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    • 专利摘要:
    The subject of the invention is a method for manufacturing succinic acid crystals, comprising a double crystallization and in which at least one surfactant is used during the first crystallization step. The invention also relates to a composition containing succinic acid crystals, characterized in that it has a color number b, measured in the reference frame L, a, b, less than or equal to 1.00, preferentially less than or equal to 0.90, very preferably less than or equal to 0.80.
    公开号:FR3028864A1
    申请号:FR1461470
    申请日:2014-11-26
    公开日:2016-05-27
    发明作者:Pierrick Duflot；Pierre Lanos；Baptiste Boit；Frederick Dehay；Laurent Rossi
    申请人:Roquette Freres SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to an improved method for recovering succinic acid crystals, one of whose originalities is based on a double crystallization and the use of surfactants during the first crystallization step. Very advantageously, crystals are finally obtained with a color number b in the reference frame (L, a, b) of less than or equal to 1.00, which is the guarantee of products of excellent stability, capable of be used to make polymeric materials without altering their color. Succinic acid (or butanedioic acid) is an organic acid with two carboxyl groups, semi-developed COOH-CH2-CH2-000H, which today has many applications in the fields of cosmetics, food, pharmaceuticals, textiles and in the plastics industry. As an example for this latter application, it can be used as synthesis intermediate in the manufacture of 1,4 butanediol, tetrahydrofuran and gamma-butyrolactone. Initially, succinic acid was produced synthesized by processes centered on raw materials of fossil origin. Alternatives to these methods were then developed, involving bio-sourced products. As such, succinic acid can today be produced from renewable raw materials: in this case through fermentation processes. Various microorganisms are known for their ability to produce succinic acid along this pathway such as Actinobacillus succinogenes, Mannheimia succiniciproducens, Escherichia coli, or Aspergillus piger and Saccharomyces cerevisiae. This being the case, the fermentation products contain substantial quantities of impurities (biomass debris, sugars, amino acids, trace elements, salts, etc.) which are all precursors of coloration likely by their presence, even in trace amounts. in the final product, to influence the quality of the purified succinic acid, and consequently the quality of the polymer synthesized from the purified succinic acid. Those skilled in the art today know many processes for manufacturing succinic acid which implement various steps of purification and / or discoloration. Processes using solvents may be mentioned. This is for example the case of the method described in US 6,265,190 which teaches the recovery of succinic acid by addition of ammonium sulfate in a fermentation medium concentrated in succinate ions. Methanol is then used to purify the succinic acid obtained.
    [0002] Nano filtration is also a recognized technique for purifying succinic acid crystals: CN 101475464 is one example. Processes using ion exchange resins or activated carbon are also known. Thus, US 5,168,055 teaches the reaction between sulfuric acid and a fermentation medium rich in calcium succinate, so as to produce calcium sulfate and succinic acid together. The latter is purified thanks to a strong cationic resin and a weak anionic resin. The document WO 2013/169447 describes the use of non-functionalized resins. The document WO 2009/082050 proposes treating the fermentation medium before crystallization, using activated carbon. Two patent applications filed by the applicant company are also an illustration of the methods mentioned in the previous paragraph: patent applications WO 2011/044151 and WO 2013/144471. It should be noted that the processes described here combine the use of coal active with the implementation of resins, while relying on a double crystallization. There is also a part of the prior art that combines nanofiltration and techniques based on ion exchange resins and / or activated carbon. In this set, mention may be made of the documents US 2012/0289742, CN 101215583, US 2010/0317891 and WO 2014 / 106532. However, to the best knowledge of the applicant company, none of the existing methods for the production of succinic acid is unlikely to lead to a product having a sufficiently low level of coloring impurities, so as ultimately to obtain polymers whose color is not impaired. More specifically, the applicant company has already shown in the patent application WO 2013/144471 that an appropriate colorimetric measurement perfectly reflected the level of impurities responsible for a discoloration of succinic acid, this discoloration being perfectly related to discoloration of the final polymer made with this succinic acid. It is recalled that any colorimetric measurement is based on the opposing color theory which specifies that the responses of the cones (cells of the retina of the human eye responsible for color vision) to the colors red, green and blue are recombined into opposite signals. "Black-white", "red-green" and "yellow-blue" when transmitted to the brain by the optic nerve. This measure is based in particular on the widely used color scales 3028864 3 in the food and polymer industries, called scales "L", "a", "b" HUNTER. We also speak of "reference (L, a, b)". In the aforementioned patent application, it has been demonstrated in particular that the best result is an index "b" of 1.1 (measured in reference L, a, b) for succinic acid crystals, which themselves In addition, it was possible to manufacture a polymer of the PBS (polybutylene succinate) type having an "acceptable colorimetric quality", the latter being measured through the yellow "YI" index (according to the ASTM D1925 standard). However, as a result of numerous works, the applicant company has managed to develop a particularly simple process, leading to succinic acid crystals having a colorimetric index "b", as measured in the reference (L, a, b), never yet reached to be less than or equal to 1.00 and even in some cases less than or equal to 0.90 and very preferably less than or equal to 0.80. This process is based in particular on the introduction of surfactants during a first crystallization step. This is followed by subsequent steps of dissolution of the crystals formed, purification of the solution obtained in particular by treatment with activated carbon and / or ion exchange resins, by a second crystallization step, then by drying and cooling the crystals obtained. Moreover, the process according to the present invention implements 2 crystallization steps. Advantageously, the first crystallization step leads to crystals in the form of "beads", which will be seen to improve certain aspects of the process in question. In particular, the "balls" are contrasted with the "needles" which are the other most common form according to which succinic acid crystals can be obtained. Nevertheless, said beads may be positively defined through a so-called "sphericity" index. This index is throughout the present Application determined visually from the Rittenhouse standard definition of form ("Agglomeration in Industry", W. Pietsch, p.600, Vol 2, 2005 Wiley-VCH), which consists of associating a sphericity index to a visual appreciation of the shape of the particles observed. Figure 1 shows in particular the evaluation grid and award ratings according to this test. In the case of the present invention, the use of surfactant leads to the formation of beads in the form of beads in the first crystallization step, this form being retained subsequently in the process. Here, the expression "crystal beads" having a sphericity index, as measured according to the Rittenhouse test, is understood to mean at least 0.70, preferably at least 0.75, very preferably at least 0.85. . However, it is particularly advantageous to have crystals in the form of beads, and not in the form of needles, insofar as it is easier to separate the first crystallizing mother liquors during a centrifugation or filtration step. . This is particularly reported in the document "Chirality in Industry II: Developments in the Commercial Manufacture and Applications of Optically Active Compounds" (N.A. Collins, G. Sheldrake N., J. Crosby, John Wiley & Sons, 1997 - p 125). It is also known that the crystals in the form of needles are more difficult to rinse after crystallization and the separation between said crystals and the flow of mother liquor: this rinsing step consists of removing the residual mother liquors on the surface of the crystals. In this regard, reference can be made to the documents "Handbook of Industrial Drying" (Arun S. Mujumdar, 4th Edition, CRC Press, p. 1273, 64.1.5 Crystal purity) and Crystal Shape Enhancement: A Processing Solution to a Product Problem (Snyder , RC, Studenar, S., Doherty, MF, AIChE 2006 Annual Meeting). In addition, needle crystals tend to have more impurities in the form of mother liquors, that is, mother liquors that are physically trapped in the crystal. This results in a less good purification power that the surfactant can improve ("Handbook of Industrial Crystallization, 2nd Edition, Allan S. Myerson, p 259). Given the state of the art, such a result is particularly surprising. Indeed, WO 01/07389 is known which teaches the use of surfactants at the time of formation of succinic acid crystals. It is clearly explained in this document that the use of surfactants then leads to the formation of crystals in the form of needles, and not beads. The Applicant Company has also shown that the addition of surfactant makes it possible to recycle a portion of the mother liquors of crystallization and washing at the top of the first crystallization, which improves the yield of recovery of succinic acid and makes it possible to obtain a " b "according to the invention. The recovery yield is defined as the ratio of the mass of succinic acid crystals obtained after drying on the mass of succinic acid contained in the acidified fermentation juice (before step b)). This return can also be expressed as a percentage.
    [0003] Also, not only did the plaintiff company have to select the ad-hoc starting method from all the methods previously available: that described in the documents WO 2011/064151 and WO 2013/144471, based on a double crystallization. Then, it went against what the state of the art taught: by using surfactants in a crystallization stage of succinic acid to improve the quality thereof by greatly reducing the number of impurities, but also to favor the formation of crystals in the form of beads and not needles. It has also shown that the surfactants should be used during the first crystallization step and not during the second crystallization step. The use of surfactants during the second crystallization step again generates needles and values of "b" unsatisfactory). Finally, it has demonstrated that the products obtained had an index "b" (in the reference L, a, b) lower than those obtained through the processes of the prior art involving only one crystallization and the combination of different steps based on ion exchange resins and activated carbon. It has shown that this index is less than or equal to 1.00 advantageously less than or equal to 0.90 and very preferably less than or equal to 0.80. Also, a first object of the present invention is a method of making succinic acid crystals from a succinic acid-containing fermentation medium, comprising the steps of: a) bringing the fermentation medium to a pH between 1.0 and 4.0, b) crystallizing the succinic acid from the fermentation medium resulting from step a) so as to form succinic acid crystals, separating the succinic acid crystals from the mother liquors crystallization and then washing the crystals obtained with water, c) dissolving the succinic acid crystals obtained after step b) in water at a temperature between 30 ° C and 70 ° C so as to obtain a solution containing dissolved succinic acid, d) purifying the succinic acid solution obtained in step c) by treatment with active charcoal and on ion exchange resin, e) crystallizing the succinic acid contained in the solution obtained in step d) so to form crystals of succinic acid, then to separate the crystals of succinic acid from the mother liquors of crystallization and then to wash the crystals obtained with water, f) to dry the crystals of succinic acid at a moisture of less than 0 , 5% and cool to a temperature below 30 ° C, characterized in that before and / or during step b) at least one surfactant is introduced. Preferably, said surfactant is introduced during step b). Throughout the present application, the term "surfactant" means a compound that modifies the surface tension between two surfaces. Said surfactant is preferably chosen from nonionic surfactants, and preferably from polysorbates having an HLB greater than 15, for example of the Tween 20 type, from surfactants based on alkylene oxide block copolymers, preferentially block copolymers. propylene oxide and ethylene oxide, and among those having, in particular, antifoaming properties of the Erol 18 (OUVRIE PMC) or Supra NS 1342 (HYPRO-Food) type, without this list being exhaustive. The first step a) of the process according to the invention therefore consists in bringing the fermentation medium to a pH of between 1.0 and 4.0. The pH may especially be brought to a value of between 1.5 and 3.5 and preferably between 1.5 and 3.0. The fermentation medium typically contains bacteria selected from the bacterial strains of the genus Mannheimia, Anaerobiospirillum, Bacillus, or Escherichia, or among the fungal cells. The fungal strains may be chosen from Saccharomyces cervisiae, Saccharomyces uvarum, Saccharomyces bayanus, Schizosaccharomyces pombe, Aspergillus piger, Penicillium chrysogenum, P. symplissicum, Pichia stipidis, Kluyveromyces marxianus, K. lactis, K. thermotolerans, Yarrowia lipolytica and Candida sonorensis. glabrata, Hansenula polymorpha, Torulaspora delbrueckii, Brettanomyces bruxellensis, Rhizopus orizae, lssatchenkia orientalis or Zygosaccharomyces bailiff. The bacterial strains can be chosen from Mannheimia succiniciproducens, Anaerobiospirillum succiniciproducens Bacillus amylophyllus, B. ruminucola or col. The fermentation medium consists of any fermentation medium capable of generating succinic acid. It may include a carbon source such as glucose, fructose, galactose, xylose, arabinose, sucrose, lactose, raffinose or glycerol.
    [0004] The fermentation may be aerobic or anobasic in nature, or in particular conditions of oxygen deficiency, or results from a combination of these conditions, as described in WO 2009 / 083756. Usually, a carrier agent is then introduced. neutralization in the fermentation medium, such as potassium hydroxide or sodium hydroxide. The regulation of the pH in the desired zone, that is to say between 1.0 and 4.0, preferably between 1.5 and 3.5, very preferably between 2.0 and 3.0, can be carried out by all means accessible to those skilled in the art and likely to change the pH in this area. Dipolar electrodialysis can be mentioned in combination with strong or weak cationic resins (for example resins of the polystyrene divinylbenzene (DVB) type with sulphonic groups or resins based on maleic and fumaric acids), weak cationic resins or strong alone, or acidification by direct addition of hydrochloric acid or sulfuric acid. At the end of step a), the acidified fermentation juice typically has a solids content of between 5% and 10% by weight. This juice is then concentrated by evaporation, at a solids content of between 15% and 50%, preferably between 20% and 40% by weight, very preferably between 30% and 35% by weight. The second step b) of the process according to the invention consists in crystallizing the succinic acid from the fermentation medium resulting from step a) so as to form succinic acid crystals, and then separating the succinic acid crystals from the mother waters of crystallization and finally washing the acid crystals with water. Crystallization occurs according to all methods well known to those skilled in the art, either in batch or continuously and by cooling, in particular by direct contact with the crystallization medium or by flash cooling. The separation between the crystals and the mother liquors can be carried out by any technique well known to those skilled in the art, and in particular by filtration or centrifugation. As for the washing, it is carried out with water, preferably with deionized water, at a temperature of between 15 ° C. and 25 ° C., preferably at about 20 ° C. In addition, it is advantageous to recycle a portion of the mother liquor crystallization and washing at the head of step b). This recycling relates to at most 70% by weight of all the mother liquors and rinse, more preferably from 20% to 60% more preferably from 30% to 50% by weight thereof. This step is especially characterized in that at least one surfactant is introduced during this step and / or before this step, that is to say directly in the fermentation medium before crystallization. The surfactant or surfactants are introduced batchwise or continuously by pump via a metering pump. The amount of surfactant is preferably between 100 ppm to 5000 ppm, preferably between 500 ppm and 3000 ppm, more preferably between 1000 ppm and 2000 ppm, relative to the mass of succinic acid solution from step a) and arriving at the head of step b). The third step c) of the process according to the invention consists in dissolving the succinic acid crystals obtained following step b) in water, preferably deionized water, at a temperature of between 30 ° C. and 70 ° C to obtain a solution containing dissolved succinic acid. The succinic acid is dissolved so as to obtain a solids content of between 5% and 50% by weight of the total weight of said solution, preferably between 10% and 20%. The fourth step d) of the process according to the invention consists in purifying the succinic acid solution obtained in step c) by a treatment with active charcoal and with ion exchange resin. The coal in question may be in the form of a powder, or granular, more preferably in granular form on a column operating in a fixed bed or in a moving bed. The ion exchange resins (IEX) may be strong cationic resins such as polystyrene divinylbenzene (DVB) resins of strong cationic type with weak anionic and sulfonic groups with quaternary or tertiary amine groups. The fifth step e) consists of crystallizing the succinic acid contained in the solution obtained in step d) to recover succinic acid in the form of crystals and to separate crystals of succinic acid and mother liquors of crystallization and wash the resulting succinic acid crystals with water. The steps of crystallization, separation and washing can take place according to the same recommendations as for the first crystallization step. In addition, it is advantageous to recycle all the mother liquors of crystallization and washing step e) at the head of step b).
    [0005] The sixth step f) consists in drying the succinic acid crystals at a humidity of less than 0.5%, preferably less than 0.4%, very preferably less than 0.3% by weight of water relative to dry weight of succinic acid, and to cool them to a temperature below 30 ° C, preferably below 25 ° C. Another subject of the present invention consists of a composition containing succinic acid crystals, characterized in that it has a color number b, measured in the reference frame L, a, b, less than or equal to 1.00 preferably less than or equal to 0.90, very preferably less than or equal to 0.80. This composition is in particular a powder consisting of succinic acid crystals having the value of index "b" above. Throughout the present Application, the measurement of the parameter "b" is carried out as follows: 1) a crystalline powder of succinic acid having less than 1% residual water content is prepared, in particular by drying the powder so as to obtain this content; 2) a sample of said crystalline powder is placed in an oven at 220 ° C for 2 h, 3) the crystalline powder thus treated is crushed and sieved, so that its particle size distribution is as follows, as determined on RETSCH vibrating screen: from 0 to 10%, preferably from 4 to 6% by weight of the particles having a size greater than 500 μm, from 20% to 40%, preferably from 25% to 35% by weight of the particles having a between 200 μm and 500 μm from 50% to 75%, preferably from 55% to 70% by weight of the particles having a size of less than 200 μm, 4) the measurement of the color is carried out in a spectrophotometer of the ground and sieved powder and determine the average value of the index "b" The measurement is carried out 10 times on the same sample which gives an uncertainty of +/- 0.05 on the result. Said measurement is performed on a spectrocolorimeter for measuring the reflection of the wavelength between 400 nm and 700 nm, such as for example the Dataflash 100 marketed by DATACOLOR. (Measuring aperture: 9 mm in diameter "Reading illuminant:" C2 Deg ").
    [0006] The crystals of this composition have in particular a sphericity index, as measured according to the Rittenhouse test, at least equal to 0.70, preferably at least 0.75, and very preferably at least 0.85. Advantageously, the crystals of this composition also have a reducing sugar content of less than 20 ppm, preferably less than 10 ppm, relative to the total weight of anhydrous crystals. The sugars found are typically glucose, mannose, trehalose, isomaltose, maltose, maltulose, gentobiose and panose. The measurement is carried out according to the DIONEX 2004 technical brochure "Analysis of Carbohydrates by High Performance Anion Exchange Chromatography with Pulsed Amperometric Detection (HPAE-PAD)". The following examples illustrate the demand better without limiting its scope.
    [0007] EXAMPLES Example 1 Fermentation A fermentation medium is prepared under the stringent conditions of Example 1 of document WO 2011/064151. Only the devices used differ: the pre-culture step is carried out on a Puntbus 6 L reactor. , the growth phase on a 7 m3 fermenter and the production phase on 2 fermenters of 70 m3. The flow of fermentation juice is then about 1.5 m3 / h. Separation of biomass and fermentation juice and carried out by microfiltration. The latter is carried out at a temperature of 80 ° C in batch followed by a diafiltration step. The module is equipped with 2 casings of 25 m2, ceramic "Kerasep", with a porosity equal to 0.1 The average flow of permeate is about 2 m3 / h with a transmembrane pressure of about 1 bar. Acidification step a) The fermentation juice is treated with a weak cationic resin of AMBERLITE IRC 747 type at a rate of 2 BV / h at 60 ° C. in order to reach a divalent ion concentration of less than 5 ppm. The regeneration of the resins is carried out after having passed a volume of fermentation juice of between 30 and 40 times the volume of resin. The solution obtained is then acidified on an EDB (Electrolytic Electrodialysis bipolar) module Aqualyzer® EDBM EUR40 marketed by the EURODIA company at a pH of about 3.5. The solution is then treated with a strong cationic resin of the PUROLITE C150 type at a flow rate of 2 BV / h and a temperature of 40 ° C. in order to reach a pH of 2.0. The regeneration of the resins is carried out after having passed a volume of fermentation juice of between 15 and 20 times the volume of resin.
    [0008] First crystallization: step b) The acidified solution is concentrated on a vacuum evaporator forced circulation plate sold by the company ALFA LAVAL at a concentration of 35% solids and at a temperature of 80 ° C. It is then crystallized continuously by flash cooling on two stages, each consisting of an external loop vacuum crystallizer marketed by GEA KESTNER. The vacuum in the crystallizers is set so as to obtain a temperature on the first stage of 40 ° C and on the second stage of 20 ° C. The residence time is about 5 hours. In the case of the use of the surfactant, the latter is introduced continuously with the aid of a dosing pump at a flow rate equal to 1200 ppm with respect to the flow of solution which feeds the crystallizer. The surfactant chosen is EROL18 marketed by the company PMC OUVRIE. The crystallized mass is then separated on a SC 1200 batch centrifuge marketed by ROBATEL in order to recover the succinic acid crystals. During this step, the crystals are washed with deionized water at 20 ° C. with an amount equal to 1 kg / kg of crystals. Between 0 and 70% by weight of the mother liquors of crystallization and washing recovered on the centrifuge are recycled. at the top of the evaporator. Step c) Dissolving the crystals Dissolving the succinic acid crystals is carried out at a temperature of 45 ° C. with demineralized water so as to obtain a 10% solution of dry matter. Step d) Purification The activated carbon treatment step is carried out with a CHEMVIRON CPG LF 12x40 granular charcoal on a column operating in a fixed bed. The solution flow rate in the column is set at 0.5 BV / h and the treated solution volume before bed renewal is variable depending on the desired operating conditions and quality. It is between 40 and 500 times the volume of coal in the column. The treatment step on ion exchange resins is carried out at a rate of 2 BV / h at 60 ° C on a strong cationic resin of DOWEX 88 type and then on a weak anionic resin 3028864 13 of Lanxess Lewatit S4528 type. The regeneration of the resins is carried out after passing a volume of solution equal to 40 times the volume of resin. Second crystallization step e) The purified succinic acid solution is concentrated on a falling film vacuum evaporator marketed by WIEGAND at a concentration of 30% solids and a temperature of 80 ° C. It is then crystallized continuously by flash cooling on two stages, each consisting of an external loop vacuum crystallizer marketed by GEA KESTNER. The vacuum in the crystallizers is set so as to obtain a temperature on the first stage of 40 ° C and on the second stage of 20 ° C. The residence time is approximately 7 hours. The crystallized mass is then separated on a SC 1200 batch centrifuge marketed by ROBATEL in order to recover the succinic acid crystals. During this step, the crystals are washed with deionized water at 20 ° C. with a quantity of crystals equal to 1 kg / kg. All the mother liquors of crystallization and washing is recovered on the centrifuge and recycled at the top of the evaporator in step b) Step f) of drying The product is dried on a rotary drier so as to obtain a humidity residual equal to 0.3% by weight of water relative to the total weight of product, then cooled on a fluidized bed at a temperature of 25 ° C. EXAMPLE 2 Fermentation A fermentation medium is prepared under the strict conditions of Example 5 of the document WO 2011/064151. Only the devices used differ: the pre-culture step is carried out on a Puntbus 6 L reactor, the growth phase on a 7 m3 fermenter and the production phase on 2 fermentors of 70 m3.
    [0009] 3028864 14 The separation of biomass and fermentation juice and carried out by microfiltration. The latter is carried out at a temperature of 80 ° C in batch followed by a diafiltration step. The module is equipped with 2 25 m2 ceramic Kerasep casings with a porosity equal to 0.1 μm. The average permeate flow rate is about 2 m 3 / h with a transmembrane pressure of about 1 bar. Step a) Acidification The fermentation juice is then treated on a strong cationic resin PUROLITE C150 type at a rate of 2 BV / h and a temperature of 40 ° C to reach a pH of 2.0. The regeneration of the resins is carried out after having passed a volume of fermentation juice of between 15 and 20 times the volume of resin. All the other steps b) to f) are carried out as described in Example 1. EXAMPLE 3 example corresponds to carrying out tests according to or outside the invention (with or without surfactant), in a double crystallization process. Six attempts were made to evaluate the influence of two parameters: the value of the ratio between the volume of solution treated and the volume of coal in step c) ("Bed Volume" or BV = Volume of solution / volume of activated carbon) and the% of mother liquors of crystallization recycled in step b). Tests No. 1 to 3 are carried out according to the protocol given in Example 1 and without surfactant. Tests Nos. 4 to 6 are carried out according to the protocol given in Example 1 and without surfactant. Tests No. 7 and 8 are carried out according to the protocol given in Example 1, with 1200 ppm of EROL 18 as a surfactant. Tests Nos. 9 to 11 are carried out according to the protocol given in Example 2, with 1200 ppm of EROL 18 as a surfactant.
    [0010] 3028864 The measurement of the "b" index is carried out on an average sample: a sample is taken every 12 hours for 15 days, then all of these samples are mixed together. Tests BV% recycling Index Yielding mother liquor% "b"% total (ppm) 1 50 0 1.80 81 58 2 100 0 2.50 80 98 3 50 50 4.20 89 158 4 50 0 1.75 80 41 5 100 0 2.10 79 59 6 50 50 3.90 90 157 Table 1 Tests BV% Recycling Index Yield Sugars for mother liquors "b"% total (ppm) 7 300 0 0.71 82 4 8 300 50 0.91 90 16 9 300 0 0.65 81 2 10 300 50 0.87 90 10 11 300 60 0.95 94 16 Table 2 The comparison between Tables 1 and 2 clearly shows the positive influence of the surfactant on the values of the index "b". In addition, one can play both on the value of this index and on the yield of the succinic acid process, through the recycling of all or part of mother liquors of first crystallization. Finally, Figure 2 shows the morphology of the crystals obtained without surfactant (test No. 1) which are needles while Figure 3 (test No. 7) shows beads. These photos were made on a LEICA EZ4HD microscope.
    [0011] EXAMPLE 4 This example corresponds to carrying out tests outside the invention (with or without surfactant), in a single crystallization process. During the various tests, crystals are taken before step c) of dissolution in some of the tests of the preceding example. The crystals are then dried on a RETSCH laboratory fluidized bed to obtain a moisture content of 0.3% by weight of water relative to the total product weight. Tests Index '13 '1a 9.01 7a 5.05 4a 8.27 9a 4.39 Table 3 The results in Table 3 demonstrate that single-crystallisation processes, in the presence of surfactant or not, do not lead to values of' b ' satisfactory. Example 5 For tests Nos. 1, 4, 8 and 10 the stability of the process was tested by operating the process continuously over several days. Samples were taken 24 hours apart for analysis. The values "b" thus determined are summarized in Table 4 below.
    [0012] 3028864 17 Days Trial 1 Trial 4 Trial 8 Trial 10 1 1.43 1.52 0.97 0.95 2 2.10 1.13 0.96 0.81 3 1.75 1.90 0.82 0.85 4 1.60 2.04 0.97 0.78 5 2.56 1.38 0.82 0.74 6 2.13 1.54 0.78 0.79 7 1.50 1.52 0.85 0 , 74 8 2.46 1.68 0.82 0.71 9 2.05 1.41 0.89 0.87 10 1.99 1.78 0.92 0.81 11 1.81 1.65 0, 78 0.79 12 1.49 1.98 0.75 0.91 13 1.79 2.70 0.82 0.94 14 1.84 2.14 0.89 0.91 15 1.96 1.85 0.91 0.85 Mean value 1.92 1.75 0.86 0.83 Standard deviation 0.37 0.38 0.07 0.08 Table 4 This table clearly establishes the stability of the process according to the invention, the measurements being much more reproducible than in the case of the prior art.
    权利要求:
    Claims (4)
    [0001]
    CLAIMS 1 - Process for producing succinic acid crystals from a fermentation medium containing succinic acid, comprising the steps of: a) bringing the fermentation medium to a pH of between 1.0 and 4.0 b) crystallizing the succinic acid from the fermentation medium resulting from step a) so as to form succinic acid crystals, then separating the succinic acid crystals from the mother liquors of crystallization and then washing the crystals obtained with water, c) dissolving the succinic acid crystals obtained following step b) in water at a temperature between 30 ° C and 70 ° C to obtain a solution containing succinic acid dissolves, d) purifying the succinic acid solution obtained in step c) by treatment with active charcoal and ion exchange resin, e) crystallizing the succinic acid contained in the solution obtained in step d) to form succinic acid crystals Then, separate the crystals of succinic acid from the mother liquors of crystallization, then wash the crystals obtained with water, f) dry the crystals of succinic acid at a moisture of less than 0.5% and cool them to a temperature less than 30 ° C, characterized in that before and / or during step b) at least one surfactant is introduced, preferably during step b).
    [0002]
    2 - Process according to claim 1, characterized in that said surfactant is chosen from nonionic surfactants, and preferably from polysorbates having an HLB greater than 15, or from surfactants based on alkylene oxide block copolymer.
    [0003]
    3 - Method according to one of the preceding claims, characterized in that the first step a) is therefore to bring the fermentation medium to a pH between 1.5 and 3.5 and preferably between 2.0 and 3.0. 3028864
    [0004]
    4 - Process according to one of the preceding claims, characterized in that the fermentation medium contains bacteria selected from bacterial strains of the genus Mannheimia, Anaerobiospirillum, Bacillus, or Escherichia, or among the fungal strains. - Method according to one of the preceding claims, characterized in that in the second step b) the crystallization occurs either in batch or continuously and by cooling. 6 - Process according to one of the preceding claims, characterized in that the separation of the crystals of the mother liquors is carried out by filtration or centrifugation. 7 - Method according to one of the preceding claims, characterized in that the washing is carried out with water, preferably with demineralised water, at a temperature between 15 ° C and 25 ° C, preferably at about 20 ° C . 8 - Process according to one of the preceding claims, characterized in that a portion of the mother liquor crystallization and washing is recycled at the head of step b). 9 - Process according to one of the preceding claims, characterized in that step c) consists in dissolving the succinic acid crystals in water so as to obtain a solids content of between 5% and 50% by weight of the total weight of said solution, preferably between 10% and 20%. - Method according to one of the preceding claims, characterized in that during step d) the activated carbon is in powder or granular form, more preferably in granular form. 11 - Process according to one of the preceding claims, characterized in that during step e) is recycled all the mother liquor crystallization and washing at the head of step b). 12 - Method according to one of the preceding claims, characterized in that step f) comprises drying the succinic acid crystals at a moisture of less than 0.5%, preferably less than 0.4%, very preferably less than 0 , 3% by weight of water relative to the dry weight of succinic acid, and to cool them to a temperature below 30 ° C, preferably below 25 ° C. - Crystals of succinic acid, characterized in that they have a color index b, measured in the standard L, a, b, less than or equal to 1.00, preferably less than or equal to 0.90, very preferably less than or equal to 0.80. 14 - Composition containing succinic acid crystals, characterized in that it has a color number b, measured in the standard L, a, b, less than or equal to 1.00, preferably less than or equal to 0.90, very preferably less than or equal to 0.80. 15. Composition according to the preceding claim, characterized in that it has a reducing sugar content of less than 20 ppm, preferably less than 10 ppm, relative to the total weight of anhydrous crystals.
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    US20170362157A1|2017-12-21|
    ES2703198T3|2019-03-07|
    EP3224232B1|2018-09-26|
    BR112017010932A2|2018-01-09|
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    CA2968485A1|2016-06-02|
    CN107001224B|2021-07-20|
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    法律状态:
    2015-11-30| PLFP| Fee payment|Year of fee payment: 2 |
    2016-05-27| PLSC| Publication of the preliminary search report|Effective date: 20160527 |
    2016-11-30| PLFP| Fee payment|Year of fee payment: 3 |
    2017-11-30| PLFP| Fee payment|Year of fee payment: 4 |
    2018-11-29| PLFP| Fee payment|Year of fee payment: 5 |
    2019-11-29| PLFP| Fee payment|Year of fee payment: 6 |
    2020-11-30| PLFP| Fee payment|Year of fee payment: 7 |
    2021-11-30| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1461470A|FR3028864B1|2014-11-26|2014-11-26|PROCESS FOR RECOVERING SUCCINIC ACID CRYSTALS WITH IMPLEMENTATION OF SURFACTANTS DURING CRYSTALLIZATION, CRYSTALS OBTAINED AND USES THEREOF|
    FR1461470|2014-11-26|FR1461470A| FR3028864B1|2014-11-26|2014-11-26|PROCESS FOR RECOVERING SUCCINIC ACID CRYSTALS WITH IMPLEMENTATION OF SURFACTANTS DURING CRYSTALLIZATION, CRYSTALS OBTAINED AND USES THEREOF|
    PCT/FR2015/053226| WO2016083749A1|2014-11-26|2015-11-26|Method for recovering succinic acid crystals using surfactants during crystallisation, and resulting crystals|
    CN201580064285.8A| CN107001224B|2014-11-26|2015-11-26|Method for recovering succinic acid crystals using surfactants in crystallization process and crystals produced|
    ES15808746T| ES2703198T3|2014-11-26|2015-11-26|Procedure for recovering succinic acid crystals using surfactants during crystallization, and crystals obtained|
    EP15808746.0A| EP3224232B1|2014-11-26|2015-11-26|Method for recovering succinic acid crystals using surfactants during crystallisation, and resulting crystals|
    US15/529,648| US20170362157A1|2014-11-26|2015-11-26|Method for recovering succinic acid crystals using surfactants during crystallisation, and resulting crystals|
    CA2968485A| CA2968485A1|2014-11-26|2015-11-26|Method for recovering succinic acid crystals using surfactants during crystallisation, and resulting crystals|
    BR112017010932-8A| BR112017010932B1|2014-11-26|2015-11-26|crystals of succinic acid and its production process, as well as a composition containing said crystals|
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