FI118564B - Process for separating betaine - Google Patents

Description

118564

Method for separating betaine

Field of the Invention

The present invention relates to a process for the chromatographic separation of betaine with a weakly acidic cation exchange resin 5 in H + form from sugar beet-based solutions. Suitable sugar beet-based solutions include, for example, solutions obtained from the treatment of beet-derived solutions, me-Lasses, fermentation process solutions and vinasse. The present invention also relates to a method for chromatographic separation of other compounds, such as polyols and / or carboxylic acids, with a weakly acidic cation exchange resin in H + form from sugar beet based solutions.

Background of the Invention

Chromatographic separation has been used to recover betaine from natural materials such as beet molasses, betaine molasses and vinasses. The most commonly used resins in the known chromatographic separations have been strongly acidic cation exchangers, i.e. sulfonated polystyrene crosslinked with 3.5-8% by weight of divinylbenzene, in which the resin is in monovalent or divalent form. Water has generally been a preferred eluent, but the problem with using water has been that different products such as betaine, erythritol, inositol, sucrose and mannitol have similar retention times, with fractions overlapping.

U.S. Patent 4,359,430 describes a process for recovering betaine from molasses and vinasse using a polystyrene sulfonate salt as a cation exchange resin on a chromatographic column and eluting with water. The strongly acidic cation exchange resin is in the alkali metal form. The first fraction to be separated is the waste fraction, the second fraction contains a substantial proportion of the sugars in the feed solution and the third fraction consists mainly of betaine.

U.S. Patent Application 2002/0120135 describes a method for chromatographically separating rhamnose and arabinose from other monosaccharides from the nucleus of the crystallization of xy: ***: lose using a weakly cation exchange resin in the H + / Mg 2+ form.

US Patent Application 2005/0161401 describes a chromatographic method for separating betaine, mannitol, glycerol and inositol using a weakly basic anion exchange resin.

*: ··· U.S. Patent 6,770,757 discloses a process for the preparation of betaine and other compounds such as erythritol, inositol, mannitol, glycerol and amino acids from starting materials containing the corresponding compounds using the weak Na + form. acidic cation exchange resin in a chromatographic separation system. The pH values of the feed solutions range from pH 6 to pH 11 and the effluent from the column is between pH 6.511.

5 Betaine is eluted from the system after salts, followed by erythritol, mannitol and glycerol. Inositol is eluted as the last discrete peak.

U.S. Patent 5,032,686 describes a process for recovering citric acid from fermentation solutions using a strongly acidic cation exchange resin in the H + form. The first eluted fractions contained high molecular weight compounds such as sucrose, maltose and isomaltose. The following fractions contained citric acid and the final fractions contained for example betaine and various organic acids such as gluconic acid, oxalic acid.

Tanaka K. et al. (Journal of Chromatography 850 (1999), 187-196) describe an analytical ion removal chromatography method for the separation of carboxylic acids with a weakly acidic cation exchange resin in the H + form. When water was used as eluent, the shape and resolution of the carboxylic acid peak were not satisfactory. To improve peak shape, dilute sulfuric acid solution was tested as eluent. In addition, the addition of methanol to this eluent was found to reduce the retention times of the hydrophobic carboxylic acids. In addition to molecular size exclusion and ion exclusion, the order of elution was influenced by the pKa values and hydrophobic / hydrophilic nature of the carboxylic acids.

·: ·: It has surprisingly been found that when using a weakly acidic cation exchange resin in the H + form, betaine can be separated from sugar beet base. 25 icy solutions such as fermentation solutions, vinasse and other · »·«. . ·. sugar beet as a separate fraction from the derived solutions eluting with them. ···. compounds previously known to elute after betaine. Thus, the order of elution of betaine with the weakly acidic cation exchange resin in the H + form is different from the prior art with strong acid cation exchange resins or the weakly acidic cation exchange resin in the Na * form. This phenomenon is particularly advantageous when fractionating solutions of mono-*** containing betaine and other compounds having similar or almost identical retention times with other separation media. SUMMARY OF THE INVENTION The present invention relates to a process for the chromatographic separation of betaine from sugar beet-based solutions with an acidic cation exchange resin in the H + form. The present invention also relates to a process for the chromatographic separation of other compounds, such as polyols and / or carboxylic acids, from sugar beet-based solutions with a weakly acidic cation exchange resin in the H + form. Furthermore, the present invention relates to a process for the chromatographic separation of betaine from other carboxylic compounds with a weakly acidic cation exchange resin in the H + form. Further, the present invention relates to a process for separating betaine from a sugar beet-based solution in a chromatographic separation system, wherein the weakly acidic cation exchange resin 10 in H + is used in at least one chromatographic column or part of the column for chromatographic separation. The present invention also relates to a process for the chromatographic separation of betaine from sugar beet-based solutions with a weakly acidic cation exchange resin in the Ι-Γ form wherein the pH of the chromatographic system is used to adjust and / or control the retention factor of be-15. Furthermore, the present invention relates to the use of a weakly acidic cation exchange resin in H + form for chromatographic separation of betaine and optionally from a sugar beet solution of other compounds such as polyols and / or carboxylic acids. The present invention also relates to the use of a weakly acidic cation exchange resin 20 in the H + form for the chromatographic separation of betaine from other carboxylic compounds.

··· ♦

Brief Description of the Drawings e ·. ···. The following drawings are illustrative of the invention and are not intended to limit the scope of the invention as defined in the claims.

*; “* Figure 1 is a graph showing the elution profiles of 1 * ··· * and pH according to Example 1.

Figure 2 is a graphical representation of the elution profiles • · • * ·· and pH according to Example 2.

Figure 3 is a graphical representation of the elution profiles according to Example 3. ···. japH: STA3.

• ·

Figure 4 is a graphical representation of the elution profiles of Example 4. and pH 4.

Fig. 5 is a graph of the elution profiles of Example 5 ·: ··: 35 and pH 5.

4, 118564

Figure 6 is a graphical representation of the elution profiles and pH 6 of Example 6.

Detailed Description of the Invention

There is a continuing need to utilize additional raw materials to recover industrially and / or nutritionally valuable compounds such as betaine, polyols and carboxylic acids. One alternative solution for recovering these compounds is to use sugar beet-based fermentation process solutions, such as citric acid, yeast or ethanol fermentation process solutions, or vinasse, such as citric acid or ethanolol vinasse, as raw materials. It has now surprisingly been found that when using a weakly acidic cation exchange resin in the H + form, betaine can be separated as a very pure fraction from the fermentation process solutions. In addition, the acidic fermentation process solution or the vinasse in general, and in particular the vinasse obtained from the citric acid fermentation broth, was found to be suitable for the chromatographic separation of chromium-15 by the weakly acidic cation exchange resin in the H + form. Thus, pre-treatment of the solution to adjust the pH prior to chromatographic separation would not be necessary.

Under the conditions described above, for example, the strongly acidic cation exchange resin (SAC) in the H + form would not remain stable. When salts are present in the feed solution 20, the functional group of the SAC resin is very easily converted from ··· l-f to the metal cation form, even in an acidic environment, unlike the weakly acidic cation exchange resin.

. ···. According to the present invention, the weakly cation exchange resin in the H + form is used in a process for the separation of betaine chromatography from ur ♦ ♦ ”Y from sugar beet solutions. According to the present invention, the weakly acidic cation exchange resin in the H + form is also used in the process for the chromatographic separation of compounds other than betaine, such as polyols and carboxylic acids, from caspase-based: *** solutions. In addition, according to the present invention, the weakly acidic cation exchange resin in the form hi * - 30 is used in a process. pulp for chromatographic separation of betaine from other carboxylic compounds.

• ·

According to the present invention, the weakly acidic ka- ♦ ♦ in H + form. The thion exchange resin is used in at least one chromatographic separation step to separate the betaine. Further, according to the present invention, the weakly acidic cation exchange resin in the form of H + - * "* 35 is used in at least one chromatographic column or in one column packed partially in a chromatographic separation system for separating betaine from sugar beet solutions.

In the present invention, the weakly acidic cation exchange resin in the 1-T form refers to the weakly acidic cation exchange resin mainly in the non-dissociated COOH form. The amount of the weakly acidic cation exchange resin in the non-dissociated COOH form according to the invention is more than 50%, preferably at least 67% and more preferably more than 90%.

The beet-based solution of the present invention is any beet-derived solution, hydrolyzate and / or extract. The solution may be obtained by further treatment of such beet-derived solutions by fermentation, for example by fermentation of citric acid, yeast or ethanol, or by treatment of solutions derived from sugar beet, such as beet and / or betaine molasses or vinasse. Fermentation solutions, molasses and vinasse additionally contain a large amount of inorganic salts and various types of organic compounds. Other compounds to be isolated by the process of the present invention are polyols such as erythritol, inositol, mannitol and glycerol and / or carboxylic acids such as citric acid, lactic acid, acetic acid, oxalic acid and pyrrolidone carboxylic acid and / or mixtures thereof. In the chromatographic separation of the present invention, the compounds are separated into fractions which are enriched for the target compound. The enriched fraction contains a higher concentration of · ··· based on the dry weight of the compound than the feed solution.

· ***: The method according to the present invention could be performed by it ···:. 25 as such or it could be combined with other process steps or it could be! ”·! such as, for example, additional chromatographic separation, crystallization, evaporation, ion exchange, filtration, membrane filtration, and / or any other known process step. Preferably, the process of the invention can be combined with or comprise one or more of the aforementioned lisä ** 30 additional processing steps.

! ...: An additional chromatographic separation step could be performed. ***. using, for example, a highly acidic cation exchange resin (SAC),

• M

freshly basic anion exchange resin (SBA) or weakly basic; anion exchange resin (WBA) according to the composition of the sugar beet stock solution and / or compounds selected for resolution.

♦ • · 6 118564

The process of the invention may advantageously be combined with or comprise an additional step for the recovery of betaine. For example, betaine recovery could be accomplished by crystallization. The process of the invention may also optionally be combined with, or may comprise, an additional step for recovering another compound or compounds, such as polyols and / or carboxylic acids.

The chromatographic column or part of the column (partially packed column of the column) used in the process of the present invention is filled with a weak (ions cation exchange resin, preferably an acrylic cation exchange resin having carboxyl functionalities, preferably acrylic methylethyl), in Ι-Γ form. , butyl acrylate, methyl methacrylate or acrylonitrile or acrylic acids or mixtures thereof The resin may be crosslinked with a crosslinking agent, e.g., di-vinylbenzene (DVB) A suitable level of crosslinking is 1-20%, preferably 3-8%. the particle size is usually 10 to 2000 µm, preferably 100 to 400 µm.

The chromatographic separation is preferably carried out at temperatures between 10 ° C and 95 ° C, more preferably between 30 ° C and 95 ° C, most preferably between 65 ° C and 95 ° C. It is known that a higher separation temperature reduces viscosity and improves the separation performance, but is more detrimental to sensitive compounds in the feed solution.

The eluent used in the chromatographic separation according to the present invention is preferably water or pH adjusted water.

·: *: Optional pre-treatment of the beet-based solution to be fractionated · **; ie, prior to chromatographic separation by filtration, which may be carried out. 25 using a pressure filter with or without filter aid. Further, if necessary, the pH of the solution used as the feed solution is adjusted to below pH 6, preferably below pH 5.1, more preferably between pH 1.4 and 5.1. *** Nile, and most preferably between pH 3 and pH 4.5 When the feed solution has a high pH (> 4.2), the weakly acidic cation exchange resin of the invention is partially converted from its original H + form to an ionic form and thus equilibrated to a particular H + form, the type of lone is dependent on the ions of the feed solution.

. ***. The feed solution can be filtered before or after pH adjustment.

· · ·

Prior to chromatographic separation, the solids of the feed solution are adjusted to an appropriate level.

• ♦ · * ··· * 35 The feeder is used to feed the solution to the column. Most preferably, the temperature of the column, the feed solution and the eluent is approximately the same as the temperature of the chromatographic separation of the chromium. This is achieved by preheating the feed solution. The feed solution is eluted on the column by feeding water, for example de-mineralized water or condensate water or some other aqueous solution to the column. Pre-heated eluent is preferably used. The flow rate in column 5 is adjusted to a suitable level. Fractions of effluent solutions are collected at appropriate intervals and analyzed. The outflow from the column can be monitored with on-line instruments. Fractionated products, e.g. betaine, and optionally also polyols such as erythritol, mannitol, inositol, glycerol and / or carboxylic acids such as citric acid, oxalic acid, lactic acid, acetic acid and / or pyrrolidone carboxylic acid may be recovered, e.g. crystallization.

The process of the present invention could be carried out as a separate step in the multistep process, using, for example, chromatographic separation, crystallization, evaporation and / or filtration at least once as an additional step in the multistep process. Further, it is possible to arrange two or more chromatographic columns in a sequence in which at least one column or part of the column contains a weakly acidic cation exchange resin in hT form, wherein the other column or columns contain the same or different types of resin such as a strongly acidic cation exchange resin. The chromatographic system used may be either a batch process or a simulated moving bed system. The simulated moving bed system can be J · either continuous or sequential.

··· · It is also possible to combine with some other process unit. Handle two chromatographic columns or column sections containing weakly acidic cation exchange resin in H + - form. Process units may be, for example, filtration, membrane filtration, pH adjustment, or XI * concentration by evaporation. It will be apparent to one skilled in the art that the order of the process units * * may be varied and varied.

In one embodiment, the process of the invention is carried out as an independent process. In this embodiment, the beet-based solution of the beet can be fractionated with the weakly acidic ka · ··· thion exchange resin in the H-form to the betaine-containing fraction and optionally to the other compound-containing fraction. Preferably betaine and optionally other. the compound is further recovered from the fraction containing the specific compound. Other compounds which can be resolved by the process of the present invention are polyols such as erythritol, inositol, mannitol, glycerol and / or carboxylic acids, such as citric acid, lactic acid, acetic acid and / or their pyrrolidonic carboxylic acids and / or .

In another embodiment, the process of the invention is performed as a separate step in a multistep process, whereby it is compounded into at least one further process step. In this embodiment, the sugar-beet-based solution may be fractionated on a first column containing, for example, a strongly acidic cation exchange resin coupled to a second column containing a weakly acidic cation exchange resin in H + form, optionally containing the other compound. Preferably betaine and optionally also the other compound is further recovered from the fraction containing the specific compound. Such an arrangement further improves the performance of the separation and increases the yield and purity of the products. The yield of betaine is also improved when the by-products are removed from the process.

In yet another embodiment, the method of the invention comprises at least one additional process step, wherein the method of the invention is a separate step in a multistep process. An additional process step could be, for example, chromatographic separation, crystallization, evaporation, filtration and / or membrane filtration.

In general, the elution order of the various compounds on weakly acidic cation exchange resins appears to be influenced by hydrophobic / hydrophilic interaction of the compounds with the resin in addition to molecular size exclusion and ionic lysis. According to previous studies, the order of elution of the various compounds. The weakly acidic cation exchange resin in the H + form of carboxylic acids (eg, carboxylic acids) affects the pKa of the compounds. Generally, the lower the pKa value of e · 1 "Y, the shorter the retention time of the same compound. However, the elution order of betaine (pKa = 1.832) on the weakly acidic cation exchange resin in the H + form does not follow these rules. Surprisingly, the weakly acidic cation exchange resin in the H + form appears to be more hydrophobic: *** than the metal cation form and has a very high affinity for betaine, which is a hydrophobic molecule.

, ···. In the process of the present invention, the elution order of the isolated compounds on the chromatographic column is different from that of the +. the order obtained by prior methods e.g. based on the use of a weakly acidic cation exchange resin in Na form or the use of highly acidic cation exchange resins and this feature can advantageously be used to separate the components of the multicomponent compound. betaine is eluted after erythritol, inositol, mannitol, glycerol and carboxylic acids, and, for example, inositol elutes before glycerol and betaine in the process of the invention.

Surprisingly, the volume retention of betaine and the retention factor were found to vary with pH, particularly with the pH of the feed solution; the lower the pH, the higher the retention factor. Elution of betaine from the chromatographic separation column is affected by changes in the pH of the feed solution, whereas most carboxyl compounds elute approximately simultaneously, regardless of the pH of the feed solution. The betaine retention factor can be controlled and / or regulated by adjusting the pH of the chromatographic separation. Adjustment of the pH of the chromatographic separation can be accomplished by adjusting the pH of the eluent and / or feed, but is preferably accomplished by adjusting the pH of the feed solution to the desired level. For example, by changing the pH of the feed solution from 5.1 to pH 1.4, the retention factor of betaine is changed from 1.3 to 2.9. Thus, by adjusting the pH of the feed solution, the chromatographic separation of betaine from other compounds in sugar beet-based solutions can be optimized with a weakly acidic cation exchange resin in the H + form. The pH adjustment of the feed solution may also be used to control and / or regulate the chromatographic separation of betaine from other carboxylic compounds with a weakly acidic cation exchange resin in the H + form.

*: **: The process of the present invention enables the concentration of betaine from a sugar beet-based solution to a betaine fraction having a maximum purity of more than 50% on a dry matter basis (DS), preferably above 70% DS.

• · *. ···. The process of the present invention enables the separation and optionally also recovery of betaine in high yields and high purity (80-95% DS) from sugar beet-based solution, • t **, // from fermentation process solutions and / or vinasse. , which has been laborious by known procedures using, for example, a weakly acidic: ***: cation exchange resin or a strongly acidic cation exchange resin in the Na + form. For example, when a strongly acidic cation exchange (SAC) resin is used to chromatographically separate betaine, the same yields and purity are achieved by two chromatographic separations at the same time as required. only *: one difference with weakly acidic cation exchange resin in H + form.

10 118564

In addition, the process of the present invention also enables the isolation and recovery of other compounds such as polyols such as erythritol, inositol, mannitol, glycerol and / or carboxylic acids such as citric acid, lactic acid and / or pyrrolidone carboxylic acid in good yield and purification by fermentation, which has also been laborious with known methods.

In one embodiment of the process of the invention, using citric acid vinegar as a feed solution, betaine can be enriched in a beta-fraction having a purity greater than 60% DS, more preferably greater than 80% DS, and sit-10 tartaric acid as a separate fraction greater than 20% DS, more preferably greater than 35% DS .

An advantage of the process of the present invention is that one eluent, water, could be used effectively to separate the desired compounds with a weakly acidic cation exchange resin in H1 form and also in optional additional chromatographic steps. When water is used as eluent for chromatographic separation, handling is easier, costs are lower and reliability is improved. The different elution order of the separation of betaine and, for example, inositol provides an additional advantage in the process of the present invention, allowing the separation of betaine and other compounds such as erythritol, inositol, mannitol, glycerol, citric acid, lactic acid and / or pyrrolidonic carboxylic acid.

m The terms related to IUPAC (International Union of Pure and Applied Chemistry) mu - *: **, chromatographic process and chromatography theory include: ··· •; 1; · Hold-up volume (time) (VM, tM) is equal to the re-♦ ·· · of the non-retentated compound. . ·. tenti volume (time).

. ···. · The adjusted retention volume (time) (VR ', tR') is the total recovery volume ♦ · (time) minus the hold-up volume (time).

.. · The retention factor (k) is the ratio of the mathematically adjusted retention volume (time) • · Σ., 1 '30 to the hold-up volume (time): k = VR' / VM = tRVtM.

1 * ·· ** The following examples illustrate the present invention. The examples are not intended to limit the claims in any way.

··· • · ··· * · · · ··· · 11 118564 EXAMPLE11

Comparative Example of Chromatographic Separation of Betaine from Sputum with Mild Acid Cation Exchange Resin in Na + (pH 8.9) 5 Betaine from Sputum was derived from chromatographic separation of beet molasses and contained several compounds such as betaine, inositol, erythritol, mannitol. As a feed solution, it was subjected to chromatographic separation, which was performed on a laboratory-scale chromatographic separation column as a batch process. A column of 0.045 m in diameter was filled with acrylic-10 weakly acid cation exchange resin (Finex CA 12 GC), manufactured by Finex Oy, Finland. The resin was an ethyl acrylate based resin. The resin had a height of about 0.70 m. The degree of crosslinking of the resin was 6.0% DVB and the average particle size of the resin was 0.26 mm. The resin was in Na + form. The pH of the resin was high after the manufacturing process. The feeder was placed on top of the resin layer. The temperature of the column, the feed solution and the eluent water was about 80 ° C. The column flow rate was adjusted to 4 ml / min. The feed solution was filtered through a filter using diatomaceous earth as a filter aid. The pH of the feed solution was 8.9.

Chromatographic separation was carried out as follows:

Step 1: The dry solids of the feed solution were determined and adjusted to 20 g of dry solids per 100 g of solution according to the refractive index of the solution (R1).

Step 2: 100 ml of preheated feed solution was pumped over the resin layer (through the feeder).

· · ·

Step 3: The feed solution was eluted down the column by injecting preheated ion exchange water over the column.

: Step 4: Samples of 10 ml of the effluent were collected for 3 min ···; ***. every tin. The concentration, conductivity (mS / cm) and pH of the samples were determined.

The composition of the samples was analyzed by HPLC (Ca 2+ column, 0.6 mL / min, 0.001 M Ca (NO 3) 2, 85 ° C).

• «« I · .., 30 Betaine eluted from the column after the salts. Sucrose had almost the same retention time as betaine. With a 99 minute hold-up volume and a 168 minute elution time, a retention factor of 0.7 was obtained for betaine. Erythritol, mannitol *: **, and glycerol had almost the same retention time eluting as a single peak after beta. Inositol eluted as the last single peak. The elution order appears to be consistent with the hydrophobic / hydrophilic nature of the components. The resin separated the betaine and inositol well from the other main components. The pH of the effluent (i.e., the effluent solution) was 8-11. The separation profile is shown in Figure 1.

EXAMPLE 2

Chromatographic separation of Vinass with weak 5 (cation exchange resin, pH 3.6) in H +

The starting solution used for the separation was vinasse from the citric acid fermentation process. Vinassi contained mainly betaine, glycerol, inorganic salts and organic acids such as citric acid and had the following composition (% by RDS): 10 Betaine 17.1

Glycerol 1.8 Citric acid 7.8 Other 73.3 The pH of the solution was 3.6.

The solution was filtered through a pad of diatomaceous earth as a filter aid. Vinass was used as a feed solution and subjected to chromatographic separation. Separation was performed on a test-scale chromatographic separation column as a batch process. A 0.09 m diameter column was filled with weakly acid cation exchange resin (Finex CA 16 GC, 8% DVB, 4.4 eq / l), manufactured by Finex Oy, Finland. The resin was an acrylate based t> 1: 2 resin and the average resin particle size in the form of sodium was 0.41 mm.

···: The resin was regenerated to hydrogen (H +) form, followed by a resin layer height of .3. The temperature of the column, the feed solution and the eluent water was:. 75 ° C. The flow rate in the column was adjusted to 3 L / h.

• 1 · 2V 25 Chromatographic separation was performed by repeating the following steps: * · ***** Step 1: The feed solution solids were adjusted to 35 g solids per 100 g solution refractive index ( Rl).

: 3 Step 2: 640 ml of preheated feed solution was pumped onto a resin layer.

.3. Step 3: The feed solution was eluted down the column by injecting preheated ion exchange water over the column.

• ·

Step 4: 50 ml samples of the effluent solution were collected at 5 minute intervals. The concentration, conductivity (mS / cm) and pH of the samples were determined. The composition of the samples was analyzed by HPLC (Na + column, 3 0.6 ml / min, 85 ° C, 0.003 M Na 2 SO 4).

118564 13

Elution began with inorganic salts and continued with organic acids and alditols. Betaine eluted from the column as the last of the major components. The pH of Effluent ranged from 1.9 to 4.6. A total of 5 feeds were made during which the ionic form of the resin was not completely stabilized. After these separations, 93% of the 5 resins were in hydrogen form over the resin layer. The resin separated the betaine very well from the other components; hold-up volume was 75 min and elution time 278 min. The retention factor for betaine in this difference was 2.7. Betaine could be collected as a high purity (80-95% / DS) fraction in good yield (> 90%). Citric acid was collected as a fraction having a purity of 20-50% DS. The organic acid retention factors (k) for betaine and some of its feed solutions are shown in Table 1. The pKa values in Table 1 are derived from Lange's Handbook of Chemistry, (15th Edition), 1999. It can be seen that these acids elute with their pKa (1). .) by value. Surprisingly, betaine with a pKa of 1.832 is an exception and elutes as the last component. The separation profile 15 is shown in Figure 2.

Table 1_______ compound Hold-up time k Elution time pKa 1/2./3. dissociation constant _ [min] ___ [min] at -25 ° C_ oxalic acid 75_0.6 120_ 1.271 / 4.272_ citric acid 75_0.941_3.128 / 4,761 / 6,396_ lactic acid 75__1.5 186_ 3.858_ • •• 5 acetic acid 75 2, 4,258 4,756 • 1 .... ....... "· · - - 1" betaines 75 2,7 278 1,832 «« · _ '—1 • · t · ··· • φ • *! * EXAMPLE 3 • · ·

Chromatographic separation of vinassin with weakly acidic cation exchange resin (pH 5.1) in H + form

The starting solution used in the separation was vinassin obtained from the ethanol fermentation process. Vinassi contained mainly betaine, glycerol, inorganic salts and organic acids and had the following composition (% by RDS): ·: · * · 25 Betaine 13.8

Glycerol 12.3 · · ** ·· [Other 73.9 * * The pH of the solution was 5.1.

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The solution was filtered through a pad of diatomaceous earth as a filter aid. Vinass was used as a feed solution and subjected to chromatographic separation. Separation was carried out on a test-scale chromatographic separation column as a batch process. The column, 0.09 m in diameter, was filled with 5 weakly acidic cation exchange resins (Finex CA 16 GC, 8% DVB, capacity 4.4 eq / l), manufactured by Finex Oy, Finland. The resin was an acrylate-based resin and the average particle size of the resin in the sodium form was 0.41 mm. The resin was regenerated to the hydrogen (H +) form, after which the height of the resin layer was approximately 1.7 m. The temperature of the column, the feed solution and the eluent water was 10 75 ° C. The flow rate in the column was adjusted to 3 L / h. Chromatographic separation was carried out as follows:

Step 1: The feed solution solids were adjusted to 35 g of solids per 100 g of solution according to the solution refractive index (R1).

Step 2: 0.6 L of preheated feed solution was pumped onto the resin layer.

Step 3: The feed solution was eluted downward in the column by introducing onto the column preheated ion exchange water, the pH of which was adjusted to 3-4 with formic acid.

Step 4: 50 ml samples of the effluent were collected at 5 min intervals of 20 min. The concentration, conductivity (mS / cm) and pH of the samples were determined. The composition of the samples was analyzed by HPLC (Na + column, 0.6 ml / min, 85 ° C, 0.003 M Na 2 SO 4).

*

Elution began with inorganic salts and continued with organic acids and alditols. Betaine eluted from the column later than the other major components. The position of the betaine peak moved backward (i.e. closer to the peaks of the other * ·· ·. Components) before the resin ionic equilibrium was reached.

. * ··. After 53 feeds, 67% of the resin on the resin layer was in the H + form.

At this point, the betaine hold-up volume was 75 min and the elution time was 180 min. The betaine retention factor was 1.3 and the maximum purity of the betaine peak was more than 30 75% / DS. The pH of Effluent ranged from 4.4 to 6.3. 53. the input separation profile is shown in Fig. 3.

· * • * example a

Chromatographic separation of vinassin with weakly acidic cation exchange resin (pH 4.2) in H + 35 The starting solution used for the separation was vinasse from the ethanol fermentation process. Vinassi contained mainly betaine, glycerol, inorganic salts and organic acids and had the following composition (% RDS):

Betaine 15.8 Glycerol 11.5 5 Other 72.7.

Vinass was used as a feed solution and subjected to chromatographic separation. Separation was carried out on a test-scale chromatographic separation column as a batch process. The column, 0.09 m in diameter, was filled with a weakly acidic cation exchange resin (Finex CA 16 GC, 8% DVB, 4.4 eq / liter capacity). The resin was an acrylate-based resin and the average particle size of the resin in the sodium form was 0.41 mm. The resin was regenerated to the hydrogen (H +) form, after which the height of the resin layer was approximately 1.7 m. The temperature of the column and the feed solution and eluent water was 75 ° C. The flow rate in the column was adjusted to 3 L / h. The pH of the feed solution was adjusted to 4.2 with sulfuric acid 15 (H2SO4). The feed solution was filtered through a filter using diatomaceous earth as a filter aid.

Chromatographic separation was carried out as follows:

Step 1: The feed solution solids were adjusted to 35 g of solids per 100 g of solution according to the solution refractive index (R1).

Step 2: 2 L of preheated feed solution was pumped onto the resin layer.

*

Step 3: The feed solution was eluted downward on the column by introducing into the column *: * · pre-heated ion exchange water, adjusted to pH: ***: 4.2 with formic acid.

·· «:. *. Step 4: 50 ml samples of the effluent were collected for 5 minutes * · · ·. . ·. every tin. Concentration of samples, conductivity (mS / cm) and pH · ·. ritettiin. The composition of the samples was analyzed by HPLC (Na + column, 0.6 ml / min, 85 ° C, 0.003 M Na 2 SO 4).

Elution began with inorganic salts and continued with organic acids and alditols. Betaine eluted from the column later than the other major: ···: components, but somewhat earlier compared to the difference in Example 2, where the feed pH was lower. Hold-up volume was 75 min and ··· elution time was 205 min. The retention factor of betaine at this pH was 1.7 and a maximum purity of more than 80% in the beta-fraction was achieved with DS. The purity of the glycerol fraction · · '··· eluted before betaine was more than 20% DS. A total of 20 feeds were made during which the ionic form of the resin stabilized; 89% of the resin was in the form of hydrogen on top and bottom of the resin. The pH of Effluent ranged from 4.0 to 6.4. The 20th input separation profile is shown in Figure 4.

EXAMPLE 5

Chromatographic separation of Vinass with weakly acidic cation exchange resin (pH 3.1) in H +

The starting solution used for the separation was vinasse from the citric acid fermentation process. Vinassi contained mainly betaine, glycerol, inorganic salts and organic acids and had the following composition (% by RDS): 10 Betaine 19.8

Glycerol 3.0 Other 77.2.

Vinass was used as a feed solution and subjected to chromatographic separation. Separation was performed on a test-scale chromatographic separation column as a batch process. A 0.09 m diameter column was filled with weakly acid cation exchange resin (Finex CA 16 GC, 8% DVB, 4.4 eq / L capacity). The resin was an acrylate-based resin and the average particle size of the resin in the sodium form was 0.41 mm. The resin was regenerated to the hydrogen (H +) form, after which the resin layer had a height of approximately 1.6 m. Co-20 l and the temperature of the feed solution and eluent water was 75 ° C. The flow rate at the volume * i * lonn was adjusted to 3 l / h. The pH of the feed solution was 3.1.

The chromatographic separation was carried out as follows:. Step 1: The feed solution solids were adjusted to 35 g of solids per 100 g of solution according to the solution refractive index (R1).

Step 2: 1.5 L of preheated feed solution was pumped onto the resin layer.

Step 3: The feed solution was eluted down the column by introducing into the column pre-heated ion exchange water, the pH of which was adjusted to 3: 4 by 4 with formic acid.

Step 4: 50 mL samples of the effluent were collected for 5 min · * ·. every tin. The concentration, conductivity (mS / cm) and pH of the samples were determined. The composition of the samples was analyzed by HPLC (Na + column, 0.6 ml / min, 85 ° C, 0.003 M Na 2 SO 4).

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Elution begins with inorganic salts and continues with organic "" · 35 acids and alditols. Betaine elutes from the column as the last of the main components. Betaine had a hold-up volume of 75 min, an elution time of 245 min, and a 17,18856 retention factor of 2.3. The pH of the effluent (e.g. effluent) ranged from 2.4 to 4.3. A total of 54 feeds were made during which the ionic form of the resin stabilized and> 99% of the resin was in the hydrogen form. The resin separates betaine very well from the other components and a maximum purity of more than 85% in the 5 betaine was achieved in the betaine fraction. The separation profile is shown in Figure 5.

EXAMPLE 6

Chromatographic separation of vinassin with weakly acidic cation exchange resin (pH 1.4) in H * form

The starting solution used for separation was vinasse from the ethanol fermentation process. Vinass, which mainly contained betaine, glycerol, inorganic salts and organic acids, had approximately the following composition (% RDS):

Betaine 14.0 Glycerol 10.6 15 Other 75.4.

Vinass was used as a feed solution and subjected to chromatographic separation. Separation was performed on a test-scale chromatographic separation column as a batch process. A 0.09 m diameter column was filled with weakly acidic cation exchange resin (Finex CA 16 GC, 8% DVB, 20 eq. 4.4 eq / l). The resin was an acrylate-based resin and the average particle size of the resin in the sodium form was 0.41 mm. The resin was regenerated to form hydrogen · * · * · (H), after which the resin layer had a height of approximately 1.6 m. ton and the temperature of the feed solution and eluent water was 75 ° C. Flow rate co-: * [·. was adjusted to 3 l / h. The pH of the feed solution was adjusted with strong sulfuric acid to · · ·) * Y 25 (H2SO4) 1.4 and filtered through a pad of diatomaceous earth as a filter aid.

The chromatographic separation was carried out as follows:

Step 1: The feed solution dry substance was adjusted to 35 g dry matter ··· *** 100 g solution according to the solution refractive index (R1).

· * · 30 Step 2: 0.7 L of preheated feed solution was pumped with a layer of resin ···. on top of it.

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Step 3: The feed solution was eluted down the column by feeding the column. Ion-exchange water preheated to pH 2.2 with strong C: H 2 SO 4.

*: · *: 35 Step 4: 50 ml samples of the effluent solution were collected every 5 minutes. The concentration, conductivity (mS / cm) and pH of the samples were determined.

The composition of the samples was analyzed by HPLC (Na + column, 0.6 ml / min, 85 ° C, 0.003 M Na 2 SO 4).

Elution begins with inorganic salts and continues with organic acids and alditols. Betaine elutes from the column as the last of the major component 5 pathways. Betaine hold-up volume was 75 min, elution time 290 min, and retention factor 2.9. The pH of the effluent (e.g. effluent solution) ranged from 1.3 to 3.3. The resin separates betaine very well from the other components and the betaine fraction achieved a maximum purity of more than 85% with DS. The separation profile is shown in Figure 6.

10 EXAMPLE 7

Crystallization of betaine

The betaine-containing feed liquid was added to a 400-liter boiling crystallizer. Evaporation was started. The first spontaneous crystals were observed on DS at about 79% at 99 ° C. After spontaneous seeding, the boiling crystallization was continued for 3 hours at about 100 ° C and fresh medium was added to the continuously boiling crystallizer. A 400 liter batch of pulp obtained by cooking crystallization (87% pulp DS) was removed. The pulp was centrifuged and the betaine anhydrous product was dried.

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Claims (36)

A process for chromatographic separation of betaine from a sugar-based solution in which a weakly acidic cation exchange resin in H + form is used in the chromatographic separation. The process according to claim 1, wherein the sugar beet based solution is a fermentation process solution. The process according to claim 2, wherein the fermentation process solution is a citric, yeast or ethanol fermentation solution. 10 The process according to claim 1, wherein the sugar beet based solution is a process solution derived from sugar beet. The method of claim 4, wherein the process solution derived from sugar beet is vinasse, molasses or betaine molasses. The method of claim 1, wherein at least one column or part of a column containing a weakly acidic cation exchange resin in H + form is used in the chromatographic separation. The method of claim 1, wherein the slightly acidic cation exchange resin is acrylic resin. The process according to claim 7, wherein the acrylic resin is derived from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and acrylonitrile or acrylic acids or mixtures thereof. The process according to claim 7, wherein the resin is crosslinked with divinyl ··· benzene (DVB). The method of claim 9, wherein the crosslinking degree of the resin i. 25 is 3-8% by weight. • · ♦ "X The method of claim 1, wherein the eluent used in the chromatographic separation is water. The method of claim 1, wherein the temperature of the eluent used in the chromatographic separation is between 10 ° C and 95 ° C. The method of claim 12, wherein the temperature of the eluent is between 65 ° C and 95 ° C. · ***. The method of claim 1, wherein the particle size of the slightly acidic cation exchange resin is 10-2000 µm. The method of claim 14, wherein the particle size of the slightly acidic cation exchange resin is 100-400 µm. • * 118564 The method of claim 1, wherein the pH of the feed solution is below 6. The process of claim 16, wherein the pH of the feed solution is below 5.1. 5 The method of claim 1, wherein the chromatographic separation is a batch process. The method of claim 1, wherein the chromatographic separation is a simulated moving bed process. The method of claim 19, wherein the simulated moving bed process is a sequential process. The method of claim 19, wherein the simulated moving bed process is a continuous process. The process of claim 1, wherein the process further comprises separating polyol and / or carboxylic acid as an adjunct compound. 15 The method of claim 22, wherein the polyol is inositol and / or glycerol. The process of claim 22, wherein the carboxylic acid is citric acid, lactic acid and / or pyrrolidone carboxylic acid. The process of claim 22, wherein the betaine fraction and citric acid fraction are separated from the solution. The method of claim 1, wherein the process further comprises recovering betaine from the separated fraction. The process of claim 26, wherein the recovery is carried out by crystallization. 25 The method of claim 1, wherein pH control of the chromatographic separation is used for controlling or controlling the betaine retention factor. The process according to claim 28, wherein the chromatographic separator is:. the pH of the ration is controlled with the pH of the feed solution. 30. The method of claim 28, wherein betaine is separated from the carboxylic compounds and / or polyols. »* · The process according to claim 30, wherein the carboxyl compound is cis-: * ·: tronic acid, lactic acid and / or pyrrolidone carboxylic acid. The process according to claim 30, wherein the betaine fraction and the citric acid fraction are separated from the solution. • · 118564 The process of claim 30, wherein the betaine is separated from the polyol compounds. The method of claim 33, wherein the polyol is inositol and / or glycerol. 35. Use of a weakly acidic cation exchange resin in H + form for chromatographic separation of betaine from a sugar beet based solution. Use according to claim 35, wherein the betaine is separated from other carboxyl compounds and / or polyols. • · · • · · · • ♦ ·· «• · t · * · ♦ • · • · · • · ♦ ··· 1 ·· m * · · • ♦ ♦ • ·« «» • «··« ·· • · • ·· «M • · • · ··· • · · ♦ ♦ · · · • · · 1» • m • · «· 1 ·