oe cu») United States S 201501974691 cz) Patent Application Publication — co) Pub. No.: US 2015/0197469 AL FERREIRA et al. (5) PROCESS OF CRUDE GLYCERIN PURIFICATION ORIGINATED FROM. ‘TRANSESTERIFICATIONS WITH ALKALINE CATALYSIS WITHOUT USING ACIDIFICATION AND DISTILLATION PRODUCING PURIFIED GLYCERIN 96% AND 99% PURITY, (71) Applicant: Glycerosotution Quimica Ltda., Sao Paulo (BR) (72) Inventors: Josse Givan Bombardi FERREIRA, adit Busstt (BR): Mareelo Fiji Borges ;ATO, Sao Paulo (BR) Setsuo SATO, Sao Paulo (BR): Silvio Anto CAZZOLATO, Seo Jose Dos 1e Meira da SILVA, 1a (BR) (21) Appl. Nos 14/897,274 (22) Filed: Jan. 15,2015: (43) Pub, Date Jul. 16, 2015 G0) Foreign Application Priority Data Jan.15,2014 (BR) 10 2014 001003 3 Publication Classification GI) Ince. Core 2976 (2006.01) Corc 3122 (2006.01), (52) US.C ce CITC 29/76 (2013.01); COTE 31/228 201301) on ABSTRACT A process of erude glycerin purifca ‘runsesterification with alkaline catalysis without usin fication and disilltion producing purified glycerin 96% and 99% purty, wherein the purification technigue of glyeeria ‘obtained from productions of fatty esters using the alkaline catalysis.US 2015/0197469 AI PROCESS OF CRUDE GLYCERIN PURIFICATION ORIGINATED FROM ‘TRANSESTERIFICATIONS WITH ALKALINE, ‘CATALYSIS WITHOUT USING. ACIDIFICATION AND DISTILLATION PRODUCING PURIFIED GLYCERIN 96% "AND 99% PURITY, FIELD OF THE INVENTION [0001] The present invention prevents a new purification Technique of glycerin generated in the processes of transes- terficationof triglycerides that use alkaline catalysis, oxides, hydroxides, soinm alkoxides, potassium, ithium, Such pro- ‘cesses are used in lange scale for production of biodiesel and industrial esters. technique used sims to take advantage of ‘existing molecular interactions benseen components oferade plyeerin generated in the process of tunsesterification, com- pounds oF free glycerin, alkaline soaps of fatty acids, fatty testers, monoglyeerides, diglyeerides, water fee methanol, ‘here this mixture is usally ina single homogenowss phase The very simple but very innovative developed technique ‘consists of modifying this composition with very specific felations so tht this homogeneous balance is unbalanced ‘creating light phase composed of soaps, esters, mono- and diglyeerides, and a heavy phase composed of fee glycerin, ‘ethanol and water, With this technique, the separated glye- ‘erin is free of salts and the ight pats treated with organic oF ganic acide to transform the falty soaps into free fatty ds, which arused to make the unbalance of homogeneous ‘onide glycerin. The glycerin phase after removal af methanol and water has purity above 96%, fee of salts, BACKGROUND OF THE INVENTION [0002] The glycerin is compound! whose scientific name 1.23-propanetio! naturally occurs in animal oils and fats ‘combined in the Form of wiglycerides. After leaving te pro- ‘duction proces, itis presented as an oily, colorless and vis ‘ous Figuiland sweet taste, soluble in water and aleohol and insolublein hydrocarbon, has meting point of17.8°C. andits ‘evaporation with respective decomposition occurs at 290° C, 10003] Currently its production is obtained by saponiti ‘ion of els and fs, synthetically as secondary product of propylene manufacturing and also asa byproduct of transes- ‘erfleation to form faty esters (approximately 102% of mass ‘ofthecrude material used), which technique used for produc tion of biodiesel is presented as innovative form inthe inven- tion EP 13152268-2, in which the maximum production of biodiesel is aimed. Ths plycerin obtained has low cost and high quali 10005] Inthe present times, biodiesel emerged as a viable fematve in terms of renewable fuel, The transesterification js the curently most used process for the production of biodiesel. It consists of a chemical reaction ofthe vegetable oils. or animal fats with common alcohol (ethanol) or meth nol stimulated by a catalyst, from which the crude or Blond _lycerin also extrated, which after its dsilation becomes Jnput used with several applications in the chemical industry. [0005] As with biodiesel, the catalysts interfere in the pro- duction and quality of glycerin proxivced. Among the used, there are many types as homogeneous, heterogencous, and sthey can be de acid and basic. Thebasic homog- ists are more used (CH,ONa, CH,OK, CH.O13, COHI, LiOHH) for allowing high reactivity and effi- Jul. 16, 2015 ica at fw temperate, aod 60°C, and ati kw ont Te disadvan ol this tod isthe formation of Soapsand mineral sats, forcing tis pleein to esto an expensive and high-enegyconsmpiontechnigus have stl use Aly the sed extalssusedwhen thorwiction nen has high acidity inde, ths eto has ae yl however thor isthe problem of corona it JSncdd tobe donc in igh tempertes using peat excess ‘aloo! essay sniydrovs methanol or ethanol. The het recone (asim onde, nsanesin exe, = ont, laminin, chi an ther derives, soporte Snsbasd ently or aa) are remave mone eal Tom ‘eaction mixture and ean inimite the environmental prob ier, aartfrom beng easily removed fom reneion medium but they work in high temperatures andor use excess of alco ange when compared with catalina linealoides.Aleady the enzymatic atlyst allow under standing an es separation between the Bde nd lye= erin, the glycerin produced by this mean is of high purity. The teat reoicton of thie tec sth excoss of rogents od, cost of enzymes, mostly the ones supported that ean be ‘eevee and a rection conenion mite maximum of 48% ‘Riring the use of othermetbnds achieve 99% of conver Son to achicse the quality indexes ried by bids TRuulton. The use of some buffers fo rpulte the pl af nym ection main, any them based on sai Sets nt up contaminating crue glycerin [0006] |The glycerin generated in the biodiesel Production {homogeneous alkaline catalysis) has port fom 0 0 80%, Sut thegrarinconveniat consist ofthe presence of int fac ste as acum sole and sim ehorde making the proces of gycerin urfiation expensive and with ovoson Problems inthe equipment wed onl he pheein. These {thin ler sc s very ited de othe presence of those stn aon fo the prods apt tre the Formation af lage amet of sid waste that mst be i end into cavirnment With al thew negative pests, the “afc of hk lycarin s marin, ene Benga pele Forthe great biodiesel prosicers. [0007] Several techniques of pusifaton ofthis glycerin have Boon practiced among thom is hgh the dist. lation of geen in igh acini, in Temperate above 100" C. and below 209°C, thnogh Ive seam injection, ‘ecase. above his tempertre lie yeerol can polymerize and aha decompose sell. The septation of ghee fom ‘ater is made by condenston with cone empertie Providing the separation of these two miscible components {0008} The obtained lycra, inthis condensation proces, presentuptoo%of pry tocininate de odor thealveein Pas thogh a process of dcodorization na high vacoum ‘esse (ah) wi drag steam, following t the proces of Clacton corn active coal and fitaon to it elimina- Sian. this proces, ts ao obtained an impure alcool of Jower commer vale, which semploysdththe denon nation of technical or instil pieerin [0009] The puriication by son exeinge sims the exine= thn of existent imporitcs in he geen, such techn onitng of passing by micessve eae bas made of Stong cto evn and wes anion ein. os fer thet, thoetie product is pase by successive evaporite. {W010} Approximate 30,000 ons per year of bond ge erin regenerate proetion aise! det BS tht $Simandsory the mixureof 3% of bods! in mineral sel Aan expecaive no 2013 of ene of 7 that woul elevateUS 2015/0197469 AI this volume to about de 420,000 tas per year of blond glve- ‘erinexists. The blond glycerin contains inarganic salts, water. residual of monoglyeerides and it isthe raw material used 10 the distillation, many times biistilaion, with post-treatment ‘with absorbents systems, usually activated coal fo produce the distilled glycerin, which now is consumed inthe market. Basically, al the glycerin use by food, pharmaceutical, paint and varnish industry. The value of the market of Blond glye- ‘erinis very low because the production of dsilled slyeerinis| ‘expensive, typically the value of the distilled glycerin is 3t0 44 greater than the blond glycerin, it has 3 high-energy ‘demand, the typical process of distillation ues temperatures from 220° C. 10 250" C. under negative pressure. Its neces- sary investment ina specific plant for production of distilled lyeerin, The national demand of distilled glycerin is of ‘approximately $0,000 tons per year. all the remaining glye~ ‘erin is exported with blond glycerin fo China with very low ‘alues, In the firs semester of 2013, about 90,000 toas of blond glycerin were exported. [0011] With this current scenario of market and existent technologies that really ean be implemented industrially, an innovative process was developed to prodice glycerin with ‘minimom purty of 96%, that does not need disillation, from ‘enide glycerin generated inthe procestes of transesterifics tion of the biodiesel plans, Such process has a very low ‘energy cost compared (o the distillation, it generates less resid, it does not use any chemical input, as chemical sol- ‘vent, and that ean be integrated in the existent biodiesel plants using alkaline catalysis, without the neod of investments in 2 cationtocreate the unbalance of enude glycerin, whichis in homogeneous phase 3. The process according to claim 1, wherein the tempera ture of extraction is from 40° C. 10 95°C 4. The process according to claim 3, wherein the tempera ture of extraction is from 60° C, and 80° C. 8. The process according to claim 1, wherein the mixtureof fatty: materials containing soups is acidified with mineral acids or short carboxylic acid to release the fee fatty acids, preferably using phosphoric aid to goneratea solution with sodium monophosphate. 6. Products of purified glycerin 96% and 99% purity, wherein the enude glycerin fom the process according 10 claim 1 without the process of acidification using inorganic acids suelt as sulluric acid, hydrochlori acid, phosphoric acid andor shor carboxylic aids suchas lactic, oxalic, and citric acid, comprises a composition of contents of total glye~ erin from 20% to 90%, fatty materials in the form of soups. esters, partial and volatile plyeerdes from 2% to 45%, com- pound of water and fee aleohol from 0% fo 706, free alka Tinty from 0 10 80 expressed in milligram of potasinm hydroxide per | gram of product, 7. The products according wo claim 6, wherein the extrac- ‘ion agent oF the initially omogencous system unbalance existent inthe enue glycerin are fatty acids in the pure form ‘or their mixtuees thereof with esters andlor partial glycerides ‘with content from 30% 10 100% of carboxylic fatty avis, 8, The products socording to claim 7 using the Fatty acid recovered from own process, the composition of which is between 60% wo 100%6 of compounds of carbon cin C12 v0 C20, preferably composed of saturated or unsaturated fatty acids of eazhon chain C16 and C18, 9. The products according to claim 6, wherein the mass relation between the extraction agent—crudeglyeerin of dry base wed —is from 30 10 0.2. 10, The products according to elim 9, whersin the mass relation between the extraction agent—erude glycerin of dry base used —is fom 1.5 10 0.50, 11. The products according to claim 6, wherein theyieldof alyecrinextraetion elative its initial contents from 85 58% by mass, more specifically above 9P% depending on the quality of eride glycerin used, consequence of dierent peo- ‘cesses used hy biodiesel producers or industrial fatty esters. 12. The products according to claim 6, wherein the glycerin with purity above 99% is obtained with an additonal treat ‘ment using filter clays and active col