BR112020014048A2 - separation and purification process of glycerol derivatives - Google Patents

Abstract

“process of separation and purification of glycerol derivatives”. the present patent application describes a new and innovative method for purifying glycerol derivatives by simulated moving bed chromatography. the method of the present patent application allows the separation of at least one glycerol derivative present in the feed solution. glycerol derivatives purified by the published method include dihydroxyacetone (dha), hydroxypyruvic acid (hpa), glycolic acid (gco), oxalic acid (oxa), mesoxalic acid (meo), tartronic acid (tta), glyceric acid (gca) , glyceraldehyde (gla), glyoxalic acid and the unreacted glycerol. the presently published method can be applied by any simulated moving bed chromatography device, including but not limited to multi-valve static column systems and rotating column systems

Description

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DESCRIPTION REPORT "PROCESS OF SEPARATION AND PURIFICATION OF GLYCEROL DERIVATIVES" Technical Field

01. The present patent application is related to a new method for purifying glycerol derivatives, including dihydroxyacetone (DHA), hydroxypyruvic acid (HPA), glycolic acid (GCO), oxalic acid (OXA), mesoxalic acid (MEO), tartronic acid (TTA), glyceric acid (GCA), glyceraldehyde (GLA), glyoxalic acid and unreacted glycerol by simulated moving bed chromatography.

State of art

02. One of the main alternatives in the search for new energy sources to replace fossil fuels are biofuels, such as biodiesel. Its production generates a secondary product, Glycerol, which represents about 10% of the total weight of biodiesel produced. Although this compound has several industrial uses, the growing production of biodiesel has led to Glycerol being considered as an industrial waste. Thus, in addition to its low price, problems related to its environmental impact have gained increasing relevance (Scharlemann and Laurance 2008).

03. Crude glycerol has a very low commercial value due to its impurities, however if it can be converted into value-added products, the viability of the biodiesel industry can be increased.

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04. Its conversion through catalytic reactions such as selective oxidation, selective hydrogenolysis, catalytic dehydration, pyrolysis and gasification, among others, has been the focus of many researchers with the objective of converting glycerol into chemicals and fuels of interest for chemical, cosmetic, and pharmaceutical industries (Fan, Burton, and Zhou 2010).

05.Despite advances in the development of processes to produce valuable compounds from Glycerol, some challenges still persist in the purification step. Furthermore, it is known that the purification stage can determine the commercial viability of an industrial process. This means that a production route or a complete industrial process can be discarded if purification is not energetically and/or commercially favorable. The difficulty is even greater in those cases where the compounds of interest are produced in low concentrations or are chemically similar, as is the case with the separation of DHA, HPA, GCO, OXA, MEO, TTA, GCA, GLA and GOX.

06. So far, there are no reports of the production of DHA, HPA, GCO, OXA, MEO, TTA, GCA, GLA and GOX, or even of another compound including glycerol derivatives, by catalytic oxidation of glycerol and its purification by simulated moving bed.

07.The oxidation of glycerol to form tartronic acid through a gold catalyst supported on Zeolites HY was described at laboratory scale, (Cai et al. 2014), and the purification step was not included. Probably the first industrial process to obtain TTA was described in

3/41 1981 in (Hurley 1982). In that document, a chemical process is described comprising the following steps: - conversion of a starting material (malic acid, fumaric acid, tartaric acid, maleic anhydride, tartaric anhydride, or any of the water-soluble esters of maleic acid, of the acid fumaric or tartaric acid) in a salt (the resulting salt should have a pH between 10 and 14); - oxidation of the saline solution with potassium permanganate (KMnO4); - removing the first precipitate from the oxidized saline solution; - adding a water-soluble salt to the solution where oxylates are acid-insoluble and tartronates are acid-soluble; - Separation of the second precipitate resulting from the addition of the metallic salt; dissolving the tartronate by adding a mineral acid to the second precipitate. In that case, the production as well as the purification method is different from that disclosed in the present present application.

08.(Habe et al. 2010) published a microbiological production of GCA and DHA from glycerol after 4 days of incubation in a closed reactor with pH control. In addition to the fact that this process is totally different from the one proposed in this document, the work is still in the laboratory scale and needs improvement.

09.Currently, OXA can usually be obtained through four methods.

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- a glucose solution obtained from the hydrolysis of starch is placed in a reactor with sulfuric acid, vanadium pentoxide, iron(III) sulfate and nitric acid (65%) under vigorous stirring; crude oxalic acid is obtained after lowering the temperature and centrifuging the reaction mixture; oxalic acid is again dissolved in hot water, passing through an oil separator and then recrystallized; after a second centrifugation and drying oxalic acid dihydrate is obtained; - an ethylene glycol solution is oxidized by means of an oxidizing mixture of sulfuric acid and nitric acid, in the presence of vanadium pentoxide and iron(III) salts. Crude oxalic acid is obtained after crystallization and separation steps.

The final product is obtained after a sequence of steps, including: steam dissolution, crystallization, separation and then drying; - a solution of propene is introduced into a solution of nitric acid to produce soluble intermediates of α-nitratolactic acid and lactic acid.

In a second step, the solution of these partially oxidized products is treated with oxygen in the presence of a catalyst.

Oxalic acid is formed, crystallized, filtered and dried; - carbon monoxide (CO) and a short-chain alcohol are reacted under pressure and in the presence of a catalyst to form the corresponding oxalic acid diester.

Palladium on charcoal and alkyl nitrates are used as catalysts and the reaction is conducted at 10-11MPa.

The diester is hydrolyzed in the second step to oxalic acid, which is crystallized and dried.

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10.OCG is usually produced by hydrolysis of liquefied monochloroacetic acid with aqueous sodium hydroxide (Zhang and Meng, 2013). The resulting glycolic salt can be obtained by evaporative concentration, followed by extraction of the acid with acetone (LEUPOLD et al., 1979). Another process, which is commercially used in the United States, produces GCO by treating formaldehyde or trioxylmethylene with carbon monoxide and water in the presence of acid catalysts at high pressure (>30MPa) and high temperatures (140-220 oC) (Shattuck 1948; Larson 1939; John 1939). Glycolic acid can be recovered from the concentrated solution by crystallization or separated from this crude mixture by distillation. However, this new residue must be neutralized, for example, with calcium carbonate, to convert the glycolic acid to an easily separable salt, or the residue must be treated with an alcohol suitable for removing the glycolic acid as an ester. None of these processes use a production step followed by a purification step, such as the process published in this application.

11.Similar to GCA, the DHA production process involves a microbiological procedure (Green 1960; Charney 1978). Although it is an industrial process, the fermentation step requires up to 48 hours, requiring numerous reagents for microbial growth and the entire process has low yields and low productivity. In addition, this process presents the usual problems of industrial biotechnology: discontinuous processing, difficulties in maintaining microbial growth, contamination by other microorganisms, high sterilization costs and high product recovery costs (Chen 2012). At the end of the process, the product is isolated by methods known in the

6 / 41 literature, such as filtration of the fermented product, removal of cations and/or inorganic anions (when present) through adsorption with ion exchange resins, concentration of the resin effluent and crystallization of DHA from the concentrate. Again, this technology is also based on an entirely different process than that described in the current patent application.

12.On the other hand, the literature reports many processes for purification of organic acids, which include compounds similar to DHA, HPA, GCO, OXA, MEO, TTA, GCA, GLA and GOX, but through methods very different from the one proposed in this document:

13.US 4621153A (Hatch 1986) describes the method for recovering phenylalanine from an aqueous mixture comprising: providing a calcium salt to the aqueous mixture; precipitating a complex of phenylalanine and calcium; separating the precipitated complex from the aqueous mixture; dissolving the precipitated complex in an aqueous solution at a pH below 8.5; and separating phenylalanine from Ca2+.

14. The patent US5254729A (FUJIWARA et al., 1993) reports a method for obtaining substantially colorless glycine from an aqueous solution of glycine. This method comprises the following steps: reacting glycolnitrile, carbon dioxide (gas) and ammonia in the presence of water to obtain a solution containing glycine; removing most of the carbon dioxide and ammonia by adjusting the pH of the remaining alkaline aqueous glycine solution to 3.5-6 with a cation exchange resin; discolor the aqueous glycine solution by contacting the solution with charcoal

7/41 activated and; evaporate the water from the solution to obtain pure glycine crystals.

15. The work JP2003221359A (HIROYUKI and AKIHIRO 2003) describes a method to produce dicarboxylic acids from the reaction mixture obtained when introducing a cycloalkane in contact with oxygen in the presence of a compound with an imide functional group. A treatment with an ion exchange resin is used to separate the dicarboxylic acid. Such an ion exchange resin treatment can be carried out by feeding the liquid to be treated to a vessel containing an ion exchange resin (ion exchange resin wash treatment). The ion exchange resin treatment tank can be of the column type. Additionally, a fixed bed, fluidized bed system or any other continuous treatment can be used. This work describes the separation of compounds containing an imide group, or the products of its decomposition, from carboxylic acids obtained through the oxidation of a cycloalkane, thus comprising a set of compounds to be separated completely different from those that are the focus of the present. patent application, which are still obtained from a different raw material, namely, glycerol. Furthermore, this process does not specify whether or which continuous treatment represents the best in the invention.

16. Patent EP1441823B1 (Herman 2013) contemplates methods for isolating one or more specific compounds from a complex mixture, however using a centrifugal chromatography device described in the document.

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17. WO2016083455A1 (KOLFSCHOTEN and Sanders 2016) describes a process for precipitating one or more organic acids and/or amino acids from a liquid feed comprising a plurality of organic acids and/or amino acids. In a precipitation tank, a solution of organic acids and/or amino acids from a given feed that is in a mixture of solvent and anti-solvent passes through a zone capable of selectively removing the solvent and/or adding an anti-solvent to the mixture. from an external source. A solvent-poor and anti-solvent-rich mixture is obtained, thereby increasing the concentration of amino acids and/or organic acids in the new solvent/anti-solvent mixture, allowing the precipitation of solid particles of the amino acids and/or organic acids to from the solvent/anti-solvent mixture in the precipitation tank at a certain temperature. In other words, a crystallization procedure. A very different process from the one described in this document.

18. Finally, patent US5245078A (Maeda and Nakazawa 1993) describes a non-continuous chromatographic process for separating tartaric acid, citric acid, lactic acid, gluconic acid and glycolic acid from a solution containing organic acids. The solution is obtained by a fermentation method in which glucose is used as the starting material, and which comprises: contacting said organic acid-containing solution with a sulfonic acid-functionalized polystyrene type cross-linked divinylbenzene cation exchange resin to have the organic acid or acids adsorbed onto the cation exchange resin;

9/41 contacting the cation exchange resin with an eluent solution, dilute sulfuric acid, to obtain the desorbed organic acid(s) and then; separating from the eluate a solution containing the organic acid or acids, where the solution containing the organic acid or acids is contacted with a second cation exchange resin under such a condition that the pH or the solution containing the organic acid or acids is maintained at a level lower than the pKa of the species(s). This is a discontinuous process and different from the one described in this document.

19. Simulated moving bed chromatography (LMS) has been applied to a variety of industrial processes as an alternative to batch processes.

20.Originally, the LMS was developed for the petroleum refining and petrochemical industries, through the known SORBEX process (BROUGHTON; GERHOLD, 1961). Alternative processes using LMS technology for the production of p-xylene (PAREX), for the separation of n-paraffins from branched and cyclic hydrocarbons (MOLEX), for the separation of olefins from paraffins and for the separation of fructose from glucose ( SAREX) were developed later.

21. The purification of amino acids, such as phenylalanine from fermentation broths (MCCULLOCH; GOODMAN, 1991) and the development of large-scale separations of hydrocarbons and carbohydrates, initiated a new approach where LMS technology found applications in the fields of biotechnology, pharmaceuticals and fine chemicals.

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22. Conventionally, an LMS has two input currents (Figure 1), eluent (Figure 1 – 5) and supply (Figure 1 -6), and two output currents, extract (Figure 1 – 7) and raffinate (Figure 1 – 8). These currents divide the unit into four sections or zones, each of which is responsible for a different function. In section 1 (Figure 1-1) the most retained compound must move with the liquid phase to be collected at the extract port in order to regenerate the solid in this section. While in section 4 (Figure 1 – 4) the compost less retained must move with the solid to be collected in the raffinate in order to regenerate the liquid in this section. In sections 2 (Figure 1 – 2) and 3 (Figure 1 – 3) the most retained compost should move with solid to be collected in the extract port and the least retained compost should move with the liquid towards the port raffinate collection.

23.From figure 1, it is possible to see that in section 1 the species must move in the direction of the liquid phase flow (Figure 1 - 9), in sections 2 and 3 the least retained compound must move in the direction of the liquid phase flow, while the most retained must move in the opposite direction to the liquid phase flow, and finally in section 4 the species must move in the opposite direction to the liquid phase flow. In the conventional operating mode of an LMS the input and output currents move to the next column in the direction of liquid phase flow at regular time intervals, called the Switching time, t*, and so the solid phase movement is simulated. A cycle is complete when the initial injection/collection positions of all streams are obtained. So it can be concluded that during

11 / 41 a cycle, the same column takes on different roles in the separation process depending on the section the column is in.

24. Patent US6875349B2 (HEIKKILÄ et al., 2005) was the first to describe a simulated moving bed process comprising the separation of organic acids, among other compounds. The document describes the method for fractionating a solution into two or more fractions rich in different components, by LMS. At the time, the method was different from state of the art LMS methods where only one profile moved through the chromatographic system circuit. In the new method described, two or more dissolved material profiles (dry solids profiles) move through the entire bed (all columns in the circuit). However, in this process, the selected raw material comes from different groups from those in the present application (eg consisting of molasses, vinasse, sulfite cooking liquid, fructose/glucose syrup, beet derivatives, sugar beet molasses, sugar residue xylitol, invert sugar mixtures, starch hydrolysates, wood hydrolysates, solutions containing lactose, solutions containing amino acids, fermentation broth containing organic acids, bagasse hydrolysates, solutions containing inositol, solutions containing mannitol, solutions containing sorbitol, solutions containing xylitol, solutions containing erythritol, solutions containing glutamic acid and solutions containing glycerol).

25. Later, (PAANANEN et al., 2012) published the invention EP2316551B1, which describes a system and process for fractionating a solution into two or more fractions. Although, the solution products to be recovered may include one or more of the following, glucose, fructose, sucrose, betaine, rhamnose, arabinose, mannose, raffinose, lactose, lactulose,

12 / 41 maltose, malthiol, inositol, mannitol, glycerol, xylitol, xylose, sorbitol, erythritol ribose, 6-O-α-D-glucopyranoside-D-Sorbitol (1,6-GPS) and 1-O-α-D -glucopyranoside-D-Manitol (1,1-GPM), and organic acids or amino acids, such as glutamic acid, the document limiting the following original solutions: molasses, especially B-molasses and/or C-molasses, vinasse , fructose and/or glucose syrups, beet-derived juices, wood hydrolysates, milk solutions and other solutions containing lactose, solutions containing lactulose, solutions containing maltose, solutions containing maltitol or amino acid solutions. This process is different from the process to be patented which is focused on the recovery of glycerol derivatives not requiring the alternative mode of operation previously described.

26. Patent document FR2900654A1 (THEOLEYRE; BAUDOUIN, 2007) provides a process for separating organic acids through a chromatographic bed packed with an anionic resin. This method is also characterized in such a way that the organic acid is citric acid and the aqueous solution is a fermentation product which generates said organic acid.

27. In the work EP2212004B1 (LANG; SIMPKINS, 2015), a process to produce bioactive compounds is described, in which a plurality of these substances come into contact with an adsorbent polymer. This polymer has selectivity for at least one of the bioactive compounds present in the mixture. The document further suggests gravity fed columns and flash chromatography as suitable configurations or moving bed chromatography devices. However, it also discloses that the adsorbent polymer may be non-ionic, such as Alimentech P495 Inert Adsorbent Polymer supplied by Bucher Foodtech.

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28. US8951416B2 (SARMALA et al., 2015) is based on the use of a combination of strong cationic acidic ion exchange resins to weak cationic acidic ion exchange resins in a specific order and in specific proportions in an LMS chromatographic separation system . Specifically, this document US8951416B2 describes a method of separating betaine from at least one other compound coming from a fermentative solution based on sugar beet saccharin, in which the other compound to be separated can be glycerol, an organic acid or inositol.

29.Finally, patent US20130345473A1 (ARCHER et al., 2013) discloses a process for separating at least one dicarboxylic acid from a mixture comprising at least one monocarboxylic acid and at least one dicarboxylic acid by a chromatographic process . Although, the aforementioned document describes that the separation can be carried out through simulated moving bed technology using ion exchange resins, it also restricts that the chromatographic medium for the exchange should be an anion exchange resin chosen from specific commercial examples and that the feed stream is specifically derived from the oxidation of glucose.

30. Thus, there is still a need to develop a separation process capable of purifying glycerol derivatives obtained from the catalytic chemical conversion of glycerol, such as dihydroxyacetone, pyruvic acid, glycolic acid, oxalic acid, mesoxalic acid, tartronic acid, glyceric acid , glyceraldehyde or acid

14 / 41 glyoxallic acid, for example, efficiently, generating a smaller amount of chemical residues, producing highly pure compounds and achieving high productivity.

Short Description

31. In one embodiment, the simulated moving bed chromatographic method for the separation of glycerol derivatives from a feed solution containing said glycerol derivative and one or more other glycerol derivative, or impurities, comprises: (a ) selecting a simulated moving bed chromatographic device comprising at least two chromatographic columns interconnected in series; wherein said columns contain a separation medium (stationary phase) or a mixture of a variety of separation means capable of effecting ion exchange; sequentially comprising an eluent port, an extract port, a feed port and a raffinate port; and simultaneously, (b) contacting, through said feed port, a feed solution with the balanced separation means with an acidic or basic solution or a water-organic mixture or water; and (c) contacting, through said eluent port, an acidic or basic eluent with the separating material, where the eluent may be an acidic solution or a basic solution or a water-organic or water mixture; and (d) allowing the collection, through said raffinate or extract ports, of a stream of raffinate or extract, respectively, comprising the liquid phase and mainly one of the glycerol derivatives, and may also have a percentage of one of said derived from

15 / 41 glycerol, and/or unreacted glycerol, and/or impurity present in said feed solution.

32. In one embodiment, the simulated moving bed chromatographic device may further comprise a second eluent port for performing eluent gradients within the unit; promoting contact, through said second port of an eluent, an acidic solution or a basic solution or a water-organic mixture or water with said separation means.

33. In one embodiment, said glycerol derivatives may be dihydroxyacetone (DHA), hydroxypyruvic acid (HPA), glycolic acid (GCO), oxalic acid (OXA), mesoxalic acid (MEO), tartronic acid (TTA), glyceric acid (GCA), glyceraldehyde (GLA) and glyoxalic acid.

34. In one embodiment, the feed solution is the product of chemical conversion of glycerol from a variety of processes such as selective oxidation, selective hydrogenolysis, catalytic dehydration, pyrolysis, gasification, selective glycerol transesterification and esterification, selective etherification and carboxylation.

35. In one embodiment, the pH of said feed solution is comprised between 1 and 13 through the addition of acidic or basic species. In a preferred embodiment, the pH of said feed solution is comprised between 1 and 7 by the addition of acidic or basic species. In a preferred embodiment, the pH of said feed solution is comprised between 1 and 5 by the addition of acidic or basic species.

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36. In one embodiment the feed solution may be pretreated by any suitable process to obtain a solution of two or more glycerol derivatives with or without the unreacted glycerol and/or without impurities from the chemical conversion process of glycerol including, but not limited to, ion exchange, distillation, centrifugation and filtration.

37. In one embodiment, the separation medium is a chromatographic material where said cation exchange chromatographic material is selected from alumina, magnesium silicates, silica, glass, controlled pore glass, carbon, porous carbon, zirconium phosphate, hydroxyapatite, calcium phosphate, magnesium carbonate, and polymers or resins. In a particular embodiment said polymers or resins for cation exchange chromatography are selected from hydroxyalkylmethacrolate, polyacrylamide, polyacrylamine, polymacrolate, poly(hydroxyethyl macrolate), polystyrene, styrene-divinylbenzene polymers, poly(ethyleneglycoldimethacrolate), poly(vinylalcohol), poly(vinylacetate) and poly(vinylpyridine).

38. In another embodiment, the cation exchange chromatographic material from each chromatographic column is equilibrated (conditioned) with an acidic solution. In one embodiment, the separation medium is a chromatographic material where said anion exchange chromatographic material is by selecting among polymers, resins, silica, zirconia, carbon and alumina, where said polymers or resins for anion exchange chromatography are selected between poly(vinyl alcohol), poly(methacrylates), polystyrene with high cross-linked density and poly(ethylene oxide) and styrene polymers or

17 / 41 ethylvinylbenzene or copolymers crosslinked with divinylbenzene (eg, ethylvinylbenzene-divinylbenzene (EVB-DVB) and styrene or polystyrene-divinylbenzene acrylonitrile, acrylic acid, or methacrylic acid. anionic within each column can be balanced (conditioned) with a basic solution.

39. In one embodiment, said anion exchange chromatographic material within each column may be equilibrated (conditioned) with a basic solution.

40. In one embodiment, the eluent is an acidic or basic solution or a water-organic or water mixture.

41. Simulated moving bed chromatography can be practiced by any simulated moving bed device, including but not limited to multi-valve static column systems and rotating column systems.

Detailed Description

42. A new and innovative method for the purification of glycerol derivatives obtained from glycerol by simulated moving bed has been discovered.

43. The present patent application describes a simulated moving bed chromatographic method for separating a glycerol derivative from a feed mixture, containing said glycerol derivative and at least one additional compound, such as another organic compound and/or another

18 / 41 derived from glycerol and/or unreacted glycerol and/or impurities, comprising: (a) selecting a simulated moving bed chromatographic device containing at least two chromatographic columns interconnected in series; wherein said columns contain a separation medium (stationary phase) or a mixture of a variety of separation means capable of effecting ion exchange; comprising, sequentially, an eluent port, an extract port, a feed port and a raffinate port; and simultaneously, (b) contacting, through said feed port, a feed solution with the separation means balanced with an acidic or basic solution or a water-organic mixture or water; and (c) o contacting, through said eluent port, an acidic or basic eluent with the separating material, where the eluent may be an acidic or basic solution or a water-organic or water mixture; (d) allowing the collection, through said raffinate or extract ports, of a stream of raffinate or extract, respectively, comprising the liquid phase and mainly one of the glycerol derivatives, and may also have a percentage of one of said derivatives of the glycerol, and/or unreacted glycerol, and/or impurity present in said feed solution.

44. The feed solution can be a stream containing glycerol (or so-called raw glycerol) obtained from the production of biodiesel, and which may come from different raw materials, or a solution of refined glycerol in any concentration, where the feed solution may contain impurities.

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45. The materials or separation media can be silicas, functionalized silicas, aluminas, carbon, functionalized or non-functionalized zeolites, polystyrene, polyacrylamide, cross-linked polystyrene, polyacrylates or other resins and the eluent can be an acidic or basic solution or water- organic or water.

Separation Process

46. The current patent application describes a simulated moving bed chromatographic method for separating one or more glycerol derivatives from a feed solution from chemical conversion processes of glycerol into glycerol derivatives comprising: (a) selecting a simulated moving bed device comprising at least two chromatographic columns interconnected in series; wherein said columns contain a separation medium (stationary phase) or a mixture of a variety of separation means capable of effecting ion exchange; comprising, sequentially, an eluent port, an extract port, a feed port and a raffinate port; and simultaneously, (b) contacting, through said feed port, a feed solution with the balanced separation means with an acidic or basic solution or a water-organic mixture or water; (c) contacting, through said eluent port, an acidic or basic eluent with the separating material, where the eluent may be an acidic or basic solution or a water-organic or water mixture; and (d) allowing the collection, through said raffinate or extract ports, of a stream of raffinate or

20 / 41 extract, respectively, comprising the liquid phase and mainly one of the glycerol derivatives, which may also contain a percentage of one of said glycerol derivatives, and/or unreacted glycerol, and/or impurity present in said feed solution.

47. The simulated moving bed chromatographic device may also comprise additional raffinate or extract streams allowing the execution of ternary, pseudo-ternary or higher order separations; the collection, through said outlet ports, a stream of raffinate or extract comprising the fluid mobile phase, an acidic solution or basic solution or mixture of water-organic or water and mainly one of said glycerol derivatives, which may also have a percentage of one of said glycerol derivatives, and/or unreacted glycerol, and/or impurity present in said feed solution; it may further comprise a second eluent port for performing eluent gradients within the unit; promoting contact, through said second eluent port, of an acidic solution or a basic solution or a water-organic mixture or water with said separation means.

48. Although the above description refers to a feed stream containing various glycerol derivatives, such as monocarboxylic or dicarboxylic acids, it may also comprise these acids in salt form, which salts may include sodium, potassium, calcium and magnesium salts (eg, tartronate, glycerate, oxalate, glycolate, dihydroxyacetonate), or ketones or aldehydes or esters or ethers, among others.

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49. Prior to the contact described in (b), the pH of said feed solution can be adjusted to a pH between 1 and 13, which can be adjusted to values between 1 and 7 or between 1 and 5, by adding an acidic or basic material. The pH of the feed solution can be adjusted by adding any suitable compound to correct the chosen pH. Suitable acidic compounds include, but are not limited to, hydrochloric acid, sulfuric acid and phosphoric acid. Preferably sulfuric acid should be used. Suitable basic compounds include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide and ammonia.

Separation Means

50. The second aspect of the present patent application is related to the chromatographic separation process for separating a glycerol derivative, from a mixture containing a glycerol derivative, and one or more other components, which may be another derivative of unreacted glycerol and/or glycerol and/or impurities where the desorbent may be an acidic solution or a basic solution or a water-organic mixture or water, and the separation medium is a chromatographic material.

51. As shown above, the eluent can be an acidic solution or a basic solution or a water-organic or water mixture. Any of these solutions should be prepared in such a way that their pH is between 1 and 13, ideally between 1 and 7 or more ideally between 1 and 5. A chromatographic separation process that uses low acidic water as eluent is advantageous because it reduces the environmental impacts and because it reduces the need for

22 / 41 additional equipment for separating the glycerol derivative from the eluent.

52. Said column or columns may contain a chromatographic material capable of effecting ion exchange comprising a functional group selected from a group consisting of sulfonates, alkylsulfonates, phenylsulfonates, alkylphenylsulfonates or any mixture thereof. The. The chromatographic material can be a strong cation exchange resin. The strong cation exchange resin chromatographic material may comprise a sulfonate group.

B. The cation exchange chromatographic material of the present application preferably comprises one or more chromatographic support materials (i.e., stationary phases).

ç. Chromatographic support materials suitable for cation exchange chromatography include, but are not limited to, alumina, magnesium silicates, silica, glass, glass with controlled pores, carbon, porous carbon, zirconium phosphate, hydroxyapatite, calcium phosphate, carbonate magnesium, and polymers or resins.

d. Suitable polymers or resins for cation exchange chromatography include, but are not limited to, hydroxyalkylmethacrolate, polyacrylamide, polyacrylamine, polymacrolate, poly(hydroxyethyl macrolate), polystyrene, styrene-divinylbenzene polymers, poly(ethyleneglycoldimetaacrolate), poly(vinylalcohol),

23 / 41 poly(vinylacetate) and poly(vinylpyridine). Preferably, the polymers and resins should be styrene-divinylbenzene.

and. The cation exchange chromatographic material of the present application further comprises a plurality of linkers selected from one or more functional groups suitable for ion exchange. Such functional groups include, but are not limited to, sulfonic acid, alkylsulfonic acid, phenylsulfonic acid, alkylphenylsulfonic acid and salts thereof. Preferably the functional groups are sulfonic acids and their salts.

f. Specific examples of silica-based cation exchange chromatographic materials include, but are not limited to, ADSORBOSPHERE SCX, BAKERBOND SCX, PARTISIL SCX, SPHERISORB S SCX, SUPELCOSIL LC-3SCX, ULTRASILCX, and ZORBAX 300 SCX.

g. Specific examples of cation exchange polymers or resins that can be used include, but are not limited to, AMBERLITE 200, AMBERLITE IR-118H, AMBERLITE IR-120PLUS, AMBERLITE IR-122, AMBERLITE IR-130C, AMBERLITE I6641, AMBERLITE IRP- 69, DOWEX 50X1-100, DOWEX 50X2-100, DOWEX 50X2-200, DOWEX 50X2-400, DOWEX 50X4-100, DOWEX 50X4-200, DOWEX 50X4-200R, DOWEX 50X4-400, DOWEX 18880, DOWEX 50X8-100, DOWEX 50X8-200, DOWEX 50X8-400, DIAION 1-3561, DIAION 1-3565, DIAION 1-3570, DIAION 1-3573, DIAION 1-3577, DIAION 1-3581, DUOLITE D 5427, and DUOLITE D 5552, the which can be supplied by Sigma-Aldrich, St. Louis Missouri, USA; DIAION HPK25, DIAION PK208, DIAION PK228,

24 / 41 DIAION SK1B, DIAION SK1BS, DIAION SK104, DIAION SK112, DIAION SK116, DOWEX HCR-S, DOWEX HCR-W2, DOWEX MSC-1, DOWEX 650C, DOWEX G-26, DOWEX 88, DOWEX MONOSPHERENOS 88, DOWEX 99K/320, DOWEX MONOSPHERE 99K/350, DOWEX MONOSPHERE 99Ca/320, DOWEX MONOSPHERE 99Ca/350, DOWEX Marathon C, DOWEX -032, DOWEX -406, DOWEX -437, DUOLITE C-280, and DUOLITE C-291, the which may be provided by Supelco, Inc., Bellefonte, Pennsylvania, USA; AMBERLITE IR-120, AMBERLITE IR-120B, AMBERLITE IR-200C, AMBERLITE CG 6000, DIAION SK-1B, DOWEX XUS

40406.00, DOWEX XUS 43518, and DOWEX C500ES.

H. The cation exchange chromatographic material from each chromatographic column can be equilibrated (conditioned) with an acidic solution.

The anion exchange chromatographic material of the present application preferably comprises one or more chromatographic support materials. i. Suitable chromatographic support materials for anion exchange chromatography include, but are not limited to, polymers, resins, silica, zirconia, carbon and alumina.

j. Suitable polymers or resins for anion exchange chromatography include, but are not limited to: poly(vinylalcohol), poly(methacrylates), high density crosslinked polystyrene and poly(ethylene oxide) and styrene or ethylvinylbenzene polymers or copolymers cross-linked with divinylbenzene (eg, ethylvinylbenzene-divinylbenzene (EVB-DVB) and styrene or polystyrene-divinylbenzene acrylonitrile, acrylic acid, or

25 / 41 metharyl acid. For example: acrylate-divinylbenzene copolymer, methyl acrylate-divinylbenzene copolymer, polyacrylonitrile polymer, polyacrylate polymer, or polymethacrylate polymer.

k. The anion exchange chromatographic material of the present application further comprises a plurality of linkers selected from one or more functional groups suitable for ion exchange. These functional groups are obtained through an amination procedure during the production process of the anion exchange chromatographic material. Such amination process can use, but is not limited to, trimethylamine, trihexylamine, diethylenetriamine, unsymmetrical dimethylhydrazine, dimethylethanolamine, methylamine, dimethylamine, methyldiethanolamine or triethanolamine.

l. Specific examples of anion exchange chromatographic materials include, but are not limited to, LCA01/"Sykam" (Germany); Gelpack GL-IC-A23/“Hitachi”, (Japan); PRP-X100/“Hamilton”, PRP-X110/“Hamilton”, ICSep AN1/“Transgenomic”, ICSep AN1-SC/“Transgenomic”, ICSep AN300/“Transgenomic”, CSep AN300B/“Transgenomic”, Star Ion A300/ “Phenomenex” (USA); Metrosep A Supp 1/“Metrohm”, Metrosep A Supp 1 HS/“Metrohm”, Metrosep A Supp 3/“Metrohm”, Metrosep A Supp 10/“Metrohm”, Metrosep A Supp 15/“Metrohm”, Metrosep A Supp 16 /“Metrohm” (Switzerland); m. Said anion exchange chromatographic material from each column can be equilibrated (conditioned) with a basic solution.

26 / 41

53. In another aspect of the present application, the separation process published herein may also include a selective membrane separation (e.g. nanofiltration membranes) in combination with the chromatographic separation process described herein. Selective membrane separation can be performed before or after chromatographic separation. For example, selective membrane separation techniques, such as nanofiltration membrane separation, can be used to reduce the amount of impurities contained in a mixture (eg, a reaction mixture obtained from the oxidation process of glycerol containing its derivatives) before feeding the mixture to the chromatographic separation device.

Glycerol Derivatives

54. The feed solution may result from a chemical conversion process of glycerol through a variety of processes such as selective oxidation, selective hydrogenolysis, catalytic dehydration, pyrolysis, gasification, selective glycerol transesterification and esterification, selective etherification, and carboxylation.

55. In one embodiment the feed solution can be pretreated by any suitable process to obtain a solution of two or more glycerol derivatives with or without the unreacted glycerol and/or without impurities from the chemical conversion process of glycerol including, but not limited to, ion exchange, distillation, centrifugation and filtration.

27 / 41

56. Derivatives can be dihydroxyacetone (DHA), hydroxypyruvic acid (HPA), glycolic acid (GCO), oxalic acid (OXA), mesoxalic acid (MEO), tartronic acid (TTA), glyceric acid (GCA), glyceraldehyde (GLA ) and glyoxalic acid.

57. The method disclosed herein can be performed with any simulated moving bed chromatography device, including but not limited to multi-valve static column systems and rotating column systems.

58. The method of the present patent application is described in greater detail in the following examples and is not limited by these.

Example 1

59. This example describes the purification of a binary mixture containing glyceric acid and tartronic acid produced from the catalytic oxidation of glycerol. A 4mM sulfuric acid solution was used as eluent and a polystyrene divinibenzene (PS/DVB) resin (brand Dowex® 50WX-2), in hydrogen form (2%), 200-400 mesh, from The Dow Chemical Company (USA) was used as a means of separation.

60. Simulated moving bed separation (LMS) was performed in a unit containing 6 stainless steel columns 100mm high and 20mm in diameter packed with Dowex® 50WX-2 acid resin.

61. Samples of the internal concentration profiles were taken at 25%, 50%, 75% of the switching time, through a 6-way valve installed between two columns. With the valve fixed, as in LMS technology, there is a continuous and cyclical change of position of all columns in relation to the

28 / 41 input and output currents, these samples provided the information needed to determine the internal concentration profile of the compounds.

62. A mixture of glyceric acid (10/L) and tartronic acid (5g/L) was separated. The flow rates were: 6.93ml/min for the eluent stream, 1.16ml/min for the feed stream, 4.81ml/min for the raffinate stream,

3.5ml/min for extract stream and 8.4ml/min for recycle stream. The switching time was set to 2 min.

63. Additionally, one column per section was used in sections 1 and 4 (from fig. 1) (located between the eluent and extract streams and between the raffinate and recycle streams, respectively) and two columns per section in sections 2 and 3 (located between the extract and feed streams and between the feed and raffinate streams, respectively). This is the first industrial method and production of glyceric and tartronic acid.

64. The internal concentration profiles at half the switching time after reaching the steady-cycle state are shown in FIG 2. The main performance parameters are shown in table 1A.

TABLE 1A Main Performance Parameters Extract Productivity (kg m−3ads day−1) 115 Raffinate Productivity (kg m−3ads day−1) 79 Eluent Consumption (m3sesorbent kg−1product) 0.5 Extract Purity (%) 100

29 / 41 Raffinate Purity (%) 80 GCA Recovery (%) 83 TTA Recovery (%) 100 Example 2

65. This example describes the purification of a pseudo-binary mixture, whereby two fractions of glycerol derivatives (A and B plus C) can be purified. In this case, the separation of fraction A (oxalic acid) from fraction B (glyceric acid and unreacted glycerol) plus fraction C (tartronic acid).

66. A 4mM sulfuric acid solution was used as eluent and a polystyrene divinibenzene (PS/DVB) resin (brand Dowex® 50WX-2), in the form of hydrogen (2%), 200-400 mesh, from The Dow Chemical Company (USA) was used as a means of separation.

67. Simulated moving bed separation (LMS) was performed in a unit with 6 stainless steel columns 100mm high and 20mm in diameter packed with Dowex® 50WX-2 acid resin.

68. Samples of the internal concentration profiles were taken at 25%, 50%, 75% of the switching time, through a 6-way valve installed between two columns. Since the valve is fixed, as in LMS technology there is a continuous and cyclical change of position of all columns in relation to the input and output currents, these samples provided the necessary information to determine the internal concentration profile of the compounds.

30 / 41

69. A mixture of oxalic acid (16.5g/L), tartronic acid (7.2g/L), glyceric acid (0.6g/L), and unreacted glycerol (0.6g/L) was separated. The flow rates were: 8.37mL/min for the eluent stream, 1.24mL/min for the feed stream, 2.78mL/min for the raffinate stream,

6.83mL/min for the extract stream and 9.07mL/min for the recycle stream. Switching time has been set to

2.02 min.

70. Additionally, one column per section was used in sections 1 and 4 (from fig. 1) located between the eluent and extract streams and between the raffinate and recycle streams, respectively) and two columns per section in sections 2 and 3 (located between the extract and feed streams and between the feed and raffinate streams, respectively).

71. The internal concentration profiles at the middle of the switching time after reaching the steady-cycle state are shown in FIG 3. The main performance parameters are shown in table 2A.

TABLE 2A Main Performance Parameters Extract Productivity (kg m−3ads day−1) 110.25 Raffinate Productivity (kg m−3ads 215.36 day−1) Eluent Consumption (m3desorbent kg−1product) 0.31 Extract Purity (%) 97.94 Purity Raffinate (%) 99.94 Recovery of Fraction B+C Extract (%) 99.39 Recovery of Fraction A (%) 99.83

31 / 41 Example 3

72. This example describes the purification of a pseudo-ternary mixture, whereby three fractions of glycerol derivatives (A, B and C) can be purified. In this case, the separation of fraction A (oxalic acid) from fraction B (glyceric acid and unreacted glycerol) plus fraction C (tartronic acid) was first performed following the procedure described in example 2. Then, another LMS unit interconnected in series with the previous one, it performed the final purification between fraction B (glyceric acid and unreacted glycerol) and fraction C (tartronic acid).

73. A 4mM sulfuric acid solution was used as eluent and a polystyrene divinibenzene (PS/DVB) resin (brand Dowex® 50WX-2), in the form of hydrogen (2%), 200-400 mesh, from The Dow Chemical Company (USA) was used as a means of separation.

74. Simulated moving bed separation (LMS) was performed in a unit with 6 stainless steel columns 100mm high and 20mm in diameter packed with Dowex® 50WX-2 acid resin.

75. Samples of the internal concentration profiles were taken at 25%, 50%, 75% of the switching time, through a 6-way valve installed between two columns. Since the valve is fixed, as in LMS technology there is a continuous and cyclic change of position of all columns in relation to the input and output currents, these samples provided the necessary information to determine the internal concentration profile of the compounds.

32 / 41

76. A mixture of tartronic acid (7.83g/L), glyceric acid (0.65g/L) and unreacted glycerol (0.65g/L) was purified in the second LMS unit. The flows were:

5.02ml/min for the eluent stream, 1.21ml/min for the feed stream, 2.69ml/min for the raffinate stream, 3.55ml/min for the extract stream and 9.07ml/min for the recycle stream. The switching time was set to 2.00 min.

77. Additionally, one column per section was used in sections 1 and 4 (from fig. 1) located between the eluent and extract streams and between the raffinate and recycle streams, respectively) and two columns per section in sections 2 and 3 (located between the extract and feed streams and between the feed and raffinate streams, respectively).

78. The internal concentration profiles at the middle of the switching time after reaching the steady-cycle state are shown in FIG 4. The main performance parameters are shown in table 3A.

TABLE 3A Main Performance Parameters Extract Productivity (kg m−3ads day−1) 17.17 Raffinate Productivity (kg m−3ads 105.72 day−1) Eluent Consumption (m3desorbent kg−1product) 0.68 Extract Purity (%) 97.27 Purity of Raffinate (%) 99.61

33 / 41 Recovery of Fraction B (%) 97.22 Recovery of Fraction C (%) 99.37 Brief description of the figures

79. For an easier understanding of the present patent application, attached figures represent the preferred forms of implementation, however they are not intended to limit the disclosed technique.

80.FIG. 1 is a schematic diagram of a simulated moving bed chromatographic process used to separate two fractions, A (with lower affinity for separation medium) and B (with higher affinity for separation medium). Section 1 is the separation medium regeneration zone (solid phase) and where fraction B moves with the eluent until it is removed at the extract port. Sections 2 and 3 are the zones where fraction B moves with the separation medium to be removed at the extract port and where fraction A moves with the eluent (or liquid phase) to be removed at the raffinate port. Section 4 is the eluent regeneration zone and where fraction A moves with the separation medium to be removed at the raffinate port.

81. FIG. 2 shows the internal concentration profile at half the switching time after reaching the cyclic steady state. Dotted lines represent the GCA and solid lines represent the TTA. The horizontal coordinate shows the axial position of the LMS equipment columns and the vertical coordinate shows the concentration (g/L).

34 / 41

82. FIG. 3 shows the internal concentration profile at half the switching time after reaching the cyclic steady state. Dotted lines represent fraction A and solid lines represent fraction B plus fraction C. The horizontal coordinate shows the axial position of the columns within the LMS equipment and the vertical coordinate shows the concentration (g/L).

83. FIG. 4 shows the internal concentration profile at halfway through the switching time after reaching the cyclic steady state. Dotted lines represent fraction C and solid lines represent fraction B. The horizontal coordinate shows the axial position of the columns within the LMS equipment and the vertical coordinate shows the concentration (g/L).

Best way to conduct the invention

84. Preferred embodiments of the present application will be described in detail later. However, the embodiments described herein are not intended to limit the scope of the present application.

85. In one embodiment, the simulated moving bed chromatographic method for the separation of glycerol derivatives from a feed solution containing said glycerol derivative and one or more other glycerol derivative, or impurities, comprises: (a ) selecting a simulated moving bed chromatographic device comprising at least two chromatographic columns interconnected in series; where said columns contain a means of separation (stationary phase) or a

35 / 41 mixing of a variety of separation media, capable of effecting ion exchange; sequentially comprising an eluent port, an extract port, a feed port and a raffinate port; and simultaneously, (b) contacting, through said feed port, a feed solution with the balanced separation means with an acidic or basic solution or a water-organic mixture or water; and (c) contacting, through said eluent port, an acidic or basic eluent with the separating material, where the eluent may be an acidic solution or a basic solution or a water-organic or water mixture; and (d) allowing the collection, through said raffinate or extract ports, of a stream of raffinate or extract, respectively, comprising the liquid phase and mainly one of the glycerol derivatives, and may also have a percentage of one of said glycerol derivatives, and/or unreacted glycerol, and/or impurities present in said feed solution.

86. In one embodiment, the simulated moving bed chromatographic device may further comprise additional raffinate or extract streams allowing the execution of ternary, pseudo-ternary or higher order separations; the removal, through said outlet ports, a stream of raffinate or extract comprising the fluid mobile phase, an acidic solution or basic solution or mixture of water-organic or water and mainly one of the glycerol derivatives, which may also have a percentage of one of said glycerol derivatives, and/or unreacted glycerol, and/or impurity present in said feed solution.

36 / 41

87. In one embodiment, the simulated moving bed chromatographic device may further comprise a second eluent port for performing eluent gradients within the unit; promoting contact, through said second port of an eluent, an acidic solution or a basic solution or a water-organic mixture or water with said separation means.

88. In one embodiment, said glycerol derivatives may be dihydroxyacetone (DHA), hydroxypyruvic acid (HPA), glycolic acid (GCO), oxalic acid (OXA), mesoxalic acid (MEO), tartronic acid (TTA), glyceric acid (GCA), glyceraldehyde (GLA) and glyoxalic acid.

89. In one embodiment, the feed solution is the product of chemical conversion of glycerol from a variety of processes such as selective oxidation, selective hydrogenolysis, catalytic dehydration, pyrolysis, gasification, selective glycerol transesterification and esterification, selective etherification and carboxylation.

90. In one embodiment, the pH of said feed solution is comprised between 1 and 13 through the addition of acidic or basic species. In a preferred embodiment, the pH of said feed solution is comprised between 1 and 7 by the addition of acidic or basic species. In a preferred embodiment, the pH of said feed solution is comprised between 1 and 5 by the addition of acidic or basic species.

91. In one embodiment the feed solution may be pretreated by any suitable process to obtain

37 / 41 a solution of two or more glycerol derivatives with or without unreacted glycerol and/or without impurities from the chemical glycerol conversion process including, but not limited to, ion exchange, distillation, centrifugation and filtration .

92. In another embodiment prior to step (b), the feed solution is pretreated by any other suitable process to obtain a solution of two or more glycerol derivatives with or without the unreacted glycerol and/or without impurities from the chemical glycerol conversion process including, but not limited to, ion exchange, centrifugation and filtration, including ultrafiltration.

93. In one embodiment, the separation medium is a chromatographic material where said cation exchange chromatographic material is selected from alumina, magnesium silicates, silica, glass, controlled pore glass, carbon, porous carbon, zirconium phosphate, hydroxyapatite, calcium phosphate, magnesium carbonate, and polymers or resins. In a particular embodiment said polymers or resins for cation exchange chromatography are selected from hydroxyalkylmethacrolate, polyacrylamide, polyacrylamine, polymacrolate, poly(hydroxyethyl macrolate), polystyrene, styrene-divinylbenzene polymers, poly(ethyleneglycoldimethacrolate), poly(vinylalcohol), poly(vinylacetate) and poly(vinylpyridine).

94. In another embodiment, the cation exchange chromatographic material from each chromatographic column is equilibrated (conditioned) with an acidic solution.

38 / 41

95. In one embodiment, the separation medium is a chromatographic material where said anion exchange chromatographic material is by selecting between polymers, resins, silica, zirconia, carbon and alumina, where said polymers or resins for anion exchange chromatography are selected from poly(vinylalcohol), poly(methacrylates), polystyrene with high density crosslinks and poly(ethylene oxide) and polymers of styrene or ethylvinylbenzene or copolymers crosslinked with divinylbenzene (eg, ethylvinylbenzene-divinylbenzene (EVB-DVB) ) and styrene or polystyrene-divinylbenzene acrylonitrile, acrylic acid, or methacrylic acid In one embodiment, said anion exchange chromatographic material within each column may be equilibrated (conditioned) with a basic solution.

96. In one embodiment, the eluent is an acidic or basic solution or a water-organic or water mixture.

97. Simulated moving bed chromatography may be practiced by any simulated moving bed device, including but not limited to multi-valve static column systems and rotating column systems.

98. This description is in no way restricted to the forms of implementation presented here and anyone with an average knowledge of the field can use several possibilities to modify this description without departing from the general idea as defined by the claims. The preferred embodiments for the implementation described above can obviously be combined

39 / 41 each other. The following claims further define preferred forms of implementation.

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Claims (22)

1 / 6 CLAIMS “PROCESS OF SEPARATION AND PURIFICATION OF GLYCEROL DERIVATIVES 1. SEPARATION AND PURIFICATION PROCESS OF GLYCEROL DERIVATIVES characterized by being chromatographic by simulated moving bed to separate a glycerol derivative from a feed mixture, containing the glycerol derivative and at least one other compound, such as another organic compound and/ or another unreacted and/or impure glycerol and/or glycerol derivative, comprising: (a) selecting a simulated moving bed chromatographic device comprising at least two chromatographic columns interconnected in series; wherein said columns contain a separation medium (stationary phase) or a mixture of a variety of separation means capable of effecting ion exchange; sequentially comprising an eluent port, an extract port, a feed port and a raffinate port; and simultaneously, (b) contacting, through said feed port, a feed solution with the balanced separation means with an acidic or basic solution or a water-organic mixture or water; and (c) contacting, through said eluent port, an acidic or basic eluent with the separating material, where the eluent may be an acidic or basic solution or a water-organic mixture or water; (d) allow the collection, through said raffinate or extract ports, of a stream of raffinate or extract, respectively, comprising the liquid phase and 2 / 6 mainly one of the glycerol derivatives, it may also have a percentage of one of said glycerol derivatives, and/or unreacted glycerol, and/or impurity present in said feed solution. Process according to claim 1, characterized in that the simulated moving bed chromatographic device further comprises additional streams of raffinate or extract; to collect, through said outlet ports, a stream of raffinate or extract comprising the eluent, an acidic or basic solution or a mixture of water-organic or water and mainly one of the glycerol derivatives, which may also have a percentage of one of said glycerol derivatives, and/or unreacted glycerol, and/or impurity present in said feed solution. Process according to any one of the preceding claims, characterized in that the simulated moving bed chromatographic device may further comprise a second eluent port for performing eluent gradients within the unit; promoting contact, through said second eluent port, of an acidic solution or a basic solution or a water-organic mixture or water with said separation means. Process according to any one of the preceding claims, characterized in that said glycerol derivative is selected from dihydroxyacetone (DHA), hydroxypyruvic acid (HPA), glycolic acid (GCO), oxalic acid 3 / 6 (OXA), mesoxalic acid (MEO), tartronic acid (TTA), glyceric acid (GCA), glyceraldehyde (GLA), glyoxal acid (GOX) or any other glycerol derivative 5. Process according to any one of the preceding claims, characterized in that the feed solution is the product of chemical conversion of glycerol from a variety of processes such as selective oxidation, selective hydrogenolysis, catalytic dehydration, pyrolysis, gasification, selective transesterification of glycerol and esterification, selective etherification and carboxylation. Process according to claim 5, characterized in that the pH of said feed solution is comprised between 1 and 13 through the addition of acidic or basic species. Process according to claim 6, characterized in that the pH of said feed solution is comprised between 1 and 7 through the addition of acidic or basic species. Process according to claim 7, characterized in that the pH of said feed solution is comprised between 1 and 5 through the addition of acidic or basic species. Process according to any one of the preceding claims, characterized in that the feed solution is pretreated by any other suitable process to obtain a solution of two or more glycerol derivatives with or without the unreacted glycerol and/or no impurities. 4/6 Process according to claim 9, characterized in that the pre-treatment process is a process selected from ion exchange, distillation, centrifugation or filtration. Process according to any one of the preceding claims, characterized in that said separating material is a chromotographic material of cation or anion exchange. Process according to any one of the preceding claims, characterized in that said cation exchange chromatographic material is selected from alumina, magnesium silicates, silica, glass, controlled pore glass, carbon, zirconium phosphate, hydroxyapatite, phosphate of calcium, magnesium carbonate, and polymers or resins. Process according to claim 12, characterized in that said polymers or resins for cation exchange chromatography are selected from hydroxyalkylmethacrolate, polyacrylamide, polyacrylamine, polymacrolate, poly(hydroxyethyl macrolate), polystyrene, styrene-divinylbenzene polymers, poly(ethylene glycol dimethacrolate ), poly(vinylalcohol), poly(vinylacetate) and poly(vinylpyridine). Process according to any one of claims 12 and 13, characterized in that said chromatographic material 5/6 cation exchange of each chromatographic column be balanced with an acidic solution or a water-organic mixture or water; Process according to claim 11, characterized in that said anion exchange chromatographic material is selected from polymers, resins, silica, zirconia, carbon and alumina. Process according to claim 11, characterized in that said polymers or resins for anion exchange chromatography can be selected from poly(vinylalcohol), poly(methacrylates), polystyrene with high cross-linked density and poly(ethylene oxide ) and polymers of styrene or ethylvinylbenzene or copolymers crosslinked with divinylbenzene (eg, ethylvinylbenzene-divinylbenzene (EVB-DVB) and styrene or polystyrene-divinylbenzene acrylonitrile, acrylic acid, or metharyl acid. Process according to any one of claims 15 and 16, characterized in that said anion exchange chromatographic material of each chromatographic column is balanced with a basic solution or a mixture of water-organic or water; Process according to any one of the preceding claims, characterized in that the eluent is an acidic solution or a basic solution or a mixture of water-organic or water; 6/6 Process according to claim 18, characterized in that the pH of said feed solution is comprised between 1 and 13 through the addition of acidic or basic species. Process according to claim 18, characterized in that the pH of said feed solution is comprised between 1 and 17 through the addition of acidic or basic species. Process according to claim 18, characterized in that the pH of said feed solution is comprised between 1 and 5 through the addition of acidic or basic species. Process according to any one of the preceding claims, characterized in that simulated moving bed chromatography can be performed with any simulated moving bed chromatographic device but not limited to static column systems with multiple valves and rotating column systems. 1 / 4 Figure 1 2/4 Figure 2 3/4 Figure 3 4/4 Figure 4