• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:SU1836326A3
    申请号:SU894742831
    申请日:1989-12-21
    公开日:1993-08-23
    发明作者:Dalkanale Enriko；Bonsinore Stefanio；Dyu Vosel Annik
    申请人:Inst Gvido Donegani S P A；
    IPC主号:
    专利说明:

    The invention relates to a process for the recovery of lactic acid from solutions containing it, in particular to a process for the recovery of lactic acid from aqueous solutions containing it, which are formed during the production of vegetable products, using the axial arrangement of the crown configuration substituents.
    OH in which R is a linear or branched alkyl radical C5H11-C18H37, b) a solution of at least one organic solvent immiscible with water, selected from saturated, possibly halogenated (cyclo) alkane hydrocarbons, possibly halogenated and / or alkylated aromatic hydrocarbons. of letrole ether at a pH of 1-6, the organic phase is formed by a complex of lactic acid - octol, dissolved in an organic solvent, is separated from the aqueous phase, and the organic phase is then treated with water at a pH in the range of 7-10 or methanol, while the complex with milk acid is destroyed and this lactic acid is then recovered by a known method. 2 wpp, 4 tab.
    a system consisting of a complexing agent and an organic extractant selective for lactic acid, which is then released and recovered.
    Thus obtained lactic acid is an important
    1836326 AZ product, which has interesting prospects for application at the industrial level. In fact, this product can be used in the production of dairy products as an acidifier and a spreading agent in the food industry, as an intermediate in the production of plasticizing agents, adhesives, pharmaceuticals in the production of lactates, as an etchant for wool dyes, etc.
    A separate area of application, which has significant prospects for industrial use, is the production of biocompatible and / or biodegradable polymers from lactic acid, useful for packaging, film applications, in the field of sanitation, etc.
    These latter applications, which are currently costly, can find a cheap and simple alternative in the process according to this invention for the recovery of lactic acid from aqueous solutions, which are very cheap by-products of industrial processes, for example, from residual enzymatic solutions, extracts vegetable raw materials; by-products of agricultural raw materials, such as by-products of grain fermentation. those. the so-called soaked grain solution, which is a diluted aqueous solution obtained by soaking corn kernels in a warm 0.2% sulfur dioxide solution for 48 hours as the first stage in the process of obtaining corn starch, corn oil and gluten from corn.
    Extraction of lactic acid from such aqueous solutions is a serious problem due to the extremely high solubility of lactic acid and the presence in the above aqueous media obtained from industrial processes of a large number of other substances and / or compounds of an organic and inorganic nature in quantities exceeding the amount of lactic acid contained .
    The extraction of lactic acid from fermentation solutions or from aqueous extracts is currently carried out in several ways. A known method, which is most widely used and according to which lactic acid is salted with calcium carbonate with the formation of calcium lactate. After filtering the enzymatic residues, the salt is treated with sulfuric acid. The lactic acid thus obtained is further purified by filtration, treatment with activated carbon, passing through ion-exchange resins, etc.
    There is also known a method according to which calcium lactate is converted to zinc lactate, which is then purified by fractional crystallization. Lactic acid is then released when hydrogen sulfide is added.
    A known method comprising the stage of esterification, purification and saponification. A method based on neutralization with organic amines was also proposed, followed by extraction of the salts formed with organic solvents.
    All these cleaning methods in industrial applications are associated with big problems (corrosion, residual salts, the use of ion-exchange salts, etc.) to the extent that they make a predominant contribution to the final price of the product.
    The closest in technical essence and the achieved result is a method for the separation of lactic acid from aqueous solutions containing it, which consists in the fact that the solution is treated with organic amines, and then the salts formed are extracted with organic solvents.
    The disadvantage of this method is its high cost, as well as the difficulty of isolating a pure product from dilute solutions with a high content of other impurities.
    The purpose of the invention is to simplify and cheapen the process of selective recovery of lactic acid from aqueous solutions, such as fermentation solutions and solutions from vegetable raw materials, such as the so-called solution from soaking grain, etc., which is devoid of the above-described disadvantages of the processes known from previous works, as well as the recovery of lactic acid, based on aqueous solutions obtained as by-products, as well as with a low content of lactic acid and / or a significant amount of other their components and / or organic and / or inorganic products, without preconcentration.
    This goal is achieved by the method of separation of lactic acid from an aqueous medium containing it, which consists in the fact that the aqueous medium is treated with a system consisting of a complexing agent containing one macrocyclic crown octane with an axial arrangement of substituents of the general formula (I) but he
    I y•I n / a I- I'm n ° oSleep " but IC <he n-bnI n R) I-BUTHE
    where R is a linear or branched alkyl radical of CbNc-CbcNc and an organic extractant selective with respect to lactic acid in which the complexing agent is dissolved, in which case an organic solvent not miscible with water, selected from halogenated alkane hydrocarbons, is used as the extractant, and the process is carried out at pH values of 1.4-5, while the organic the phase formed by the octol-lactic acid complex, dissolved in an organic solvent, is separated from the aqueous phase and then treated with water in the pH range of 7-10, while the lactic acid releases Xia and it are separated.
    Typically, CCU or benzene or toluene is used as the organic solvent. Typically, octol is used in molar excess with respect to acid.
    'The hallmark of the process is that; that the treatment is carried out by a system consisting of a complexing agent containing one macrocyclic octole crown configuration with an axial arrangement of the substituents of the formula (I) and an organic extractant selective for LACTIC ACID; in which the complexing agent is dissolved, while an organic solvent not miscible with water, selected from halogenated alkane hydrocarbons or aromatic or aromatic alkylated hydrocarbons, is used as the extractant, while the process is carried out at pH values of 1.4-5 and the organic phase formed by the octol complex -lactic acid, dissolved in an organic solvent, is separated from the aqueous phase, and then treated with water in the pH range of 7-10, while lactic acid is released and its cherish, which allows to simplify the process.
    Thus, with the help of preliminary complexation, selective extraction into the organic phase of lactic acid dissolved in the aqueous phase used as a starting material is achieved. Bound lactic acid is then released upon treatment with water in the range of pH 7-10, preferably from 7 to about 9. and a more or less concentrated lactic acid solution is formed which can be used either alone or more concentrated, pure lactic acid can be obtained by a method known from previous works (concentration, etc.). R is a linear or branched alkyl radical having from 5 to 18 carbon atoms with an axial arrangement.
    Among the group of octols of general formula (1), those are preferred in which R is an alkyl radical containing from 6 to 15 carbon atoms, in particular those in which R = C2H5, CbHo, C11H23, C15H31.
    Mixtures thereof may also be used.
    The aforementioned macrocyclic octols can be obtained by acid-catalyzed condensation of resorcinols with suitable alkyl aldehydes (4).
    As mentioned above, in the complexing agent – extractant system according to this invention, macrocyclic octol with axial symmetry of R groups, as defined here above (a. Component of the above mixture), is soluble in at least one organic solvent selective for the resulting complex with lactic acid (b. system component).
    Solvents should have the following characteristics. They should not be mixed with water. They should be good solvents of the macrocyclic tetramer of general formula (I). For their part, they should not form preferred bonds (e.g., hydrogen) with the extractant of the general formula (I).
    Within the above region, solvents selected from saturated hydrocarbons may be used.
    The most advantageous results were obtained using carbon tetrachloride, toluene, benzene, and mixtures thereof.
    The process is carried out with vigorous stirring, under conditions of temperature and pressure, corresponding to room temperature.
    The aqueous solution used as the starting material is treated with values from 1.4 to 5 with that amount of the organic solution that contains micromolecular octol (1) in a molar excess with respect to the lactic acid contained in the said aqueous medium. However, this amount is optional and may depend on the solubility of octole in the solvent and on similar parameters.
    The resulting solution in the organic phase containing the octolactate complex is separated from the aqueous phase using known methods (decantation, etc.) and treated with water at pH values in the range of 7-10, preferably 7-9. As for the amount, for example, in the case of a solution from soaked grain, the amount of water or methanol that is needed should be about twice as large as the amount of the organic solution containing the complex to be treated.
    The released acid remains in the aqueous phase, while the organic phase containing macrocyclic octole is separated from the aqueous phase by decantation, centrifugation, etc., and, if necessary, is returned to the process.
    To complete the recovery process, it takes a time of 1 to 12 hours, depending on mixing conditions, temperature, etc.
    Aqueous solutions containing lactic acid are mainly fermentation solutions, aqueous extracts of vegetable raw materials, the so-called grain soaking solution and the like, which are available on the market at low prices, the molar titer of lactic acid in these aqueous solutions usually lies in the range from 0.06 to about 12.1, not counting a large number of other organic and inorganic components,
    However, the process of the present invention is not limited to the minimum or maximum value of such a titer.
    Thus, an aqueous solution that has a molar titer of lactic acid of from 0.06 to 12.1, preferably from 0.1 to 3.6, can be processed.
    The process can be carried out with a very dilute solution of lactic acid (0.5%), as well as with a concentrated solution of almost 90% by weight, without prior concentration or dilution of the initial solution.
    The solution may be subjected to one or more treatment cycles according to this invention.
    The complexation process - extraction of lactic acid according to this invention, if the solution is processed by soaking the grain, is carried out by bringing the aqueous phase containing lactic acid in contact with the organic phase selected from the group of previously listed solvents in which the extracting agent of the general formula (I ) in an excess molar ratio, with stirring for about 8 hours at a temperature of 25 ° C. Selective complexation takes place from the interface between the two phases, followed by migration of the resulting complex to the organic phase. Then these two phases are separated by decantation or centrifugation. The organic phase thus obtained contains a complex of lactic acid - macrocyclic tetromer (1). Lactic acid is released, for example, by reextraction with distilled water at a volume ratio of 2: 1, which destroys the complex and leads to the release of lactic acid, lactic acid migrates to a new aqueous phase, and the macrocyclic octol released also remains in the organic phase.
    If necessary, lactic acid can be obtained from the aqueous phase in any concentration by evaporation, etc.
    Due to its simplicity and moderate conditions, the process of this invention is very advantageous.
    Examples 1-5, Lactic acid is extracted from an aqueous solution of known concentration at pH values in the range 1.4-1.9 with a 1x10 ' 2 molar solution of octol (1) (R = Scnhz) with carbon tetrachloride Xcm. Ta6n.1J. ~
    A two-phase mixture (1: 4 by volume) of 10 ml of the aqueous phase and 40 ml of the organic phase is stirred at 25 ° C for 8 hours. After the completion of the phase separation, the organic phase is separated and analyzed. The quantitative determination of extracted lactic acid is carried out using high pressure relative to a standard comparison solution (conditions: Licfirosorb RP18 column (according to Merck), eluent mixture 73: 6: 1 Н2О (СНзС1Ч) НзРО4- 80%, flow rate 1 ml / min).
    The organic phase thus obtained is then extracted again with distilled water (pH 7). The latter is analyzed using HPLC. The reverse extraction of lactic acid with water is carried out as follows: 1 ml of the organic phase is mixed with 2 ml of distilled water. After 8 hours of stirring at 25 ° C., the aqueous phase is centrifuged and analyzed. The results are presented in table 1.
    PRI me R 6. Also; as in Examples 1-5, extracted with 12.10 molar aqueous solution of lactic acid with 5 x 10 '2 molar solution of octol (1) chetyrehhlo9 Risto carbon. The results are presented in table 1.
    Examples 7-11. Lactic acid was extracted from the solution at a known concentration in the range of pH 1.4-1.9 with care 1x 10 5 '2 molar solution of octol (1) toluene (See. Table 2).
    The biphasic mixture (1: 1 by volume) of 50 ml of the aqueous phase and 50 ml of the organic phase is kept under vigorous stirring at 25 ° C for 8 hours. After finished. phase separation, the aqueous phase is separated and analyzed by acylimetric titration.
    A quantitative determination of the content of lactic acid is carried out by reverse titration of the excess alkali, which went to neutralize the solution. A weighted amount of the organic solution is titrated with an excess of 0.1 and a NaOH solution. The resulting 20 two-phase mixture was stirred for 30 minutes and the excess base was titrated with 0.1 N aqueous solution of H2SO4. Potentiometric pure CCU. 0.33 mol / L of lactic acid is extracted.
    Example 22. The same. as in examples 7-11, comparative extraction of lactic acid at 12, JM aqueous solution is carried out with pure toluene. Extracted 1 x 10 ' 2 mol / l of lactic acid.
    PRI me R 23. Lactic acid is extracted from a solution from the soaking of grain (containing about 8-15% by weight of lactic acid) at pH 4.2 using a 1 x 10 2 molar solution of octol (1) in toluene.
    The two-phase mixture (2: 1 by volume) containing 50 ml of the organic phase and 25 ml of the solution from the soaking of the grain, is intensively stirred at 25 ° C for 8 hours. After phase separation, lactic acid is re-extracted from the organic phase with an equal volume of distilled water. The concentration was re-extracted lactic acid is determined via HPLC, as described in Example 1. Obtained value of 5.7 x 10 "2 mole / l to 1 x 10" 2 mole / l at ekstrakrivaya makes it possible to determine the concentration by weight of extracted mo. lactic acid in toluene and with very high accuracy. The results are presented in table 2. The reverse extraction with distilled water gives the corresponding results.
    Examples 12-16. Same. as in Examples 7-11, a plurality of aqueous solutions of lactic acid was extracted at a pH in the range 1.9-2.5 with 1 x 10 '2 molar solution of octol (1) in toluene. The results are presented in table.Z. Back extraction with distilled water gives the corresponding results.
    Examples 17/18. Just as in Examples 1-5, 12.10 M aqueous solution of lactic acid, respectively, extracted with 1 x 10 '2 molar solution of octol 1 (R = S11N23) and 1 x 10' 2 molar solution of octol 2 (R = SbZhz) in benzene. The results are presented in table 4. Reextraction with distilled water gives corresponding results.
    PRI me R s 19.20. Just as in Examples 1-5,12,10 M aqueous solution of lactic acid, respectively, extracted with 1 x 10 '2 molar solution of octol 3 (R = Sunray) and 1 x 10' 2 molar solution of octol 4 (R = e Ci5H3i) in carbon tetrachloride. The results are presented in table 4. Reextraction with distilled water gives the corresponding results.
    parts of the solution from soaking the grain with pure toluene under the same conditions.
    Example 24 Lactic acid was extracted from the same corn steep liquor from with 1 x 10 '2 molar solution of octol (1) in the SCC.
    In the same manner as in Example 23, with a two-phase mixture (4: 1 v / v) containing 100 ml of the organic phase and 25 ml of the solution from soaking the grain, 5 x 10 2 mol / L of lactic acid was extracted, compared to 0.55 x 10 ' 2 mol / l upon extraction with pure CCI4.
    权利要求:
    Claims (3)
    [1]
    Claim
    1. A method for isolating lactic acid from an aqueous medium containing it using an organic extractant treatment, characterized in that, in order to simplify the process, the treatment is carried out by a system consisting of a complexing agent containing one macrocyclic octole crown configuration with an axial arrangement of substituents general formula
    HE ,
    HE
    Example 21. As in examples 1-5, a comparative extraction of a 12.10 M aqueous solution of lactic acid is carried out where R is a linear or branched radical C5H11-C18H37, and an organic extractant selective with respect to lactic acid in which the complexing agent is dissolved, this as an extractant using an organic solvent that is not miscible with water, selected from halogenated alkane hydrocarbons or aromatic or aromatic alkylated hydrocarbons and the process is carried out at a pH of 1.4-5.0, while the organic phase formed by the octol-lactic acid complex dissolved in an organic solvent.
    separated from the aqueous phase, and then treated with water in the range of pH 7-10, while. lactic acid is released and separated.
    5
    [2]
    2. The method according to claim 1, characterized in that CCU or benzene or toluene is used as an organic solvent.
    [3]
    3. The method according to claim 1, from l and h and y with 10 I that the octol is used in molar excess with respect to acid.
    Table!
    OkTol (1) lactic acid extraction in SSC
    Example Lactic acid concentration * (mol / L) in water Octol concentration 1 (mol / L) in CCU Concentration of extracted lactic acid (mol / L) in WSSL ' 2 ) Lactic acid (%) extracted from the aqueous phase (xU ' 2 ) Molar ratio extracted lactic acid / octol1 1 1.14 10 ' z1.7 (1.2) 1.5 1.7 (1,2) 2 3.571.9 (1.3) 0.53 1.9 (1.3) 3 6.20 - 2.1 (1.5) 0.34 2.1 (1.5) 4 9.053.9 (2.8) 0.43 3.9 (2.8) 5 12.10 - 4.8 (3.5) 0.40 4.8 (3.5) 6 12.10 5 x 10 ' 216.0 (8.0) 1.3 3.2 (1.6)
    * By HPLC
    Table 2
    Extraction of lactic acid with octol (1) in toluene
    Example The concentration * of lactic acid (mol / l) in water Octol concentration! (mol / l) in toluene Concentration * of extracted lactic acid (mol / L) in toluene (x10 * 2 ) Lactic acid (%) extracted from the aqueous phase (x-10 * 2 ) The molar ratio of extracted lactic acid / octol 1 7 1.14 10 z0.94 0.82 0.94 8 3.57  - 1.16 0.32 1.16 9 6.20 - 1.44 0.23 1.44 10 9.05 - ' 1.94 0.21 1.94 eleven 12.102,30 0.18 2,30
    * Acidimetric titration.
    Extraction of lactic acid with octol (1) in toluene
    Table 3
    Example The concentration * of lactic acid (mol / l) in water The concentration of octol 1 (mol / l) in toluene Concentration * of extracted lactic acid (mol / L) in toluene (x 10 ' 2 ) Lactic acid (%) extracted from the aqueous phase (x Yu ' 2 ) The molar ratio of extracted lactic acid / octol 1 12 0.06 10 ' 10.84 14.0 0.08 thirteen 0.11 - 1.06 9.6 0.11 14 0.220.70 3.2 0,07 fifteen 0.56 - 1.06 1.9 0.11 16 1.12  -. 1.36 1,2 0.14
    * Acidimetric titration.
    Table 4
    Octolomi lactic acid extraction 1,2, 3, 4
    Example Octol Radical The concentration of lactic acid (mol / l) in water The concentration of octol in the organic phase (mol / l) The concentration (x) of extracted lactic acid (mol / L) in the organic phase (x 10 ' 2 ) 17 1 -C11H23 12.10 10 ' 2 (2) 4.8 18 2 -Now - (2) 3.4 19 3 -CgH 19 - (1) 3.8 20 4 -C15NE1 - ........-.......(1) 2,3
    (1) in SSC (2) in SeNb (x) by HPLC
    Compiled by E. Utkina Editor B. Fedotov ^ Tehred M. Morgenthal Corrector P. Gereshi
    Order 3003 Circulation Subscription
    VNIIIPI State Committee for Inventions and Discoveries under the State Committee for Science and Technology of the USSR 113035, Moscow, Zh-35. Raushskaya nab ,, 4/5
    Production and Publishing Combine Patent, Uzhgorod, 101 Gagarin St.
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT8823057A|IT1227895B|1988-12-22|1988-12-22|PROCESS FOR THE RECOVERY OF LACTIC ACID FROM SOLUTIONS THAT CONTAIN IT|
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