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    • 专利摘要:
    The process for producing polyhydroxyalkanoates or PHAs from volatile fatty acid (VFA) molecules, known as precursors, produced by anaerobic fermentation from fermentable biomass, characterized in that it comprises at least the following steps: extracting the volatile fatty acid (VFA) molecules, without interruption of the fermentation, by an extraction means chosen from means which are, at least, insoluble in the fermentation medium, b) collecting, outside the reactor fermentation, the volatile fatty acid molecules (AGV) once extracted, - c) synthesize, by halogenation, from a type of volatile fatty acid (VFA) chosen from the volatile fatty acids collected at the stage b) and defined according to the desired PHA type, a given α-halogenated acid, - d) synthesize from this α-halogenated acid molecules of a given α-hydroxy acid by reaction with a base, - e) polymerize at from α-hydroxyacid e obtained a polyhydroxyalkanoate (PHA) defined.
    公开号:FR3033168A1
    申请号:FR1551672
    申请日:2015-02-27
    公开日:2016-09-02
    发明作者:Regis Nouaille；Jeremy Pessiot；Marie Thieulin
    申请人:Afyren SAS；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to a process for the production of polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass. BACKGROUND OF THE INVENTION Subsequently, for ease of reading, the polyhydroxyalkanoates will be designated by their acronym: PHA. This family comprises several molecules, depending on the number of carbons. PHAs are thermoplastic polyesters which can be produced by microbial fermentation from sugars of plant origin, in particular corn starch or vegetable waste. Microorganisms produce PHA when deficiency conditions occur in certain metabolites associated with excess carbon supply. In other words, the microorganisms then accumulate the carbon, coming from the sugars, in the form of PHA granules. PHAs are used, for example, as a constituent material for packaging or in the medical field as suture material. They replace the polymers derived from petroleum. Fermentation processes using selected pure strains of microorganisms and a specific substrate to produce PHAs are known. Such a solution is difficult to exploit on an industrial scale for an acceptable production cost. EP-A-2 749 650 also discloses a process suitable for industrial use. The substrate used is derived from effluents and enriched with volatile fatty acids (VFAs), known to be precursors of PHAs. By using a bacterial consortium and alternating growth phases of biomass and deficiency phases, in a controlled manner, bacterial growth and PHA production are stimulated. However, such a method involves a precise control of the fermentation conditions and a suitable treatment for extracting the PHAs produced, which implies a relatively heavy installation. Moreover, such extraction can not be done continuously and it does not allow production of any type of PHA. Another disadvantage of this process is its specificity: it can produce only microbial PHA, that is to say produced by microorganisms.
    [0002] The invention aims more particularly at remedying these drawbacks by proposing a process for producing PHA making it possible to produce various types of PHAs, easily and without the constraints related to the production methods known from the state of the art. To this end, the subject of the invention is a process for producing polyhydroxyalkanoates or PHAs from volatile fatty acid (VFA) molecules, referred to as precursors, produced by anaerobic fermentation from fermentable biomass, characterized in that it comprises at least the following steps: a) extracting the volatile fatty acid (VFA) molecules, without interruption of the fermentation, by an extraction means chosen from means which are, at least, insoluble in the medium fermentation, - b) collect, outside the fermentation reactor, the volatile fatty acid (VFA) molecules once extracted, - c) synthesize, by halogenation, from a type of volatile fatty acid (AGV) ) selected from the volatile fatty acids collected in step b) and defined according to the desired PHA type, a given α-halogenated acid, - d) synthesize from this α-halogen acid molecules of a- hydroxyacid given by reaction with a base, - e ) polymerizing from the α-hydroxy acid obtained a polyhydroxyalkanoate (PHA) defined.
    [0003] Thus, such a method makes it possible to couple a phase of continuous production of precursors by microorganisms with a synthesis phase carried out without fermentation, which allows easy control of the various parameters, while allowing greater variability in the type of polyhydroxyalkanoates (PHAs) produced.
    [0004] Such a process makes it possible to dispose, continuously, precursors, namely volatile fatty acids, while preserving the production capacity of the microorganisms present in the bioreactor. Indeed, the extraction and collection steps a) and b) not only make it possible to extract and continuously collect the volatile fatty acid molecules produced in the fermentation reactor, but also to preserve the microorganisms responsible for this process. production. Indeed, extraction, and de facto collection, is carried out under conditions that are at least non-lethal for all the microorganisms, that is to say in biocompatible extraction and collection conditions, that being the case. that the extraction preserves the activity of the microorganisms and that the collection is carried out outside the fermentation reactor. In this way, the problems associated with the accumulation of metabolites in the fermentation reactor are overcome, for example acidification of the fermentation medium by accumulation of volatile fatty acids produced which are harmful to the microorganisms. The amount and activity of the microorganisms are maintained at a high level, close to the initial level, throughout the fermentation cycle. By having a continuous and regular production of AGV, we have a source of varied precursors easily usable and quickly. In the process which is the subject of the invention, this use is carried out, starting from stage c), by chemical synthesis and therefore under easily controllable and modifiable conditions, this also offering a great variability in the type of molecules. synthesized. Indeed, during step c), according to the VFA retained for carrying out the halogenation, a given type of α-halogenated acid is obtained and therefore, subsequently, a defined type of α-hydroxy acids and therefore a given type of a-PHA. The invention also makes it possible to combine several α-hydroxy acids thus obtained in order to produce heteropolymers during the last stage of the process. There are several types of PHAs of interest for industrial, cosmetic, medical, food or other uses. By way of example, mention may be made of polyhydroxybutyrate or PHB, poly (3-hydroxybutyrate-co3-hydroxyvalerate) or PHBV. It is also possible, among the types of PHAs, to produce glycolic polyacid 3033168 4 or PGA or poly lactic acid or PLA, knowing that, by the method known from the state of the art, it is not possible to produce directly PLA, the latter must be polymerized from a production by fermentation of lactic acid. In other words, by virtue of the invention, it is possible to synthesize several types of PHA, namely of homo, co or heteropolymeric types, in a regular and controlled manner, from a biobased substrate. combining a biological production with a chemical production. Such a method makes it possible, during the anaerobic fermentation phase, to use fermentable biomass. By fermentable biomass, is meant here an organic substrate, preferably non-food, obtained from waste, by-products and co-products formed from organic materials, that is to say biomass, resulting from human activities, that they are domestic, industrial, agricultural, forestry, aquaculture, agro-industrial, resulting from breeding or other. By way of non-limiting example, mention may be made, as an organic substrate, of manure, the organic fraction of domestic refuse, slaughterhouse by-products, cellulosic or lignocellulosic residues originating from agro-industry, such as those derived from sugar cane (bagasse), sunflower or soy. By anaerobic fermentation is meant a fermentation carried out under anaerobic conditions by microorganisms, eukaryotic or prokaryotic, such as bacteria, fungi, algae or yeasts. According to advantageous but non-obligatory aspects of the invention, such a method may comprise one or more of the following characteristics: in step c), the halogenated compound used is bromine. In step c), the halogenated compound used is different from the dibrome. In step c), acetic anhydride is used in a molar percentage relative to the volatile fatty acid close to 12%. In step c), an anhydride corresponding to the volatile fatty acid (VFA) to be halogenated is used. In step c), the temperature at which the bromination reaction is carried out is 20 ° C to 40 ° C below the boiling point of the volatile fatty acid. - In step d), the base used is sodium hydroxide. In step d), the sodium hydroxide is in equimolar amount with the α-halogenated acid. 5 - In step d), the reaction of the α-halogen acid with the sodium hydroxide is carried out between 20 ° C. and 120 ° C., advantageously between 50 ° C. and 90 ° C. - In step d), the reaction of α-halogenated acid with sodium hydroxide is optimal for a temperature of 50 ° C if the halogenated acid has at least four carbons and a temperature of 90 ° C if the halogenated acid has less than four carbons.
    [0005] The invention will be better understood and other advantages thereof will appear more clearly on reading the description of several embodiments of the invention, given by way of non-limiting example. The various steps of the method are now described with reference to several embodiments, it being understood that the steps known per se are not detailed. First of all, the substrate used is advantageously untreated, namely that it has not undergone any physicochemical or enzymatic pretreatment. This substrate is mainly constituted by fermentable biomass. By way of nonlimiting complementary example, mention may be made of agricultural or plant waste (straw, bagasse, maize, grass, wood, mowing matter) paper waste (cardboard, paper), agro-food waste, waste paper slaughterhouses, the organic fraction of household waste, livestock manure (manure, manure, droppings), algae, aquaculture waste, forestry waste or fermentable co-products of the cosmetics industry. Some substrates contain organic molecules, such as organic acids, which will not, or only marginally, influence the fermentation process. On the other hand, these molecules can be found in the fermentation medium and participate, for example, in the production of the defined final organic molecules.
    [0006] As a reminder, and in a known manner, the substrate is introduced into a fermentation reactor, known per se and dimensioned for the desired production, whether the latter is on a laboratory scale to carry out tests or on an industrial scale in the case of a production. In other words, the fermentation reactor or bioreactor has a volume ranging from a few liters to several hundred cubic meters, as needed. Microorganisms are advantageously introduced initially into the fermentation reactor, in an amount sufficient to start the fermentation. The microorganisms are advantageously inoculated in the form of a consortium. By the term consortium, is meant a mixture or mixture of eukaryotic and prokaryotic microorganisms, whether bacteria, yeasts, fungi or algae. These different microorganisms come mainly from natural ecosystems, advantageously but not exclusively, anaerobic ecosystems such as, by way of non-limiting example, the anaerobic zone of aquatic environments such as the anoxic zone 15 of certain lakes, soils, marshes , sewage sludge, ruminant rumen or termite gut. It should be kept in mind that the qualitative and quantitative distribution of the different types and species of microorganisms in the consortium is not precisely known and above all can vary significantly. It turns out that this qualitative and quantitative diversity surprisingly provides a robustness and adaptability of the microorganisms which make it possible to ensure optimal use of the substrates, whatever the composition of the latter and this under variable fermentation conditions. Moreover, because the substrate is used as it is, that is to say, it is not sterilized or, more generally, that it is not rid of the microorganisms that it contains beforehand. its introduction into the bioreactor, it turns out that the microorganisms endemic to the substrate are, de facto, incorporated into the consortium or at least associated with the latter in the bioreactor. Furthermore, the fermentation takes place under anaerobic conditions, more specifically when the redox potential is less than -300mV, advantageously between 3033168 7 -550mV and -400mV and when the pH is less than 8, preferably between 4 and 7. The fermentation is, advantageously, limited to the production of so-called precursor fermentative metabolites, namely volatile fatty acids or AGV having from two to eight carbons, preferably from two to six. A reaction similar to the acidosis phenomenon encountered in ruminants is thus induced while having a methane production close to zero. Methane is usually one of the final fermentative metabolites obtained during anaerobic fermentation by microorganisms from natural ecosystems. Fermentation leads, initially, to the formation of volatile fatty acids having mainly two to four carbons such as, for example, acetic acid, propionic acid and butyric acid. Less volatile fatty acids with a long chain, and thus greater than four carbons, such as valeric and caproic, heptanoic or octanoic acids, are also obtained. By continuing the fermentation and / or increasing the amount of microorganisms in the bioreactor, if necessary with selected microorganisms, it is possible to promote the production of long-chain carbon-based VFA, thus greater than four carbons. In other words, the volatile fatty acids produced in quantity during the fermentation are essentially volatile fatty acids of two to six carbons. The fermentation is in all cases conducted to ensure the production of AGV in the liquid phase. Typically, the fermentation period is between 1 and 7 days, preferably between 2 and 4 days. The concentration of metabolites obtained in the fermentation medium at the end of this period is variable, but, for volatile fatty acids, is generally of the order of 10 to 20 g / L, depending on the volatile fatty acids, being understood that under certain conditions it may be greater than 35 g / l, for example close to 50 g / l. At the end of the fermentation step, the fermentation medium is at an acidic pH, which is generally between 4 and 6, because of the presence of volatile fatty acids in the fermentation medium. When the production of AGV reaches a defined quantity, generally during the steady state phase of the fermentation, the step a) of extraction of the molecules is initiated. Preferably, but not obligatory, this defined amount of AGV corresponds to a slowing down of the growth of the microorganisms, therefore in the vicinity of a threshold of inhibition of the microorganisms. The extraction means is selected from extraction means, liquid or solid, which are at least insoluble in the fermentation medium. When the extraction means is liquid, so when it is a solvent, preferably, the density of the solvent is lower than that of the fermentation medium. More specifically, the extraction is carried out with an extraction means, solid or liquid, the conditions of which make it possible to preserve the activity and / or the growth of the microorganisms under the fermentation conditions prevailing in the plant. bioreactor and which are defined to carry out the fermentation. The AGV molecules are preferably extracted by molecular families and then advantageously separated individually by techniques known per se. When molecules such as volatile fatty acids are extracted from the fermentation medium, de facto acidification of the fermentation medium is reduced by these acids. Thus, the fermentation, and therefore the production of metabolites, continues under conditions similar to the initial conditions, the fermentation medium remaining slightly acidic. The extraction is advantageously carried out continuously or at least sequentially, for example with extraction every 12 hours. In other words, it is possible to continue the fermentation while extracting the metabolites produced, either as they are produced or on a regular basis. The liquid-liquid extraction with organic solvents as extraction means is the extraction mode, preferably but not exclusively, retained. In one embodiment, the extraction is not carried out in a separate member of the fermentation reactor but directly in the latter. The solvent is, for example, introduced by a bubbler type device located in the lower part of the reactor. Alternatively, an extraction member is coupled with the reactor, a communication with the fermentation medium being arranged.
    [0007] After the extraction, the collection step b) is implemented. During this step, the AGVs are collected from the organic phase by techniques known per se, such as distillation or evaporation. The collection is carried out either in a mixture of AGV or by type of AGV. It is understood that the choice of AGV or AGV mixture is determined by the type of final molecule (s) desired. For this, the collection conditions, typically the evaporation or distillation parameters, are adapted. Once this collection step has been performed, the following step c) is carried out. This is, advantageously but not exclusively, carried out following the collection step.
    [0008] Alternatively, it is carried out at another time and / or another place, the produced AGV being transported and / or stored, according to techniques known per se. This halogenation step consists of reacting a halogen with an AGV to produce an α-halogen acid which is a type of highly reactive molecule and therefore of particular interest for producing other molecules. Such a reaction, known per se, is carried out by addition of bromine, this preferably, it being understood that it is possible to use the other halogens, namely chlorine, fluorine or iodine, or halogenated molecules such as phosphorus trihalides, halogenated acids or acyl halides. The bromine was retained because a brominated α-haloacid is more reactive than the corresponding chlorinated α-haloacid, a carbon-brominated bond being easier to break than a carbon-chlorine bond. In addition, the bromine is easier to handle because of its liquid form. To carry out the synthesis of α-bromo acid, the route using an anhydride, here acetic anhydride, and pyridine was retained. It is conceivable that other synthetic routes, for example with polyphosphoric acid or phosphorus trihalides, are known per se. Tests with polyphosphoric acid were conducted but the results were inconclusive, among other things because of the high viscosity of this compound which makes handling difficult.
    [0009] Chlorination tests have also been conducted by the applicant for the synthesis of α-chlorinated acids, for example with trichloroisocyanuric acid. The results obtained are inferior in terms of efficiency and ease of implementation to those obtained with bromine.
    [0010] The synthetic route employing an anhydride corresponding to the volatile fatty acid that is to be halogenated is of interest and makes it possible to obtain an α-halogen acid, here an α-bromo acid of a given type. The use of acetic anhydride with other VFAs and / or a mixture of two to six carbons of AGV makes it possible to obtain a mixture of α-halogenated acids of two to six carbons.
    [0011] Trials using acetic acid (two-carbon AGV), propionic acid (three-carbon AGV), butyric acid (four-carbon AGV), caproic acid (VFA) six carbons) and an AGV mixture of two to six carbons were made by varying the amount of acetic anhydride as well as other parameters such as temperature.
    [0012] During the various tests, a protocol is respected. It is a preliminary phase of refluxing an initial mixture of AGV, acetic anhydride and pyridine. Then, during the actual bromination, the bromine is added slowly, for several hours, at a temperature below the boiling point of the mixture, once the bromine is added, the mixture is brought to reflux again before being Cooled. At the end of the reaction, advantageously, water is added to destroy the anhydride present. The α-bromo acid is then extracted by different methods, depending on the acid. It is for example, distillation, separation extraction. The initial temperature, to bring the mixture to reflux, is between 12000, for AGV with two carbons and 200 ° C, for AGV with six carbons. The bromination temperature ranges from 80 ° C to 180 ° C, whereas the VFAs have from two to six carbons. The time of the bromination reaction, thus de facto the time of addition of the dibroma, varies from about one hour for the six carbons AGV to about four hours for the two carbons AGV.
    [0013] 3033168 11 Two, three, four, six carbons volatile fatty acid bromination tests were carried out as well as a test on a mixture of volatile fatty acids: Acetic acid (02): 0.53 mol Propionic acid (03) ): 0.53 mol 5 Butyric acid (04): 0.53 mol Caproic acid (06): 0.24 mol AGV mixture from 02 to 06: 0.54 mol. The amount of bromine added is 0.21 mol or 0.11 mol so that the volatile fatty acid is in excess. Advantageously, the Applicant has found that a molar ratio of 2: 1 in favor of AGV is optimal. The amount of anhydride added is, for each acid, 0.06 mol for one test and 0.03 mol for another test. The AGV mixture comprises acetic (02), propionic (03), butyric (04), valeric (05) and caproic (06) acids. The reflux temperatures during the preliminary phase vary according to AGV: 120 ° C for acetic acid; 120 ° C and 140 ° C for some tests with propionic acid; 150 ° C and 160 ° C for butyric acid; 200 ° C for caproic acid and 180 ° C for mixing. The bromination temperatures for the various tests with each acid are less than 10 ° C to 50 ° C, and preferably 200 to 40 ° C, at reflux temperatures, thus boiling the volatile fatty acid. The yields and purities of the α-brominated acids obtained at the end of the various tests are given below in Table 1. The AGVs are, for simplicity, designated by the number of carbons.
    [0014] Acids Quantity Amount Temperature Time Temperature Yield Anhydride Purity reflux bromination (0/0) (0/0) (mol) (h) (° C) bromination (° C) 02 0.06 2.2 120 100 87 98 02 0.03 4 120 90 80 93 03 0.06 3 120 80 to 110 77 80 03 0.03 3 140 125 100 93 04 0.06 1.25 160 140 80 95 04 0.03 3 150 110 to 140 100 96 06 0.03 0.92 200 150 100 NC mixture 0.06 1.5 180 130 100 NC TABLE 1 The analysis and the yield calculations were carried out by analytical techniques known per se, namely by NMR. (Nuclear Magnetic Resonance) and HPLC (High Performance Liquid Chromatography). Yields are defined by the amount of AGV consumed. The applicant has found that the reaction rate, illustrated by the discoloration of the reaction mixture after addition of the dibrome, is faster when the amount of anhydride is greater, the purity being little affected. Nevertheless, it is appropriate that the temperature of the two stages, preliminary and bromination, be optimal.
    [0015] For this, the Applicant has noted that a bromination temperature below the boiling point of the volatile fatty acid is necessary, without being too far from this temperature. The various tests have made it possible to define a bromination temperature of about 10 ° C. to 50 ° C. lower than the temperature (Munition of the volatile fatty acid and, advantageously, less than 20 ° C. allowed, other condition being identical, to obtain an optimal yield, typically between 60% and 100% with a reaction time of 1h to 4h.
    [0016] As regards the role of acetic anhydride, in view of the results in the table, it appears that the molar percentage of anhydride relative to the AGV must be close to 12% for an optimal bromination reaction, it being understood that a percentage between 5% and 20% is acceptable.
    [0017] From the α-brominated acids obtained, or more precisely from a given α-bromo acid, the synthesis is then carried out, during step d), of an α-hydroxylated acid, also called α- hydroxy acid, given. For this we add a base. Advantageously, but not exclusively, it is soda. Tests were carried out by the applicant by substitution of sodium hydroxide (NaOH) on α-bromoacids, namely on bromoacetic acid, α-bromopropionic acid, α-bromobutyric acid, on -bromocaproic acid and a mixture of α-bromoacids having from two to six carbons. Such a substitution makes it possible to obtain α-hydroxy acids having a carbon chain of, respectively, two, three, four, five or six carbons, namely glycolic acid, lactic acid, α-hydroxybutyric acid, α-hydroxyvaleric acid or α-hydroxycaproic acid. These α-hydroxy acids are among the most used for, after polymerization, producing cosmetics or food packaging. It is easily understood that the process which is the subject of the invention makes it possible to produce other types of acids which allow the polymerization of other types of PHA. By way of example, mention may be made of α-hydroxydecanoic acid. For the various tests, the protocol consisted in refluxing an equimolar mixture of soda and α-brominated acid for a period of one to two hours. The heating temperature ranges from 80 ° C to 120 ° C. Samples at regular intervals have shown that the yield is between 60% and 100% and advantageously between 80% and 100% for acids having at least three carbons. It also appears that optimal yield is achieved during the gradual rise in temperature for compounds with more than four carbons. The Applicant has thus found that the yield is optimal when the temperature remains below a temperature from which there is a beginning of degradation of the α-hydroxy acid, this temperature being de facto lower than the temperature of 30.degree. boiling of the α-brominated acid. In particular, the Applicant has surprisingly found that the temperature at which the optimum efficiency is achieved is between 20 ° C and 120 ° C, preferably between 50 ° C and 90 ° C. The Applicant has found that, unexpectedly, the temperature at which the optimum yield is reached is close to 50 ° C for α-brominated acids having at least four carbons and close to 90 ° C for α-brominated acids having less than four carbons, it being understood that, for the α and β-hydroxylated acids, a temperature above 100 ° C entails degradation of the compound. Indeed, once the optimum efficiency has been achieved, an increase in the reaction time gives only a minimal gain, for example a gain of 4% in efficiency for a reaction time of two hours instead of one hour for one hour. four-carbon α-bromo acid.
    [0018] Table 2 below shows some of the tests carried out. TABLE 2 Halo Acid Mole Acid Mole NaOH Temperature Reflux Yield (0/0) Heating (h) (° C) BrC2 0.05 0.05 110-120 2 80 BrC2 0.05 0.05 110-120 2 85 BrC3 0.05 0.05 110-120 2 80 BrC4 0.05 0.05 110-120 2 100 BrC4 0.05 0.05 110-120 1 96 BrC6 + BrC2 0.041 + 0.0019 0.043 100 1 95 BrC3 + BrC2 0.05 + 0.014 0.064 100 2 62 Mixture 0.042 0.042 80 2 83 BrC2-BrC6 3033168 The analysis and yield calculations were carried out by the analytical techniques of NMR and HPLC, already mentioned. The yields are defined with respect to the amount of initial halogenated acid.
    [0019] The last step of the process is to polymerize the corresponding polyhydroxyalkanoate or PHA from the resulting α-hydroxy acid. By way of example, mention may be made of poly lactic acid or PLA, which is used in food packaging, glycolic polyacid or PGA used in the medical field as suture material. PLA is derived from lactic acid obtained from α-bromopropionic acid. PGA 10 is derived from glycolic acid obtained from bromoacetic acid. This polymerization, known per se, is advantageously carried out in three ways: by ring-opening polymerization, by solid-state polymerization or by direct polycondensation. This polymerization is followed by a recovery of the known PHA.
    权利要求:
    Claims (10)
    [0001]
    CLAIMS 1.- A process for producing polyhydroxyalkanoates or PHAs from volatile fatty acid (VFA) molecules, called precursors, produced by anaerobic fermentation from fermentable biomass, characterized in that it comprises at least the following stages: a) extracting the volatile fatty acid (VFA) molecules, without interruption of the fermentation, by an extraction means chosen from means which are, at least, insoluble in the fermentation medium, - b) collecting, outside of the fermentation reactor, the volatile fatty acid molecules (AGV) once extracted, - c) synthesize, by halogenation, from a type of volatile fatty acid (VFA) chosen from the volatile fatty acids collected at the same time. step b) and defined according to the desired PHA type, a given α-halogenated acid, - d) synthesizing from this α-halogen acid molecules of a given α-hydroxy acid by reaction with a base, - e) polymerize from the Hydroxy-acid obtained a polyhydroxyalkanoate (PHA) defined.
    [0002]
    2. A process according to claim 1, characterized in that, in step c), the halogenated compound used is bromine.
    [0003]
    3. A process according to claim 1, characterized in that, in step c), the halogenated compound used is different from the dibrome.
    [0004]
    4. A process according to claim 1 or 2, characterized in that in step c), acetic anhydride is used in a molar percentage relative to the volatile acid close to 12%.
    [0005]
    5. A process according to claim 1 or 2, characterized in that in step c), an anhydride corresponding to the volatile fatty acid (AGV) to be halogenated. 3033168 2
    [0006]
    6. A process according to one of claims 2, 4, 5, characterized in that during step c), the temperature at which the bromination reaction is carried out is 20 ° C to 40 ° C below the temperature of 20 ° C. boiling of the volatile fatty acid.
    [0007]
    7. A process according to one of the preceding claims, characterized in that, in step d), the base used is sodium hydroxide.
    [0008]
    8. A process according to claim 7, characterized in that, in step d), the sodium hydroxide is in equimolar amount with the α-halogenated acid.
    [0009]
    9. A process according to claim 7 or 8, characterized in that during step d), the reaction of the α-halogen acid with the sodium hydroxide is carried out between 20 ° C and 120 ° C, advantageously between 50 ° C. ° C and 90 ° C.
    [0010]
    10. A process according to claim 9, characterized in that during step d), the reaction of α-halogenated acid with sodium hydroxide is optimal for a temperature of 50 ° C if the α-halogenated acid at least four carbons and at a temperature of about 90 ° C if the α-halogen acid has less than four carbons. 15
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2810975A1|1978-03-14|1979-09-27|Hoechst Ag|glycolic acid prodn. by hydrolysis of mono:chloro-acetic acid - in aq. soln. avoids pollution and contamination with salt|
    EP0110761A1|1982-11-22|1984-06-13|Rhone-Poulenc Specialites Chimiques|Preparation of alpha-chloroacid chlorides|
    US5686275A|1991-12-23|1997-11-11|Genzyme Ltd.|Synthesis of homochiral 2-hydroxy acids|
    WO2003062439A1|2002-01-16|2003-07-31|University Of Hawaii|Production of biodegradable thermoplastic materials from organic wastes|
    WO2013022998A2|2011-08-09|2013-02-14|Cornell University|Production of carboxylates and methane from biomass waste|
    WO2014170603A1|2013-04-19|2014-10-23|Bio-Think|Method for producing hydrocarbides|
    US3642887A|1966-12-19|1972-02-15|Ethyl Corp|Preparation of amino-substituted carboxylic acids|
    US4377638A|1981-06-29|1983-03-22|University Patents, Inc.|Microbiological production of lower aliphatic carboxylic acids|
    DE3719872A1|1987-06-13|1988-12-29|Basf Ag|METHOD FOR PRODUCING D-ALANINE FROM L-CHLORINE PROPIONIC ACID|
    CN1086203C|1999-02-04|2002-06-12|清华大学|Method for building multi-functional genetic engineering bacillus to produce beta-hydroxy-butyrates|
    DE102008002715A1|2008-06-27|2009-12-31|Evonik Röhm Gmbh|2-hydroxyisobutyric acid producing recombinant cell|
    WO2010003463A1|2008-07-11|2010-01-14|Metabolic Explorer|Method for polymerising glycolic acid with microorganisms|
    CN101555314B|2009-05-22|2011-12-07|同济大学|Method for synthesizing polyhydroxyalkanoates by excess sludge fermentation broth as carbon source|
    CN102030669B|2009-09-25|2014-07-23|李其奎|Production method for glycine|
    US20110159556A1|2009-12-08|2011-06-30|Pieja Allison J|Use of hydroxyalkanoic acids as substrates for production of poly-hydroxyalkanoates by methane-oxidizing bacteria|
    WO2011070544A2|2009-12-10|2011-06-16|Veolia Water Solutions & Technologies Support|Method for accumulation of polyhydroxyalkanoates in biomass with on-line monitoring for feed rate control and process termination|
    CN102558529B|2011-12-28|2013-10-02|河南农业大学|Method for separating and extracting PHB from photosynthetic bacteria hydrogen-producing fermentation residual liquid|
    EP2749650B1|2012-12-27|2019-03-06|Veolia Water Solutions & Technologies Support|Method for producing polyhydroxyalkanoates by microorganisms|
    KR101359819B1|2013-04-18|2014-02-11|정휘동|Tubing conjunction structuer for water purifying path|
    FR3033166B1|2015-02-27|2017-03-10|Afyren|PROCESS FOR THE PRODUCTION OF AMINO ACIDS FROM PRECURSORS OBTAINED BY ANAEROBIC FERMENTATION FROM FERMENTABLE BIOMASS|
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    FR3074174B1|2017-11-30|2020-02-07|Afyren|PROCESS FOR THE VALORIZATION OF COPRODUCED POTASSIUM SALTS FROM FERMENTATION PROCESSES|
    FR3075222A1|2017-12-19|2019-06-21|Afyren|VINASSE AS A MEDIUM OF FERMENTATION|
    CN108823097A|2018-06-20|2018-11-16|桂林电子科技大学|A method of high poly- PHA Mixed Microbes are enriched with using sulfate-containing organic wastewater acclimation sludge|
    FR3087449A1|2018-10-19|2020-04-24|Afyren|PROCESS FOR THE PREPARATION OF ORGANIC MOLECULES BY ANAEROBIC FERMENTATION|
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    FR1551672A|FR3033168B1|2015-02-27|2015-02-27|PROCESS FOR THE PRODUCTION OF POLYHYDROXYALKANOATES FROM PRECURSORS OBTAINED BY ANAEROBIC FERMENTATION FROM FERMENTABLE BIOMASS|FR1551672A| FR3033168B1|2015-02-27|2015-02-27|PROCESS FOR THE PRODUCTION OF POLYHYDROXYALKANOATES FROM PRECURSORS OBTAINED BY ANAEROBIC FERMENTATION FROM FERMENTABLE BIOMASS|
    LTEP16712944.4T| LT3262095T|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    TR2019/03731T| TR201903731T4|2015-02-27|2016-02-17|Method for producing polyhydroxyalkanates from precursors obtained by anaerobic fermentation from fermentable biomass.|
    CA2977438A| CA2977438C|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    CN201680006864.1A| CN107207710B|2015-02-27|2016-02-17|For by by anaerobic fermentation can fermentation of biomass obtain precursor prepare polyhydroxyalkanoates method|
    AU2016225310A| AU2016225310B2|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    RU2017126668A| RU2682657C1|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursor used with anaerobic fermentation from fermented biomass|
    SI201630192T| SI3262095T1|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    ES16712944T| ES2714597T3|2015-02-27|2016-02-17|Procedure to produce polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    EP16712944.4A| EP3262095B1|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    PT16712944T| PT3262095T|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    HUE16712944A| HUE042799T2|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    BR112017017756-0A| BR112017017756B1|2015-02-27|2016-02-17|PROCESS TO PRODUCE POLYHYDROXYALKANOATES FROM PRECURSORS OBTAINED BY ANAEROBIC FERMENTATION OF FERMENTABLE BIOMASS|
    PCT/FR2016/050363| WO2016135396A1|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    DK16712944.4T| DK3262095T3|2015-02-27|2016-02-17|PROCEDURE FOR THE PREPARATION OF POLYHYDROXYAL CANOATES FROM SUBSTANCES OBTAINED BY ANAEROBIC FERMENTATION FROM FERMENTABLE BIOMASS|
    PL16712944T| PL3262095T3|2015-02-27|2016-02-17|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    US15/053,666| US9650469B2|2015-02-27|2016-02-25|Process or producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
    HRP20190577TT| HRP20190577T1|2015-02-27|2019-03-25|Process for producing polyhydroxyalkanoates from precursors obtained by anaerobic fermentation from fermentable biomass|
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