EP 2 431 085 A1 (19) (12) (43) Date of publication: ty EP 2 431 085 A1 EUROPEAN PATENT APPLICATION (61) Int. 21.03.2012. Bulletin 201212 BorD 17/609 core 2arr6(e601) co7c 2aya6'eo") (21) Application number: 11982223.3, (22) Date of ling: 04.07.2011 (84) Designated Contracting States: * Lorenzo Ibarreta, Leire AL AT BE BG CH CY CZ DE DK EE ES FIFRGB 48160 Dero (Vizcaya) (ES) GRHRHUIEISITLILTLULVMCMKMTNLNO | + Torrecilla Soria, Jesis PLPTRO RS SESISK SMTR 48160 Dero (Vizcaya) (ES) Designated Extension States: + Gomez Jiménez de Aberasturi, Olga BAME 148160 Derio (Vizcaya) (ES) + Marquinez Porres, Rosa (80) Priory: 20.09.2010 ES 201031399 48160 Dero (Vizcaya) (ES) (71) Applicant: FUNDACION TECNALIA RESEARCH & INNOVATION 48160 Derio Vizcaya (ES) (72) Inventors: * Belausteg! Ituarte, Yolanda (74) Representative: Carpintero Lopez, Francisco etal Herrero & Asociados, S.L. Alcala 35 28014 Madrid (ES) 48160 Derio (Vizcaya) (ES) (64) Process for purifying glycerin derived from biodiesel production (87) _Aprocess for purtying glycerin derived from bi ‘diesel production is described, the process comprises acicfying the glycerin; neuvalizing the acidified glycerin; feeding the glycerin ito an electrocalysis unit compris: ing atleast one cation exchange membrane and at least ‘one anion exchange membrane separated between an ‘anode and a cathode, such that they define atleast one diluted compartmentand at least one concentrated com: partment located between the anode and the cathode, wherein the glycerin is fed int the luted compartment ‘and an NaCl solution is fed into the concentrated com partment; applying a potential ifference so that the ions Present in the glycerin migrate through the anion and cation exchange membranes from the diluted compart- ments to the concentrated compartments, where they ‘are rapped, purifying the glycerin; and extracting the pu- ‘fied glycerin,EP 2.431 085 A1 Description Field ofthe Invention [0001] The present invention relates to the techniques used inthe chemical industry for purifying substances, and it ‘more particularly relates to a process for purifying glycerin produced as a byproduct in the biodiesel manufacture. Background ofthe Invention [0002] Giycerinhas the potential of beingan extremely versatile “bullding block in borefning. However, crude glycerin derived frombiodiesel production has a very low quality due te the presence ef mpurtes, thelr concentration percentage ranging between approximately 50 and 80%. The substances accompanying glycerin are mainly water, methanol, nor ganic salts, fatty acids, unreacted triglycerides and other matter in variable amounts. [0003] ‘The decision of how to subsequently refine crude glycerin depends on the economies ofthe production scale ‘andlor on the availablity of purification facts. [0004] Major biodiesel producers usually refine the glycerin produced and sel It for other industries. Generally, the ‘operations used for puriying glycerin are: fitration, addtion of chemicals and vacuum fractional distiation, producing various commercial qualties or grades. [0005] However, ifthe glycerin is to be used in food, cosmetics and pharmacy, a higher degree of purification is required, including phases of bleaching, deodorizing and fon exchange for removing trace impurities and salts. [0006] The purication to thatgrade is expensive and generally not within the economic capacity of small-andmedium- scale plants, As a result, the glycerin is often incinerated, which can give rise to toxic acrolein emissions, ‘Summary ofthe Invention [0007] To overcome the problems of the prior art, a new process is provided for purifying glycerin by means of an economically viable treatment adaptable to small-and medium-sized enterprises for puriying the glycerin, particularly the process ofthe present invention is based on membrane technology, and specially, electrodialysis [0008] More parioularly, the process ofthe present invention comprises: «) acaitying the glycerin; ») treating the aciified glycerin wth a base; 6) feeding the glycerin nto an electrodialysis unit comprising atleast one cation exchange membrane and atleast ‘one anion exchange membrane separated between an anode and a cathode, such that they define at least one iluted compartment and at least one concentrated compartment located between the anode and the cathode, \wherein the glycerin is fed into the diluted compartment and an NaC! solution is fed into the concentrated compart- ment; «) applying a potential ciference between the anode and the cathode so tha the ions presentin the glycerin migrate through the anion and cation exchange membranes from the diluted compartments to the concentrated compart- ‘ments, where they are trapped, puriying the glycerin; ane «@) extracting the purified glyearin from the electrocialysis unt. [0009] In an embodiment ofthe invention, after the phase of neutralization withthe base, the glycerin is clluted with Water up to 50% to improve electrodialysis. In yet another embodiment, the glycerin that is extracted from the electro dialysis unit is clarified with an adsorber. In another addtional embodiment, the water is removed from the treated alycerin, preferably by means of evaporation. [0010] The process of the present invention allows purfying glycerin in a practical and cost-effective manner and in ‘continuous manner. Briet Description of the Drawings [0011] Tocomplementthe description thatis being made andforthe purpose of aiding tobetter understandthe features ‘ofthe invention according to preferred practical emboclment thereof, a set of drawings is attached as an Integral part ofthis description in which the following is depicted with an ilustrative and non-liriting character Figure 1 Is a schematic depiction of an example of an electrodialysis unit where the main phase of the process of the present invention Is performed. Figure 2 shows an infrared spectrum of the glycerin produced by means of the process of the invention.EP 2.431 085 A1 Figure 3 shows a reference infrared spectrum with glycerin 85%. Detailed Description of the Preferred Embodiments ofthe Invention [0012] The process ofthe present invention stats with acicltying the glycerin with an inorganic ac, the aciafication allows removing soaps, fats, etc, from the glycerin to be treated, hydrochloric acid is preferably used for this phase, ‘though sulfuric acid, phosphoric acid or ancther acid can also be used, The acisfication is performed up to a pH af 4 105. The acid concentration used is usually 2-3 mol. In the case of HCI since ithas a commercial race purty of 26%, ‘a concentrated form is normally used. [0013] The acidied glycerin is subsequent treated with a base such as sodium hydroxide, sodium borohydride, calcium hydroxide, potassium hydroxide, mixtures thereof and other similar bases, The treatment with the base is performed until reaching pH=B and is carried out with approximately 15% of the base used [0014] Once the glycerin has been treated withthe base, electroiytc treatment is performed in an electrodialysis unt 10, such as the one depicted in Figure 1; electrodialysis is a membrane technology which, under the influence of a Continuous electric ied allows extracting ionized organic and inorganic substances dissolvedin aqueous solution through selective ion exchange membranes. In an embodiment ofthe invention, the glycerin is diluted using up to 60% water before subjecting ito electrodialysis. [0015] More particulary, it can be seen in Figure 1 that the electrodaiysis unt 10 comprises at least one cation ‘exchange membrane 20 (permeable only to cations) and atleast one anion exchange membrane 30 (permeable only to anions) arranged in an altemating manner between an anode 11 and a cathode 12, such thatthey give rise to at least tone dlluted compartment 13 and at least one concentrated compartment 14, [0016] The glycerin solution, the lons of which are to be extracted, enters and circulates in each dlisted compartment 18, and an NaC! solution with a concentration of up to 30 g/l, preferably 10 gil, in which sald ions are going to be concentrated, enters and crculatesin each concentrated compartment 14. When applying potential difference between the anode and the cathode 11 and 12, the anions X° migrate through the anion exchange membranes 30, from the compartments 13 to the compartments 14, where they are trapped, because the ion barrier formed by any one of the cation exchange membranes 20 are placed in thelr path [0017] Analogousiy, the cations M* migrate, through the can exchange membranes 20, from the compartments 13. to the compartments 14, where they are concentrated since the anionic membranes prevent thelr migration towards the cathode. The electrode reactions are only used forthe purpose of providing the electric field necessary for the process to take place. [0018] In the electrodialysis unt, the anionic membrane can be a Neosepta AMX, Neosepta AFN or AFX type mem- brane, whereas the cationic membrane is Neosepta CMX or others that are well know in the art In order to make this phase of the process more efficient, the applied current density is 100 to 800 Am? [0019] After electrodialysis, necessary, the glycerin is subjactedto a step of clafcation, for his an adsorbent agent, such as activated charcoal, clays and ion exchange resins. [0020] Likewise, in order to concentrate the glycerin, this one is subjected to a step of removing the water, which can bbe done by evaporation [0021] The process of the present invention wil be more clearl illustrated by means ofthe examples described below Which are presented for merely ilusttative and non-limiting purposes, sald exemples being the followings Examples [0022] The process ofthe present invention was put into practice for purifying glycerin produced in a biodiesel man- facturing process, the feed current ofthe glycerin to be purified had a concentration of approximately 60%, including ‘among its impurities unconverted tiglyeerides, methanol, soaps, ete, it furthermore had a drk brown color. [0023] Before the electrodatysis phase, the glycerin produced as a byproduct in biodiesel production was treated with HCl forthe purpose of producing @ soap and fat-ree glycerin, and then it was treated with sodium hydroxide to remove the excess acid, obtaining a brown colored glycerin solution contaminated with salts, water and methanol, having the properties indicated in Table 1 Table 1 Properties of elycein pH 57 % Giyoarin | 858 Condvetivty [ 294 wSiem