in the wastewater.
On the other hand, acid anhydrides are even more expensive than acid chlorides and are not economically and environmentally attractive because the side stream of the acid anhydride-fed process contains a high organic load, i.e. has a high Chemical Oxygen Demand (COD) value, due to the carboxylate salt formed.
The situation will change if the carboxylic acid can be separated from the aqueous side stream and reused in a peroxide production process, in another chemical process (e.g. production of esters) or in any other application (e.g. as an animal feed ingredient).
CN108423908 discloses a process for separating 4-methylbenzoic acid from a waste stream of a di (4-methylbenzoyl) peroxide production process by precipitation. However, this method is only applicable to acids having a small solubility in water. In addition, the precipitate can cause fouling of the equipment used.
For carboxylic acids that are water soluble or do not precipitate sufficiently or otherwise separate from the aqueous side stream, separation is not easy or cannot be directly accomplished.
Disclosure of Invention
It is therefore an object of the present invention to provide a process for separating such carboxylic acids from an aqueous side stream of an organic peroxide production process and making them suitable for reuse.
The object is achieved by a method comprising the steps of:
a) Providing an aqueous side stream of an organic peroxide production process, said stream comprising at least 1 wt.% of a metal carboxylate salt dissolved or homogeneously mixed in said stream,
b) Protonating the carboxylate salt to a carboxylic acid in the aqueous side stream, thereby forming a biphasic mixture of two liquid phases,
c) Separating the biphasic mixture into (i) an aqueous liquid phase comprising water and a small amount of carboxylic acid and (ii) an organic liquid phase comprising carboxylic acid and a small amount of water,
d) Optionally separating, preferably distilling, carboxylic acid from the organic liquid phase,
wherein residual peroxide present in the aqueous side stream is removed by (i) extraction before or after step b) and/or (ii) adding a reducing agent, heat or radiation to the stream, to the biphasic mixture and/or to the organic liquid phase.
Detailed Description
The aqueous side stream is preferably obtained from the production of diacyl peroxides and/or peroxyesters. The organic peroxide production process to produce the aqueous side stream may involve the use of an acid chloride or anhydride, preferably an anhydride, as a reactant.
It may be noted that EP 2 666 763 discloses a process for recovering carboxylic acid from magnesium carboxylate mixtures by replacing the magnesium ions in the carboxylate with protons and in this way providing an acidic ion exchanger for the carboxylic acid. However, this document is not directed to recovery from peroxide process streams nor to any further biphasic liquid-liquid separation to recover carboxylic acid.
The diacyl peroxide may be symmetrical or asymmetrical.
Examples of suitable symmetrical diacyl peroxides are di-2-methylbutyryl peroxide, diisopentanoyl peroxide, di-n-pentanoyl peroxide, di-n-hexanoyl peroxide, diisobutanoyl peroxide and di-n-butanoyl peroxide.
Examples of suitable asymmetric diacyl peroxides are acetyl isobutyryl peroxide, acetyl 3-methylbutyl peroxide, acetyl lauroyl peroxide, acetyl isononyl peroxide, acetyl heptanoyl peroxide, acetyl cyclohexylformyl peroxide, acetyl 2-propylheptanoyl peroxide and acetyl 2-ethylhexanoyl peroxide.
Examples of suitable peroxy esters are tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, 1, 3-tetramethylbutyl 1-peroxy-neodecanoate, tert-butyl peroxy-neodecanoate, tert-amyl peroxy-neodecanoate, tert-hexyl peroxy-neodecanoate, 1, 3-tetramethylbutyl peroxyneoheptanoate, t-butyl peroxyneoheptanoate, t-amyl peroxyneoheptanoate, t-hexyl peroxyneoheptanoate, 1, 3-tetramethylbutyl peroxyneononanoate, t-butyl peroxyneononanoate, t-amyl peroxyneononanoate, t-hexyl peroxyneononanoate, t-butyl peroxypivalate tert-amyl peroxypivalate, tert-hexyl peroxypivalate, 1, 3-tetramethylbutyl 1-peroxypivalate, tert-butyl peroxy-3, 5-trimethylhexanoate, tert-amyl peroxy-3, 5-trimethylhexanoate, tert-hexyl peroxy-3, 5-trimethylhexanoate, 1,3, 5-trimethylhexanoate, 1, 3-tetramethylbutyl tert-amyl peroxypivalate, tert-hexyl peroxypivalate, 1, 3-tetramethylbutyl 1-peroxypivalate, tert-butyl peroxy 3, 5-trimethylhexanoate tert-amyl peroxy 3, 5-trimethylhexanoate, tert-hexyl peroxy 3, 5-trimethylhexanoate, 1, 3-tetramethylbutyl ester, tert-butyl peroxy-m-chlorobenzoate, tert-amyl peroxy-m-chlorobenzoate, tert-hexyl peroxy-m-chlorobenzoate, 1, 3-tetramethylbutyl peroxy-m-methylbenzoate, tert-butyl peroxy-m-methylbenzoate, tert-amyl peroxy-m-methylbenzoate, tert-hexyl peroxy-m-methylbenzoate, 1, 3-tetramethylbutyl peroxy-phenylacetate, tert-butyl peroxy-phenylacetate, tert-amyl peroxy-phenylacetate, tert-hexyl peroxy-phenylacetate, tert-butyl peroxy-2-chloroacetate, tert-butyl peroxy-cyclododecanoate, tert-butyl peroxy-n-butyrate, tert-butyl peroxy-2-methylbutanoate, tert-amyl peroxy-2-methylbutanoate, 1-dimethyl-3-hydroxybutyl peroxy-1, 1-dimethyl-3-hydroxybutyl-1-peroxy-2-ethylhexanoate, 1-dimethyl-3-hydroxybutyl-peroxy-3, 5-trimethyl-1, 1-dimethyl-3-dimethylbutyrate and 1-diisobutyl peroxy-1-dimethylbutylate.
Preferred peroxy esters include t-butyl peroxyisobutyrate, t-amyl peroxyisobutyrate, 1, 3-tetramethylbutyl 1-peroxyisobutyrate, t-butyl peroxyn-butyrate, t-amyl peroxyn-butyrate, 1, 3-tetramethylbutyl 1-peroxyn-butyrate, t-butyl peroxyisovalerate tert-amyl peroxyisovalerate, tert-butyl peroxy2-methylbutyrate, tert-amyl peroxy2-methylbutyrate, 1, 3-tetramethylbutyl 1-peroxyisovalerate, tert-butyl peroxy-n-valerate, tert-amyl peroxy-n-valerate and 1, 3-tetramethylbutyl 1-peroxy-n-valerate.
The aqueous side stream of the organic peroxide production process comprises at least 1 wt.%, preferably at least 3 wt.%, more preferably at least 5 wt.%, more preferably at least 10 wt.%, even more preferably at least 20 wt.% and most preferably at least 25 wt.% of the metal carboxylate salt dissolved or homogeneously mixed therein. The metal carboxylate concentration is preferably no more than 50 wt%, more preferably no more than 40 wt% and most preferably no more than 35 wt%.
The metal carboxylate is dissolved in or homogeneously mixed with the flow, which means that the flow consists of a single phase and is not, for example, a suspension comprising metal carboxylate particles. The carboxylic acid can be easily separated from such a suspension by, for example, filtering the metal carboxylate. However, such easy separation is not possible from the aqueous stream of the present invention and requires more steps to separate the carboxylic acid.
In addition to water and metal carboxylate salts, the aqueous side stream will contain some peroxide residues such as organic hydroperoxides, hydrogen peroxide, peroxyacids, diacyl peroxides, and/or peroxyesters. The peroxide content of the aqueous side stream is typically in the range of 0.01 to 3 wt.%. The side stream may also contain some residual peroxide decomposition products.
In order to successfully isolate, purify and reuse the carboxylic acid, any residual peroxide must be removed from the aqueous side stream. This is done by extraction and/or addition of a reducing agent. Furthermore, it may be desirable to heat the side stream.
Examples of suitable reducing agents are sodium sulfite, sodium (poly) sulfide (Na 2 S x ) Sodium thiosulfate and sodium metabisulfite.
The reducing agent is added to the aqueous side stream, to the biphasic mixture and/or to the organic liquid phase. In a preferred embodiment, the reducing agent is added to the aqueous side stream during step b) or more preferably before step b).
The reducing agent may destroy hydrogen peroxide, organic hydroperoxides and peroxy acids. To destroy any other peroxygen species, it may be desirable to raise the temperature of the aqueous side stream by 10-80 ℃, preferably 10-50 ℃ and most preferably 10-30 ℃. This temperature increase may be carried out before step b) or during step b). If performed during step b), any heat released by protonation (e.g. acidification) can be used to achieve this temperature increase.
It should be noted that the temperature of the aqueous side stream prior to heating or protonation is typically in the range of 0-20 c, preferably 0-10 c, as the peroxide production process is typically carried out at low temperatures.
The extraction may be carried out before or after step b), preferably before step b). The extraction may be performed with an organic solvent, an acid anhydride, and a mixture of an acid anhydride and a solvent.
Examples of suitable solvents for extraction are alkanes (e.g. isododecane,And->Mineral oil), chlorinated alkanes, esters (e.g., ethyl acetate, methyl acetate, dimethyl phthalate, ethylene dibenzoate, cumene, dibutyl maleate, diisononyl 1, 2-cyclohexanedicarboxylate (DINCH), dioctyl terephthalate or 2, 4-trimethylpentanediol diisobutyrate (TXIB), ethers, amides and ketones.
Examples of suitable anhydrides are anhydrides that have been or can be used in the organic peroxide production process and include symmetrical and asymmetrical anhydrides. Examples of symmetrical anhydrides are n-butyric anhydride, isobutyric anhydride, pivalic anhydride, valeric anhydride, isovaleric anhydride, 2-methylbutyric anhydride, 2-methylpentanoic anhydride, 2-methylhexanoic anhydride, 2-methylheptanoic anhydride, 2-ethylbutyric anhydride, hexanoic anhydride, octanoic anhydride, isohexanoic anhydride, n-heptanoic anhydride, nonanoic anhydride, isononyl anhydride, 3, 5-trimethylhexanoic anhydride, 2-propylheptanoic anhydride, decanoic anhydride, neodecanoic anhydride, undecanoic anhydride, neoheptanoic anhydride, lauric anhydride, tridecanoic anhydride, 2-ethylhexanoic anhydride, myristic anhydride, palmitic anhydride, stearic anhydride, phenylacetic anhydride, cyclohexane-formic anhydride, 3-methyl-cyclopentanecarboxylic anhydride, and mixtures of two or more of the foregoing anhydrides.
Examples of suitable mixtures of symmetrical anhydrides are mixtures of isobutyric anhydride and 2-methylbutyric anhydride, mixtures of isobutyric anhydride and 2-methylpentanoic anhydride, mixtures of 2-methylbutyric anhydride and isovaleric anhydride and mixtures of 2-methylbutyric anhydride and valeric anhydride.
The asymmetric anhydride is generally provided as a mixture of asymmetric and symmetric anhydrides. This is because the asymmetric anhydride is typically obtained by reacting a mixture of acids with, for example, acetic anhydride. This produces an anhydride mixture comprising an asymmetric anhydride and at least one symmetric anhydride. Such anhydride mixtures can be used for extraction. An example of a suitable asymmetric anhydride is isobutyric acid 2-methylbutanoic anhydride, which is preferably present as a mixture with isobutyric anhydride and 2-methylbutanoic anhydride; isobutyric acid acetic anhydride, preferably present as a mixture with isobutyric anhydride and acetic anhydride; 2-methylbutyric anhydride valeric anhydride, which is preferably present as a mixture with 2-methylbutyric anhydride and valeric anhydride; and butyric anhydride, preferably as a mixture with butyric anhydride and valeric anhydride.
More preferred anhydrides are isobutyric anhydride, 2-methylbutanoic anhydride, 2-methylhexanoic anhydride, 2-propylheptanoic anhydride, n-nonanoic anhydride, isononyl anhydride, cyclohexane carboxylic anhydride, 2-ethylhexanoic anhydride, octanoic anhydride, n-pentanoic anhydride, isopentanoic anhydride, hexanoic anhydride and lauric anhydride. Most preferred are isononyl anhydride and isobutyric anhydride.
In step b), the carboxylic acid is released by protonation. Protonation results in a biphasic mixture of two liquid phases. In other words: it does not lead to precipitation of the carboxylic acid which can then be easily separated from the mixture by, for example, filtration. In contrast, from the mixture of the present invention, such easy separation is not possible and requires more steps to separate the carboxylic acid.
In one embodiment, protonation may be achieved by acidifying the aqueous side stream.
The preferred acid for acidifying and protonating carboxylic acids is pK a Acids below 5, e.g. H 2 SO 4 、HCl、NaHSO 4 、KHSO 4 Formic acid, acetic acid, and combinations thereof. Preferably, pK is used a An acid below 3; most preferably H is used 2 SO 4 . If H is used 2 SO 4 It is preferably added as a 90-96% by weight solution.
Acidification is preferably carried out to a pH below 6, more preferably below 4.5 and most preferably below 3. The pH value obtained is preferably not less than 1.
Depending on the acid used, the temperature of the stream may rise to up to about 80 ℃ during this step.
Acidification results in the formation of a biphasic mixture comprising (i) an aqueous layer comprising water and a small amount of carboxylic acid and (ii) an organic liquid phase comprising carboxylic acid and a small amount of water.
Depending on the acid used for acidification and the base used during the production of the organic peroxide, the salts produced by acidification (e.g. Na 2 SO 4 、K 2 SO 4 、NaHSO 4 、KHSO 4 NaCl, sodium formate or sodium acetate) will be present mainly in the aqueous liquid phase, although small amounts may also be present in the organic liquid phase.
In this document, "minor amount" is defined as 0 to 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.1 wt%, more preferably less than 0.01 wt% and most preferably less than 0.001 wt%, based on the total weight.
In another embodiment, the protonation is achieved by electrochemical membrane separation. Examples of electrochemical membrane separation techniques are membrane electrolysis and bipolar membrane electrodialysis (BPM). BPM is the preferred electrochemical membrane separation method.
Electrochemical membrane separation results in the separation of metal carboxylate carboxylic acid and metal hydroxide (e.g., naOH or KOH) and the separation of these two species. Thus, resulting in (i) a mixture comprising carboxylic acid and (ii) NaOH or KOH solution separated by a membrane.
The NaOH or KOH solution can be reused in any step of the process of the invention to produce an organic peroxide or a base needed or desired.
Depending on the temperature, salt concentration and solubility of the carboxylic acid in water, the carboxylic acid-containing mixture may be a biphasic mixture or a homogeneous mixture of two liquid phases. If a homogeneous mixture is formed under electrochemical membrane separation conditions (typically 40-50 ℃), cooling the mixture to a temperature below about 30 ℃ and/or adding salt will ensure that a biphasic mixture is formed. The organic liquid layer of the biphasic carboxylic acid-containing mixture may then be separated from the aqueous layer of the biphasic mixture in step c).
Optionally, a solvent is added to the biphasic mixture.
Examples of suitable solvents are (mixtures of) alkanes, such as isododecane,Octane, decane, toluene, o-, m-, p-xylene, esters such as dimethyl phthalate, long chain acetate, butyl acetate, ethyl butyrate, cumene, trimethylpentanediol diisobutyrate (TXIB), adipates, sebacates, maleates, trimellitates, azelates, benzoates, citrates and terephthalates, ethers such as methyl tert-butyl ether (MTBE), and carbonates such as diethyl carbonate.
Alkanes and mixtures of alkanes are preferred solvents. Isododecane is the most preferred solvent.
If the carboxylic acid is to be reused in a process where the presence of the solvent is desired, the addition of solvent is particularly desirable so that removal of solvent from the carboxylic acid is not required prior to such reuse. Examples of such processes are organic peroxide production processes in which the presence of solvents is often required for safety reasons.
In step c), the liquid phase is separated.
The separation may be carried out by gravity using conventional separation equipment such as liquid/liquid separators, centrifuges, (pulsed and/or packed) countercurrent columns, mixer-settlers (combinations) or continuous (plate) separators.
In some embodiments, the salt may be prepared by using a concentrated salt solution, e.g., 20-30 wt% NaCl, naHSO 4 、KHSO 4 、Na 2 SO 4 Or K 2 SO 4 The solution salts precipitate out of the organic liquid phase to facilitate separation. The salt reduces dissolution of the carboxylic acid in the aqueous liquid phaseDegree. Such extraction may be performed in any suitable device such as a reactor, centrifuge or mixer-settler.
The preferred separation method in step c) is gravity separation rather than extraction.
Regardless of how the phases are separated in step c), it is preferred to separate or distill step d) to further purify the carboxylic acid. Distillation is particularly preferred for purifying carboxylic acids having less than five carbon atoms and for organic liquid phases having a water content of 5% by weight or more. For lower water content, molecular sieves or dry salts can be used to dry to remove water.
Distillation may be used to evaporate volatile impurities including water from the carboxylic acid and/or to distill the carboxylic acid from any impurities having a boiling point higher than the boiling point of the carboxylic acid.
The term "distillation" in this specification includes any form of removal by evaporation of the components. Thus, it also includes stripping and similar techniques.
Between separation step c) and separation or distillation step d), it may be desirable to remove any salts resulting from the acidification from the organic liquid phase to prevent settling of solids in the distillation column. Salts can be removed by washing with water, cooling (e.g., freezing) and separating the resulting aqueous layer. Cooling is preferably carried out to <20 ℃, more preferably <10 ℃ and most preferably <5 ℃, and will force the salt into the aqueous layer.
The separated aqueous layer may be recycled to the protonation step.
The water content of the resulting carboxylic acid is preferably below 2 wt.%, more preferably below 1 wt.%, even more preferably below 0.5 wt.% and at most below 0.1 wt.%. This is especially preferred in case the carboxylic acid is to be reused in the peroxide production process. Further distillation of the carboxylic acid may be required to achieve this water content.
The aqueous liquid phase formed in protonation step b) may contain some residual carboxylic acid. This includes, in particular, lower molecular weight acids such as butyric acid, isobutyric acid, valeric acid and methyl or ethyl branched valeric acid. The residual acid may be recovered by adsorption, (azeotropic) distillation or extraction, preferably distillation. Optionally, a salt (e.g., sodium sulfate) as an aqueous liquid distillate can be added to the recovered carboxylic acid to reduce the solubility of the carboxylic acid. To further optimize the carboxylic acid yield, the recovered residual carboxylic acid distillate may be recycled by adding it to the above aqueous side stream after protonation step b) and before separation step c).
Preferred carboxylic acids to be obtained by the process of the present invention include isobutyric acid, n-butyric acid, propionic acid, pivalic acid, neodecanoic acid, neoheptanoic acid, isononanoic acid, 2-methylbutyric acid, cyclohexylformic acid, lauric acid, isovaleric acid, n-valeric acid, n-hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, 2-propylheptanoic acid, octanoic acid, nonanoic acid, decanoic acid and lauric acid. More preferred carboxylic acids are isobutyric acid, n-butyric acid, n-heptanoic acid, n-octanoic acid, pivalic acid, isononanoic acid, 2-methylbutanoic acid, cyclohexylformic acid, isovaleric acid and n-valeric acid.
The carboxylic acid resulting from the process of the present invention may be recycled to the organic peroxide production process from which it originates, which may be used to produce another organic peroxide, may be used to prepare esters (e.g. ethyl esters) for use as solvents or fragrances, for example, or for agricultural applications.
The carboxylic acid or salt thereof may also be used in animal feed. For example, butyrate is known to improve gastrointestinal health in poultry and to prevent microbial infections and diseases in poultry, pigs, fish and ruminants.
Examples
An aqueous side stream of a diisobutyryl peroxide process containing 23 wt% sodium isobutyrate, 300ppm diisobutyryl peroxide, and 0.1 wt% diisobutyryl peroxide at a temperature of 0 ℃ and a pH of about 10 was treated as follows: the flow of constant flow is passed through a column with four stirring sections and maintained at a temperature of 20-25 ℃. The residence time of each zone was about 5 minutes. 30 wt% of Na 2 SO 3 Adding a solution to the column to reduce the peroxyisobutyric acid in the stream and produce a liquid having<50ppm residual peroxide.
The resulting stream is collected in a vessel.
From this vessel 8.2kg of the flow was loaded into a stirrer equipped with a cooling jacket, equidistant blades (pitch blade impeller) and thermometerIs contained in a 10 liter glass reactor. 810.4g of 96 wt% H are added to the stirred contents over 2 minutes 2 SO 4 To reduce the pH to 2.3. The temperature was noted to rise to 42 ℃. After stirring for 5 minutes, the layers were separated by gravity. The two phases were separated to obtain 7.6kg of an aqueous liquid phase and 1.4kg of an organic liquid phase.
The organic phase was cooled to 2 ℃ resulting in 40g of additional aqueous phase separated, which was then combined with 7.6kg of aqueous phase.
The organic liquid phase comprising predominantly wet isobutyric acid is fed to a continuous distillation column. The bottom stream contains >99 wt% isobutyric acid and the water content is 200ppm.
The aqueous liquid phase was loaded into a 10 liter glass reactor and heated at 55℃and<The aqueous isobutyric acid solution was distilled off at 160 mbar. The residue is Na 2 SO 4 An aqueous solution.
To further optimize isobutyric acid yield, H was used in 2 SO 4 After acidification and prior to gravitational separation of the resulting layers, the aqueous isobutyric acid solution was recycled by adding it to the aqueous side stream described above.
Claims (23)
1. A process for separating carboxylic acid from an aqueous side stream of a diacyl peroxide or peroxyester production process, said process comprising the steps of:
a) Providing an aqueous side stream of an organic peroxide production process, said stream comprising at least 1 wt.% of a metal carboxylate salt dissolved or homogeneously mixed in said stream,
b) Protonating the carboxylate salt to a carboxylic acid in the aqueous side stream, thereby forming a biphasic mixture of two liquid phases,
c) Separating the biphasic mixture into (i) an aqueous liquid phase comprising water and a small amount of carboxylic acid and (ii) an organic liquid phase comprising carboxylic acid and a small amount of water,
d) Optionally separating the carboxylic acid from the organic liquid phase,
wherein residual peroxide present in the aqueous side stream is removed by (i) extraction before or after step b) and/or (ii) adding a reducing agent, heat or radiation to the stream, to the biphasic mixture and/or to the organic liquid phase.
2. The process according to claim 1, wherein the process comprises d) separating carboxylic acid from the organic liquid phase, optionally by distillation.
3. The method of claim 1, wherein the carboxylic acid is selected from the group consisting of isobutyric acid, n-butyric acid, propionic acid, pivalic acid, neodecanoic acid, neoheptanoic acid, isononanoic acid, 2-methylbutyric acid, cyclohexylformic acid, lauric acid, isovaleric acid, n-valeric acid, n-hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and lauric acid.
4. A process according to claim 3, wherein the carboxylic acid is selected from isobutyric acid, n-butyric acid, n-heptanoic acid, n-octanoic acid, pivalic acid, isononanoic acid, 2-methylbutanoic acid, cyclohexylformic acid, isovaleric acid and n-valeric acid.
5. The process of any one of claims 1-4, wherein the aqueous side stream in step a) comprises at least 3 wt% metal carboxylate salt.
6. The process of claim 5 wherein the aqueous side stream in step a) comprises at least 5 wt.% metal carboxylate salt.
7. The process of claim 5 wherein the aqueous side stream in step a) comprises at least 10 weight percent metal carboxylate salt.
8. The process of claim 5 wherein the aqueous side stream in step a) comprises at least 20 weight percent metal carboxylate salt.
9. The process of claim 5 wherein the aqueous side stream in step a) comprises at least 25 weight percent metal carboxylate salt.
10. The process of any one of claims 1-4, wherein protonating the carboxylate salt to the carboxylic acid in step b) is performed by acidification of the aqueous side stream.
11. The process of any one of claims 1-4, wherein protonating the carboxylate salt to the carboxylic acid in step b) is performed by electrochemical membrane separation of the aqueous side stream.
12. The method of claim 11, wherein the protonation of the carboxylate salt to the carboxylic acid in step b) is performed by bipolar membrane electrodialysis (BPM) of the aqueous side stream.
13. The process of any one of claims 1-4, wherein peroxide present in the aqueous side stream is destroyed by adding a reducing agent to the aqueous side stream prior to or during step b).
14. The method of claim 13, wherein the reducing agent is selected from sodium sulfite, sodium sulfide, sodium polysulfide, sodium thiosulfate, and sodium metabisulfite.
15. The process according to any one of claims 1-4, wherein in step c) the phases are separated by gravity.
16. The process according to any one of claims 1 to 4, wherein in step c) the phases are separated by extraction with an organic solvent.
17. The process according to claim 16, wherein in step c) the phases are separated by extraction with alkanes and alkane mixtures.
18. The process according to claim 16, wherein in step c) the phases are separated by extraction with isododecane.
19. The process according to any one of claims 1 to 4, wherein in step c) the phases are separated by extraction with a salt solution.
20. The process according to claim 19, wherein in step c) the phases are separated by extraction with 20-30% by weight NaCl solution.
21. The process according to any one of claims 1-4, comprising an additional step e) wherein the carboxylic acid is separated from the aqueous liquid phase by distillation.
22. The process of claim 21, further comprising recycling at least a portion of the carboxylic acid separated in step e) to the biphasic mixture of step b).
23. The process of any one of claims 1-4, further comprising recycling at least a portion of the carboxylic acid separated in step c) or step d) to the organic peroxide production process, using the carboxylic acid separated in step c) or step d) to produce an ester, or using the carboxylic acid separated in step c) or step d) in an animal feed.
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| PCT/EP2020/066232 WO2020249692A1 (en) | 2019-06-12 | 2020-06-11 | Method for isolating carboxylic acid from an aqueous side stream |
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| FR2366059A1 (en) * | 1976-10-01 | 1978-04-28 | Chem Systems | CATALYST RECOVERY PROCESS |
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| JPH08245605A (en) * | 1995-03-06 | 1996-09-24 | Daicel Chem Ind Ltd | Separation of carboxylic acid from epoxy compound |
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