RO130749A2

RO130749A2 - Process and catalyst for preparing fatty acid methyl esters

Info

Publication number: RO130749A2
Application number: ROA201400440A
Authority: RO
Inventors: Emil Stepan; Sanda Velea; Elena Emilia Oprescu; Gabriel Vasilievici; Elena Radu; Adrian Radu
Original assignee: Institutul Naţional De Cercetare-Dezvoltare Pentru Chimie Şi Petrochimie - Icechim
Priority date: 2014-06-13
Filing date: 2014-06-13
Publication date: 2015-12-30
Also published as: RO130749B1

Abstract

The invention relates to a heterogeneous base catalyst and to a process for preparing fatty acid methyl esters by using said catalyst. According to the invention, the catalyst comprises sodium metasilicate, hydrotalcite with the Mg:Alatomic ratio of 2...3:1 and bentonite. According to the invention, the process consists in treating fats with methanol and a solid superacid catalyst, at the temperature of 66...70°C, wherefrom the filtrate is treated with the claimed heterogeneous base catalyst, at a temperature of 65...69°C, for 60...90 min, after which the catalyst is removed, the glycerine is separated from the fatty acid methyl esters which are further on treated with the previously separated base catalyst together with methanol, wherefrom methyl esters result and they are further filtered through an inorganic filtering layer.

Description

I nvenția se referă la un catalizator bazic heterogen și la lin procedeu pentru obținerea esterilor metilici ai acizilor grași, care folosește acest catalizator. Catalizatorul conform invenției este constituit din metasilicat de sodiu, hidrotalcit CU raportul atomic Mg²7AI³⁺ de 2...3:1 și bentonitâ. Procedeul conform invenției constă în tratarea grăsimilor cu metanol și cu catalizator solid superacid, la temperatura de ©6...70*C, din care filtratul se tratează cu catalizatorul bazic heterogen:, conform invenției, la o temperatură de 65....69°C, timp de 60...90 min, se îndepărtează catalizatorul, se separă glicerina de esterii metilici ai acizilor grași, care se tratează în continuare cu catalizatorul bazic separat anterior, împreună cu metanol, din care rezultă esterii metilici care se filtrează printr-un strat filtrant anorganic.The invention relates to a heterogeneous basic catalyst and to a smooth process for obtaining methyl esters of fatty acids, which uses this catalyst. The catalyst according to the invention consists of sodium metasilicate, hydrotalcite with the atomic ratio Mg ² 7AI ³⁺ of 2 ... 3: 1 and bentonite. The process according to the invention consists in treating the fats with methanol and with superacid solid catalyst, at a temperature of 6 ... 70 * C, of which the filtrate is treated with the heterogeneous basic catalyst: according to the invention, at a temperature of 65 .... 69 ° C, for 60 ... 90 min, remove the catalyst, separate the glycerine from the fatty acid methyl esters, which is further treated with the previously separated basic catalyst, together with methanol, which results in the filtered methyl esters. through an inorganic filter layer.

Revendicări: 5Claims: 5

Cu începere de la data publicării cererii de brevet, cererea asigură, în mod provizoriu, solicitantului, protecția conferită potrivit dispozițiilor art:32 din Legea nr. 64/1991, cu excepția cazurilor în care cererea de brevet de invenție a fost respinsă, retrasă sau considerată Ca fiind retrasă, întinderea protecției conferite de cererea de brevet de invenție este determinată de revendicările conținute în cererea publicată în conformitate cu art.23 alin,(T) - (3).Starting from the date of publication of the patent application, the application provides, provisionally, the applicant, the protection granted according to the provisions of art: 32 of Law no. 64/1991, except where the patent application has been rejected, withdrawn or considered to be withdrawn, the extent of the protection conferred by the patent application is determined by the claims contained in the application published in accordance with article 23 paragraph, (T) - (3).

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PROCEDEU SI CATALIZATOR PENTRU OBȚINEREA ESTERILOR METILICI AI ACIZILOR GRAȘIMETHOD AND CATALYST FOR OBTAINING METHYL ESTERS OF FATTY ACIDS

Invenția se refera la un procedeu si catalizator pentru obținerea esterilor metilici ai acizilor grași, prin procesarea pe cale chimica a materiilor grase cu continui de acizi grași liberi, in vederea utilizării acestora drept biocarburanti diesel cunoscuti si sub denumirea de biodiesel, intermediari pentru biocombustibili sintetici pentru aviație, intermediari pentru detergenti, sau solventi ecologici.The invention relates to a process and catalyst for obtaining methyl esters of fatty acids, by chemically processing fatty materials with free fatty acids, for use as known biofuels and also known as biodiesel, intermediates for synthetic biofuels for aviation, intermediates for detergents, or environmentally friendly solvents.

Se cunosc numeroase procedee de obținere a esterilor alchilici ai acizilor grași, prin transesterificarea trigliceridelor din materiile grase de origine vegetala sau animala, opțional prin esterificarea prealabila a acizilor grași liberi din componenta acestora cu un alcool inferior, de preferința metanol, in prezenta unor sisteme catalitice omogene de tip acid, alcalin, sau heterogene.Numerous processes are known for the production of alkyl esters of fatty acids, by transesterification of triglycerides from vegetable or animal fats, optionally by prior esterification of free fatty acids from their component with a lower alcohol, preferably methanol, in the presence of catalytic systems. homogeneous of acid, alkaline, or heterogeneous type.

US Patent 8.624.073 descrie un procedeu pentru producerea biodieselului, prin transesterificare care cuprinde: contactarea unei ulei de origine vegetala sau animala cu un alcool alifatic monohidroxilic cu 1 - 6 atomi de carbon si un catalizator omogen, pentru a se efectua transesterificarea in vederea obținerii unui amestec de esteri alchilici ai acizilor grași si glicerina. Catalizatorul omogen este de tip non-bazic, non-acid, fiind un compus organometalic cu formula: M(OCH3)_X, în care M este un metal selectat din grupul: B, Na, Mg, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Al, Sn, Sb, Mo, Ag, Cd, iar x este un număr întreg, 2, 3 sau 4.US Patent 8,624,073 discloses a process for the production of biodiesel by transesterification comprising: contacting an oil of plant or animal origin with an aliphatic monohydroxyl alcohol of 1 to 6 carbon atoms and a homogeneous catalyst, in order to carry out the transesterification in order to obtain to a mixture of alkyl esters of fatty acids and glycerin. The homogeneous catalyst is of the non-basic, non-acid type, being an organometallic compound of the formula: M (OCH3) _X , wherein M is a metal selected from the group: B, Na, Mg, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Al, Sn, Sb, Mo, Ag, Cd, and x is an integer, 2, 3 or 4.

Procedeul prezintă unele dezavantaje legate de prețul de cost ridicat al catalizatorului.The process has some disadvantages related to the high cost price of the catalyst.

WO Patent 2006/050925 descrie un procedeu pentru producerea esterilor acizilor grași si a glicerinei, prin reacția uleiurilor vegetale sau a grăsimilor animale cu un alcool alifatic monohidroxilic, la temperaturi cuprinse in intervalul 100-250°C, in prezenta unui catalizator care conține oxid de magneziu sau amestecuri de oxizi de magneziu si aluminiu, obtinut prin calcinarea unui compus de tipul hidrotalcitului, care conține Al si Mg cu un raport atomic Mg /Al > 1. Se formează esteri ai acizilor grași si glicerina. Se indeparteaza alcoolul nereactionat, apoi se separa esterii acizilor grași de glicerina.WO Patent 2006/050925 describes a process for the production of fatty acid esters and glycerin, by reacting vegetable oils or animal fats with a monohydroxyl aliphatic alcohol, at temperatures in the range 100-250 ° C, in the presence of a catalyst containing oxide of magnesium or mixtures of magnesium and aluminum oxides, obtained by calcining a compound of the hydrotalcite type, which contains Al and Mg with an atomic ratio Mg / Al> 1. Esters of fatty acids and glycerin are formed. The unreacted alcohol is removed, then the esters of the fatty acids are separated from the glycerin.

Procedeul prezintă unele dezavantaje legate de temperatura ridicata necesara desfășurării procesului, ceea ce conduce la presiuni mari si implicit la costuri de producție semnificative.The process presents some disadvantages related to the high temperature required for the process, which leads to high pressures and implicitly to significant production costs.

RO Patent 121913 descrie un biocombustibil diesel pe baza de esteri metilici ai acizilor grași si un procedeu de obținere a acestuia, prin procesare pe cale chimica a uleiurilor vegetale in mai multe etape. In prima etapa, uleiurile vegetale se trateaza cu o soluție de acid, <*2014-- 00440î 3 -06- 20« la temperaturi de 80-95°C, timp de 15-30 minute. Se separa fracția apoasa acida cu continui de fosfatide, de fracția uleioasa care se trateaza in continuare, cu o soluție formata din hidroxid alcalin dizolvat in metanol, la temperaturi scăzute si timp scurt, pentru neutralizarea acizilor liberi. Se separa fracția metanolica de fracția uleioasa, care se trateaza in continuare cu o soluție metanolica de hidroxid alcalin, avand loc metanoliza trigliceridelor acizilor grași. Se separa prin decantare sau separare centrifugala glicerina bruta I de esterii metilici bruti I, care in etapa următoare se trateaza cu o soluție metanolica de hidroxid alcalin, avand loc finalizarea procesului de metanoliza. Se separa glicerina bruta II de esterii metilici bruti II, care se purifica prin spalare cu o soluție apoasa de metanol. Se separa fracția apoasa, de fracția esterica, din care se îndepărtează apa si volatilele prin distilare. Esterii metilici astfel obținuți îndeplinesc cerințele unui biocombustibil diesel, conform standardului EN 14214.Patent 121913 describes a diesel biofuel based on methyl esters of fatty acids and a process for obtaining it, by chemical processing of vegetable oils in several stages. In the first stage, the vegetable oils are treated with an acid solution, <* 2014-- 00440î 3 -06- 20 «at temperatures of 80-95 ° C, for 15-30 minutes. The acidic aqueous fraction is separated with phosphatide contents, from the oily fraction which is further treated, with a solution of alkali hydroxide dissolved in methanol, at low temperatures and short time, for neutralizing the free acids. The methanolic fraction is separated from the oily fraction, which is further treated with a methanolic solution of alkaline hydroxide, taking place the methanolysis of the fatty acid triglycerides. It is separated by decantation or centrifugal separation of the crude glycerine I from the crude methyl esters I, which in the next step is treated with a methanolic solution of alkaline hydroxide, and the methanol process is completed. The crude glycerin II is separated from the crude methyl esters II, which is purified by washing with an aqueous methanol solution. The aqueous fraction is separated from the esteric fraction, from which water and volatiles are removed by distillation. The methyl esters thus obtained meet the requirements of a diesel biofuel, according to standard EN 14214.

Procedeul prezintă dezavantaje datorate utilizării unor amestecuri de metanol-apa pentru purificarea esterilor metilici bruti, ceea ce poate conduce la probleme legate de ape reziduale.The process has disadvantages due to the use of methanol-water mixtures for the purification of crude methyl esters, which can lead to wastewater problems.

US Patent 6.642.399 descrie un procedeu intr-o singura faza lichida pentru esterificarea unui amestec de acizi grași si trigliceride, care cuprinde: (a) realizarea unei soluții formate din acizi grași, trigliceride, un alcool, un catalizator acid de tipul acidului sulfuric si un cosolvent, la o temperatura mai mica decât punctul de fierbere al soluției, alcoolul menționat fiind selectat dintre metanol, etanol si amestecuri ale acestora, iar raportul molar dintre alcool si trigliceride, plus o treime din acizii grași fiind in intervalul de la 15:1 la 35:1, cosolventul fiind intr-o cantitate suficienta pentru formarea unei faze lichide unice; (b) menținerea soluției pentru o perioada de timp necesara realizării esterificarii acizilor grași, catalizata de acid; (c) neutralizarea catalizatorului acid si adaugarea unei catalizator bazic de tipul hidroxidului de sodiu sau de potasiu, pentru transesterificarea trigliceridelor si (d), după o perioada de timp, separarea esterilor din respectiva soluție.US Patent 6,642,399 discloses a single-phase liquid process for the esterification of a mixture of fatty acids and triglycerides, comprising: (a) making a solution of fatty acids, triglycerides, an alcohol, an acid catalyst such as sulfuric acid and a cosolvent, at a temperature lower than the boiling point of the solution, said alcohol being selected from methanol, ethanol and mixtures thereof, and the molar ratio between alcohol and triglycerides, plus one third of the fatty acids in the range of 15: 1 to 35: 1, the cosolvent being in an amount sufficient to form a single liquid phase; (b) maintaining the solution for a period of time necessary to achieve fatty acid esterification, acid catalyzed; (c) neutralizing the acid catalyst and adding a basic catalyst of the sodium or potassium hydroxide type, for transesterification of triglycerides; and (d), after a period of time, separating the esters from the respective solution.

Procedeul prezintă dezavantaje legate de necesitatea neutralizării catalizatorului acid, de îndepărtarea cosolventului prin distilare si de utilizarea unor cantitati apreciabile de ape acide pentru purificarea esterilor alchilici bruti.The process has disadvantages related to the need to neutralize the acid catalyst, the removal of the cosolvent by distillation and the use of appreciable quantities of acidic water for the purification of crude alkyl esters.

US Patent 4.698.186 descrie un procedeu continuu pentru pre-esterificarea unei grăsimi sau a unui ulei, pentru reducerea conținutului de acizi grași liberi anterior procesului de transesterificare care cuprinde: (a) trecerea unei grăsimi brute in amestec cu metanol intrun raport molar metanol fata de conținutul de acizi grași liberi din grăsimi de la aproximativ 10:1 la 50:1, la temperaturi de 55 - 65° C, peste un pat fix heterogen de catalizator de preesterificare, de tipul unei rășini acide solide, schimbătoare de anioni, care conține o matrice λ- 2 01 4 - - 0 Ο 4 4 Ο - h£)US Patent 4,689,186 discloses a continuous process for the pre-esterification of a fat or oil, for reducing the free fatty acid content prior to the transesterification process comprising: (a) passing a crude fat mixed with methanol in a methanol to molar ratio by the fat free fatty acid content from about 10: 1 to 50: 1, at temperatures of 55 - 65 ° C, over a heterogeneous fixed bed of preesterification catalyst, of the type of a solid, anion exchange acid resin, which contains a matrix λ- 2 01 4 - - 0 Ο 4 4 Ο - h £)

3 -Β- 2βΚ de polimer cu grupări de acid sulfonic, pentru a pre-esterifica acizii grași liberi si de a reduce indicele de aciditate al grăsimilor sub valoarea de 1; (b) separarea grăsimii pre-esterificate si trecerea acesteia intr-un vaporizator pentru îndepărtarea apei si a excesului de metanol. Procedeul recomanda diluarea grăsimii inițiale, înainte de pre-esterificare cu grăsime cu continui scăzut de acizi grași liberi sau cu esteri metilici ai acizilor grași.3 -Β- 2βΚ of polymer with sulfonic acid groups, to pre-esterify the free fatty acids and reduce the fat acidity index below 1; (b) separating the pre-esterified fat and passing it into a vaporizer to remove water and excess methanol. The process recommends dilution of the initial fat, before pre-esterification with low-fat continuous free fatty acids or with fatty acid methyl esters.

Procedeul prezintă unele dezavantaje legate de limitarea conținutului inițial de acizi grași liberi din grăsime (indice de aciditate de cel mult 10)The process has some disadvantages related to the limitation of the initial fat free fatty acids content (acidity index up to 10)

Se cunosc numeroare procedee de prepararea a compușilor de tip hidrotalcit, cu utilizări in domenii variate.Numerous processes are known for the preparation of hydrotalcite compounds, with uses in various fields.

WO Patent 2014/033760 se refera la dezvoltarea unui procedeu de preparare a unui hidrotalcit sintetic, utilizând trei reziduuri industriale, deșeuri de clorura de aluminiu, rezultate din procese avand la baza reacții Freidel Crafit, deșeuri cu magneziu din evaporarea naturala a apei de mare sau a apelor din subsol si o soluție de carbonat de amoniu generata in industriile de pigmenți organici. Procesul implica prepararea precursorilor de aluminiu si îndepărtarea impurităților metalice prezente in hidroxidul de aluminiu, pregătirea precursorilor de magneziu, amestecarea precursorilor, tratarea hidrotermica a amestecului și adaugarea de agenti de modificare a suprafeței, urmata de filtrare si uscare. Hidrotalcitul se poate utiliza ca: (i) antiacid, (ii) sechestrant de halogeni, (iii) catalizator baza, sau ca suport, (iv) adsorbant pentru tratarea apelor reziduale, (v) stabilizator pentru clorura de polivinil si (vi) agent de ignifugare.WO Patent 2014/033760 refers to the development of a process for the preparation of a synthetic hydrotalcite, using three industrial residues, aluminum chloride waste, resulting from processes based on Freidel Crafit reactions, magnesium waste from natural evaporation of seawater or of groundwater and a solution of ammonium carbonate generated in organic pigment industries. The process involves the preparation of the aluminum precursors and the removal of the metal impurities present in the aluminum hydroxide, the preparation of the magnesium precursors, the mixing of the precursors, the hydrothermal treatment of the mixture and the addition of surface modification agents, followed by filtration and drying. Hydrotalcite can be used as: (i) antacid, (ii) halogen sequestrant, (iii) base catalyst, or as a carrier, (iv) adsorbent for waste water treatment, (v) stabilizer for polyvinyl chloride and (vi) agent flame retardant.

Problema tehnica pe care o rezolva invenția este simplificarea si eficientizarea procedeului, prin producerea si utilizarea unor catalizatori heterogeni performanți, la presiune atmosferica, facand posibila utilizarea unor materii grase cu continui ridicat de acizi grași liberi, de calitate inferioara sau recuperate din deșeuri.The technical problem that the invention solves is the simplification and efficiency of the process, by producing and using heterogeneous catalysts performing at atmospheric pressure, making possible the use of fatty materials with high contents of free fatty acids, of lower quality or recovered from waste.

Procedeul conform invenției înlătură dezavantajele menționate anterior prin aceea ca, in prima etapa grăsimile, alese dintre uleiul microalgal, de răpită, camelina, soia, floarea soarelui, sofranel, in, canepa, bumbac, arahide, dovleac, germeni de porumb, cocos, palmier, sâmburi de palmier, ricin, măsline, ulei microalgal, unt de cacao, untura de porc, de peste, grăsimi de ecarisaj, seu de bovine, de ovine, ca atare sau amestecuri ale acestora, in stare naturala (brute), purificate sau recuperate din deșeuri, in prima etapa, grăsimile se trateaza cu metanol in proporție de 20-58% in greutate fata de grăsime si cu catalizator solid superacid proaspăt sau recuperat de la șarjele anterioare, de tipul SO4²7SnO2, in proporție de 4-6% in greutate fata de grăsime, la temperaturi de 68±2°C, apa rezultata din reacția de esterificare a acizilor grași se separa de metanol intr-o coloana de rectificare fiind îndepărtata, iar (Κ- 2 0 1 4 - - 004401 3 -W- 20Η metanolul este recirculat, pana când indicele de aciditate al masei de reacție scade sub valoarea de 2 mg KOH/g, apoi se îndepărtează catalizatorul solid superacid prin filtrare, putând fi reutilizat, iar filtratul se trateaza in cadrul etapei următoare cu un catalizator bazic heterogen, constituit din metasilicat de sodiu, hidrotalcit cu raportul atomic Mg²⁺/Al³⁺ de 2:1, avand formula [Mg²⁺o,66Al³⁺o,33(OH)2]^0,33+ (OH')o,33 ni H20, sau hidrotalcit cu raportul atomic Mg²⁺/Al³⁺ de 3:1, avand formula [Mg²⁺o!75Al³⁺oj25(OH)2]^0,25+ (OH')o,25 m H20, si bentonita, hidrotalcitul fiind in proporție de 144-150% in greutate fata de metasilicatul de sodiu, iar bentonita in proporție de 38% fata de metasilicatul de sodiu catalizatorul fiind reutilizabil, catalizatorul bazic heterogen fiind obtinut printr-un procedeu prin care se amesteca metasilicat de sodiu pentahidrat (Na2SiO3-5H₂O) cu turta de hidrotalcit cu raportul atomic Mg²⁺/Al³⁺ de 2:1, avand 53,6% s.u., sau cu turta de hidrotalcit cu raportul atomic Mg²⁺/Al³⁺de 3:1, avand 53,6% s.u., in proporție de 161% in greutate fata de metasilicatul de sodiu pentahidrat, cu bentonita in proporție de 21,8% in greutate fata de metasilicatul de sodiu pentahidrat si cu apa in proporție de 75% in greutate fata de metasilicatul de sodiu pentahidrat, pana devine o pasta, care se extrudeaza, rezultând granule cu diametru de cca. 2 mm, care se usucă la 100°C in etuva cu vid, catalizatorul bazic heterogen fiind utilizat proaspăt sau recuperat de la șarjele anterioare, in proporție de 4-6% in greutate fata de grăsime, la temperaturi de 67±2°C, timp de 60-90 minute, se îndepărtează catalizatorul prin filtrare sau centrifugare, se separa prin decantare sau centrifugare glicerina de esterii metilici ai acizilor grași, care se trateaza in continuare cu catalizatorul bazic heterogen anterior separat, la temperaturi de 67±2°C, timp de 60-90 minute, împreuna cu metanol luat in proporție de 20-30% in greutate fata de metanolul utilizat inițial, se îndepărtează catalizatorul prin filtrare sau centrifugare, se separa prin decantare glicerina de esterii metilici ai acizilor grași, din care se îndepărtează excesul de metanol prin distilare intai la presiune atmosferica si apoi la vid, iar esterii metilici se filtrează printr-un strat filtrant anorganic, selectat dintre bentonita, bentonita tratata acid, diatomita, silicagel, cărbune activat si silicagel, cu mențiunea ca in cazul grăsimilor cu indicele de aciditate mai mic de 2 mg KOH/g si conținutul de apa mai mic de 0,1%, se poate renunța la prima etapa, de esterificare a acizilor grași liberi cu catalizator solid superacid.The process according to the invention removes the aforementioned disadvantages by the fact that, in the first stage, the fats, chosen from microalgal oil, rape, camelina, soy, sunflower, sofranel, in, hemp, cotton, peanuts, pumpkin, corn germs, coconut, palm , palm kernels, castor, olives, microalgal oil, cocoa butter, pork lard, fish, fattening fat, beef fat, sheep, as such or mixtures thereof, in natural (crude), purified or recovered from waste, in the first stage, the fats are treated with methanol in a proportion of 20-58% by weight and with a fresh superacid solid catalyst or recovered from the previous batches, of the type SO4 ² 7SnO2, in a proportion of 4-6 % by weight to fat, at temperatures of 68 ± 2 ° C, the water resulting from the esterification reaction of the fatty acids is separated from the methanol in a rectification column being removed, and (Κ- 2 0 1 4 - - 004401 3 -W- 20Η methanol e is recirculated, until the acidity index of the reaction mass drops below 2 mg KOH / g, then the superacid solid catalyst is removed by filtration, which can be reused, and the filtrate is treated in the next step with a heterogeneous basic catalyst, constituted. of sodium metasilicate, hydrotalcite with the atomic ratio Mg ²⁺ / Al ³⁺ of 2: 1, having the formula [Mg ²⁺ o, 66Al ³⁺ o, 33 (OH) 2] ^0.33+ (OH ') o, 33 ni H 2 O, or hydrotalcite with the atomic ratio Mg ²⁺ / Al ³⁺ of 3: 1, having the formula [Mg ²⁺ o! 75Al ³⁺ oj25 (OH) 2] ^0.25+ (OH ') o, 25 m H20, and bentonite, the hydrotalcite being in the proportion of 144-150% by weight compared to the sodium metasilicate, and the bentonite in the proportion of 38% compared to the sodium metasilicate, the catalyst being reusable, the heterogeneous basic catalyst being obtained by a process by which mix metasilicate sodium pentahydrate (Na2SiO3-5H ₂ O) with hydrotalcite cake with Mg ²⁺ / Al ³⁺ atomic ratio of 2: 1, having 53.6% su, or with hydrate cake otalcit with the atomic ratio Mg ²⁺ / Al ³⁺ of 3: 1, having 53.6% su, in proportion of 161% by weight compared to sodium metasilicate pentahydrate, with bentonite in proportion of 21.8% by weight Sodium metasilicate pentahydrate and with water in a proportion of 75% by weight compared to sodium metasilicate pentahydrate, until it becomes a paste, which is extruded, resulting in granules with a diameter of approx. 2 mm, which is dried at 100 ° C in a vacuum oven, the heterogeneous basic catalyst being used fresh or recovered from the previous batches, in a proportion of 4-6% by weight compared to fat, at temperatures of 67 ± 2 ° C, for 60-90 minutes, remove the catalyst by filtration or centrifugation, separate by decanting or centrifuging glycerin from the fatty acid methyl esters, which are further treated with the previously separated heterogeneous basic catalyst, at temperatures of 67 ± 2 ° C, for 60-90 minutes, together with methanol taken from 20-30% by weight compared to the methanol used initially, the catalyst is removed by filtration or centrifugation, the glycerine is separated by the fatty acid methyl esters, from which it is removed. the excess methanol by distillation first at atmospheric pressure and then under vacuum, and the methyl esters are filtered through an inorganic filter layer, selected from bentonite, bentonite treated ac id, diatomite, silica gel, activated carbon and silica gel, with the indication that in the case of fats with an acidity index of less than 2 mg KOH / g and a water content of less than 0,1%, the first step, esterification, can be waived of free fatty acids with superacid solid catalyst.

Invenția prezintă următoarele avantaje:The invention has the following advantages:

• furnizează un procedeu sustenabil, prin utilizarea unor materii grase ieftine, care nu pot fi utilizate in alimentație, avand un continui ridicat de acizi grași liberi, fiind de calitate inferioara sau recuperate din deșeuri;• provides a sustainable process, by using cheap fats, which cannot be used in food, having a high content of free fatty acids, being of poor quality or recovered from waste;

Ο 14 - - 0 0 4 4 0 1 3 -06- 2014Ο 14 - - 0 0 4 4 0 1 3 -06- 2014

• produce si utilizează in proces catalizatori heterogeni, care se îndepărtează ușor prin filtrare, fara a necesita operații costisitoare de purificare a esterilor metilici ai acizilor grași;• produces and uses heterogeneous catalysts in the process, which are easily removed by filtration, without requiring expensive operations to purify the fatty acid methyl esters;

• asigura consumuri reduse de materii prime si posibilitatea reutilizarii catalizatorilor si a produselor secundare, contribuind la reducerea costurilor de fabricație;• ensures low consumption of raw materials and the possibility of reusing catalysts and by-products, contributing to the reduction of manufacturing costs;

• asigura consumuri energetice reduse, prin conducerea operațiilor tehnologice la temperaturi relativ scăzute;• ensures low energy consumption, by conducting technological operations at relatively low temperatures;

• nu necesita investiții costisitoare, datorita conducerii procesului la presiune atmosferica.• does not require costly investments, due to the process's management at atmospheric pressure.

Se dau in continuare 9 exemple de realizare a invenției:The following are 9 examples of embodiments of the invention:

EXEMPLUL 1EXAMPLE 1

Intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru, pâlnie de picurare, condensator si baie de apa încălzită electric, se introduc 250 g Mg(NO3)₂6H₂O si 180,06 g A1(NO3)3 9H₂O dizolvate in 1170 g apa distilata. Raportul atomic Mg²⁺/Al³⁺ este de 2:1. Peste aceasta soluție se picura a doua soluție formata prin dizolvarea a 88,66 g NaOH si 73,52 g Na2CC>3 in 520 g apa. pH-ul amestecului de reacție este menținut la valoarea 10, timp de 30 min. Precipitatul rezultat este maturat la 60°C timp de 2 ore, după care este filtrat, spalat cu apa deionizată, uscat la 110°C si calcinat la 500°C, timp de 3 ore. Produsul rezultat se suspenda in apa distilata mentinandu-se sub agitare 3 ore, pentru refacerea structurii de hidrotalcit. Suspensia se filtrează rezultând 184 g turta de hidrotalcit avand 53,6% s.u. si formula [Mg²⁺o;66Al³⁺o;33(OH)2]⁰’³³⁺(OH')o,33 m H20.In an installation consisting of a 4-necked flask equipped with electrically operated stirring, thermometer, drip funnel, condenser and electrically heated water bath, 250 g Mg (NO3) ₂ 6H ₂ O and 180.06 g A1 are introduced. (NO3) 3 9H ₂ Dissolved in 1170 g of distilled water. The Mg ²⁺ / Al ³⁺ atomic ratio is 2: 1. Over this solution the second solution formed by dissolving 88.66 g NaOH and 73.52 g Na2CC> 3 in 520 g water is dripped. The pH of the reaction mixture is maintained at 10 for 30 minutes. The resulting precipitate is aged at 60 ° C for 2 hours, then filtered, washed with deionized water, dried at 110 ° C and calcined at 500 ° C for 3 hours. The resulting product is suspended in distilled water and kept under stirring for 3 hours to restore the hydrotalcite structure. The suspension was filtered to give 184 g of hydrotalcite cake having 53.6% su and the formula [Mg ²⁺ o; 66Al ³⁺ o; 33 (OH) 2] ⁰ ^'33+ (OH') o, 33 m H2O.

Intr-un malaxor se introduc 184 g turta hidrotalcit de tip Mg :A1 = 2 :1, avand 53,6% s.u., 114,3 g metasilicat de sodiu pentahidrat (Na₂SiO3.5H₂O), 86 g apa distilata si 25 g bentonita. Se omogenizează amestecul, pana devine o pasta, care se extrudeaza, rezultând granule cu diametru de cca. 2 mm. Granulele se usucă la etuva cu vid, la temperatura de 100°C.In a mixer, 184 g of Mg: A1 = 2: 1 hydrotalcite cake was introduced, having 53.6% su, 114.3 g sodium metasilicate pentahydrate (Na ₂ SiO3.5H ₂ O), 86 g distilled water and 25 g bentonite. The mixture is homogenized, until it becomes a paste, which is extruded, resulting in granules with a diameter of approx. 2 mm. The granules are dried in a vacuum oven at 100 ° C.

EXEMPLUL 2EXAMPLE 2

Intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru, pâlnie de picurare, condensator si baie de apa încălzită electric, se introduc 250 g Mg(NO3)₂ 6H₂O si 122,54 g A1(NO3)3 9H₂O, dizolvate in 1170 g apa distilata. Raportul atomic Mg²⁺/Al³⁺ este de 3:1. Peste aceasta soluție se picura a doua soluție formata prin dizolvarea a 88,66 g NaOH si 73,52 g Na₂CO3 in 520 g apa. pH-ul amestecului de reacție este menținut la valoarea 10, timp de 30 min. Precipitatul rezultat este maturat la 60°C timp de 2 ore, după care este filtrat, spalat cu apa deionizată, uscat la 110°C si calcinat la 500°C,In an installation consisting of a 4-necked flask equipped with electrically operated stirring, thermometer, drip funnel, condenser and electrically heated water bath, 250 g Mg (NO3) ₂ 6H ₂ O and 122.54 g A1 are introduced. (NO3) 3 9H ₂ O, dissolved in 1170 g of distilled water. The Mg ²⁺ / Al ³⁺ atomic ratio is 3: 1. Over this solution the second solution formed by dissolving 88.66 g NaOH and 73.52 g Na ₂ CO3 in 520 g water is dripped. The pH of the reaction mixture is maintained at 10 for 30 minutes. The resulting precipitate is aged at 60 ° C for 2 hours, then filtered, washed with deionized water, dried at 110 ° C and calcined at 500 ° C,

CĂ- 2 O H - - 0 0 4 4 01 3 -06- 2014CĂ- 2 O H - - 0 0 4 4 01 3 -06- 2014

timp de 3 ore. Produsul rezultat se suspenda in apa distilata mentinandu-se sub agitare 3 ore, pentru refacerea structurii de hidrotalcit. Suspensia se filtrează rezultând 170 g turta de hidrotalcit avand 51,5% s.u. si formula [Mg²⁺o,75Al³⁺o_j25(OH)2]°’²⁵⁺(OH')o,25 ni H2O.for 3 hours. The resulting product is suspended in distilled water and kept under stirring for 3 hours to restore the hydrotalcite structure. The suspension was filtered, yielding 170 g cake with 51.5% hydrotalcite and its formula [Mg ²⁺ O ^{3 +} 75Al a _j 25 (OH) 2] ° ^'25+ (OH) O H2O 25 s.

Intr-un malaxor se introduc 170 g turta hidrotalcit de tip Mg :A1= 3:1, avand 51,5% s.u., 105,6 g metasilicat de sodiu pentahidrat (Na2SiO3.5H2O), 79 g apa distilata si 23 g bentonita. Se omogenizează amestecul, pana devine o pasta, care se extrudeaza, rezultând granule cu diametru de cca. 2 mm. Granulele se usucă la etuva cu vid, la temperatura de 100°C.170 g of Mg: A1 = 3: 1 hydrotalcite cake were introduced into a mixer, having 51.5% s., 105.6 g of sodium metasilicate pentahydrate (Na2SiO3.5H2O), 79 g of distilled water and 23 g of bentonite. The mixture is homogenized, until it becomes a paste, which is extruded, resulting in granules with a diameter of approx. 2 mm. The granules are dried in a vacuum oven at 100 ° C.

EXEMPLUL 3EXAMPLE 3

Intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru si baie de ulei încălzită electric, avand balonul asamblat cu o coloana de rectificare cu umplutura structurata de tip Sulzer, alimentata median cu vaporii de apametanol rezultați din balonul cu 4 gaturi, coloana fiind cuplata la partea superioara cu un distribuitor de reflux, un termometru, un condensator si un balon colector metanol, iar la partea inferioara cu un balon colector distilat apos, se introduc in balonul cu 4 gaturi 100 g ulei microalgal, cu indicele de saponificare 203,54 mg KOH/g, indicele de aciditate de 87,54 mg KOH/g, si 0,12% apa. Acesta se trateaza cu 58 g metanol si 6 g catalizator solid superacid de tipul SO4^2_/SnO2· Se pornește agitarea si se încălzește amestecul din balon la 68±2°C. Vaporii de metanol cu apa rezultata din reacția de esterificare a acizilor grași liberi, alimentează coloana de rectificare. Se separa la partea superioara a coloanei o fracție metanolica iar la cea inferioara o fracție apoasa. Se reglează rația de reflux astfel incat temperatura vaporilor din vârful coloanei sa se mențină la 65±0,2°C. Fracția metanolica se colectează intr-un balon si este reintrodusa in balonul cu 4 gaturi iar fracția apoasa, separata in balonul colector inferior se indeparteaza. Se menține agitarea si încălzirea cca. 6 ore, pana nu mai separa fracție apoasa in balonul inferior, iar indicele de aciditate al masei de reacție scade la valoarea de 0,91 mg KOH/g. Se indeparteaza catalizatorul superacid prin filtrare, urmând a fi utilizat la șarjele ulterioare, iar filtratul se transvazeaza intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru, condensator si baie de ulei încălzită electric. Se introduc peste filtratul din balon, 5 g catalizator bazic heterogen obtinut conform exemplului 1 si se pornește agitarea si încălzirea. Se menține masa de reacție sub agitare la 67±2°C timp de 60 minute, apoi se indeparteaza catalizatorul prin filtrare. Se separa prin decantare 43,2 g glicerina de concentrație 22,84%, de esterii metilici ai acizilor grași bruti, care se reintroduc in balon împreuna cu catalizatorul anterior separat prin filtrare si cu 11,6 g metanol. Se menține masa de reacție sub agitare la 67±2°C timp de 60In an installation consisting of a 4-necked balloon provided with electrically operated stirring, thermometer and electrically heated oil bath, the balloon being assembled with a rectifier column with structured filling of Sulzer type, fed medially with the apamethanol vapors resulting from the balloon with 4 drops, the column being coupled at the top with a reflux dispenser, a thermometer, a condenser and a methanol collecting flask, and at the bottom with a distilled aqueous collecting flask, 100 g of microalgal oil is introduced into the 4-flask, with the saponification index 203.54 mg KOH / g, the acidity index of 87.54 mg KOH / g, and 0.12% water. It is treated with 58 g of methanol and 6 g of solid acid catalyst of the SO4 type ^2_ / SnO2 · Stirring is started and the mixture in the flask is heated to 68 ± 2 ° C. Methanol vapors with water resulting from the esterification reaction of free fatty acids feed the rectification column. At the top of the column a methanolic fraction is separated and at the lower one an aqueous fraction. The reflux ratio is adjusted so that the temperature of the vapor at the top of the column is maintained at 65 ± 0.2 ° C. The methanol fraction is collected in a flask and is re-introduced into the 4-neck flask and the aqueous fraction, separated into the lower flask, is removed. Stirring and heating approx. 6 hours, until the aqueous fraction no longer separates into the lower flask, and the acidity index of the reaction mass drops to 0.91 mg KOH / g. The super-acid catalyst is removed by filtration, to be used at subsequent batches, and the filtrate is transferred to an installation consisting of a 4-neck flask equipped with electrically operated stirring, thermometer, condenser and electrically heated oil bath. 5 g of the heterogeneous basic catalyst obtained according to example 1 is introduced over the flask filtrate and the agitation and heating are started. The reaction mass is stirred at 67 ± 2 ° C for 60 minutes, then the catalyst is removed by filtration. Separate by 43.2 g of 22.84% glycerin in concentration, from the methyl esters of the crude fatty acids, which are reintroduced into the flask together with the catalyst previously separated by filtration and with 11.6 g of methanol. The reaction mass is kept under stirring at 67 ± 2 ° C for 60

0\“ 2 Ο 1 4 - - 0 0 4 4 01 3 -06- 2014 minute, apoi se îndepărtează catalizatorul prin filtrare. Se separa prin decantare 5,4 g glicerina bruta de concentrație 17,6% de esterii metilici ai acizilor grași bruti, din care se îndepărtează excesul de metanol prin distilare intai la presiune atmosferica si apoi la vid, apoi se filtrează printr-un strat filtrant de bentonita tratata acid. Se obțin 93,9 g esteri metilici ai acizilor grași cu compoziția in acizi grași conform tabelului 1 si caracteristicile conform tabelului 2.0 \ "2 Ο 1 4 - - 0 0 4 4 01 3 -06- 2014 minutes, then the catalyst is removed by filtration. 5.4 g of crude glycerin, 17.6% of the crude fatty acid methyl esters are separated by decanting, from which excess methanol is removed by first distillation at atmospheric pressure and then in vacuo, then filtered through a filter layer. of acid-treated bentonite. 93.9 g of fatty acid methyl esters are obtained with the fatty acid composition according to Table 1 and the characteristics according to Table 2.

EXEMPLUL 4EXAMPLE 4

Intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru si baie de ulei încălzită electric, avand balonul asamblat cu o coloana de rectificare cu umplutura structurata, alimentata median cu vaporii de apa-metanol rezultați din balonul cu 4 gaturi, coloana fiind cuplata la partea superioara cu un distribuitor de reflux, un termometru, un condensator si un balon colector metanol, iar la partea inferioara cu un balon colector distilat apos, se introduc in balonul cu 4 gaturi 100 g grăsime reziduala recuperata din industria de prelucrare a pieilor, cu indicele de saponificare 194,21 mg KOH/g, indicele de aciditate de 9,32 mg KOH/g, si 0,15% apa. Acesta se trateaza cu 44 g metanol si 5 g catalizator solid superacid de tipul SO4^2_/SnO2, recuperat de la șarja 3. Se pornește agitarea si se încălzește amestecdl din balon la 68±2°C. Vaporii de metanol cu apa rezultata din reacția de esterificare a acizilor grași liberi, alimentează coloana de rectificare. Se separa la partea superioara a coloanei o fracție metanolica iar la cea inferioara o fracție apoasa. Se reglează rația de reflux astfel incat temperatura vaporilor din vârful coloanei sa se mențină la 65±0,2°C. Fracția metanolica se colectează intr-un balon si este reintrodusa in balonul cu 4 gaturi iar fracția apoasa, separata in balonul colector inferior se îndepărtează. Se menține agitarea si încălzirea cca. 5 ore, pana nu mai separa fracție apoasa in balonul inferior, iar indicele de aciditate al masei de reacție scade la valoarea de 0,82 mg KOH/g. Se îndepărtează catalizatorul superacid prin filtrare, urmând a fi utilizat la șarjele ulterioare, iar filtratul se transvazeaza intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru, condensator si baie de ulei încălzită electric. Se introduc peste filtratul din balon, 6 g catalizator bazic heterogen obtinut conform exemplului 2 si se pornește agitarea si încălzirea. Se menține masa de reacție sub agitare la 67±2°C timp de 50 minute, apoi se îndepărtează catalizatorul prin filtrare. Se separa prin decantare 37,5 g glicerina de concentrație 25,96%, de esterii metilici ai acizilor grași bruti, care se reintroduc in balon împreuna cu catalizatorul anterior separat prin filtrare si cu 8,8 g metanol. Se menține masa de reacție sub agitare la 67±2°C timp de 50 minute, apoi se indeparteaza catalizatorul prin filtrare. Se separa prin decantare 3,4 g glicerina bruta de concentrație 17,93% de esterii metilici ai acizilor grași bruti, din care se indeparteaza excesul de metanol prin distilare intaiIn an installation consisting of a 4-necked balloon provided with electrically operated stirring, thermometer and electrically heated oil bath, the balloon being assembled with a rectified column with structured filling, fed medially with the water-methanol vapors resulting from the balloon with 4 drops, the column being coupled at the top with a reflux dispenser, a thermometer, a condenser and a methanol collecting balloon, and at the bottom with a distilled aqueous collecting balloon, 100 g of residual fat recovered from leather processing industry, with saponification index 194.21 mg KOH / g, acidity index 9.32 mg KOH / g, and 0.15% water. This is treated with 44 g methanol and 5 g solid acid catalyst type SO4 ^2_ / SnO2, recovered from batch 3. Start stirring and heat the mixture in the flask at 68 ± 2 ° C. Methanol vapors with water resulting from the esterification reaction of free fatty acids, feed the rectification column. At the top of the column a methanolic fraction is separated and at the lower one an aqueous fraction. The reflux ratio is adjusted so that the temperature of the vapor at the top of the column is maintained at 65 ± 0.2 ° C. The methanol fraction is collected in a flask and is re-introduced into the 4-neck flask and the aqueous fraction, separated into the lower flask, is removed. Stirring and heating approx. 5 hours, until the aqueous fraction no longer separates into the lower flask, and the acidity index of the reaction mass drops to 0.82 mg KOH / g. The super-acid catalyst is removed by filtration, to be used at subsequent batches, and the filtrate is transferred to an installation consisting of a 4-neck flask fitted with electrically operated stirring, thermometer, condenser and electrically heated oil bath. 6 g of heterogeneous basic catalyst obtained according to example 2 is introduced over the flask filtrate and the agitation and heating are started. The reaction mass is stirred at 67 ± 2 ° C for 50 minutes, then the catalyst is removed by filtration. Separate 37.5 g of glycerin of 25.96% concentration, from the methyl esters of the crude fatty acids, which are reintroduced into the flask together with the previously catalyst separated by filtration and with 8.8 g of methanol. The reaction was stirred at 67 ± 2 ° C for 50 minutes, then the catalyst was removed by filtration. Decant 3.4 g of crude glycerin with 17.93% concentration of methyl esters of crude fatty acids, from which excess methanol is removed by first distillation

Ο 1 4 - - 004401 3 -06- 20« la presiune atmosferica si apoi la vid, apoi se filtrează printr-un strat filtrant de diatomita. Se obțin 94,4 g esteri metilici ai acizilor grași cu compoziția in acizi grași conform tabelului 1 si caracteristicile conform tabelului 2.4 1 4 - - 004401 3 -06- 20 «at atmospheric pressure and then under vacuum, then filtered through a diatomite filter layer. 94.4 g of fatty acid methyl esters are obtained with the fatty acid composition according to Table 1 and the characteristics according to Table 2.

EXEMPLUL 5EXAMPLE 5

Intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru si baie de ulei încălzită electric, avand balonul asamblat cu o coloana de rectificare cu umplutura structurata de tip Sulzer, alimentata median cu vaporii de apametanol rezultați din balonul cu 4 gaturi, coloana fiind cuplata la partea superioara cu un distribuitor de reflux, un termometru, un condensator si un balon colector metanol, iar la partea inferioara cu un balon colector distilat apos, se introduc in balonul cu 4 gaturi 100 g ulei rezidual colectat din unitati de alimentație publica de tip fast food, cu indicele de saponificare 191,43 mg KOH/g, indicele de aciditate de 12,25 mg KOH/g, si 0,11% apa, care se trateaza cu 33 g metanol si 4 g catalizator solid superacid de tipul SO4²~/SnO₂. Se pornește agitarea si se încălzește amestecul din balon la 68±2°C. Vaporii de metanol cu apa rezultata din reacția de esterificare a acizilor grași liberi, alimentează coloana de rectificare. Se separa la partea superioara a coloanei o fracție metanolica iar la cea inferioara o fracție apoasa. Se reglează rația de reflux astfel incat temperatura vaporilor din vârful coloanei sa se mențină la 65±0,2°C. Fracția metanolica se colectează intr-un balon si este reintrodusa in balonul cu 4 gaturi iar fracția apoasa, separata in balonul colector inferior se indeparteaza. Se menține agitarea si încălzirea cca. 6 ore, pana nu mai separa apa, iar indicele de aciditate scade la valoarea de 0,85 mg KOH/g. Se indeparteaza catalizatorul superacid prin filtrare, iar filtratul se transvazeaza intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru, condensator si baie de ulei încălzită electric. Se introduc peste filtratul din balon 5 g catalizator bazic heterogen obtinut conform exemplului 2 si se pornește agitarea si încălzirea. Se menține masa de reacție sub agitare la 67±2°C timp de 90 minute, apoi se indeparteaza catalizatorul prin centrifugare. Se separa prin decantare 24 g glicerina de concentrație 38,71%, de esterii metilici ai acizilor grași bruti, care se reintroduc in balon împreuna cu catalizatorul anterior separat prin filtrare si cu 9,9 g metanol. Se menține masa de reacție sub agitare la 67±2°C timp de 90 minute, apoi se indeparteaza catalizatorul prin filtrare. Se separa prin decantare 4,9 g glicerina bruta de concentrație 23,14% de esterii metilici ai acizilor grași bruti, din care se indeparteaza excesul de metanol prin distilare intai la presiune atmosferica si apoi la vid, iar esterii se filtrează printr-un strat filtrant de cărbune activat si silicagel. Se obțin 94,7 g esteri metilici ai acizilor grași cu compoziția in acizi grași conform tabelului 1 si caracteristicile conform tabelului 2.In an installation consisting of a 4-necked balloon provided with electrically operated stirring, thermometer and electrically heated oil bath, the balloon being assembled with a rectifier column with structured filling of Sulzer type, fed medially with the apamethanol vapors resulting from the balloon with 4 drops, the column being coupled at the top with a reflux dispenser, a thermometer, a condenser and a methanol collecting flask, and at the bottom with a distilled aqueous collecting flask, 100 g of residual collected oil is introduced into the 4-flask from fast food units, with the saponification index 191.43 mg KOH / g, the acidity index of 12.25 mg KOH / g, and 0.11% water, which is treated with 33 g methanol and 4 g superacid solid catalyst type SO4 ² ~ / SnO ₂ . Stirring is started and the mixture is heated to 68 ± 2 ° C. Methanol vapors with water resulting from the esterification reaction of free fatty acids feed the rectification column. At the top of the column a methanolic fraction is separated and at the lower one an aqueous fraction. The reflux ratio is adjusted so that the temperature of the vapor at the top of the column is maintained at 65 ± 0.2 ° C. The methanol fraction is collected in a flask and is re-introduced into the 4-neck flask and the aqueous fraction, separated into the lower flask, is removed. Stirring and heating approx. 6 hours, until the water no longer separates, and the acidity index drops to 0.85 mg KOH / g. The super-acid catalyst is removed by filtration, and the filtrate is transferred to an installation consisting of a 4-neck flask equipped with electrically operated stirring, thermometer, condenser and electrically heated oil bath. 5 g of the heterogeneous basic catalyst obtained according to example 2 is introduced over the filtrate in the flask and the agitation and heating are started. The reaction mass is stirred at 67 ± 2 ° C for 90 minutes, then the catalyst is removed by centrifugation. Separate 24 g of glycerin 38.71% concentration, from the methyl esters of crude fatty acids, which are reintroduced into the flask together with the previously catalyst separated by filtration and with 9.9 g methanol. The reaction mass is stirred at 67 ± 2 ° C for 90 minutes, then the catalyst is removed by filtration. 4.9 g crude glycerin is separated by decanting 23.14% from the methyl esters of the crude fatty acids, from which excess methanol is removed by distillation first at atmospheric pressure and then in vacuum, and the esters are filtered through a layer. activated carbon filter and silica gel. 94.7 g of fatty acid methyl esters are obtained with the fatty acid composition according to Table 1 and the characteristics according to Table 2.

(λ 2 01 4 - - 00440t 3 Ό6- 20K(λ 2 01 4 - - 00440t 3 Ό6- 20K

EXEMPLUL 6EXAMPLE 6

Intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru, baie de ulei încălzită electric si condensator se introduc 100 g ulei de camelina, cu indicele de saponificare 189,62 mg KOH/g, indicele de aciditate de 0,47 mg KOH/g, si 0,07% apa, împreuna cu 22 g metanol recuperat de la șarjele anterioare si 4 g catalizator bazic heterogen preparat conform exemplului 1, recuperat de la șarjele anterioare. Se pornește agitarea si încălzirea. Se menține masa de reacție sub agitare la 67±2°C timp de 90 minute, apoi se indeparteaza catalizatorul prin filtrare. Se separa prin decantare 17 g glicerina 54,13%, de esterii metilici ai acizilor grași, care se reintroduc in balon împreuna cu catalizatorul anterior separat prin filtrare si cu 6,6 g metanol. Se menține masa de reacție sub agitare la 67±2°C timp de 90 minute, apoi se indeparteaza catalizatorul prin filtrare. Se separa prin decantare 5 g glicerina de concentrație 17,81%, de esterii metilici ai acizilor grași bruti, din care se indeparteaza excesul de metanol prin distilare intai la presiune atmosferica si apoi la vid, iar esterii se filtrează printr-un strat filtrant de bentonita. Se obțin 95,3 g esteri metilici ai acizilor grași cu compoziția in acizi grași conform tabelului 1 si caracteristicile conform tabelului 2.In a system consisting of a 4-neck flask equipped with electrically operated stirring, thermometer, electrically heated oil bath and condenser, 100 g of camelina oil is introduced, with the saponification index 189.62 mg KOH / g, the acidity index 0.47 mg KOH / g, and 0.07% water, together with 22 g methanol recovered from the previous batches and 4 g heterogeneous basic catalyst prepared according to Example 1, recovered from the previous batches. Stirring and heating is started. The reaction mass is stirred at 67 ± 2 ° C for 90 minutes, then the catalyst is removed by filtration. Separate by 17 g glycerin 54.13%, from the fatty acid methyl esters, which are reintroduced into the flask together with the previously catalyst separated by filtration and 6.6 g methanol. The reaction mass is stirred at 67 ± 2 ° C for 90 minutes, then the catalyst is removed by filtration. Separate 5 g of glycerin of concentration 17.81%, from the methyl esters of crude fatty acids, from which excess methanol is removed by first distillation at atmospheric pressure and then in vacuum, and the esters are filtered through a filtering layer. bentonite. 95.3 g of fatty acid methyl esters are obtained with the fatty acid composition according to Table 1 and the characteristics according to Table 2.

EXEMPLUL 7EXAMPLE 7

Intr-o instalație formata dintr-un balon cu 4 gaturi prevăzut cu agitare actionata electric, termometru, baie de ulei încălzită electric si condensator se introduc 100 g ulei de palmier, cu indicele de saponificare 201,44 mg KOH/g, indicele de aciditate de 0,47 mg KOH/g, si 0,06% apa, împreuna cu 20 g metanol si 4 g catalizator bazic heterogen preparat conform exemplului 2, recuperat de la șarjele anterioare. Se pornește agitarea si încălzirea. Se menține masa de reacție sub agitare la 67±2°C timp de 90 minute, apoi se indeparteaza catalizatorul prin filtrare. Se separa prin decantare 16,4 g glicerina 59,95%, de esterii metilici ai acizilor grași, care se reintroduc in balon împreuna cu catalizatorul anterior separat prin filtrare si cu 6 g metanol. Se menține masa de reacție sub agitare la 67±2°C timp de 90 minute, apoi se indeparteaza catalizatorul prin filtrare. Se separa prin decantare 5,4 g glicerina de concentrație 15,83%, de esterii metilici ai acizilor grași bruti, din care se indeparteaza excesul de metanol prin distilare intai la presiune atmosferica si apoi la vid, iar esterii se filtrează printr-un strat filtrant de silicagel. Se obțin 95,2 g esteri metilici ai acizilor grași cu compoziția in acizi grași conform tabelului 1 si caracteristicile conform tabelului 2.In a plant consisting of a 4-neck flask equipped with electrically operated stirring, thermometer, electrically heated oil bath and condenser, 100 g of palm oil is introduced, with the saponification index 201.44 mg KOH / g, the acidity index 0.47 mg KOH / g, and 0.06% water, together with 20 g methanol and 4 g heterogeneous basic catalyst prepared according to Example 2, recovered from the previous batches. Stirring and heating is started. The reaction mass is stirred at 67 ± 2 ° C for 90 minutes, then the catalyst is removed by filtration. Separate 16.4 g glycerin 59.95%, from the fatty acid methyl esters, which are reintroduced into the flask together with the previously separated catalyst by filtration and with 6 g methanol. The reaction mass is stirred at 67 ± 2 ° C for 90 minutes, then the catalyst is removed by filtration. Separate 5.4 g of 15.83% glycerin by decantation, from the methyl esters of the crude fatty acids, from which excess methanol is removed by first distillation at atmospheric pressure and then under vacuum, and the esters are filtered through a layer. silica gel filter. 95.2 g of fatty acid methyl esters are obtained with the fatty acid composition according to Table 1 and the characteristics according to Table 2.

EXEMPLUL 8EXAMPLE 8

Se respecta procedeul descris in exemplul 3, 4 sau 5, inlocuindu-se uleiul microalgal, grăsimea reziduala recuperata din industria de prelucrare a pieilor, sau uleiul rezidual colectatFollow the procedure described in example 3, 4 or 5, replacing the microalgal oil, the residual fat recovered from the leather processing industry, or the residual oil collected

Or 10 1 4 - - 0 0 4 4 0 1 3 -06- 2014 din unitati de alimentație publica de tip fast food, cu uleiuri de răpită, soia, floarea soarelui, camelina, sofranel, in, cînepa, bumbac, arahide, dovleac, germeni de porumb, cocos, palmier, sâmburi de palmier, ricin, măsline, unt de cacao, untura de porc, de peste, grăsimi de ecarisaj, seu de bovine, de ovine, ca atare sau amestecuri ale acestora, in stare naturala (brute), purificate sau recuperate din deșeuri, avand indicele de aciditate mai mare de 2 mg KOH/g. Randamentele si caracteristicile produselor astfel obținute, se incadreaza in limitele valorilor prezentate in exemplele de mai sus.Or 10 1 4 - - 0 0 4 4 0 1 3 -06- 2014 from fast food units with rapeseed oil, soybean, sunflower, camelina, sofranel, in, hemp, cotton, peanuts, pumpkin , maize germs, coconut, palm, palm kernels, castor, olives, cocoa butter, pork lard, fish, squash fat, beef fat, sheep, as such or mixtures thereof, in their natural state ( crude), purified or recovered from waste, having an acidity index greater than 2 mg KOH / g. The yields and characteristics of the products thus obtained, fall within the limits of the values presented in the examples above.

EXEMPLUL 9EXAMPLE 9

Se respecta procedeul descris in exemplul 6, sau 7, inlocuindu-se uleiul de camelina, sau de palmier, cu uleiuri de răpită, soia, floarea soarelui, sofranel, in, cînepa, bumbac, arahide, dovleac, germeni de porumb, cocos, sâmburi de palmier, ricin, măsline, ulei microalgal, unt de cacao, untura de porc, de peste, grăsimi de ecarisaj, seu de bovine, de ovine, ca atare sau amestecuri ale acestora, in stare naturala (brute), purificate sau recuperate din deșeuri, avand indicele de aciditate mai mic de 2 mg KOH/g si conținutul de apa mai mic de 0,1%. Randamentele si caracteristicile produselor astfel obținute, se incadreaza in limitele valorilor prezentate in exemplele de mai sus.Follow the procedure described in Example 6, or 7, replacing camelina or palm oil with rapeseed, soybean, sunflower, sofranel, in, hemp, cotton, peanuts, pumpkin, corn germs, coconut, palm kernels, castor bean, olives, microalgal oil, cocoa butter, pork lard, fish, fats, beef fat, sheep fat, as such or mixtures thereof, in natural (crude), purified or recovered from waste, having an acidity index of less than 2 mg KOH / g and a water content of less than 0.1%. The yields and characteristics of the products thus obtained, fall within the limits of the values presented in the examples above.

Claims

1. Heterogeneous basic catalyst for obtaining biodiesel based on fatty acid methyl esters, characterized in that it is made of sodium metasilicate, hydrotalcite with the atomic ratio Mg ²⁺ / Al ³⁺ of 2: 1, having the formula [Mg ²⁺ o66A ³⁺ o> 33 (OH) 2] ^0.33+ (OH ') o, 33 m H 2 O, or hydrotalcite with the atomic ratio Mg ²⁺ / Al ³⁺ of 3: 1, having the formula [Mg ²⁺ 0175A1 ^{3 +} 0,25 (OH) 2] ⁰ '25 ⁺ (OH) (), 25 m H ₂ 0, and bentonite, hydrotalcite being in the proportion of 144-150% by weight compared to sodium metasilicate, and bentonite in proportion 38% compared to sodium metasilicate catalyst being reusable.

2. Process for obtaining the heterogeneous basic catalyst, characterized in that it mixes metasilicate sodium pentahydrate (Na ₂ SiO3.5H2O) with hydrotalcite cake with the atomic ratio Mg ²⁺ / Al ³⁺ of 2: 1, having 53.6% su, or hydrotalcite cake with the atomic ratio Mg ²⁺ / Al ³⁺ of 3: 1, having 53.6% su, in proportion of 161% by weight compared to sodium metasilicate pentahydrate, with bentonite in proportion of 21, 8% by weight compared to sodium metasilicate pentahydrate and water 75% by weight compared to sodium metasilicate pentahydrate, until it becomes a paste, which is extruded, resulting in granules with a diameter of approx. 2 mm, which is dried at 100 ° C in a vacuum oven.

3. Process for obtaining methyl esters of fatty acids, by chemically processing the fats with free fatty acids, in several stages, characterized in that in the first stage, the fats are treated with methanol in a proportion of 20-58%. by weight against fat and with solid superacid catalyst fresh or recovered from the previous batches, of the type SO4 ² 7SnO ₂ , in a proportion of 4-6% by weight against fat, at temperatures of 68 ± 2 ° C, water resulting from the esterification reaction of the fatty acids is separated from the methanol in a rectifying column and the methanol is recirculated, until the acidity index of the reaction mass drops below 2 mg KOH / g, then the superacid solid catalyst is removed by filtration, which can be reused, and the filtrate is treated in the next step with a basic heterogeneous catalyst, fresh or recovered from the previous batches, 4-6% by weight fat versus fat at temperatures of 67 ± 2 ° C for 60-90 minutes, remove the catalyst by filtration or centrifugation, separate by decanting or centrifuging glycerine from the fatty acid methyl esters, which is further treated with the catalyst previously heterogeneous base separated, at temperatures of 67 ± 2 ° C, for 60-90 minutes, together with methanol taken in a proportion of 20-30% by weight compared to the methanol used initially, the catalyst is removed by filtration or centrifugation, separated by decanting glycerin from the fatty acid methyl esters, from which the excess of (* 2014-- 0 0 4 4 01 3 -06- 2014 methanol is removed by distillation first at atmospheric pressure and then in vacuum, and the methyl esters are filtered through an inorganic filter layer.

4. Process according to claim 1, characterized in that the fats are chosen from microalgal oil, rapeseed, camelina, soybean, sunflower, sofranel, in, hemp, cotton, peanuts, pumpkin, corn germs, coconut, palm kernels, castor bean, olives, microalgal oil, cocoa butter, pork lard, fish, fattening oil, beef fat, sheep fat, as such or mixtures thereof, in their natural state (raw), purified or recovered from waste, and Inorganic filter layer is selected from bentonite, acid treated bentonite, diatomite, silica gel, activated carbon and silica gel.

5. Process according to claim 1, characterized in that in the case of fats with an acidity index of less than 2 mg KOH / g and a water content of less than 0.1%, the first step of esterification of fatty acids can be given up. free with superacid solid catalyst.