EP2681184A1 - Verfahren zur gewinnung von organischen carbonsäuren aus wässrigen gemischen - Google Patents
Verfahren zur gewinnung von organischen carbonsäuren aus wässrigen gemischenInfo
- Publication number
- EP2681184A1 EP2681184A1 EP12707238.7A EP12707238A EP2681184A1 EP 2681184 A1 EP2681184 A1 EP 2681184A1 EP 12707238 A EP12707238 A EP 12707238A EP 2681184 A1 EP2681184 A1 EP 2681184A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- metal
- carboxylic acid
- particles
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/02—Processes using inorganic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
- B01J49/07—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds containing anionic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
- B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/363—Anion-exchange
Definitions
- the invention relates to a process for obtaining organic carboxylic acids, for example succinic acid, from aqueous mixtures, for example from
- Fermentation broth in which the acids to be separated are brought into contact with a metal oxide, so that an adsorption of the acids takes place on the metal oxide and separation from the aqueous mixture is possible.
- the production of fermentatively produced succinic acid can be carried out for example by means of bipolar electrodialysis, which, however, requires a high expenditure of energy.
- the succinic acid can be precipitated by means of calcium hydroxide; the resulting calcium succinate is subsequently treated with sulfuric acid to isolate the succinic acid.
- Caicium sulfate must be disposed of costly.
- An object of the invention is to provide a method by which organic carboxylic acids can be obtained from aqueous mixtures which is improved over the prior art, for example because it is less expensive or requires less use of auxiliary materials for separation or sufficient egenerieriana guaranteed this auxiliary materials.
- Carboxylic acid salts from aqueous mixtures comprises the following steps:
- aqueous mixture Containing carboxylic acid and / or a carboxylic acid salt, wherein the aqueous mixture has a pH of 1 to 10;
- Metal hydroxide particles such that the organic carboxylic acid and / or the carboxylate is at least partially adsorbed to the particles;
- the use of a metal oxide and / or metal hydroxide for obtaining carboxylic acids / carboxylic acid salts from aqueous mixtures is very suitable.
- the metal oxide / metal hydroxide particles can be regenerated well since step C) can be carried out in such a way that a substantially complete desorption takes place.
- the process does not generate large amounts of waste, as for example in the precipitation of
- Metal oxide / metal hydroxide particles can also be added to ongoing reactions, for example, reactions in which carboxylic acids or carboxylates are formed, the metal oxide / metal hydroxide particles running the reaction equilibrium Carboxylate / carboxylic acid withdraw without the reaction itself by the
- carboxylic acid can be continuously recovered from fermentation broths. This has the positive side effect that moderately salt-tolerant strains can be used for the production of carboxylic acids, since the salt load of the fermentation broth is constantly reduced and thus no high salt concentrations, which can be caused by neutralizing agents according to the prior art, are recorded.
- step A) can be carried out according to step A) both at alkaline and at acidic pH. Accordingly, whether a given carboxylic acid in the form of the carboxylic acid or in the form of the
- Corresponding carboxylate anion is in solution or what ratio of acid and corresponding anion in solution. If in the context of the present application of organic carboxylic acids and / or
- Carboxylic acid is spoken, it is to be understood that depending on the pH, the carboxylate groups of the present in the aqueous mixture of organic compounds may be in the protonated or in the deprotonated form. The same applies to those obtained after carrying out step C)
- an aqueous mixture is understood to mean any mixture in which a carboxylic acid or a carboxylate in dissolved or else only partially dissolved form is present in water as solvent or an aqueous solvent mixture.
- alcohols e.g. Ethanol
- Salts such as phosphates and / or carbonates (which may also be present in partially protonated form depending on the pH) and nitrates, halides and / or sulfates present in the solution may be mentioned here as inorganic compounds.
- organic compounds for example, carbohydrates, such as saccharides, proteins, lipids, and DNA or components thereof, such as purines and Pyrimidines.zu call.
- the aqueous mixture may also be a fermentation broth;
- the aqueous mixture in addition to inorganic and / or organic components and biomolecules, especially bacteria contain.
- the latter can - but need not - be easily separated from the aqueous mixture by conventional methods.
- the measures required for this purpose are known to the person skilled in the art.
- the aqueous mixture can be present according to the invention as a suspension or as a true solution; also in fermentation broths and the like, if the biomolecules are disregarded as a suspension or as a true solution.
- any aqueous mixture which is basically suitable as an aqueous mixture from the pH value is suitable for the process according to the invention; if, however, the pH is ⁇ 1 or> 10, the pH of the mixture must be brought to a value of 1 to 10 before carrying out the process by adding a base or an acid, wherein As bases in particular alkali metal hydroxides and as acids in particular dilute mineral acids into consideration.
- a metal oxide or a metal hydroxide is understood as meaning a chemical compound which contains "oxide ions" and / or hydroxide ions (ie, O 2 " and / or OH-ions) in addition to the metal, and which as a rule does not contain any metal ions
- a metal is understood to be a true metal, but not a semi-metal, and metals are therefore in particular not the elements boron, silicon, germanium, arsenic, antimony or tellurium to understand.
- the metal is a transition metal or a metal of the 2nd or 3rd main group, which is usually present in an oxidation state> 0.
- the organic carboxylic acid and / or the carboxylate in step B) is adsorbed on particles of the metal oxide and / or metal hydroxide. Accordingly, the metal oxide according to the invention and / or
- Metal hydroxide in the aqueous mixture is not or only slightly soluble. To a lesser extent, this may mean that the solubility product L of the metal oxide and / or metal hydroxide in pure water at room temperature is less than 1.10 ⁇ 10 -6 .
- Adsorption on the particle does not mean that the metal oxide and / or metal hydroxide have reacting the carboxylic acid and / or the carboxylate to form a Metallcarboxylats which precipitates from a solution as a solid, but in particular that on the solid (undissolved) particles adsorption of carboxylic acid and / or carboxylate (on the surface of the particle) takes place.
- step C) of the process the adsorbed carboxylic acid molecules and / or carboxylates by alkaline solution of the metal oxide and / or
- Metal oxide and / or metal hydroxide is accompanied.
- compounds suitable as metal oxides and / or metal hydroxides are those which allow adsorption at low pH values and desorption of carboxylic acid and / or carboxylate groups at high pH values.
- the metal oxide and / or metal hydroxide particles may therefore comprise or consist of compounds having an isoelectric point.
- the isoelectric point is often referred to as point of zero charge (PZC). The PZC then indicates the pH at which the
- Metal oxide / metal hydroxide usually be greater than the pH of the aqueous mixture. Accordingly, in step A), the pH is usually chosen to be lower than the PZC of the metal oxide / metal hydroxide.
- the pH of the alkaline solution added in step C) will generally be above the pH of the aqueous mixture. This is usually required to ensure separation. However, too - depending on the aqueous mixture and the alkaline solution from step C), which normally contains no further substances in addition to the alkaline compound - also sufficient pH values between 7 and 10, for example, when the aqueous mixture and the alkaline solution are basically different from each other and attack The hydroxide ions of the alkaline solution on the particles with adsorbed carboxylic acid / carboxylate can therefore be made easier than the attack of basic components that in the aqueous
- step C basically any aqueous bases (or even bases in other solvents than water) can be used.
- particles are used in step B)
- Metal oxide and / or metal hydroxide or consist of a metal oxide and / or metal hydroxide, wherein the metal is selected from one or more metals of the group consisting of beryllium, magnesium, calcium, aluminum,
- Oxides or hydroxides with one, two or more metals from this group as the only cationic component or in combination with other metals as cationic components generally have a PZC, which is in the relevant pH range of pH 1 to 12 here.
- PZC which is in the relevant pH range of pH 1 to 12 here.
- Iron or chromium has a PZC between about pH 7 and pH 8.5 (see GA Parks, Journal of Physical Chemistry 1962, 66, 967-973, which is also referred to in the measurement of PZC).
- Corundum (a-AI203) has a PZC at pH 9.1, ⁇ - ⁇ a PZC at pH 8.2, goethite ( ⁇ -FeOOH) a PZC at pH 7.8, hematite (a-Fe203) a PZC at pH 8.5, Fe (OH) 3 a PZC at pH 8.5, ß-Mn02 a PZC at pH 7.2 and
- step B) particles of a metal oxide and / or metal hydroxide are used in which the or a contained therein
- Metal oxide and / or metal hydroxide forms a layered structure. This has the advantage that the particles have a particularly large surface at which the
- Carboxylic acids / carboxylates can adsorb.
- the PZC can be tailored by selecting the at least two different metals. For example, it is possible to use metals which are present in the same oxidation state, in particular +2; Alternatively or simultaneously, metals may also be present in different oxidation states; for example in the oxidation states +2 and +3 or also +2 and +4. Under a double salt structure is understood that a regular structure with the at least two metal ions is formed or that in a
- Metal oxide / metal hydroxide structure of a first metal lattice sites of the first metal are replaced by the second metal.
- a double salt structure is in particular not understood that in a particle two different metal oxides or
- Metal hydroxides are present side by side, without the one component has an influence on the structure of the other component or without (metal) cations of the one component are incorporated into the structure of the other.
- the metal oxides / metal hydroxides are present in various embodiments. According to a further embodiment, the metal oxides / metal hydroxides
- Double layer hydroxides in particular double layer hydroxides of the formula
- M 1 is a divalent metal and M 2 is a trivalent metal;
- A is a singly or multiply charged anion, whereby a mixture of singly charged or singly and / or multiply charged anions may also be present.
- index x 0 ⁇ x ⁇ 1
- x can be between 0.2 and 0.4
- y is any number greater than or is 0 and may be 0 to 10 in particular; where y is not limited to integer numbers, but can also be a decimal number, z is an integer or decimal number for which 1> z ⁇ 3. If there is only one sort of anions, z is an integer.
- z will hold: 1 ⁇ z ⁇ 2, in particular 1 ⁇ z ⁇ 1, 5.
- z is often 1, but even with anion mixtures, there will often be substantially simply negatively charged anions A). Essentially means more than 75%, and usually more than 90% of the anions are simply negatively geiads.
- Bilayer hydroxides according to the present invention are two-dimensional inorganic polycations with intracrystalline charge compensation by mobile interlayer anions A). Particularly noteworthy are bilayer hydroxides, which derive their structure from the mineral brucite, the divalent metal ions are partially replaced by trivalent metal ions. The anions are accordingly required for charge balancing.
- a naturally occurring double layer hydroxide of this type is hydrotalcite, in which the divalent magnesium ions are partially replaced by aluminum ions. Frequently, the charge balance is carried out by carbonate anions. In addition, there is water of crystallization between the bilayers.
- double-layer hydroxides are described many times in the literature and can be prepared, for example, according to DE 40 34 305 A1 or DE 198 36 580 A1 and the literature cited therein.
- the use of double layer hydroxides has the advantage that solid particles with a relative to the carboxylic acid / carboxylate adsorption very relevant
- Natural hydrotalcite for example, has a PZC in the basic pH range, so that for aqueous media with a pH ⁇ 7 a suitability for the adsorption of carboxylic acids / carboxylates is present.
- the divalent metal M 1 is selected from one or more of the metals beryllium, magnesium, calcium, manganese, iron, cobalt, nickel, copper and zinc.
- the trivalent metal M 2 is selected from one or more metals of the group boron, aluminum, gallium, lanthanum, scandium, titanium, chromium, manganese, iron, cobalt, nickel.
- the double-layer hydroxides will contain both one of the abovementioned divalent metals and one of the abovementioned trivalent metals.
- the anion A of the bilayer hydroxides is selected from the group consisting of halides, perchlorate, nitrate, nitrite, sulfate, Sulfonate, carbonate, bicarbonate, hydroxide and borate or mixtures thereof.
- Chlorides, bromide and iodide are to be mentioned in particular as halides.
- a monovalent anion, in particular a halide ion such as chloride (or even bromide) or a nitrate ion as anion A) is particularly common. Especially with monovalent anions, it has been observed that a very effective adsorption of the carboxylic acids / carboxylates is observed, presumably because of easier exchangeability.
- the organic carboxylic acid recovered from the aqueous mixture is selected from aromatic and / or
- carboxylic acids should have good water solubility in order to be able to be recovered from an aqueous mixture.
- acids with poor solubility in water can in principle also be obtained, they can often be separated well by crystallization processes.
- carboxylic acids having more than 12 carbon atoms are generally less suitable.
- water solubility can be increased by customary substituents such as, for example, hydroxyl groups, so that, in principle, carboxylic acids having more than 12 carbon atoms may also be suitable.
- Suitable aromatic and / or aliphatic carboxylic acids according to the invention are carboxylic acids having one, two, three or more than three carboxylic acid groups.
- the aliphatic and / or aromatic radicals can also carry functional groups, for example hydroxy groups, as are contained, for example, in many naturally occurring carboxylic acids.
- substituents are not limited to hydroxyl groups, but rather any functional groups can be present on the aromatic and / or aliphatic radicals of the carboxylic acid groups, in particular amino groups, ester groups, keto groups, thiol groups, To name ether groups, thioether groups and phosphate groups,
- aromatic radicals hereby mono- and polycyclic aromatic compounds may be present, including in addition to the known homocyclic compounds and the heterocyclic aromatics may be mentioned.
- Aliphatic groups can be branched, unbranched and / or cyclic and also be saturated or unsaturated.
- the organic carboxylic acid is made
- Dicarboxylic acids in particular oxalic acid, malonic acid, maleic acid,
- succinic acid for example, is of interest, since it can be obtained as a C 4 building block, for example by means of fermentation processes, and then can serve as a valuable starting material for organic syntheses by derivatization or reduction.
- the monocarboxylic acids for example acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, acrylic acid, levulinic acid and also the natural amino acids are to be mentioned in principle.
- Tricarboxylic acid is the citric acid to mention.
- the process according to the invention is carried out with an aqueous mixture which has a pH of from 5.5 to 7.5, preferably from 6 to 7. Often, the pH can be 6.5 to 7. In the case of mixtures which have such a pH, it is generally possible to continuously separate carboxylic acid or carboxylates formed during ongoing chemical reactions from the mixture, without the chemical reaction proceeding as a result of a particularly high or particularly low pH is impaired.
- an aqueous mixture in the form of a fermentation broth may be mentioned, with which carboxylic acids or carboxylates are prepared.
- the process according to the invention is carried out under atmospheric pressure and at a temperature between 20 and 100.degree. C., in particular 20 to 60.degree. In principle, however, other temperatures and increased or reduced pressures are conceivable.
- aqueous mixture As an aqueous mixture, however, one
- the process according to the invention is furthermore generally carried out at atmospheric pressure. Regardless of this, aerobic or anaerobic conditions may prevail.
- Step A) is then usually also a process step of the fermentation process, because the provision of the aqueous
- step B) the contacting of the particles obtained in step B) with an alkaline solution (according to step C)) is not carried out in the fermentation broth in which the reaction continues. It makes sense to first separate the particles with the absorbed carboxylate or the adsorbed carboxylic acid from the fermentation broth. However, in the individual case, the complete separation of the fermentation broth outside the
- step C this should be removed to ensure a high degree of purity of the desorbed carboxylic acid.
- the inventive method is not only used for the separation of carboxylic acids but also for separation
- the inventive method can be used to the more coordinating carboxylic acid or the acidic carboxylic acid of the other
- Monocarboxylic acids can be easily separated.
- the process according to the invention is suitable for obtaining, from mixtures with a plurality of carboxylic acids, the carboxylic acid separated off as specified above substantially pure.
- Essentially pure means that in addition to the carboxylic acid to be isolated at most 10 wt .-% (based on the total amount of carboxylic acids) of a further carboxylic acid are included, in particular less than 5% and often even less than 1%.
- an alkaline solution is added in step C) but additionally an inorganic salt.
- inorganic salts of the formula M + X ⁇ where M is a monovalent cation, in particular a metal cation or an ammonium cation (wherein organically substituted ammonium cations are included), and X is any monovalent anion, for example, alkali halides or alkali metal nitrate.
- Double layer hydroxide-containing particles regeneration of the particles occur simultaneously with the desorption of the carboxylic acid / carboxylate. It has also been observed that, in general, easier desorption of the carboxylic acid / carboxylate can also take place.
- a double-layer hydroxide is used in step B), in which the anion A) is not, at least but not exclusively
- Carbonate anion is (not exclusively means that at least 10 mol% of another anion, usually more than 50 mol% of another anion and often more than 90 mol% of another anion is included).
- carbonate anion is (not exclusively means that at least 10 mol% of another anion, usually more than 50 mol% of another anion and often more than 90 mol% of another anion is included).
- the carbonate anion can be exchanged for another anion.
- the carbonate ion can be driven off by addition of an acid, for example a mineral acid (for example aqueous hydrochloric acid), or thermally (for example by heating to 300 ° C.) and released in the form of carbon dioxide.
- an acid for example a mineral acid (for example aqueous hydrochloric acid), or thermally (for example by heating to 300 ° C.) and released in the form of carbon dioxide.
- a mineral acid for example aqueous hydrochloric acid
- thermally for example by heating to 300 ° C.
- other ways of removing the carbonate are conceivable, for example by complex formation with correspondingly strong complexing agents, which then to some extent wash out the carbonate from the double-layer hydroxide.
- EXAMPLE 1 1.5 g of hydrotalcite (Synthal 969 from Sudchemie - a magnesium- and aluminum-containing talcite) are treated with a 1 molar HCl solution in order to drive off the bound carbonate. Subsequently, the material is washed twice with distilled water and dried at 105 ° C.
- hydrotalcite Sudchemie - a magnesium- and aluminum-containing talcite
- the aqueous mixture used here is a solution of succinic acid in water which has a concentration of 10 g / l.
- 1 g of the pretreated hydrotalcite is added and incubated on the shaker.
- the abovementioned succinic acid solution (which has a pH of 2.5) is brought to a pH of 6.5 by means of sodium hydroxide solution and likewise incubated on the shaker.
- an ion chromatograph from Metrohm the concentration of succinic acid in the remaining solution is determined and thus determines the amount of adsorbed carboxylate or the adsorbed acid.
- FIG. 1 shows a bar graph of the measured values on the left with an incubation time of 3 hours, on the right with an incubation time of 24 hours, wherein the left bar in each case relates to the pH 2.5 and the right bar to the pH 6.5.
- Figure 2 shows the results obtained as a bar chart. The results show that the addition of hydrogen phosphate does not affect the adsorption of the
- Succinic acid has. While succinic acid solution without further additives (referred to in Figure 2 BS) shows approximately an adsorption of 53 mg / g hydrotalcite, the adsorption in the presence of hydrogen phosphate (in Figure 2 P0 4 called) even slightly increased. In contrast, carbonate ions have a negative influence on the adsorption. Both the solutions, which contain only carbonate ions in addition to succinic acid (in 1 C0 3 denotes - measured value 30.1 ⁇ 2.9 mg / g hydrotalcite) as well as the solutions which contain both hydrogen phosphate and also carbonate (in FIG. 2 P0 4 + C0 3 - measured value 22.9 mg / g hydrotalcite) show a clear
- Example 3 the selective separation of a dicarboxylic acid in the presence of a monocarboxylic acid is carried out using an aqueous mixture which is a fermentation broth.
- Figure 3 shows the concentration of succinic acid and acetic acid before treatment with hydrotalcite and of succinic acid and acetic acid in the remaining solution after treatment with hydrotalcite.
- the succinic acid concentration decreased by the adsorption from 22.8 ⁇ 1.0 g / l to 10.7 ⁇ 0.1 g / l, while the concentration of acetic acid remained constant at 6 g / l. Accordingly, selective adsorption of succinic acid on hydrotalcite occurs.
- the centrifuged hydrotalcite was re-eluted by means of a solution containing 3 mol / L of common salt and 3 mol / L of NaOH. From the eluate, the succinic acid crystallized in the freezer.
- a solution of 10 g / l citric acid in water is adjusted to pH 6.5 by means of sodium hydroxide solution.
- 1 g of hydrotalcite are added according to Example 1 and incubated for 3 hours with shaking.
- the supernatant aqueous phase after incubation contains only a concentration of 3 g / l citric acid.
- a solution of 10 g / l lactic acid in water is brought to pH 6.5 by means of sodium hydroxide solution. 10 ml of this solution are mixed with 1 g of hydrotalcite according to Example 1 and incubated for 3 hours with shaking. In the supernatant aqueous phase, only a concentration of 4 g / l of lactic acid could be determined after incubation.
- Goethite A solution of 10 g / l succinic acid in water is brought to pH 2.5 using sodium hydroxide solution. 10 ml of this solution are mixed with 1 g of goethite and incubated for 3 hours with shaking. In the supernatant aqueous phase, only a concentration of 8 g / l of succinic acid could be determined after incubation.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011012857A DE102011012857A1 (de) | 2011-03-02 | 2011-03-02 | Verfahren zur Gewinnung von organischen Carbonsäuren aus wässrigen Gemischen |
PCT/EP2012/000896 WO2012116820A1 (de) | 2011-03-02 | 2012-03-01 | Verfahren zur gewinnung von organischen carbonsäuren aus wässrigen gemischen |
Publications (1)
Publication Number | Publication Date |
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EP2681184A1 true EP2681184A1 (de) | 2014-01-08 |
Family
ID=45808749
Family Applications (1)
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EP12707238.7A Withdrawn EP2681184A1 (de) | 2011-03-02 | 2012-03-01 | Verfahren zur gewinnung von organischen carbonsäuren aus wässrigen gemischen |
Country Status (3)
Country | Link |
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EP (1) | EP2681184A1 (de) |
DE (1) | DE102011012857A1 (de) |
WO (1) | WO2012116820A1 (de) |
Families Citing this family (2)
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JP7358393B2 (ja) * | 2018-05-07 | 2023-10-10 | リオ・ティント・アイアン・アンド・チタニウム・カナダ・インコーポレーテッド | スカンジウムを含む酸性溶液から金属汚染物質を取り除く方法 |
CN111926357B (zh) * | 2020-08-19 | 2021-04-02 | 北方工业大学 | 一种镁合金复合结构层材料的制备方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4034305A1 (de) | 1990-10-29 | 1992-04-30 | Henkel Kgaa | Hydrophobierte doppelschichthydroxid-verbindungen, verfahren zur herstellung und ihre verwendung als alkoxylierungskatalysatoren |
IL119389A (en) * | 1996-10-09 | 2001-10-31 | Cargill Inc | Process for the recovery of lactic acid by liquid-liquid extraction using a cation exchanger |
DE19836580A1 (de) | 1998-08-12 | 2000-02-17 | Sued Chemie Ag | Verbundmaterial mit Polymermatrix und anionisch interkalierten schichtförmigen Doppelhydroxiden |
-
2011
- 2011-03-02 DE DE102011012857A patent/DE102011012857A1/de not_active Withdrawn
-
2012
- 2012-03-01 EP EP12707238.7A patent/EP2681184A1/de not_active Withdrawn
- 2012-03-01 WO PCT/EP2012/000896 patent/WO2012116820A1/de active Application Filing
Non-Patent Citations (1)
Title |
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See references of WO2012116820A1 * |
Also Published As
Publication number | Publication date |
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WO2012116820A1 (de) | 2012-09-07 |
DE102011012857A1 (de) | 2012-09-06 |
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