METHOD FOR PURIFYING OSES WITHOUT ADJUSTING pH

Abstract

The method for purifying oses from hemicellulose originating from lignocellulosic biomass includes eliminating the cellulose matrix and the solid residues and/or the suspended materials from the acid hydrolysate containing oses in order to obtain a clarified hydrolysate, and subjecting the clarified hydrolysate, without adding any basic chemical reagent to increase the pH to at least one step of ultrafiltration and/or to at least one step of nanofiltration, so as to obtain a filtrate containing the majority of the pentoses and a retentate containing the species likely to precipitate under the effect of an increase in the pH. The filtrate is treated by at least one step of electrodialysis so as to recover the acid catalyst from an acid-supplemented solution, and obtain a deacidified filtrate.

Claims

1. A method for purification of oses being comprised of hemicellulose derived from lignocellulosic biomasses, said oses being contained in an acid hydrolysate obtained by partial hydrolysis of lignocellulosic biomasses by at least one acid catalyst, said acid hydrolysate being comprised of a cellulosic matrix, and at least one of solid residues and suspended matters, said method comprising the following steps: removing the cellulosic matrix and the at least one of solid residues and the suspended matters from the acid hydrolysate, in order to obtain a clarified hydrolysate; subjecting said clarified hydrolysate, without any addition of a basic chemical reagent to increase the pH, to at least one ultrafiltration step and/or to at least one nanofiltration step, so as to obtain a filtrate containing the majority of the pentoses and a retentate containing the species likely to precipitate under the action of an increase in pH; and treating said filtrate with at least one electrodialysis step so as to recover the acid catalyst in an acid-enriched solution and to obtain a deacidified filtrate.

2. The method for purification, according to claim 1, wherein, prior to the filtration, the cellulosic matrix is removed in a first step, then the solid residues and/or suspended matters are removed in a second step.

3. The method for purification, according to claim 2, wherein the solid residues and/or the suspended matters are removed by sedimentation and/or centrifugation and/or filtration on a press and/or filtration on a membrane.

4. The method for purification, according to claim 1, wherein the acid catalyst is comprised of sulfuric acid the concentration of which in the acid hydrolysate is advantageously between 5 and 50 g/L.

5. The method for purification, according to claim 1, wherein the cut-off threshold of the filter used during the filtration step is between 100 and 50 000 Da, preferably between 10 000 and 15 000 Da.

6. The method for purification, according to claim 1, wherein, during the electrodialysis step, acidified water is introduced into the compartments of the electrodialysis apparatus where the acid concentrates, so as to have a conductivity higher than or equal to 5 mS/cm.

7. The method for purification, according to claim 1, further comprising, after the electrodialysis step, a step in which said deacidified filtrate is demineralized by electrodialysis and/or by chromatography and/or by ion exchange.

8. The method for purification, according to claim 1, wherein said oses are pentoses.

9. The method for purification, according to claim 8, wherein said pentoses are comprised of xylose and/or arabinose.

10. The method for purification, according to claim 9, wherein, following the step of demineralization of the deacidified filtrate, the xylose is purified by concentration of the deacidified and demineralized filtrate and then by crystallization.

11. The method for purification, according to claim 10, wherein, following the crystallization step, a sweet liquor is obtained comprising xylose and at least another ose, and a separation step is carried out to separate the xylose from the other ose(s).

12. The method for purification, according to claim 11, wherein the separation of the xylose from the other ose(s) is carried out by a crystallization or by a ligand-exchange chromatography, whether or not combined with a crystallization.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0071] Further features and advantages of the invention will become clear from the following detailed description of non-restrictive embodiments of the invention, with reference to the attached drawings.

[0072] FIG. 1 is a diagram that schematically shows various steps implemented in a preferred embodiment of the method for purifying the oses according to the invention.

[0073] FIGS. 2A, 2B and 2C are graphs illustrating respectively the evolution of the pH, the conductivity (in mS/cm) and the intensity (in A) depending on the time (in min) during a first electrodialysis phase with 2 L of filtrate, corresponding to the hydrolysate having been subjected to an ultrafiltration step with a membrane with a porosity equal to 10 000 Da and 2 L of “fresh” brine corresponding to a solution of sulfuric acid H2SO4 at a mass concentration equal to 0.5 g/L.

[0074] FIGS. 3A, 3B and 3C are graphs illustrating respectively the evolution of the pH, the conductivity (in mS/cm) and the intensity (in A) depending on the time (in min) during a second electrodialysis phase with 2.2 L of filtrate, corresponding to the hydrolysate having been subjected to an ultrafiltration step with a membrane with a porosity equal to 10 000 Da and 1.2 L of brine recovered after the first electrodialysis phase.

DETAILED DESCRIPTION OF THE INVENTION

[0075] As shown in FIG. 1, the present invention relates to a method for purifying oses. Initially, these oses are contained in lignocellulosic biomasses 9, within complex macromolecules the latter are comprised of.

[0076] The starting lignocellulosic biomasses in the present method may include any kind of plant components. Thus, the starting biomasses 9 may advantageously be comprised of at least one component chosen from wood, green residues, cereal straws, fodder, forest residues, miscanthus, sugar cane bagasse and the like.

[0077] More particularly, the oses, which are purified by implementing the method according to the invention, are oses, which are part of the hemicellulose, the latter being one of the three main components of the lignocellulosic biomasses, with cellulose and lignin.

[0078] The hemicellulosic fraction from which these oses originate is derived from the partial hydrolysis 1 of lignocellulosic biomasses 9, said hydrolysis 1 being performed by bringing said biomasses 9 into contact with at least one acid catalyst 11.

[0079] Said acid catalyst 11 being used to perform the hydrolysis step 1 consists, according to a particular but non-restrictive embodiment, of sulfuric acid with the chemical formula H.sub.2SO.sub.4.

[0080] Preferably, the sulfuric acid H.sub.2SO.sub.4 has a mass concentration varying between 5 and 50 g/L, preferably between 10 and 20 g/L, and yet more preferably a concentration equal to 15 g/L, in the acid hydrolysate, or reaction medium.

[0081] However, any other kind of acid catalyst capable of permitting the hydrolysis of lignocellulosic biomasses can be used.

[0082] The primary purpose of the acid catalysis step 1 is to permit the recovery of a cellulose pulp 10 from an acid hydrolysate including namely, in addition, solid residues and/or suspended matters. As regards the cellulose pulp 10, also referred to as cellulose matrix, it is used subsequently namely in the paper industry or for the manufacture of 2nd generation biofuel, for example bioethanol.

[0083] Following the acid hydrolysis 1, and after removal of the cellulose 10, the solid residues and/or the suspended matters, is obtained a clarified acid hydrolysate particularly rich in oses, and namely in pentoses, resulting from the hydrolysis of the hemicellulose macromolecule. The pentoses are oses, or monosaccharides, which have 5 carbon atoms and have the raw formula C.sub.5H.sub.10O.sub.5. The hemicellulose is namely comprised of arabinose and especially of xylose, which are both aldopentoses, i.e. they include an aldehyde function in position 1.

[0084] However, it has already been mentioned that the hemicellulose is also formed of other oses, such as glucose, mannose, galactose and rhamnose. These oses are all hexoses, of the formula C.sub.6H.sub.12O.sub.6, and can also be dissolved in the acid hydrolysate.

[0085] It can be considered to simultaneously eliminate from said acid hydrolysate, by means of a single filtration step, the cellulosic matrix 10, the solid residues and/or the suspended matters, so as to obtain a clarified hydrolysate.

[0086] In another embodiment, the cellulosic matrix is removed in a first step by simply removing it from the acid hydrolysate, then, in a second step, the solid residues and/or the suspended matters present in the acid hydrolysate are removed.

[0087] This removal of the solid residues and/or the suspended matters is advantageously performed by implementing a treatment by sedimentation and/or centrifugation and/or by filtration on a press and/or filtration on a membrane, whereby the latter may consist of a microfiltration or an ultrafiltration.

[0088] Such a step permits to eliminate the solid residues and/or the suspended matters 12, or MES, originating for example from the starting plant components and which could eventually still be present in the acid hydrolysate. A hydrolysate clarified from all solid residues and all MES is then obtained.

[0089] In the continuation of the method, and as illustrated in the attached FIG. 1, at least one ultrafiltration step and/or at least one nanofiltration step 3 is performed on the clarified acid hydrolysate. The aim of this step is to remove, in acidic conditions, without any modification of the pH, the macromolecules likely to precipitate when the pH will inevitably be increased during a subsequent step of the method.

[0090] This filtration step permits to obtain, on the one hand, a filtrate, which corresponds to the liquid recovered at the exit of the filtration and, on the other hand, a retentate corresponding to the fraction retained at the level of the filter.

[0091] The carrying out of such a filtration treatment 3 of said clarified acid hydrolysate has the substantial advantage of promoting the removal of organic molecules, such as lignin or other proteins, which are found in the retentate. In addition, this removal is advantageously carried out without any addition of basic chemical reagent to increase the pH and to cause a precipitation of said molecules. Thus, the acid catalyst is not neutralized and can subsequently be recovered for re-use, because its catalytic power is completely preserved. Indeed, said catalyst is found at the level of the filtrate, the latter also containing, inter alia, the oses originating from hemicelluloses, which must be purified.

[0092] Preferably, the ultrafiltration and/or nanofiltration step is carried out by means of a membrane, or filter, having a cut-off threshold between 100 and 50 000 Da, and yet more preferably between 10 000 and 15 000 Da.

[0093] The ultrafiltration membranes and/or the nanofiltration membranes being used in the present method are advantageously organic membranes, which have been carefully selected for their resistance to an acidic pH of about 1 and for permitting a selective removal of the soluble impurities at the pH of the hydrolysis.

[0094] The aforementioned cut-off thresholds indeed advantageously permit an optimal removal of most of the organic molecules, which are likely to precipitate when the pH is subsequently increased.

[0095] Indeed, since the latter are likely to contaminate ionic membranes used subsequently in the method, even to precipitate during the next electrodialysis step, it is particularly important to remove the largest possible proportion of these molecules.

[0096] After the filtration step is thus performed a step of filtrate treatment by an electrodialysis technique 4, which advantageously permits to recover the major part of the acid catalyst 11 that has been used to hydrolyze the lignocellulosic biomass 9.

[0097] More specifically, said acid catalyst 11 is recovered, during the electrodialysis step 4, in an acid-enriched solution 15, and also including salts, also referred to as <<brine>>.

[0098] Following this electrodialysis step 4, the filtrate that has been cleared of the acid is also recovered, which is therefore referred to as deacidified filtrate in the continuation of the description.

[0099] The electrodialysis technique permits an extraction of ions present in a solution. It is carried out by means of an electrodialyzer, or electrodialysis cell, comprised of a plurality of compartments separated by anionic and cationic membranes. Generally, the electrodialyzer comprises an alternation of anionic and cationic membranes, forming multiple electrodialysis cells, which are positioned between two electrodes permitting the migration of the ions under the action of a difference in electrical potential.

[0100] The anionic membranes include resins with positively charged cation groups permitting the passing through of the anions of the solution, which can penetrate into the membrane and replace the anions initially present at the level of the membrane. Conversely, the cationic membranes are formed of negatively charged anionic groups, thereby permitting the penetration of the cations and to repel the anions under the action of the electric field.

[0101] The cations, which migrate in the direction of the electric current towards the negatively charged cathode, leave the first compartment through the cationic membrane and are blocked in a second compartment by the anionic membrane.

[0102] The negatively charged anions also leave the first compartment by migrating through the anionic membrane to the positively charged anode. They are then blocked in a second compartment by the cationic membrane.

[0103] As a consequence, the first compartment sees its salt concentration decreasing. This is why it is referred to as the dilution compartment. On the contrary, in the second compartment the concentration of dissolved ions increases; it is a so-called concentration compartment (<<brine>> compartment).

[0104] The electrodialysis apparatus thus includes an alternation of dilution compartments and concentration compartments.

[0105] The acid catalyst 11 can then be recovered in the concentration compartments of the electrodialyzer. More specifically, and as already mentioned above, an acid-enriched solution 15 is recovered, which in addition to the acid catalyst also includes salts, said solution 15 also being referred to as <<brine>>.

[0106] In order to be able to recycle the acid catalyst during the first step of hydrolysis 1 of the lignocellulosic biomass 9, the acid-enriched solution 15 must reach a sufficient concentration of acid. To this end, said solution 15 may again be subjected to at least one electrodialysis step 4, symbolized by the dotted arrow in the diagram of FIG. 1.

[0107] In other words, the brine 15 is not renewed between two electrodialysis steps, while a new filtrate, including a certain concentration of acid catalyst and pentoses to be purified, is treated by electrodialysis, so as to simulate a counter-current.

[0108] Thus, by means of the electrodialysis, it can be considered, on the one hand, to recycle the acid catalyst, but also, on the other hand, to readjust its concentration in order to prepare its recycling with a view to a new step of hydrolysis of lignocellulosic biomass.

[0109] In order to adjust the acid concentration, it can also be considered to control the volumes of liquid implemented during the electrodialysis, namely, on the one hand, the volume of filtrate to be treated and, on the other hand, the volume of electrodialysis solution, or water 14.

[0110] In a preferred example, the water 14, which is initially introduced into the compartments where the acid concentrates, i.e. the concentration compartments, must be slightly acidified in order to have a sufficient conductivity, higher or equal to 5 mS/cm. Indeed, the electrodialysis method is based on the transport of ions through the membranes by means of an electric field; this assumes that the circulating solutions are conductive.

[0111] Preferably, said water 14 has a pH between 1.5 and 2.5, and yet more preferably of about 2. This water 14 or <<brine>> may namely consist of a solution of sulfuric acid having a mass concentration between 0.25 and 1 g/L, preferably of about 0.5 g/L.

[0112] Advantageously, during the electrodialysis 4, the pH is monitored in the various dilution and concentration compartments of the electrodialysis apparatus. Thus, this monitoring permits an optimization of the treatment by electrodialysis. This monitoring permits in addition to identify the point at which most of the starting acid catalyst 11 has been recovered, but with as few salts as possible.

[0113] Following the electrodialysis step, a demineralization 5 of the deacidified filtrate is carried out, so as to eliminate a substantial proportion of salts 16, which could still be contained in said filtrate.

[0114] The demineralization step 5 may be of different kinds, depending on the subsequent way of recovering chosen to recover the oses originating from the hemicellulosic fraction, in particular the pentoses.

[0115] More particularly, the deacidified filtrate is demineralized by means of at least one technique chosen from electrodialysis, chromatography and ion exchange.

[0116] In other words, it can be considered to implement either one of these techniques, or also to use a combination of several of these techniques, so as to obtain a filtrate that is both deacidified and demineralized rich in oses, and namely in pentoses, derived from the hemicellulose.

[0117] The implemented demineralization technique(s) depend(s) on the way of recovering the oses, which will be chosen later, as mentioned above, but also on the nature of the salts being present (mineral or organic, monovalent or divalent salts) and their concentration. This will permit to minimize the consumption of water, energy, and also chemical reagents.

[0118] In a preferred exemplary embodiment, a demineralization step by electrodialysis or by chromatography is advantageously implemented to remove a significant proportion of salts 16 from the deacidified filtrate. The ion exchange will be better adapted as a final treatment in order to eliminate the traces of salts that could remain.

[0119] Following the demineralization step, the deacidified and demineralized filtrate rich in oses, namely in pentoses, can be recovered in various ways.

[0120] One of the pentoses present in said filtrate, xylose, may be subjected to a transformation 5, whereby the latter may be biological, chemical or enzymatic, so as to permit the production of xylitol 18 or also intermediate chemicals, surfactants, or polymers 19.

[0121] For these applications, it is necessary to separate the sugars from each other in order to obtain a pure xylose solution. Obtaining this solution is feasible, for example, by carrying out a ligand-exchange chromatography, a crystallization or a combination of these two techniques.

[0122] In another equally advantageous exemplary embodiment, the xylose is purified and extracted from the filtrate in solid form 20, by concentration 6 of said filtrate, followed by a crystallization step 7 in order to obtain crystallized xylose 20. Following this crystallization step 7, a sweet liquor 21 is also obtained, which can optionally be subjected to a ligand-exchange chromatography step 8 in order to recover the xylose 20 likely to be contained in said liquor 21 by separating them from the other sugars 23.

[0123] Such a step advantageously permits to optimize the yield of the method for extracting xylose from the hemicellulose initially contained in the biomass 9.

[0124] The interest of the method according to the invention for purifying oses, namely pentoses, is illustrated in the example below in connection with FIGS. 2 and 3 attached to the present application.

Example: Purification of a Hydrolysate of Wheat Bran Obtained after Hydrolysis of Diluted Sulfuric Acid

[0125] Table 1 below shows the characteristics of the wheat-bran hydrolysate, which was studied after a step of hydrolysis of the wheat bran by means of a solution of diluted sulfuric acid (H.sub.2SO.sub.4) at a mass concentration equal to 15 g/L.

TABLE-US-00001 TABLE 1 Composition of the acid hydrolysate Con- Arab- MS ductivity MES OD to H.sub.2SO.sub.4 Glucose Xylose inose % pH (mS/cm) (g/L) 420 nm (g/L) (g/L) (g/L) (g/L) 8.2 1.2 34.5 1.5 2.2 11.5 9 18 8

[0126] In this table, MS represents the mass fraction of the sum of the substances in solution or suspended in the hydrolysate, OD at 420 nm represents the optical density, or absorbance, measured at a wavelength of 420 nm and MES Represents the suspended matters.

[0127] Prior to proceeding to the purification of the hydrolysate, the latter is subjected to a centrifugation step in order to remove the suspended matters. After centrifugation, the solid residue pellet obtained represents approximately 10% of the centrifuged volume.

[0128] The supernatant obtained is ultrafiltered at a temperature of 40° C. with an Alfa Laval UFX10 organic polysulfone on polypropylene organic membrane resistant to the acidic pH and having a cutoff threshold of 10 000 Da (or 10 kDA) and with a transmembrane pressure of about 6 bars.

[0129] The characteristics of the supernatant (initial hydrolysate), of the retentate, and the permeate, or filtrate, were measured and are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Composition after ultrafiltration of the acid hydrolysate Con- MES at OD at Volume Brix ductivity pH 5 420 (L) (°B) pH (mS/cm) (g/L) nm Initial hydrolysate 8 8.2 1.2 34.5 3.6 2.2 Final retentate 1.8 11.6 1.4 30.2 — 6.5 Final Permeate 6.2 7.0 1.3 34.5 0.0 0.5

[0130] A substantial decrease was observed in the final permeate (or filtrate) of the absorption at 420 nm (OD). The latter represents the presence of the organic coloring macromolecules. The decrease in OD at 420 nm therefore represents the elimination of these macromolecules in the permeate.

[0131] In addition, the amount of suspended matters (MES) was measured at pH 5 before and after the ultrafiltration step, said pH having been adjusted by adding a soda solution on a sample solution. The results shown in Table 2 show the quantitative elimination of these molecules, which would have been likely to precipitate during the subsequent electrodialysis step. Indeed, in the final permeate, there is no longer any trace of suspended matter (0.0 g/L).

[0132] The possibility of carrying out the ultrafiltration step by means of a filter having a cut-off threshold of less than 10 000 Da has already been mentioned. However, the results show that, in this example, this cut-off threshold is sufficient to effectively eliminate the suspended matters and the organic macromolecules, in order to thus durably preserve the performance of the electrodialyzer membranes and to prevent the precipitation of organic compounds within the compartments of the latter.

[0133] In the next step, a conventional two-compartment electrodialysis pilot was used to recover most of the acid catalyst, the sulfuric acid (H2SO4). The characteristics of the pilot are summarized in Table 3 below.

TABLE-US-00003 TABLE 3 Characteristics of the electrodialysis pilot EUR2-10 Anionic Membranes AMX-Sb Cationic Membranes CMX-Sb Surface Area 200 cm.sup.2 Brine H.sub.2SO.sub.4 à 0.5 g/L Electrolyte NaC1 Voltage 12 V

[0134] Two electrodialysis phases were conducted. The results obtained after these two phases are given in Table 4 below.

[0135] The brine obtained after the 1st electrodialysis phase was recycled during the 2nd phase, in order to reach the acid concentration necessary for it to be recycled in a new method for hydrolysis of the lignocellulosic biomass; this acid concentration is set between 10 and 20 g/L.

[0136] 1st Electrodialysis Phase

[0137] After the ultrafiltration step mentioned above, a volume of 2 L of hydrolysate, or filtrate, was treated with 2 L of so-called <<fresh>> brine having a sulfuric acid concentration of 0.5 g/L. The use of such a brine having a conductivity higher than 5 mS/cm facilitates the electrodialysis step.

[0138] The evolution of the pH, of the conductivity and of the current intensity depending on the time are represented respectively in the attached FIGS. 2A, 2B and 2C.

[0139] The results obtained show that the product was largely demineralized after a duration of about 20 minutes of electrodialysis; indeed, after 20 min, it is observed in FIG. 2A that the residual conductivity in the product is less than 1 mS/cm. This results in addition into a drop in the current intensity.

[0140] The results in Table 4 below show that after 20 minutes of electrodialysis, more than 90% of the sulfuric acid was transferred into the brine. As regards the sugars, more than 98% remained in the product.

[0141] Therefore, it is not necessary to process the product for more than 20 min.

[0142] The brine finally reaches a pH equal to 1.3 and its acid content is about 0.12 eq/L, i.e. a concentration of sulfuric acid H.sub.2SO.sub.4 of 5.9 g/L.

TABLE-US-00004 TABLE 4 Composition of products at the end of the electrodialysis Volume Brix Conductivity H.sub.2SO.sub.4 Glucose Xylose Arabinose (L) (°B) pH (mS/cm) (g/L) (g/L) (g/L) (g/L) Product 1.sup.st ED 2 5.5 3.1 0.5 0.8 7.5 15.4 7.3 Brine 1.sup.st ED 2 1.4 1.3 27.1 5.9 0.1 0.2 0.1 Product 2.sup.nd ED 2.2 5.6 2.8 0.9 1.5 7.4 15.4 7.3 Brine 2.sup.nd ED 1.2 3.9 1.0 60.0 14.2 0.0 0.4 0.2

[0143] 2nd Phase of Electrodialysis

[0144] A volume equal to 1.2 L of previous brine is used with 2.2 L of ultrafiltered hydrolysate. The evolution of the pH, of the conductivity and of the current intensity depending on the time are represented respectively in FIGS. 3A, 3B and 3C.

[0145] Again, the product was demineralized after 20 minutes of electrodialysis, the residual conductivity being less than 1 mS/cm. Therefore, a duration of 20 min is sufficient to transfer more than 90% of the sulfuric acid into the brine and to retain more than 98% of the sugar in the product.

[0146] After the 2nd electrodialysis phase, the brine has reached a pH close to 1 and its acid content is about 0.29 eq/L, i.e. a concentration of sulfuric acid H2SO4 of 14.2 g/l.

[0147] Therefore, the brine has a sulfuric acid concentration sufficient to be recycled during the step of hydrolysis of the lignocellulosic biomass.

[0148] Finally, a finishing treatment by means of ion exchange is carried out to remove the last traces of salts and acids. The product deriving from the 2nd electrodialysis is introduced at 3.6 BV/h (<<bed volume>> per hour) into two columns mounted in series, each containing a strong cationic resin (LEWATIT S2528) and a weak anionic resin (LEWATIT S4328).

[0149] In total, up to 30 BV of product could be processed at room temperature before one of the two resins was saturated.

[0150] If a comparison is made with the reference method, in which a partial or complete neutralization of the hydrolysate is performed, it is thus possible to treat at each cycle at least 10 times more products. Therefore, it is possible, with the method according to the invention, to save water and the corresponding chemical reagents.

[0151] This treatment has permitted to divide by 5 the conductivity of the product (this being ultimately 0.17 mS/cm) and therefore its salt content.

[0152] Finally, a finishing treatment per mixed and activated-carbon bed has permitted to obtain a demineralized pentose solution with a conductivity of less than 10 μS/cm and perfectly discolored.

[0153] Of course, the invention is not limited to the examples illustrated and described above, which may have variants and modifications without departing from the scope of the invention.