Embodiment

Unless otherwise indicated, all percentage ratio is weight percentage (" weight % "), and all temperature units are ℃.Weight percentage about ion exchange resin is to be benchmark in the dried resin.Lipid acid is the no cycloaliphatic carboxylic acid who comprises 8-22 carbon atom; Most preferably it comprises 12-18 carbon atom.About C-C, described lipid acid can be saturated, monounsaturated or polyunsaturated (comprising two or three carbon-to-carbon double bonds usually).

Except glycerine, comprise methyl alcohol, water, inorganic salt and soap usually from the raw glycerine of production of biodiesel.Salt is sodium salt and/or sylvite normally.The content of soap is generally 5-50%.The content of inorganic salt is 1-5%.These content common one are reinstated total cation concentration and are represented; Its concentration is generally 0.2-5%.In some embodiments of the present invention, described total cation concentration is at least 0.5%, perhaps is at least 1%.In some embodiments, described total cation concentration is not more than 4%, perhaps is not more than 3%.Raw glycerine comprises water, goes back dilutable water, reducing the load of coupled columns (column), and helps to separate, and therefore water-content can be 5-40% usually.In some embodiments of the present invention, the glycerol concentration of introducing the raw glycerine in the resin bed is at least 20%, perhaps is at least 30%, perhaps is at least 40%, perhaps is at least 50%, perhaps is at least 60%, perhaps is at least 70%, perhaps is at least 75%.Method of the present invention also can be used to the raw glycerine available from other source (comprising the soap manufacturing) is carried out purifying.

In some embodiments of the present invention, the purifying of described glycerine carries out under 25-80 ℃ temperature.In some embodiments of the present invention, described temperature is not higher than 70 ℃, perhaps is not higher than 65 ℃, perhaps is not higher than 60 ℃.In some embodiments of the present invention, described temperature is at least 40 ℃, perhaps is at least 45 ℃.Higher temperature can be improved separation usually, but even the present invention in the temperature lower than the temperature of common employing and under than the higher concentration of the glycerol concentration that adopts usually, also can provide improved separating effect.

According to the present invention, be used for the isolating conventional flow velocity of glycerine and be 0.2-1 bed volume (" BV ")/hour.In some embodiments of the present invention, described flow velocity was at least 0.3BV/ hour, perhaps was at least 0.4BV/ hour.In some embodiments of the present invention, described flow velocity is not more than 0.9BV/ hour, perhaps is not more than 0.8BV/ hour.

Being used for ion exchange resin of the present invention is gel type resin, rather than macroreticular resin.Macroreticular resin is that surface-area is a 25-200 rice ²/ gram, mean pore size are Resin; Or surface-area is a 30-80 rice ²/ gram, mean pore size are Resin.The gel-like resin comprises usually and is not more than 10% the monomeric unit that is derived from linking agent.Suitable gel-like resin comprises for example acrylic resin, styrene resin, and their combination.Resin comprises the polymerized unit of multi-ethylenical unsaturated monomer (linking agent).In some embodiments of the present invention, the content that is derived from the monomeric unit of linking agent in the resin is not more than 7.5%, perhaps is not more than 7%, perhaps is not more than 6.5%, perhaps is not more than 6%.In some embodiments, the content of described linking agent is at least 4.5%.In some embodiments, the mean particle size of described gel resin is the 250-400 micron, perhaps is the 250-350 micron.In some embodiments of the present invention, described ion exchange resin comprises the polymerized unit of vinylbenzene and linking agent, for example divinyl aromatic compound; Two, three and four (methyl) acrylate or (methyl) acrylamide; Two-, three-and tetraallyl ether and ester; The polyenoid propyl ether of two pure and mild polyvalent alcohols and many vinyl ether (polyallyl and polyvinyl ethers of glycols and polyols).In following embodiment of the present invention, described linking agent is that two ethylenic are undersaturated, for example is Vinylstyrene (DVB).In some embodiments of the present invention, the acid functional group of described ion exchange resin comprises sulfonic group, carboxylic acid group, phosphate or its mixture.Conventional acidic ion exchange resin is that the acid functionality of benchmark is 0.4-8 milliequivalent/kilogram in the dry weight, perhaps is at least 2 milliequivalent/kilograms, perhaps is at least 4 milliequivalent/kilograms.Preferably, described acid functional group is sulfonic form.It is believed that with the positively charged ion of resin-bonded unimportant, but according to positively charged ion main in the raw glycerine, be generally sodium or potassium.

The uniformity ratio of ion-exchange resin bead grain size-grade distribution is the tolerance of size distribution curve width.Described uniformity ratio is defined as d60/d10, and wherein d60 is the size of the opening (opening) that lucky 60% bead can pass through in distributing, and d10 is the size of the opening that lucky 10% bead can pass through in distributing.In some embodiments of the present invention, the uniformity ratio of described resin beads is not more than 1.10.

In the method for the invention, than glycerine wash-out from pillar earlier, the glycerine that makes has much lower metal ion content and the color that weakens greatly usually for salt and foreign pigment.

Method of the present invention can be used mimic moving bed technique or successive simulated moving bed technology, to realize the automatization continuous purification to glycerine.

Embodiment

Embodiment 1

To there be the chromatographic column (2 meters of internal diameter 1.5 cm x) of chuck to be heated to 60 ℃.Keep temperature by making water cross described chuck from the water bath with thermostatic control cycling stream.Described chromatographic column is filled to 194 with the potassium form of acidic cation-exchange resin bead, the height of 6 centimetres (345 milliliters), described bead are by sulfonated phenylethylene/DVB copolymer, and the harmonic mean granularity is 300 microns, crosslinking degree is 5%, and uniformity ratio is not more than 1.15.Described resin bed is fixed, and makes the resin bed temperature reach balance before operation.Feedstock solution is by pure glycerin solution and Repone K preparation, and glycerol concentration is 68%, and potassium content is 4.2%, and the pH value is 5-9.At buried resin bed higher slice (layered),, make described feedstock solution pass through resin bed the feedstock solution of the amount of recording with the flow velocity (3 ml/min) of control by regulating the rotating speed of peristaltic pump.Use deionized water as eluting solvent.Detect meter successive analysis effluent by differential refractometer.Use the signal response of conductometer detector check Repone K.Find that differential refractometer detects the concentration that meter can be used for analyzing glycerine and Repone K.Inject the suitability that Repone K comes checking system after injecting some glycerine solutions.All parameters are measured with the independent color atlas of Repone K and glycerine solution.In order to check the separating property of resin, inject the resulting solution of glycerine and Repone K.

For the difference that will cause owing to the bed size of input concentration minimizes, with the overhead product volume divided by the resin bed volume, with the overhead product concentration of glycerine and Repone K respectively divided by the concentration of glycerine in the feedstock solution and Repone K.

The porosity of resin bed is measured by injecting very large molecule (making molecule can not be held).By measuring the retention time of the described molecule that does not keep, the bed porosity directly provides with bed volume.This parameter has shown the balance that resin bed is filled.

Embodiment 2

The solution that will comprise sodium-chlor and glycerine (glycerol concentration is 68%, and sodium content is 4.5%) is annotated on the sodium type according to the resin of the step of embodiment 1.

Isolating parameter is listed in the table below: