ES2585706B1 - Improved procedure for the refining and continuous esterification of any fatty material of vegetable or animal origin, specially designed for animal by-products of category 1 and 2 - Google Patents

Abstract

Procedure for the refining and continuous esterification of fatty materials, regardless of the origin of the raw material (specially designed for animal fats category 1 and 2); which consists of treating it with an acid (preferably acetic acid for animal fats and methanesulfonic acid for vegetable fats), followed by an acid esterification process in special multistage continuous reactors. The particularity of the method object of the invention is that the esterification can be carried out in two stages in series or parallel according to the degree of acidity of the raw material (two stages in series for FFA greater than 50%, and two stages in parallel for FFA less than 50%, no acidity value being limiting) continuously. Finally, a third phase is developed where methanol is recovered, the dissolved oil phase and an aqueous phase, which are reused again. # Thanks to the method, the content of free fatty acids and / or impurities of the original material of handle continuously and without thermal or chemical degradation, for any type of raw material (raw, refined, partially refined, ...). This process improvement causes an increase in the final biodiesel yields, in addition to the quality with which the product is obtained. # By including the method as an additional stage in current biodiesel manufacturing technologies, or as an independent stage to these, it is allowed to obtain a high quality liquid biofuel for use in diesel engines: i) in a total way (B100), ii) in admixture with diesel (biodiesel content> 7%), or iii) as an additive of this (mixtures <7%), from residues, (among which it is necessary to highlight the animal fats of category 1 and 2, the vegetable oleins and the pure fatty acids) giving a solution to the problem of operation with which they find most of the Biodiesel manufacturing plants on the one hand, and solving the environmental inconvenience currently faced by administrations for waste disposal (especially in animal fats of category 1 and 2).

Description

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DESCRIPTION

Improved procedure for the refining and continuous esterification of any fatty material of vegetable or animal origin, especially designed for animal by-products of categories 1 and 2.

The invention relates to an improved process for the refining and continuous esterification of any raw materials rich in acylglycerides and / or free fatty acids for their subsequent conversion into alkyl esters, and the equipment necessary for performing said process.

In particular, the invention relates to a process for conditioning animal by-products of category 1 and 2 or other materials with high fat content (without excluding any type of animal or vegetable fatty material, first or second use, waste or recycled, etc.), which consist mainly of acylglycerides and free fatty acids (any range of acidity), in order to separate a number of impurities and / or components and prepare these by-products to be subjected to a continuous esterification process in a system especially, so that a fatty material of the highest and most suitable quality is obtained, preferably for its transformation into esters of high purity alkyls (liquid biofuel industries: Biodiesel) or for other industrial purposes. Alternatively, the invention also relates to the continuous esterification process in a special system for refined raw materials of any acidity range.

BACKGROUND OF THE INVENTION

Animal by-products are defined as whole bodies (or parts) of animals or products of animal origin not intended for human consumption, including ovules, embryos and sperm, derived from their processing for obtaining food for human consumption or other use. Formerly they were considered as a by-product with an added value that could be used in the food industry to obtain meat meal, bone, fat and gelatin, as well as in the cosmetic, pharmaceutical, etc.

As is well known, the epidemic of bovine spongiform encephalopathy (BSE), which only experienced a large number of livestock farms during the 1990s in countries such as Great Britain, France, the United States, Spain, Switzerland, Israel, Japan, etc., evidenced the management incorrect of these by-products, as well as their importance in the propagation of communicable animal diseases, which sponsored in their day and, in the EU, the appearance of different laws, standards and guidelines of European, national and autonomous scope with in order to control this waste and set the guidelines for its treatment and disposal.

In Spain, approximately 300,000 tons of this type of waste are generated annually, of which, by species and number of individuals, the following are: 250,000 corpses of cattle, 890,000 pigs, 21,000 equines, 1.4 million sheep and goat, 1.86 million cunicola and 6.6 million poultry. In the field of the European Union, these figures exceed ten million tons.

Currently, the treatment, manipulation and / or transformation of any animal by-product and its derivative products not intended for human consumption (SANDACH) must be governed by

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A series of standards, and any establishment that intends to use this raw material, must ensure compliance. The regulations governing such activity are:

- Regulation (EC) No. 1069/2009 of the Parliament and of the Council, of October 21, 2009, which establishes the sanitary standards applicable to animal by-products and derived products not intended for human consumption and laying down repeals Regulation (EC) No. 1774/2002 (Regulation on animal by-products).

- Commission Regulation (EU) No. 142/2011 of February 25, 2011, establishing the provisions for the application of Regulation (EC) No. 1069/2009 of the European Parliament and of the Council, establishing the sanitary norms applicable to animal by-products and derived products not intended for human consumption are established, and Council Directive 97/78 / EC regarding certain samples and units exempt from veterinary checks at the border under it .

- Commission Regulation (EU) No. 749/2011 of July 29, 2011, and Commission Regulation (EU) No. 1063/2012 of November 13, 2012, amending Regulation (EU) No ° 142/2011.

- Royal Decree 1429/2003 of November 21, which regulates the conditions of application of the community regulations on by-products of animal origin not intended for human consumption.

Although it is not the object of this report, it is worth mentioning that animal by-products are classified into three specific categories that reflect their level of risk to public health and animal health, category 1, 2 and 3 in accordance with the lists established in Articles 8, 9 and 10, respectively of regulation 1069/2009. On the other hand, the products derived from these will be subject to the rules applicable to the specific category of animal by-products from which they are derived.

As indicated above, animal by-products are mainly generated during the slaughter of animals for human consumption, the elaboration of animal products such as dairy products and the elimination of dead animals or the application of disease control measures. Regardless of their origin, they constitute a potential risk to public health, animal health and the environment. This risk must be adequately controlled, either by channeling these products to safe disposal means or using them for various purposes, provided that strict conditions are applied that minimize health risks.

The new technologies have extended the possible use of animal by-products or derived products to different productive sectors, in particular for energy production. However, the use of these new technologies may involve health risks that must also be minimized. According to the regulations cited in previous paragraphs, there are different methods of transformation or uses for the elimination of animal by-products, among which are: i) alkaline hydrolysis process; ii) high pressure and high temperature hydrolysis process; iii) production of biogas by high pressure hydrolysis; iv) Brookes gasification process; v) fat combustion

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animal in a thermal boiler process; vi) biofuel thermomechanical production process; and vii) biodiesel production process.

Within the mentioned methods, the processes "v" and "vi", are limited to fat fractions practically exclusive for category 3; processes "ii" and "iv" can only be applied for by-products of category 2 and 3; and the processes "i", "iii" and "vii" can be applied for any category of by-products (1, 2 and 3). All materials resulting from the transformation of materials of category 1 and 2, regardless of the process carried out, must be permanently marked according to the marking requirements set forth in the regulations, except for Biodiesel. Additionally, residues resulting from the transformation of animal by-products in accordance with methods “i” to “vii” shall be disposed of in accordance with the provisions of Regulation (EC) No. 1069/2009 and 142/2011, among which incineration is cited (which implies high energy costs and control of critical emissions) or burial in remote areas and whose access is practically impossible (maximum a percentage according to member country, and with official surveillance).

Given the limitations, costs and risks mentioned in the previous methods, the use of these animal by-products for obtaining Biodiesel as a means of eliminating them is presented as an interesting alternative. Additionally, the by-products obtained in the production of Biodiesel: waste from the distillation of biodiesel (can be used as fuel without any restrictions); in the case of obtaining potassium sulfate (it can be used for the production of derivative products for its application to the land); and glycerin (if it is derived from C1 or C2, it can be used to obtain biogas and if it is derived from C3, it can be used to feed animals).

On the other hand, in the framework of biodiesel production the physical and chemical characteristics of the raw material significantly affect the process and / or the final properties of biodiesel, which must meet the quality specifications of the Reference Standard. Due to the initial development of the sector, practically all the technologies available in the market, design the construction of plants for the use of raw materials type vegetable oils (raw, partially refined and / or refined). In the case of animal fats C1 and C2 (or by-products and / or residues derived from them), due to their characteristics, it implies the need for pre-transesterification treatments (most commonly used method for obtaining biodiesel), as they are materials that, they usually have a high free acidity, a high moisture content, unsaponifiable substances, high protein, fiber and ash content, as well as a component not present in vegetable oils (or if this is at trace levels) such as the compounds polymerized (synthetic and / or natural) that hinder the refining operation, as well as the reduction in yields. In most of the technologies developed or built in biodiesel plants, they allow or consider a minimum fraction of these raw materials (such as animal fats, residues of vegetable oils and used oils), given that the purification systems implemented (in cases if they exist) do not contemplate the elimination of these components. This fact justifies the origin of the problem that occurs in almost all of the biodiesel producing plants with raw materials of animal origin, so with the development of the present invention it is intended to be able to carry

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carry out the refining of low quality raw materials (especially for C1 and C2 fats), and allow the consumption of this type of waste for the production of biodiesel.

The possible impact of this invention on the Extremaduran and national socioeconomic sectors is obvious, since on the one hand an attempt is made to revalue a waste (an alternative is presented to reduce the current amounts of these wastes such as animal fat C1 and C2) for Obtaining Biodiesel, on the other, the emissions and pollution caused by the incineration and / or combustion and / or burial processes (reduction of environmental risks) are reduced and finally, the viability of the Biodiesel sector, currently in decline, due to lack of economically viable raw materials.

Biodiesel, consisting of a mixture of alkyl esters of long-chain fatty acids obtained from biological resources (vegetable oils, animal fats, used oils, etc.), is considered a clean fuel, as long as its physical-chemical characteristics meet the quality requirements of the Reference Standards (for example, the European standard EN 14214, or the standard standard ASTM D6751 in the case of the USA).

In general, it can be considered that most commercial processes for obtaining biodiesel (on an industrial scale), follow a common milestone, regardless of the technology that develops it, is based on transesterification, reaction through the which the glycerol of the triglyceride structure (mostly species in vegetable oils and animal fats) is displaced by the incorporation of a short chain alcohol (methanol, ethanol, etc ...). The result is the formation of three esters molecules (methyl, EM; ethyl, EE; etc., depending on the alcohol used), and a glycerol molecule. In the absence of a catalyst, the transesterification reaction has an extremely low speed, so that its presence is necessary.

Transesterification is an equilibrium reaction and, consequently, both reagents and products will be present when it comes to an end. Since the products of greatest interest are alkyl esters (biodiesel), to shift the equilibrium towards the formation of these, the reaction is usually carried out in excess of alcohol. Finally, two partially miscible phases are obtained: a denser phase rich in glycerol (or glycerin); and a less dense phase rich in alkyl esters (or biodiesel). After the reaction, the glycerin is separated by decantation or centrifugation (according to technologies) and purified for use in different applications. For its part, to comply with EN14214, the biodiesel phase must also be purified before being used as diesel fuel.

Despite being a simple reaction (and widely studied), the operating conditions in which it takes place (especially the quantities of catalyst and methanol used), will determine the final quality of the product obtained and the associated production costs to the process Additionally, although the final performance of the process should not be altered by the operating conditions, in practice if it is directly related.

On the other hand, the physical and chemical characteristics of the raw material significantly affect the process and / or the final properties of biodiesel, which must meet the quality specifications of the Reference Standard. It is known that some raw fat

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They consist mainly of triglyceride components, however, they generally contain a significant proportion of other non-glyceric components such as phosphatides (gums), waxy substances, free fatty acids, coloring materials, proteins, fibers, and small proportions of metals. Additionally, for animal fats and frying oils used, depending on the transformation methods to which they have been subjected, they contain large amounts of other components resulting from thermal and / or chemical degradation among which sulfur compounds and polymers can be found Synthetic or natural

As mentioned above, in the context of the production of biodiesel that begins with triglycerides, currently, almost exclusively homogenous catalysts based on alkali metal hydroxides are used. An important drawback of these systems is that the processing and purification phases of the mixtures of intermediate products obtained require large amounts of energy, which represents the bulk of the total consumption of the biodiesel production process. Additionally, these energy requirements are exponentially increased if the raw materials are used frying oils and / or animal fats of inferior quality. In particular, the biodiesel obtained from animal fats (especially those of category 1 and 2), presents an important additional limitation: once produced, with the storage time crystallizations of components present therein gradually occur, which make The product reverses very high total contamination values, causing serious problems in its consumption, apart from other parameters that do not meet the reference standards.

This fact justifies the origin of the problem that occurs in almost all of the biodiesel producing plants with raw materials of animal origin and / or used oils: BREACH OF PARAMETERS OF SECONDNORMAL QUALITY UNE EN 14214, among which the content in ester (not exceeding 92-94%, even less than 90% for some types of animal fats, the minimum required being 96.5%) and high sulfur values (values between 15-30 ppm, the maximum being 10 ppm allowed).

On the other hand, in some biodiesel plants, the solution contributed to this problem has been the installation of biodiesel distillation columns, whose purpose is to obtain a product of high quality in terms of the parameters mentioned (higher ester content 99%, and sulfur values below 10 ppm). However, the implementation of this stage as a refining measure is correct with respect to the expected quality in the product, but it has three main drawbacks: first, the investment required for the installation of the system is very high; secondly, the exponential increase in the energy consumption of the process (already very high in itself) and finally, a significant decrease in the overall performance of the mass balance. These last two aspects translate into an INCREASE IN PRODUCTION COSTS per ton of biodiesel obtained (and / or processed raw material), which means that some of the plants that intend to maintain the activity obtain fully unviable exploitation data.

In a relatively recent biodiesel manufacturing approach, it is intended to replace the conventional processes described (alkaline homogenous catalysis) with processes that use enzymatic catalysts (such as lipases), to facilitate the production of alkyl esters from oils

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natural in an alcoholysis reaction. Examples of these processes are described in the patent application documents: EP 1111064, EP 1803819 or ES 2336008. According to these, and despite involving different forms of operation, by means of an enzymatic transesterification of low quality oils, a fuel of High purity with reduced generation of secondary products and waste, which translates into lower purification and recovery costs. On the contrary, they have the disadvantage of having to immobilize the enzymes used in support substrates, which is currently not guaranteed 100% on an industrial process scale.

In another additional approach to the one mentioned in the previous paragraph, there are those processes that are based on heterogeneous catalysis, using solid catalysts. Examples of these systems are described in WO 2005/093015 (zinc aluminates) and ES 2354334 (type X zeolites, with an Si / Al atomic ratio of less than 1.2). Although there are many other options, the main drawback of these processes are the operating conditions that must be used to ensure optimal reaction rates (high pressures and temperatures), and if they can be performed under moderate conditions, problems usually occur of inhibition of activity of the active phases of the catalyst, negative aspect more pronounced when starting from low quality raw materials (with high content of dissolved impurities, such as recycled oils or animal fats).

From a technical point of view, the solution to the problem of biodiesel quality from low quality raw materials (regardless of the available technology) involves the investigation and study of the operating parameters of each of the stages involved in the production process by alkaline homogenous catalysis, and propose a combination of prior refining processes, based on conventional processes along with changes in operating conditions, as well as in the sequence of stages developed during the process.

Conventional methods for the elimination of impurities in oil, are based on four different stages: degummed, refined, bleach and deodorized. From these four stages, degumming extracts the greatest amount of impurities, most of which are hydratable phosphatides. Refining mainly extracts non-hydratable phosphatides, soaps created from the neutralization of free fatty acids and other impurities such as metals. Bleaching then improves the color and taste of the refined oil, by decomposing peroxides and eliminating oxidation products, residual phosphatides and residual soaps. Deodorizing is the final stage of processing, and generally comprises passing steam through the refined oil at elevated temperature and under almost empty conditions in order to vaporize and eliminate unpleasant volatile components.

In general, there is a large number of bibliography describing the processes for carrying out the refining of glyceride oils through an improvement in the application of conventional degumming (US 2245537, US 2351184, US 2576958, US 2666074, NL 7709915, US 2272964 , US 2353571, US 3862054). However, all of them have certain drawbacks: not suitable for industrial application or do not offer any solution to the problems traditionally posed as: i) the fraction of non-hydratable phosphorus that continues to accompany the oil, or ii) for fats

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animals, where the problem is not the phosphorus content, but the traces of proteins, fibers, polymers, etc., which continues to accompany the fatty material,), among others.

For case i), this disadvantage is resolved with improved degumming methods such as those described in document ES 2043110, in British patent 1565569 and in EP 0195991 or FR 2442882. However, these methods do not have the critical aspect in the treatment of the oil, the question of softness, or the elimination of traces of proteins, fibers and metals in case ii) commented. Additionally, these improved systems require the need for subsequent neutralization of free fatty acids (FFA), or in some cases the absence of these free fatty acid reduction (FFA) treatments, which implies a significant decrease in yields. Other systems that resolve a priori the inconvenience of case i), are described in references ES 2064834 and ES 2248218, however, after the refining processes under moderate conditions, oil drying processes should be applied, which also do not mitigate the softness problem in treatments. Additionally, in these processes the yields in the obtaining of alkyl esters are reduced (since the neutralization of FFA is carried out in the form of soap, which is separated from the oil). In other variants of the ways of operating, the soapy phase obtained passes to the glycerol refining unit, and by means of acid rupture, the FFAs are recovered, which are subsequently esterified and converted into alkyl esters. Despite this, in these process differences, greater reagent consumption and additional stages of operation are required, which do not solve the problem of current production costs. In EP 0131991 or WO 0075098, to reduce alkali consumption in neutralization, they employ a fraction of basic glycerin obtained in the subsequent transesterification stages, however, they also do not prevent the application of excess acid to recover neutralized fatty acids such as soaps

As a reflection on all of the above, all the procedures described have some disadvantage, among which are:

- High pressures and / or operating temperatures, which implies thermal decomposition of unstable oil components, even more if animal fats of category 1 and 2 are considered, which have previously been subjected to extreme conditions.

- Ineffectiveness in the refining of animal fats, especially when it comes to category 1 and 2, despite using high concentrations of acid / bases, involving chemical degradation of oil components, and precipitation of solid residues in biodiesel throughout weather.

- Loss of performance, or failing that, consumption of additional reagents.

Therefore, it follows that in processes of obtaining biodiesel, where it is intended to apply animal fats or other types of oils with a certain degree of free acidity, manufacturing methods are required that involve the direct conversion of free fatty acids into alkyl esters. For this, there are currently procedures that carry them out, such as those reflected in the patent documents: EP 0192035 and DE 4228476, which are based on the use of resins or ionic exchange materials in a fixed bed. Other variants of the conversion process (US

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2383601, US 4164506, DE 33195590, EP 0127104), involve the conventional esterification of the oil with excess methanol, in acidic medium (sulfuric or p-toluenesulfonic), under certain operating conditions (temperature higher than alcohol boiling), and characterized in that the conversion reaction is carried out discontinuously. To give continuity to the stage, several batch-type reactor systems are required, which give continuity to a phase of phase separation by the addition of entrainment means (for example anhydrous acidified glycerin, basic glycerin from the transesterification stage basic, etc ...).

Depending on the current state of the art, the glycerin phase is used either for the washing of the starting oil, or for the washing of the reaction mixture both in the acid esterification and in the basic transesterification. These ways of operating are estimated tremendously negative, since regardless of the stage in which glycerin is used (washing means, neutralization or dragging of components), the transfer of impurities to the oil or biodiesel phase to be refined occurs, reducing considerably the quality of the final product obtained, or failing that, the need to include additional purification stages such as the distillation of the final biodiesel (with the investment costs plus operation and loss of performance that entails).

For all the above, with the present invention it is intended to reduce energy consumption by a series of conventional refining series steps (based on the processes for obtaining collagen for animal by-products or degumming processes for crude oils or waste or by-products of vegetable origin), and acid esterification in a special reaction system and in continuous (at atmospheric pressure and mild temperatures). Surprisingly, with the development of the present invention, improvements have been discovered that mainly affect parameters such as: overall process performance, energy consumption and reagents; quality of biodiesel and final glycerin; Valorization of by-products currently managed as waste and utilization of raw materials with unlimited free acidity, among others.

The results obtained in the quality of the biodiesel treated with the method of the present invention, encourage the possibility of using it as a biofuel directly in diesel engines, or in their mixtures (allowing large oil companies to comply with legislative obligations regarding percentages of mixtures), and additionally, the current trend in the consumption of biodiesel from low quality raw materials (UCOME: Used Cooking Oil Methyl Ester or TME: Tallow Methyl Ester), under certain sustainability and double certifications is enhanced in the sector accounting (ISCC and DCC), much in demand by biodiesel producers, but in many cases hindered by the low quality standards achieved in current technologies, unless evaporation processes of the alkyl esters are applied, and in such cases, the exploitation data are not viable.

SUMMARY OF THE INVENTION

The present invention provides an efficient and economical process for the processing of any type of fat material (raw vegetable oils, used frying oils, animal fat C1, C2, C3, oleins, any fatty residues of vegetable and / or animal origin, etc. .) for its transformation into fat material suitable for direct inclusion in the fat transesterification stage, and its conversion into biodiesel. Surprisingly, it has been proven that by combining

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refining stages, in series and / or in parallel, followed by a continuous esterification phase, in addition to current technologies, or as an independent phase prior to them, fatty products of suitable quality are reached for transesterification and conversion into Biodiesel.

According to the invention, there is provided a process for the refining and esterification of fatty materials, comprising: i) the treatment of the fatty matter with an acid (preferably acetic acid for animal fats and methanesulfonic acid for vegetable fats), followed by a water wash; ii) the treatment of the fat obtained in (i) with an acidified solvent B (preferably methyl alcohol acidified with methanesulfonic acid); iii) the esterification treatment in a special and continuous reaction of the phases obtained in the treatment (ii) at a temperature that can vary in the range of 25-80 ° C, preferably 50-85 ° C, and more preferably from 65-75 ° C; and iv) the treatment of the acidic methanol phase obtained in (iii) for recovery and recycling of the methyl alcohol not consumed.

The present invention thus aims at a process of extracting impurities contained in the fatty matter (refining) and formation of esters in continuous (continuous esterification process in a special reaction system) of the initial free acidity thereof, comprising least:

I. a phase in the course of which said fatty matter:

to. it is filtered and heated (up to a temperature that can vary in the range of 25-100 ° C, preferably 35-95 ° C, and more preferably 40-90 ° C) (step I.1);

b. next, it is subjected to an extraction of impurities (dissolved and undissolved), in the course of which the fatty matter obtained in (I.1) is treated with an acid (preferably acetic acid for animal fats and methanesulfonic acid for vegetable fats) for a sufficient period of time (step I.2) in a homogenization and mixing tank,

C. finally, the mixture obtained in (I.2) is washed with water, in the course of which traces of impurities (dissolved and undissolved) are carried away from the fatty material by a phase separation process (stage I.3), which can be carried out with centrifugal separators or gravimetric decanters.

II. A continuous esterification phase, which can be developed in two ways:

to. Modality A.- Two stages in series (for fatty materials whose FFA value is greater than 50%). In this case, the fatty material refined in stage I (or a raw material acquired from FFA greater than 50% and which was previously refined):

i. is subjected to a partial extraction process of fatty acids free of the fatty matrix with an acidified solvent A (preferably methyl alcohol

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acidified with methanesulfonic acid), in the course of which a fraction of these free fatty acids are solubilized in solvent A (fraction II.1-1) and separated from the main stream of fat (fraction II.1-2) by special gravimetric decanters (multilayer separators), (stage II.1);

ii. then, the light phase obtained in stage II.1 (fraction II.1-1) is subjected to an esterification process in a continuous multistage reactor, and the heavy phase extracted in stage II.1 (fraction II.1 -2), in parallel, is sent to a second continuous multistage reactor, where it is subjected to esterification with prior dosing of an additional amount of acidified solvent A (preferably methyl alcohol acidified with methanesulfonic acid). The outputs of both reactors are mixed and sent to a special gravimetric decanter (multilayer separators) (stage II.2), where phase separation takes place: on the one hand the fatty material is obtained under FFA (heavy phase, fraction II. 2-1) with traces of solvent A, suitable for inclusion in the transesterification or washing unit of the biodiesel plant (as required) and on the other, the solvent mixture A-water-acid (light phase, fraction II) .2-2) with traces of fatty material, which is subjected to phase III described below.

b. Modality B. A stage (for fatty materials whose FFA value is less than 50%). In this case, the FFA fatty material less than 50% refined in stage I (or a raw material acquired from FFA less than 50% and which was previously refined) is subjected to an esterification process in two continuous multistage reactors and in parallel, after dosing an acidified solvent A (preferably methyl alcohol acidified with methanesulfonic acid) (step II.1). The outputs of both reactors are mixed and sent to a special gravimetric decanter (multilayer separators) (stage II.2), where phase separation takes place: on the one hand the fatty material is obtained under FFA (heavy phase, fraction II. 2-1) with traces of solvent A, suitable for inclusion in the transesterification unit of the biodiesel plant and on the other, the solvent mixture A-water-acid (light phase, fraction II.2-2) is obtained with traces of fatty material, which is subjected to phase III described below.

III. a recovery phase of solvent A (preferably methyl alcohol) of the solvent mixture A-water-acid (light phase, fraction II.2-2) obtained in step II.2. On this occasion, and indifferently to the mode of operation carried out in phase II, the solvent mixture A-water-acid with traces of fatty material, prior to its inclusion in the recovery stage of solvent A must be treated :

to. first, it undergoes a polarity change, in the course of which the phase obtained in stage II.2 is mixed with an aqueous fraction, followed by neutralization with an alkaline solution (preferably

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sodium or potassium hydroxide) until neutralization of the acid traces is reached (preferably pH 3-4). Next, the resulting mixture is sent to a special gravimetric decanter (multilayer separators) (stage III.1) where phase separation takes place: on the one hand the traces of fatty material are extracted (insolubilized after the polarity change: phase heavy, fraction III.1-1), which is mixed with the esterified fatty material (fraction II.2-1) suitable for inclusion in the transesterification unit of the biodiesel plant, and on the other the solvent mixture is obtained A-neutralized water (light phase, fraction III.1-2).

NOTE.- At this point it should be noted that the order in which the polarity change and neutralization develop does not alter the final result sought.

b. finally, fraction III.1-2 obtained in stage III.1:

i. it is filtered and heated (up to a temperature that can vary in the range of 50-100 ° C, preferably 65-95 ° C, and more preferably 80-90 ° C) (step III.2);

ii. then, it is subjected to an evaporation of solvent A, in the course of which the mixture obtained in step III.2 is treated in a distillation column (step III.3), where recovery of solvent A takes place ( volatile phase, fraction III.3-1), which is reused again in the solvent A process in the esterification phase (phase II). As the tail product of the column, an aqueous phase is generated, which is reused in the polarity change stage.

To carry out the procedure according to the invention, there are different forms of realization, which are described in detail as independent cases (case A and B).

BRIEF DESCRIPTION OF THE DRAWINGS

Figures 1 to 4 constitute the embodiments of the proposed procedure, which show the typical steps and arrangements of the present invention. Figure 5 constitutes the special design of the equipment where the esterification reaction itself takes place.

Thus, Figures 1 and 2 represent the form of realization of CASE A, for a continuous system and for any fatty matter (vegetable oils, used frying oils, animal fat C1, C2, C3, oleins, any fatty residues of plant origin and / or animal, etc.)), which require a previous refining for FFA values> 50% and <50%, respectively. Figures 3 and 4 represent the ways of realization of CASE B, for a continuous system and for any fatty matter (vegetable oils, used frying oils, animal fat C1, C2, C3, oleins, any fatty residues of vegetable origin and / or animal, etc.), which do NOT require prior refining and for FFA values> 50% and <50%, respectively. All the indicated provisions can be included as a previous additional process in the current biodiesel manufacturing technologies, or as an independent process to apply to a fatty material.

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DETAILED DESCRIPTION OF THE INVENTION

The present invention can be more easily understood by referring to the detailed description that follows the preferred embodiments of the invention, and the examples included therein.

Before these provisions and procedures are set forth and described, it should be understood that the present invention is not limited to specific synthetic procedures or to particular formulations, and that both may vary, of course. Likewise, it should be understood that the terminology used herein is used solely for the purpose of describing particular forms of realization, and is not intended to be limiting.

In this report and in the claims that follow, reference will be made to various terms that will be defined with the following meanings:

The singular forms of the articles ("one" and "the one or the") include plural references if the context does not clearly specify otherwise.

The term "raw material" is defined as any fatty material known to be suitable for the manufacture of Biodiesel, regardless of its origin.

The term "biodiesel" is defined as any biodiesel that is known in the art, regardless of the raw material of origin, as well as the manufacturing process thereof.

The term "impurities of the raw material" refers to any component that presents the raw material not specified as tri-di-mono-acylglycerides, free fatty acids and alkyl esters of fatty acids. Examples of these components include: proteins, vitamins and fibers (in animal fats, mainly) or coloring agents and phosphatides (in vegetable fats, mainly), free sterols, synthetic polymers, metal content, etc. The presence of all these components are well known to those skilled in the art.

The phrase "extraction of impurities from the raw material" refers to their separation from the original raw material stream.

The term "solvent" refers to any organic or inorganic compound capable of dragging soluble and insoluble components from the raw material. Within this type of compounds as examples can be cited: hexane, cyclohexane, petroleum ether, methanol, ethanol, etc., as organic and water (acid or alkaline) as inorganic. In the application of the process according to the invention as a stage included in a biodiesel plant, it is preferably as an organic solvent, that which is used as alcohol in the transesterification, to minimize the number of reagents to be used in the process.

Detailed description of the Invention: CASE A.

The process of extraction of impurities and continuous esterification of a raw material (type vegetable oils, used frying oils, animal fat C1, C2, C3, oleins, any fatty residues of vegetable and / or animal origin, etc.), which requires a previous refining according to the invention is such (see figures 1 and 2 of the drawings) that a first phase (Phase I) is carried out consisting of the extraction of

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impurities (step 1.2) in a stirred tank contact system (6), where a predetermined amount of an aqueous acid solution (4) (preferably acetic acid for animal fats and methanesulfonic acid for vegetable fats) is mixed in a mixer dynamic (5) with the fatty material (1) (previously filtered (2) and heated (3) (step I.1)), keeping the mixture stirred (7) during the retention time of the tank, which is necessary and sufficient to achieve the desired degree of hydration and solubilization. Subsequently, the reaction mixture is removed from the tank continuously, and is pumped (8) to a phase separation system (11) (step I.3). To facilitate the separation of phases and to achieve the total drag of the impurities (dissolved and undissolved) present in the fat matrix, prior to the separator, wash water (9) is added in a dynamic mixer (10). Next, phase separation is carried out, which can be carried out in two forms of operation: by means of a centrifugal separator (11.1) or through a gravimetric decanter (11.2). Regardless of the unit used, two phases are obtained: light phase (12) which is the refined fatty material and heavy phase (13) aqueous solution with the impurities removed.

Once Phase I (refining and impurity extraction) has been carried out, then Phase II is carried out, consisting of a continuous esterification process, which can be developed in two modalities (A and B) depending on the FFA value of the fat to be esterified.

Modality A. The FFA esterification procedure of fats> 50% according to the invention is such (see figure 1) that, in the first place, a partial extraction of free fatty acids (step II.1) is carried out in a gravimetric decanter special (multilayer separator) (19), by in-line dosing in a dynamic mixer (18) of a certain amount of acidified solvent A (17) (preferably methyl alcohol (14) with methanesulfonic acid (15) prepared in a mixer static (16)) on the refined fat obtained in Phase I (12). After a contact time equivalent to the retention time of the decanter, the dissolved fraction of free fatty acids in the acidified solvent A (21) (light phase) is separated from the main stream of fat (heavy phase) (20), the which contains the rest of free fatty acids with traces of acidified solvent A. The process continues with the esterification itself (stage II.2) of the phases obtained in the decanter (19). For this, the light phase (21) is passed through a special multi-stage reactor (23); in parallel, the heavy phase (20) is sent to another reactor (24) (of the same characteristic as the previous one (23)), after dosing an additional fraction of acidified solvent A (22.1) (preferably methyl alcohol (14) with methanesulfonic acid (15) prepared in the static mixer (16)), there is also the possibility of adding an extra fraction of solvent A acid (22.2) from the collecting tank (31). Next, the reaction mixtures obtained in both reactors (25) and (26) are joined at the outlet thereof (27), and deposited in a special multilayer gravimetric decanter (28), where phase separation takes place: the light phase (30), which accumulates in a collecting tank (31) for later processing in Phase III; and the heavy phase (29) constituted by the esterified fat material with an FFA value <1% (0.3-0.5%) that accumulates in a collecting tank, which would be ready for feeding to the transesterification stage or directly to the washing phases (according to the acylglyceride values of the esterified product).

Modality B. The procedure for esterification of FFA fatty materials <50% according to the invention is such (see figure 2) that, on this occasion, the (step II.1 of modality A,

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consisting of the partial extraction of free fatty acids) and the actual esterification (step II.2) of the refined fat obtained in Phase I (12) takes place. For this purpose, a determined amount of acidified solvent A (17) (preferably methyl alcohol (14) with methanesulfonic acid (15) prepared in the static mixer is dosed onto the light phase (12) in a dynamic mixer (18). (16)). Then, the current obtained (19) is branched into two fractions (20) and (21), which are passed in parallel by two special multistage reactors (23) and (24), on this occasion, over the current at bifucar (19) it is possible to dose an extra fraction of acid phase (22) which is available in the collection tank (31). Next, the reaction mixtures obtained in both reactors (25) and (26) are joined at the outlet thereof (27), and deposited in a special multilayer gravimetric decanter (28), where phase separation takes place: the light phase (30), which accumulates in a collecting tank (31) for subsequent processing in Phase III, and the heavy phase (29) consisting of the esterified fatty material with FFA value <1% (0.3- 0.5%), which accumulates in a collecting tank, which would be ready for feeding at the transesterification stage or directly at the washing phases (according to the acylglyceride values of the esterified product).

Once Phase II (proper esterification) has been carried out, and indifferently to the form of realization of the invention carried out (mode A or mode B); Phase III is then carried out, consisting of the recovery of Solvent A used in excess during the esterification process, so that it can be reused again, and reduce consumption. For this, the current obtained in the light phase of Phase II (30), which is continuously deposited in the collecting tank (31), and consists of: solvent A + reaction water + acid + traces of fat, It must be treated before feeding the solvent recovery column A (46).

The solvent recovery process A according to the invention is such (see figure 1 or 2), that first, a fraction of the product contained in the collecting tank (31) can be pumped (32) for redosing in stage II .1 of Phase II where the esterification (22) takes place, and the remaining fraction is subjected to stage III.1, consisting of pumping (32) to a dynamic mixer (33) where mixing and homogenization takes place with an aqueous fraction (48) to cause the polarity change of the mixture (preferably process water from the biodiesel manufacturing plant where the system is installed, or a fraction of the glue obtained in the solvent distillation column is used (46) Next, the acid is neutralized in a dynamic mixer (34) by adding an alkaline solution (35) (preferably sodium hydroxide or the basic catalyst itself used in the transesterification stage of the plant). fabrication of biodiesel where the system is installed).

NOTE.- At this point it should be noted that the order in which the polarity change and neutralization develop does not alter the final result sought in stage III.1.

Next, the solvent stream A + water + neutralized fat (36), is discharged into a special multilayer gravimetric decanter (37), in which phase separation takes place: on the one hand the light phase (38) that it is deposited in the collecting tank (40) and, on the other, the heavy phase (39) which, since it is the fraction of fat dissolved in the solvent A released in the change operation of

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polarity, it can be sent and mixed with the stream of esterified fat material in phase II (29), and thus fed to the transesterification unit of the biodiesel manufacturing plant.

The product accumulated in a collecting tank (40) provided with agitation (41) whose mission is to avoid possible sedimentation of salts formed during the neutralization of the acid, is pumped (42) into a filtration system (43) to retain the salt traces , and is subjected to heating (44) (step III.2), then the resulting current (45) is fed to the solvent distillation / rectification column A (46) (step III.3), where it takes place the separation of pure solvent A (47), which is reused in the mixer (16) to reduce the dosage of solvent A again necessary in the esterification stage itself (stage II.1 or II.2) .and the fraction residual water (48) remaining in the distillation column (46) (tail phase), is extracted therefrom, the required fraction is sent to the polarity change phase (33), and the remaining amount can be processed in the by-products unit of the biodiesel manufacturing plant.

NOTE.- It is necessary to specify in this case, that according to the embodiment of the present invention, the system does not generate wastewater, and the amount that must be extracted from the system is equivalent to the amount formed during the esterification reaction in the conversion of free fatty acids (FFA + Alcohol ^ Biodiesel + Water) suitable for processing in the by-products unit of the biodiesel plant. The fraction used in the polarity change is consumed-generated in a closed cycle.

Detailed description of the invention: CASE B.

As mentioned in the previous section, the procedure described according to the invention for CASE A, is for raw materials of any value of free acidity (FFA) and that need to be refined. Likewise, in a similar way of carrying out the invention, it would be feasible to use the proposed system for raw materials of any FFA value that do not need to be refined (either because the type of product in question does not need it, or because it has been previously refined by other means). For this case, the sequence described in CASE A for Phases I and II would present changes of operation and Phase III would be identical.

The process of continuous esterification of a raw material (type vegetable oils, used frying oils, animal fat C1, C2, C3, oleins, any fatty residues of vegetable and / or animal origin, etc.), which does NOT require a previous refining according to the invention it is such (see figures 3 and 4 of the drawings) that a first phase (PHASE I) consisting of a filtrate (2) followed by a heating (3) of the fatty matter to be esterified (1) (step) I.1), to condition the input product. Next, Phase II is carried out, consisting of a continuous esterification process, which can be developed in two modalities (A and B) depending on the FFA value of the fat to be esterified.

Modality A. The FFA esterification procedure> 50% according to the invention is such (see figure 3) that, in the first place, a partial extraction of free fatty acids (step II.1) is carried out, by dosing in a dynamic mixer (5) of a certain amount of acidified solvent A (4) (preferably methyl alcohol (12) with methanesulfonic acid (13) prepared in a static mixer (14)) on the refined fat (1) obtained in Phase I (filtered (2) and heated (3)). The resulting mixture is homogenized in a stirred tank contact system (6) by agitation (7), from where it is pumped (8) to a gravimetric decanter

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special (multilayer separator) (9) (stage II.1). After the contact time equivalent to the retention time of the decanter, the dissolved fraction of free fatty acids in the acidified solvent A (11) (light phase) is separated from the main stream of fat (heavy phase) (10), the which contains the rest of free fatty acids with traces of acidified solvent A. The process continues with the esterification itself (stage II.2) of the phases obtained in the decanter (9). For this, the light phase (11) is passed through a special multi-stage reactor (16); in parallel, the heavy phase (10) is sent to another reactor (17) (of the same characteristic as the previous one (16)), after dosing an additional fraction of acidified solvent A (15.1) (preferably methyl alcohol (12) with methanesulfonic acid (13) prepared in the static mixer (14)), there is also the possibility of adding an extra fraction of solvent A acid (15.2) from the collecting tank (24). Subsequently, the reaction mixtures obtained in both esterification reactors (18) and (19) are attached to the outlet thereof (20), and deposited in a special gravimetric decanter (multilayer separator) (21), where it takes place phase separation: the light phase (23), which accumulates in a collecting tank (24) for subsequent processing in Phase III; and the heavy phase (22) constituted by the esterified fat material with an FFA value <1% (0.3-0.5%) that accumulates in a collecting tank, which will be ready for feeding to the transesterification stage or directly to the washing phases (according to the acylglyceride values of the esterified product).

Modality B. The procedure for esterification of FFA fatty materials <50% according to the invention is such (see figure 4) that, on this occasion, the (stage II.1 of modality A, consisting of partial extraction of free fatty acids) and the actual esterification takes place (step II.2) of the refined fat (1) obtained in Phase I. To do this, on the refined fat (1) (previously filtered (2) and heated (3)) a certain amount of acidified solvent A (4) (preferably methyl alcohol (12) with methanesulfonic acid (13) prepared in the static mixer (14)) is dosed in a dynamic mixer (5). The resulting mixture is homogenized in a stirred tank contact system (6) by agitation (7), and pumped (8) to the reaction system, branching the main stream extracted from the tank (9) into two fractions (10) and (11), which are passed in parallel by two special multistage reactors (16) and (17), on this occasion, it is possible to dose an extra fraction of acid phase (15) which is available in the tank collector (24) in the mainstream (9) before its division. Subsequently, the reaction mixtures obtained in both esterification reactors (18) and (19) are attached to the outlet thereof (20), and deposited in a special gravimetric decanter (multilayer separator) (21), where it takes place phase separation: the light phase (23), which accumulates in a collecting tank (24) for subsequent processing in Phase III, and the heavy phase (22) consisting of the esterified fatty material with FFA value <1% (0.3-0.5%), which accumulates in a collection tank, which will be ready for feeding at the transesterification stage or directly at the washing phases (according to the acylglyceride values of the esterified product).

Once Phase II (esterification itself) has been carried out, and indifferently of the form of realization of the invention (modality A or modality B); Subsequently, Phase III is carried out, consisting of the recovery of Solvent A, used excessively during the esterification process, so that it can be reused again, and reduce consumption. For this, the current obtained in the light phase of Phase II (23), which is continuously deposited in the collecting tank (24),

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and it is composed of: solvent A + reaction water + acid + traces of grease, it must be treated before feeding the solvent recovery column A (39).

The solvent recovery process A according to the invention is such (see figure 3 or 4), that first, a fraction of the product contained in the collecting tank (24) can be pumped (25) for redosing in Phase II where the esterification (15) takes place, and the remaining fraction is subjected to stage III.1, consisting of pumping (25) into a dynamic mixer (26) where mixing and homogenization with an aqueous fraction (41) takes place. to cause the polarity change of the mixture (preferably process water from the biodiesel manufacturing plant where the system is installed, or a fraction of the glue obtained in the solvent distillation column (39)) is used. Next, the acid is neutralized in a dynamic mixer (28) by the addition of an alkaline solution (27) (preferably sodium hydroxide or the basic catalyst itself used in the transesterification stage of the biodiesel manufacturing plant where the system is installed).

NOTE.- At this point it should be noted that the order in which the polarity change and neutralization develop does not alter the final result sought in stage III.1.

Then, the solvent stream A + water + neutralized fat (29), is discharged in a special multilayer gravimetric decanter (30), in which phase separation takes place: on the one hand the light phase (31) that it is deposited in the collecting tank (33) and on the other, the heavy phase (32) which, since it is the fraction of fat dissolved in the solvent A released in the polarity change operation, can be sent and mixed with the material stream phase II esterified grease (22), and thus fed to the transesterification unit of the biodiesel manufacturing plant.

The product accumulated in a collecting tank (33) equipped with agitation (34) whose mission is to avoid possible sedimentation of salts formed during the neutralization of the acid, is pumped (35) into a filtration system (36) to retain the salt traces , and is subjected to heating (37) (step III.2). Subsequently, the resulting current (38) is fed to the solvent distillation / rectification column A (39) (step III.3), where the separation of pure solvent A (40) takes place, which is reused in the mixer (14) to reduce the dosage of solvent A again necessary in the esterification stage itself (Phase II) and the residual aqueous fraction (41) remaining in the distillation column (39) (tail phase), is extracted from it, being sent to the polarity change phase (26) the required fraction, and the remaining amount, can be processed in the by-products unit of the biodiesel manufacturing plant.

NOTE.- It is necessary to specify in this case, that according to the embodiment of the present invention, the system does not generate wastewater, and the amount that must be extracted from the system is equivalent to the amount formed during the esterification reaction in the conversion of free fatty acids (FFA + Alcohol ^ Biodiesel + Water) suitable for processing in the by-products unit of the biodiesel plant. The fraction used in the polarity change is consumed-generated in a closed cycle.

In a preferred application of the invention of Case A (Figures 1 and 2 of the drawings), an amount of fatty material (1) (previously filtered (2) and heated (3) is contacted at a temperature that can vary in the range of 25-100 ° C, preferably 35-95 ° C, and more preferably 40-90 ° C); with the acid solution (4) (preferably acetic acid in water for

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animal fats in relation acid / water 30/70; and methanesulfonic acid in acid / water ratio 70/30 for vegetable fats) in a ratio with respect to the fed fat in the range of 0.5 to 15%, preferably 0.6 to 12%, and more preferably of 0.8-10%. The homogenized anterior mixture in the dynamic mixer (5) is fed continuously by the upper part of the homogenization tank (6), which is kept under gentle agitation (7) for the time previously established as a function of the feed rate of fat material (preferably 3 to 4 hours of contact, depending on the residence time of the tank). Then, the mixture is extracted with the pump (8) and sent to the phase separator (11.1 or 11.2, depending on the available arrangement), after dosing in a dynamic mixer (10) of a quantity of washing water (9) ( ratio with respect to the fat fed material in the range of 2 to 8%, preferably 3 to 7% and more preferably 4-5%). Once the phases have been separated, and the impurities have been removed, on the light phase (12), which contains the refined fat, the esterification phase is carried out, according to the A or B modality depending on the degree of FFA it contains. .

Modality A. Fatty material with starting FFA greater than 50%.

From the fat material obtained (12), it is esterified (Figure 1 of the drawings). For this purpose, an amount of acidified solvent A (17) equal to the amount of fat mass to be esterified (preferably methyl alcohol (14) acidified with methanesulfonic acid (15) in the mixer is dosed in the dynamic mixer (18) static (16) in relation to alcohol / acid 99.4 / 0.6), and the mixture is deposited in the phase separator (19) where the partial extraction of free fatty acids from the original fed material takes place (in this operation, 50% of the initial FFA value contained in the fat) is removed, giving rise to two phases: light phase (21) containing solvent + free fatty acids + acid; and heavy phase (20) containing the remaining fraction of free fatty acids, traces of solvent A and other starting fatty material. Then, the light phase (21) is passed through a special multi-stage reactor (23); and in parallel, the heavy phase (20) is sent to another reactor (24) (of the same characteristic as the previous one (23)), after dosing an additional fraction of acidified solvent A (22.1) equal to 25% of the amount heavy phase fed (preferably methyl alcohol (14) with methanesulfonic acid (15) prepared in the static mixer (16) in alcohol / acid 96/4 ratio) together with the same amount (25% of the amount of heavy phase fed ) (22.2) of the product available in the collecting tank (31). Next, the reaction mixtures obtained in both esterification reactors (25) and (26) are attached to the outlet thereof (27), and deposited in a special multilayer gravimetric decanter (28), where separation of phases: the light phase (30), which accumulates in a collecting tank (31) for later processing in Phase III; and the heavy phase (29) constituted by the esterified fatty material with FFA value <1% (0.3-0.5%). Finally, the heavy phase (29) is subjected to a transesterification process or directly to the washing phases (according to the acylglyceride values of the esterified product) for obtaining and characterizing the biodiesel obtained.

Modality B. Fatty material with starting FFA less than 50%.

From the fat material obtained (12), it is esterified (Figure 2 of the drawings). For this, an amount of solvent A is dosed in the dynamic mixer (18)

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acidified (17) equal to 30% of the amount of fat mass to be esterified (preferably methyl alcohol (14) acidified with methanesulfonic acid (15) in the static mixer (16) in alcohol / acid 98/2 ratio). Then, 50% (20) of the current obtained in the decanter (19) is passed through a special multistage reactor (23) and the other 50% (21) is passed through the other reactor (24) (of equal characteristics) in parallel. Prior to the division of the flow of the current to be included in the reactors, an additional quantity of the product available in the collecting tank (31) (20% of the amount of fat fed) is dosed online (22). Next, the reaction mixtures obtained in both reactors (25) and (26) are joined at the outlet thereof (27), and deposited in a special gravimetric decanter (multilayer separator) (28), where separation takes place phase: the light phase (30), which accumulates in a collecting tank (31) for subsequent processing in Phase III; and the heavy phase (29) constituted by the esterified fatty material with FFA value <1% (0.3-0.5%). Finally, the heavy phase (29) is subjected to a transesterification process or directly to the washing phases (according to the acylglyceride values of the esterified product) for obtaining and characterizing the biodiesel obtained.

To finish with the application of preference according to the invention, the recovery of solvent A used in excess is carried out, in which the light phase (30) contained in the collecting tank (31) is pumped (32) into a dynamic mixer ( 33) where mixing and homogenization take place with a fraction of water (48) equal to the amount required to obtain 15% moisture in the resulting mixture. Next, the acid is neutralized in a dynamic mixer (34) by adding an alkaline solution (35) (preferably sodium hydroxide or the basic catalyst itself used in the transesterification stage of the biodiesel manufacturing plant where the system is installed) in sufficient quantity to reach a pH of 3-5. Then, the operations described above in Cases A or B for Phase III are carried out, obtaining as a final result: an oily fraction (39) that joins the esterified phase (29) in Phase II to proceed to its transformation into biodiesel; an aqueous fraction (48) that is used for the polarity change in (33); and the excess of pure solvent A (47), which is fed back into the mixer (16) for catalyst preparation.

EXAMPLES OF THE INVENTION

The following examples are set forth to provide those skilled in the art with a complete exposition and description of how the procedures and compositions claimed herein are evaluated, with the intention of constituting purely examples of the invention and not intended to limit the scope of what the inventors (Mr. Francisco Javier Masa Blanco, Mr. Miguel Angel Garcia Morales and Mr. Luis Francisco Gomez Roncero) consider as their invention.

Efforts were made to ensure accuracy with respect to numbers (for example, quantities, temperatures, times, etc.), but some errors and deviations will be justified. If not indicated otherwise, the percentages are by weight and the temperature is in ° C. No pressure data is indicated, as it is atmospheric or close to it (except that which is created in the system by the impulsion of fluid through pumps).

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Example 1.

Continuous refining and esterification system of animal fat raw material of Category 1, according to the procedure of the invention described in Case A (Figure 1 of the Drawings) .-

Phase I: Refining and Extraction of Impurities.

To carry out the experiences and tests according to the invention and continuously, prior to the realization of the procedure, the starting fatty material was subjected to an initial heating to get the fluid product available.

Stage I.1. Filtering and heating.

This stage, due to the difficulty of performing the small-scale filtering operation, was carried out in batches. Thus, small fractions of animal fat C1 were subjected to filtration tests through a filter sleeve with a pore size of 500 microns, aided by a vacuum system (equivalent to the filtering stage of Figure 1 (2)). The filtrate is accumulated and stored in a tank provided with a lining ("jacket") that received a supply of hot water to maintain the temperature (50-60 ° C), and thus prevent the cooling and freezing of the grease (not represented in the figure).

Stage I.2. System of extraction of impurities dissolved in the fat.

The extraction reactor consists of a multi-mouth glass flask (6), with a capacity of 2000 ml. By pumping, fat material C1 (1) is dosed into the impurity extraction reactor (6) by one of the mouths available in the upper lid thereof, at a rate of approximately 8.5 g / min (the device discharged into the reactor at the bottom of it). To bring the stream of fatty material to be refined to the required temperature (65 ° C), prior to entering the reactor, there is a system consisting of a pipe in the form of a coil, which is submerged in a bath of glycerin maintained at 120 ° C (continuous heating and stirring by magnetic stirrer provided with temperature controller through a Pt-100 probe) (3). In line with the previous dosage, a 30% glacial acetic acid solution in water (4) was fed through another of the reactor's upper mouths at a rate of 0.255 g / min (its discharge point also took place in the bottom). Then, the resulting mixture is kept in continuous movement inside the reactor, by means of a mechanical stirrer at a speed of 500 rpm. To avoid cooling the mixture during the contact time; through the outer lining ("jacket") of the reactor, a fluid stream was passed at a temperature slightly above 70 ° C.

The residence time of the reaction mixture in the reactor is about 3.8 h (residence time of the product in the reactor of 2000 ml, at a flow rate of 8.5 g / min). For another of the upper mouths of the reactor, the product is continuously output, in whose current (10) a constant water dosage (9) is carried out at a rate of 0.595 g / min.

Stage 1.3 Phase separation system by decantation.

Then, the resulting mixture after dosing water is deposited in a horizontal decanter (11.2) of 2000 ml capacity. After a period of permanence therein

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approximately 3.5 h (equivalent to residence time), through the two outputs of the separator the separated phases are collected: on the one hand the light phase (12) at the rate of 8,102 g / min and on the other the heavy phase ( 13) at a rate of 1,250 g / min.

At regular time intervals, (every 4 h) samples of the light phase output of the decanter were taken to proceed to the analytical determination of the ash content by calcination of a portion at 625 ° C, to assess whether the process was efficient. Likewise, on another fraction of the same sample, the content of free fatty acids (FFA) was quantified by titulometry. Table 1 shows the effects of the refining system according to the invention by comparison with the input parameters of the original raw material (FFA content, ash, unsaponifiable and water content).

Phase II: Continuous Sterification.

In order to develop the second Phase of the procedure according to the invention, since the FFA level of the raw material is greater than 50%, it is carried out according to modality A following the procedure described in case A. To do this:

Stage II.1. Partial Extraction of Free Fatty Acids (FFA).

To continue the test, by continuous pumping at a rate of 8.102 g / min, the light phase obtained in Phase I is introduced into a decanter (19) of 2000 ml capacity. Prior to its inclusion in the separator, an amount of methanol acidified with methanesulfonic acid (in a methanol / acid ratio of 99/1) (17) at a rate of 7,850 g / min is mixed in line (18). After a residence time of approximately 2 h (equivalent to the residence time), the separated phases are collected through the two outputs of the separator: on the one hand the light phase (21) at a rate of 9,389 g / min and on the other the heavy phase (20) at a rate of 6,564 g / min.

At regular time intervals, (every 2 h) samples of the light phase output of the decanter were taken to proceed to the analytical determination of the water content by Karl-Fischer of a portion, to assess whether the process was efficient. Likewise, on another fraction of the same sample, the content of free fatty acids (FFA) was quantified by titulometry. In parallel, and at the same times, the same parameters were taken and analyzed for the heavy phase output. Table 1 collects the effects of the partial fatty acid extraction system according to the invention by comparison with the input parameters of the refined raw material (FFA content, ash, unsaponifiable and water content).

Stage II 2. Continuous esterification itself.

Then, the light phase output (21) obtained in step II.1 serves as a continuous feed of the special multistage reactor (23) at a rate of 9,389 g / min. On the other hand, the heavy phase (20) together with a new dosage of methanol acidified with methanesulfonic acid (22) at a rate of 1,641 g / min, is introduced into the second reactor (24) in parallel, at an overall flow rate of 8,205 g / min Both streams are fed by the bottom of the reactor, and after a reaction time of two hours (residence time of the reactors) the outputs of the two products (25) and (26) are mixed (27) and deposited in a multilayer decanter (28) at a rate of 17,594 g / min. One time

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stabilized the system, from the separator (28) the two corresponding phases are obtained: on the one hand, the light phase (30) at the rate of 8,929 g / min and on the other the heavy phase (29) at the rate of 8,665 g / min.

Description of the reactors (see Figure 5 of the Drawings): These reactors (23) and (24) (exactly the same) consisted basically of a stainless steel tube 20 cm long and 8.2 cm internal diameter. Inside there are 15 compartments with a total capacity of 1000 ml, separated from each other by a body perforated in the center through which a vertical axis is passed from end to end. The shaft has an external extension at the top of the reactor where a motor-reducer is coupled with an agitation speed of 150 rpm. In each of the internal cavities, in the vertical axis 2 horizontal crossed vanes are anchored (30 in total) that perform the function of agitator in each sub-stage. All equipment material is built in stainless steel. The reactor is completed with two inputs at both ends for the introduction and continuous output of the stream of fatty material to be esterified. On the other hand, the heating system is inserted on the outside of it to maintain and prevent the current from losing temperature. The heating system consisted of an electric tracing cable, enveloping the stainless steel column, and on the outside, it is completely covered by a layer of glass wool fixed with aluminum tape. both to avoid heat loss and to protect the operator from possible contact burns.

At regular time intervals, (every 2 h) samples were taken of the two outputs of the reactors (25) and (26), and after centrifugation, the content of free fatty acids of each of the heavy phases was determined, to assess the degree of reaction that took place. Likewise, at the same time, samples were also taken of the heavy phase output of the decanter to proceed to the analytical determination of the water content by Karl-Fischer and the content of free fatty acids (FFA) by titulometry. Table 1 collects the effects of the system of continuous esterification of free fatty acids according to the invention by comparison with the input parameters of the refined raw material (FFA content, ash, unsaponifiable and water content).

Phase III: Solvent Recovery (Methanol).

To continue with the development of the process, the third Phase of the procedure according to the invention is carried out, which consists in recovering the excess methanol used and its inclusion again at the beginning of the test. For it:

Stage III.1. Polarity change and phase neutralization.

First, the methanol-acid-water phase recovered from the phase separator in the esterification stage (31), is subjected to a polarity change process (to recover the oily fraction containing dissolved) and neutralization (to prevent corrosion in the distillation column). Thus, by continuous pumping at a rate of 8,929 g / min, the light phase obtained in Phase II is introduced into a decanter (37) of 2000 ml capacity. Prior to its inclusion in the separator, a quantity of water (48) is mixed in line (33) at a rate of 1,016 g / min (said quantity is determined by the water content of said phase; that is, it must be reached in the resulting mixture a water content equivalent to 15%); followed by an addition (also in line) (34) of a 50% sodium hydroxide solution (35) at a rate of 0.061 g / min (this flow rate is determined by the amount of

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acid that accompanies in the phase to neutralize; that is, it is neutralized to a 1: 1 molar ratio). After the indicated dosages, the resulting mixed stream (36) is deposited in the decanter (37), at a rate of 10,006 g / min. After a residence time of approximately 3.3 h (equivalent to residence time), the separated phases are collected through the two outputs of the separator: on the one hand the light phase (38) at a rate of 8,990 g / min and on the other the heavy phase (39) at a rate of 1,016 g / min.

At regular time intervals, (every 4 h) samples of the light phase output of the decanter were taken to proceed to the determination of the pH and to evaluate the behavior of the stage. In parallel, and at the same times, the value of FFA and water were taken and analyzed for the heavy phase output. Table 1 collects the effects of the oil phase neutralization and recovery system according to the invention (FFA content, ash, unsaponifiable and water content).

Stage III.2. Filtering and heating.

This stage, as was the case at the beginning of the test, due to the difficulty of performing the small-scale filtering operation, was carried out in batches. Thus, small fractions of the methanol-water-neutralized phase in stage II.1 were subjected to filtration tests through a filter sleeve with a pore size of 100 microns, aided by a vacuum system (equivalent to the filtering stage of Figure 1 (43)). The filtrate is accumulated and stored in a tank provided with a lining ("jacket") that received a supply of hot water to maintain the temperature (5060 ° C), and thus avoid cooling the product to be distilled (represented in the figure 1 as (40).

Stage III 3. Methanol recovery by distillation.

The distillation system consists of a multi-mouth glass flask (46), of 1000 ml capacity. By pumping, methanol-neutralized water is dosed into the distillation reactor (46) by one of the mouths available in the upper lid thereof, at a rate of approximately 8,916 g / min (the device discharged into the reactor in the lower part thereof) ). To bring the neutralized methanol-water stream to the required temperature (65 ° C), prior to entering the reactor, there is a system consisting of a pipe in the form of a coil, which is submerged in a bath of glycerin maintained at 120 ° C (continuous heating and agitation by magnetic stirrer provided with temperature controller through a Pt-100 probe) (44). The glass flask is arranged inside a glycerin bath maintained at 90 ° C, which provides the heat necessary for the distillation of methanol. Connected to the top of the flask, there is a refrigeration coil, which functions as a condenser. The condensed product (47) is recovered in a collection vessel at a rate of 7,591 g / min, which is supplied again to the requirements required in Phase II, together with new methanol. Finally, at regular intervals of time, the aqueous tail phase (48) is extracted from the reactor, which is equivalent to a continuous recovery of 1,325 g / min. From this fraction, the amount necessary for inclusion in stage III.1 (33) is taken.

At regular time intervals, (every 2 h) samples were taken from the condensed methanol outlet to proceed with moisture determination and to evaluate the behavior of the phase. In parallel, and at the same times, the acid value was taken and analyzed for the exit of the heavy phase. Table 1 collects the effects of the methanol recovery system according to the invention.

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Obtaining biodiesel according to UNE EN-14214 regulations

To assess the effects of the invention on the final quality of the FAME that can be obtained, biodiesel was obtained from the esterified global oil phase (29 + 39). It is obtained by a conventional transesterification process.

According to this, a batch of 40596.97 g of esterified oil obtained according to the invention is subjected to two successive stages of transesterification with methanol (in the presence of potassium methylate as a catalyst). After the separation of the phases (biodiesel and glycerin), water washing and acid washing of the biodiesel phase is performed, according to the usual FAME purification technique. Then, to remove traces of methanol and the moisture that biodiesel may contain, the vacuum is distilled from the previous mixture. Subsequently, this fluid stream is cooled, filtered and sent to the final polishing vessel. Finally, biodiesel is centrifuged and filtered before storage as final biodiesel. The amount of biodiesel obtained from the mass fed to the transesterification inlet is 34722.11 g. On the product obtained, the parameters of the standard UNE EN 14214: 2013 of interest were determined, which are presented summarized in table 1. Likewise, in said table the same parameters are presented for a biodiesel obtained according to traditional technologies for a raw material with similar characteristics.

(Table 1 goes to next page)

ES 2 585 706 A1

 TABLE 1.- Determined parameters in the different fuses obtained in the procedure according to the invention. (CASEA example 1). Data in% (m / m).

 Sample / Stage

 Amount (g) FFA (%) WATER (° o) ASHES (%) INSAPONIFICABLE (° o) METHANOL (° o) FAME (%) PH OIL (° o)% PHASE (1)

 Original Cl Fat (1)

 35645.32 52.80 1.79 0.85 1.95 0.00 0.00 3.5 42.61 100.00

 Refined Cl Fat (12)

 33977.87 54.37 0.65 0.01 0.71 0.00 0.00 2.9 44.27 95.32

 Fat Cl Stage II. 1 (20)

 27526.02 33.83 0.11 0.01 0.87 11.86 0.00 2.5 53.21 77.22

 MeOH + FFA Stage II. 1 (21)

 39373.87 23.27 0.52 0.00 0.00 74.77 0.00 0.56 1.00 110.46

 Esterified Cl Fat Stage II.2 (29)

 36336.86 0.59 0.35 0.00 0.60 8.40 48.73 2.8 41.23 101.94

 MeOH-Acid Water Stage II.2 (30)

 37443.57 1.15 3.62 0.00 0.06 91.41 2.78 1.02 0.15 105.04

 MeOH-Neutralized Water Stage III.l (38)

 37698.85 9.66 3.50 0.09 0.28 62.29 23.53 4.3 0.64 105.76

 Phase Oil Stage III.l (39)

 4260.13 0.05 14.99 0.99 0.03 83.75 0.10 4.5 0.08 11.95

 Recovered MeOH Stage III.3 (47)

 31828.46 0.00 0.80 0.00 0.00 99.20 0.00 7.0 0.00 89.29

 Cola Water Stage III.3 (48)

 5558.03 0.34 97.39 1.09 0.22 0.01 0.69 5.00 0.55 15.59

 Oil Phase to Transesterify (29 + 39)

 40596.97 1.54 0.68 0.01 0.56 14.05 46.08 3.5 36.97 113.89

 Biodiesel from traditional technology including the invention

 34722.11 0.11 0.02 0.001 0.45 0.03 97.91 5.00 0.59 97.41

 Biodiesel from traditional technology

 3,662.81 0.34 0.06 0.10 2.45 0.07 89.56 3.00 2.42 88.83

 (1) This percentage expresses the amount of phase in relation to the original input quantity of raw material.

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The procedure described in Example 1 is followed, except that a C1 fatty material, characterized by having an FFA value of 11.74%, a humidity of 0.09%, an ash content of ashes, was used as the starting fat material. 0.15% and an unsaponifiable value of 4.05%.

Phase I: Refining and Extraction of Impurities.

It develops the same as example 1.

Phase II: Continuous Sterification.

To develop the second Phase of the procedure according to the invention, given that the FFA level of the raw material is less than 50%, it is carried out according to modality B following the procedure described in case A (see Figure 2 of the Drawings ). For it:

Stage II 2. Continuous esterification itself.

To continue the test, by continuous pumping at a rate of 8.302 g / min, the light phase obtained in Phase I (12) is introduced to a dynamic mixer (18) where an amount of methanol acidified with methanesulfonic acid is dosed in line (in a methanol / acid ratio of 96/4) (17) at a rate of 2,159 g / min. Next, the main stream (19) extracted from the mixer (18) at a rate of 10,461 g / min forks in two fractions (20) and (21) of 5,230 g / min each, and is passed in parallel by two reactors multistage specials (23) and (24). Subsequently, the reaction mixtures obtained in both esterification reactors (25) and (26) are attached to the outlet thereof (27), and deposited in a special gravimetric decanter (multilayer separator) (28) of 2000 ml of capacity. After a time of permanence in the decanter, of approximately 3 h (equivalent to the residence time), through the two exits of the separator the separated phases are collected: on the one hand the light phase (30) at the rate of 1,842 g / min and on the other the heavy phase (29) at a rate of 8.619 g / min.

At regular time intervals, (every 3 h) samples were taken of the two outputs of the reactors (25) and (26), and after centrifugation, the content of free fatty acids of each of the heavy phases was determined, to assess the degree of reaction that took place. Likewise, at the same time, samples were also taken of the heavy phase output of the decanter to proceed to the analytical determination of the water content by Karl-Fischer and the content of free fatty acids (FFA) by titulometry. Table 2 collects the effects of the system of continuous esterification of free fatty acids according to the invention by comparison with the input parameters of the refined raw material (FFA content, ash, unsaponifiable and water content).

Phase III: Solvent Recovery (Methanol).

It develops just like example 1.

Obtaining biodiesel according to UNE EN-14214 regulations

In order to evaluate the effects of the invention on the final quality of the FAME that can be obtained, biodiesel was obtained from the global esterified oil phase (29 + 39). It is obtained by a conventional transesterification process.

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According to this, a batch of 30461.48 g of esterified oil obtained according to the invention is subjected to two successive stages of transesterification with methanol (in the presence of potassium methylate as a catalyst). After the separation of the phases (biodiesel and glycerin), water washing and acid washing of the biodiesel phase is performed, according to the usual FAME purification technique. Then, to remove traces of methanol and the moisture that biodiesel may contain, the vacuum is distilled from the previous mixture. Subsequently, this fluid stream is cooled, filtered and sent to the final polishing vessel. Finally, biodiesel is centrifuged and filtered before storage as final biodiesel. The amount of biodiesel obtained from the mass fed to the transesterification inlet is 29112.96 g. On the product obtained, the parameters of the standard UNE EN 14214: 2013 of interest were determined, which are presented summarized in table 2. Likewise, in said table the same parameters are presented for a biodiesel obtained according to traditional technologies for a raw material with similar characteristics.

(Table 2 goes to next page)

ES 2 585 706 A1

 TABLE 2.- Detected parameters in the different fuses obtained in the procedure according to the invention. (Example 2 of CASOA). Data in% (nt / nt).

 Sample / Stage

 Amount (g) FFA (%) WATER (%) ASHES (%) INSAPONIFICABLE (%) METHANOL (%) FAME (%) pH OIL (%)% PHASE (1)

 Original FatCl (1)

 29535.32 11.74 0.09 0.15 4.05 0.00 0.00 4.05 83.97 100.00

 Refined Cl Fat (12)

 28846.47 11.63 0.82 0.00 1.74 0.00 0.00 3.10 85.81 97.67

 Fat Cl Stage II.2 (20) and (21)

 36346.55 9.23 0.93 0.00 1.38 19.80 0.00 0.57 68.16 123.06

 Esterified Cl Fat Stage II.2 (29)

 29575.09 0.39 0.32 0.00 0.85 4.90 9.92 2.91 83.61 100.14

 MeOH-Acid Water Stage II.2 (30)

 6908.24 0.24 8.58 0.00 3.66 77.71 6.59 0.84 0.37 23.39

 MeOH-Neutralized Water Stage III. 1 (38)

 6929.62 0.05 16.05 0.00 1.81 77.94 0.10 5.05 0.08 23.46

 Oil Phase Stage III.1 (39)

 886.39 1.46 3.50 0.01 14.16 27.78 50.55 4.21 2.22 3.00

 Recovered MeOH Stage III.3 (47)

 5163.09 0.00 0.80 0.00 0.00 99.20 0.00 7.03 0.00 17.48

 Cola Water Stage III.3 (48)

 1280.59 0.27 85.30 4.33 9.88 0.00 0.55 5.70 0.44 4.34

 Oil Phase to Transesterify (29 + 39)

 30461.48 0.42 0.41 0.01 1.24 5.57 11.10 3.15 81.24 103.14

 Biodiesel from traditional technology including the invention

 29112.96 0.08 0.03 0.001 1.09 0.02 98.14 4.95 0.64 98.57

 Biodiesel from traditional technology

 27447.17 0.24 0.04 0.05 3.70 0.05 94.04 3.85 1.88 92.93

 (1) This percentage expresses the amount of phase in relation to the original input quantity of raw material.

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The procedure described in Example 1 is followed, except that a vegetable oil residue (RAV) characterized as having an FFA value of 73.5%, a humidity of 0.965%, and a content of 189 ppm phosphorus.

System of refining and continuous esterification of raw material RAV, according to the procedure of the invention described in Case A (see Figure 1 of the Drawings) .-

As it is a raw material that contains impurities with characteristics other than C1 animal fats, Phase I of the refining process described in Case A, according to the invention, presents some changes with respect to examples 1 and 2, which describe a continuation.

Phase I: Refining and Extraction of Impurities.

Stage I.1. Filtering and heating.

Same as described in example 1, only that the heating temperatures of the fat are brought to 85 ° C instead of the 65 ° C of example 1 and 2.

Stage I.2. System for extracting impurities dissolved in fat.

The procedure is the same as described in example 1, except that:

1. - The fed fat is replaced (1) (RAV instead of C1).

2. - The feed acid stream is changed (Methanesulfonic Acid instead of acetic acid). On this occasion, in the extraction reactor (6), a solution of 70% methanesulfonic acid in water (4) at a rate of 0.021 was fed on a flow of RAV fat (1) of approximately 8.5 g / min. g / min

3. - Finally, on the output stream in the dynamic mixer (10) a constant water dosage (9) is carried out at a rate of 0.064 g / min.

At regular time intervals, (every 4 h) samples were taken of the light phase output (12) of the decanter (11.2) to proceed with the analytical determination of the gum content (phosphorus) by ICP and the value of ashes by calcination at 625 ° C, to assess whether the process was efficient. Likewise, on another fraction of the same sample, the content of free fatty acids (FFA) was quantified by titulometry. Table 3 shows the effects of the refining system according to the invention by comparison with the input parameters of the original raw material (FFA content, ashes, gums, unsaponifiable and water content).

Phase II: Continuous Esterification.

It develops just like example 1.

Phase III: Recovery of Solvent (Methanol).

It develops just like example 1 and 2.

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Obtaining biodiesel according to UNE EN-14214 regulations

To assess the effects of the invention on the final quality of the FAME that can be obtained, biodiesel was obtained from the esterified global oil phase (29 + 39). It is obtained by a conventional transesterification process.

According to this, a batch of 29561.99 g of esterified oil obtained according to the invention is subjected to two successive stages of transesterification with methanol (in the presence of potassium methylate as a catalyst). After the separation of the phases (biodiesel and glycerin), water washing and acid washing of the biodiesel phase is performed, according to the usual FAME purification technique. Then, to remove traces of methanol and the moisture that biodiesel may contain, the vacuum is distilled from the previous mixture. Subsequently, this fluid stream is cooled, filtered and sent to the final polishing vessel. Finally, biodiesel is centrifuged and filtered before storage as final biodiesel. The amount of biodiesel obtained from the mass fed to the transesterification inlet is 25748.90 g. On the product obtained, the parameters of the standard UNE EN 14214: 2013 of interest were determined, which are presented summarized in table 3. Likewise, in said table the same parameters are presented for a biodiesel obtained according to traditional technologies for a raw material with similar characteristics.

Table 3 shows all the parameters determined on the final sample after the complete test according to the invention described in Case A.

(Table 3 goes to next page)

ES 2 585 706 A1

 TABLE 3.- Parameters determined in the different phases obtained in the procedure according to the invention. (CASEA example 3). Data in% (ni / m).

 Sample / Stage

 Quantity (g) FFA (° b) WATER (° b) ASHES (° b) RUBBER (° b) INSAP. (° b) METANOE (° b) FAME (° b) pH OIL (° b) 0 0 PHASE (1)

 RAV Original (1)

 25568.0 78.77 1.25 0.11 0.76 2.74 0.00 0.00 4.35 16.37 100.00

 RAV Refined (12)

 24553.7 81.77 0.45 0.01 0.00 1.25 0.00 0.00 2.89 16.35 96.03

 RAVE cover II. 1 (20)

 15777.4 58.92 0.07 0.01 0.00 1.46 14.15 0.00 3.02 25.29 61.71

 MeOH + FFA Stage II.l (21)

 33795.5 31.90 0.32 0.00 0.00 0.23 66.89 0.00 0.49 0.07 132.18

 RAV Esterified Stage II.2 (29)

 26405.6 0.36 0.29 0.01 0.00 1.05 8.74 74.50 3.05 14.96 103.47

 MeOEI-Acid Water Stage II.2 (30)

 31055.5 0.76 4.84 0.00 0.00 0.10 89.24 3.71 0.56 0.21 121.46

 MeOEI-Neutralized Water Stage III.l (38)

 31350.95 0.05 15.19 1.38 0.00 0.05 83.15 0.10 5.01 0.08 122.62

 Phase Oil Stage III.l (39)

 3156.40 6.98 3.50 0.15 0.00 0.49 52.17 35.50 4.85 1.22 12.35

 MeOEI Recovered Stage III. 3 (47)

 26278.39 0.00 0.80 0.00 0.00 0.00 99.20 0.00 7.01 0.00 102.78

 Cola Water Stage III. 3 (48)

 4713.52 0.34 96.95 1.55 0.00 0.33 0.00 0.68 5.12 0.54 18.44

 Oil Phase to Transesterify (29 + 39)

 29561.99 1.07 0.63 0.01 0.00 0.99 13.37 70.33 4.32 13.49 115.62

 Biodiesel from traditional technology including the invention

 25748.90 0.20 0.03 0.00 0.00 0.85 0.05 98.44 5.30 0.65 100.71

 Biodiesel from traditional technology

 24432.42 0.65 0.05 0.01 0.01 1.37 0.05 95.61 5.12 1.01 95.56

 (1) This percentage expresses the amount of phase in relation to the original quantity of raw material input.

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The procedure described in example 3 is followed, except that a vegetable oil residue (RAV) characterized as having an FFA value of 36.05%, a humidity of 0.910%, and a content of 0.9% was used as the starting fat material 180 ppm phosphorus.

Phase I: Refining and Extraction of Impurities.

It develops the same as example 3.

Phase II: Continuous Sterification.

It develops the same as example 2.

Phase III: Solvent Recovery (Methanol).

It is developed in the same way as example 1, 2 and 3.

Obtaining biodiesel according to UNE EN-14214 regulations

To assess the effects of the invention on the final quality of the FAME that can be obtained, biodiesel was obtained from the esterified global oil phase (29 + 39). It is obtained by a conventional transesterification process.

According to this, a batch of 22518.11 g of esterified oil obtained according to the invention is subjected to two successive stages of transesterification with methanol (in the presence of potassium methylate as a catalyst). After the separation of the phases (biodiesel and glycerin), water washing and acid washing of the biodiesel phase is performed, according to the usual FAME purification technique. Then, to remove traces of methanol and the moisture that biodiesel may contain, the vacuum is distilled from the previous mixture. Subsequently, this fluid stream is cooled, filtered and sent to the final polishing vessel. Finally, biodiesel is centrifuged and filtered before storage as final biodiesel. The amount of biodiesel obtained from the mass fed to the transesterification inlet is 20102.78 g. On the product obtained, the parameters of the standard UNE EN 14214: 2013 of interest were determined, which are presented summarized in table 4. Likewise, in this table the same parameters are presented for a biodiesel obtained according to traditional technologies for a raw material with similar characteristics.

(Table 4 goes to next page)

ES 2 585 706 A1

 TABLE 4.- Parameters determined in the different phases obtained in the procedure according to the invention. (Example 4 of CASE A). Data in% (m / m).

 Sample / Stage

 Quantity (g) FFA (%) WATER (%) ASHES (%) RUBBER (%) INSAP. (%) METHANOL (%) FAME (%) pH OIL (%)% PHASE111

 RAV Original (1)

 20158.30 36.05 0.91 0.02 0.46 2.07 0.00 0.00 4.15 60.49 100.00

 RAV Refined (12)

 19653.35 36.82 0.45 0.00 0.00 0.93 0.00 0.00 2.69 61.64 97.50

 RAV Stage II. 1 (20) and (21)

 27119.78 26.70 0.63 0.00 0.00 0.68 26.64 0.00 0.65 44.69 134.53

 Esterified RAV Stage II. 2 (29)

 21984.50 0.19 0.32 0.00 0.00 0.42 11.81 32.26 2.92 54.99 109.06

 MeOH-Acid Water Stage II.2 (30)

 5135.28 0.39 11.13 0.00 0.00 1.78 74.22 8.54 0.35 0.47 25.47

 MeOH-Neutralized Water Stage III.l (38)

 5549.76 0.36 15.81 0.00 0.00 1.65 70.90 6.96 4.81 0.39 27.53

 Phase Oil Stage III.l (39)

 533.60 3.30 3.50 0.41 0.00 8.59 9.57 71.41 4.25 3.23 2.65

 Recovered MeOH Stage III. 3 (47)

 3914.91 0.00 0.80 0.00 0.00 0.00 99.20 0.00 6.51 0.00 19.42

 Cola Water Stage III.3 (48)

 934.13 0.29 89.44 5.27 0.00 4.95 0.00 0.57 5.42 0.46 4.63

 Oil Phase to Transesterify (29 + 39)

 22518.11 0.26 0.70 0.00 0.00 0.61 11.21 33.42 4.62 53.78 111.71

 Biodiesel from traditional technology including the invention

 20102.78 0.21 0.02 0.00 0.00 0.51 0.02 98.44 5.00 0.59 99.72

 Biodiesel from traditional technology

 19320.10 0.65 0.05 0.00 0.00 1.8 0.05 96.54 5.12 0.91 95.84

 (1) This percentage expresses the amount of phase in relation to the original quantity of raw material input.

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Continuous esterification system of raw material residue of vegetable oil (pure fatty acids). according to the procedure of the invention described in Case B (see Figure 3 of the Drawings).

Phase I: Filtering and Heating.

To carry out the experiences and trials according to the invention and continuously. prior to the realization of the procedure. The starting fatty material was subjected to an initial heating to get the fluid product available.

Stage I.1. Filtering and heating.

This stage. due to the difficulty of performing the small-scale filtering operation. It was carried out in batches. So. small fractions of fatty acids (RAV) were subjected to filtration tests through a filter sleeve with a pore size of 500 microns. assisted by a vacuum system (equivalent to the filtering stage of Figure 3 (2)). The filtrate is accumulated and stored in a tank provided with a lining ("jacket") that received a supply of hot water to maintain the temperature (50-60 ° C). and thus avoid the cooling and freezing of fatty acids (not shown in the figure).

Phase II: Continuous Esterification.

To develop the second Phase of the procedure according to the invention. since the FFA level of the raw material is greater than 50%. it is carried out according to modality A following the procedure described in case B. To do this:

Stage II.1. Partial Extraction of Liter Fatty Acids (FFA).

For the development of this example. since the starting raw material is refined. the impurity extraction system described in example 1 is used as a homogenization and mixing system for the phase of partial extraction of free fatty acids. So. The extraction tank consists of a glass flask with several mouths (6). 2000 ml capacity. By pumping RAV (1) is dosed to the homogenization tank (6) by one of the mouths available in the upper lid thereof. at a rate of approximately 8.5 g / min (the device discharged into the container at the bottom of it). To bring the fat stream to the required temperature (65 ° C). prior to entering the deposit. A system consisting of a pipe in the form of a coil is available. which is submerged in a glycerin bath maintained at 120 ° C (heating and continuous agitation by magnetic stirrer provided with temperature controller through a Pt-100 probe) (3). In line with the previous dosage. a quantity of methanol acidified with methanesulfonic acid (in a methanol / acid ratio of 99/1) (4) at a rate of 9,015 g / min was fed through another of the reactor's upper mouths (the discharge point also had place at the bottom). Then The resulting mixture. It keeps moving continuously inside the reactor. by mechanical agitator at a speed of 1000 rpm. To avoid cooling the mixture during the contact time; through the outer jacket ("jacket") of the reactor. a fluid stream was passed at a temperature slightly higher than 70 ° C.

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The residence time of the mixture in the homogenization vessels is about 2 h (residence time of the product in the 2000 ml tank, at a flow rate of 8.5 g / min). On another of the upper mouths of the container, the product is continuously output, whose current is fed to a horizontal decanter (9) of 2000 ml capacity at a rate of 17,515 g / min. After a residence time of approximately 2 h (equivalent to the residence time), the separated phases are collected through the two outputs of the separator: on the one hand the light phase (11) at a rate of 12,657 g / min and on the other the heavy phase (10) at a rate of 4,857 g / min.

Stage II 2. Continuous esterification itself.

It develops just like example 1.

Phase III: Solvent Recovery (Methanol).

It is developed in the same way as example 1, 2, 3 and 4.

Table 5 shows the effects of the esterification system according to the invention by comparison with the input parameters of the original raw material (FFA content, ashes, gums, unsaponifiable and water content)

Obtaining biodiesel according to UNE EN-14214 regulations

In order to evaluate the effects of the invention on the final quality of the FAME that can be obtained, biodiesel was obtained from the global esterified oil phase (29 + 39). On this occasion, and since it is a raw material that does not contain triglycerides, after the esterification process, all free fatty acids are transformed into methyl esters, so it is not necessary to carry out the transesterification, and simply It is subjected to washing and drying steps as indicated below.

According to this, a batch of 49198.25 g of esterified oil obtained according to the invention is subjected to two successive washing stages, the water wash and the acid wash. Then, to remove traces of methanol and the moisture that biodiesel may contain, the vacuum is distilled from the previous mixture. Subsequently, this fluid stream is cooled, filtered and sent to the final polishing vessel. Finally, biodiesel is centrifuged and filtered before storage as final biodiesel. The amount of biodiesel obtained from the mass fed to the washing steps is 36443.99 g. On the product obtained, the parameters of the standard UNE EN 14214: 2013 of interest were determined, which are presented summarized in table 5. Likewise, in said table the same parameters are presented for a biodiesel obtained according to traditional technologies for a raw material with similar characteristics.

(Table 5 goes to next page)

ES 2 585 706 A1

 TABLE 5.- Determinated parameters in the different phases obtained in the procedure according to the invention. (Example 5 of CASE B). Data in% (m / m).

 Sample / Stage

 Amount (g) FFA (%) WATER (%) ASHES (%) IN S APONIFIC ABEE (%) METHANOL (%) FAME (%) PH OIL (%)% PHASE111

 RAV Original (1)

 35625.25 98.50 0.86 0.01 0.50 0.00 0.00 3.25 0.13 100.00

 RAVE cover II. 1 (10)

 20357.15 83.95 0.18 0.01 0.87 14.66 0.00 2.95 0.22 57.14

 MeOH + FFA Stage II.1 (11)

 53050.89 33.93 0.55 0.00 0.00 64.85 0.00 0.85 0.00 148.92

 Esterified RAV Stage II.2 (22)

 44568.79 0.59 1.50 0.00 0.36 19.21 78.18 2.42 0.05 125.10

 MeOH-Acid Water Stage II.2 (23)

 45926.21 0.32 4.92 0.00 0.04 89.39 3.77 0.95 0.05 128.91

 MeOH-Neutralized Water Stage III.l (31)

 46500.70 0.05 15.36 0.31 0.02 82.62 0.50 6.40 0.04 130.53

 Oil Phase Stage III.l (32)

 4629.47 2.66 3.50 0.01 0.19 56.94 36.42 4.12 0.09 12.99

 Recovered MeOH Stage III.3 (40)

 38727.70 0.00 0.80 0.00 0.00 99.20 0.00 7.0 0.00 108.71

 Cola Water Stage III. 3 (41)

 7079.29 0.34 97.02 2.34 0.13 0.00 0.67 4.89 0.27 19.87

 Oil Phase to Transesterify (22 + 32)

 49198.25 0.79 1.69 0.01 0.34 22.76 74.25 3.8 0.06 138.10

 Biodiesel from traditional technology including the invention

 36443.99 0.21 0.03 0.001 0.42 0.02 99.24 5.10 0.07 102.30

 Biodiesel from traditional technology

 32568.60 0.64 0.05 0.01 0.50 0.05 98.60 4.00 0.02 91.42

 (1) This percentage expresses the amount of phase in relation to the original input quantity of raw material.

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The procedure described in Example 5 is followed, except that a used vegetable oil (UCO) characterized by having an FFA value of 13.5% and a moisture content of 0.52% was used as the starting fatty material.

Phase I: Filtering and Heating.

It develops just like example 5.

Phase II: Continuous Scheduling.

To develop the second Phase of the procedure according to the invention, given that the FFA level of the raw material is less than 50%, it is carried out according to modality B following the procedure described in case B (see Figure 4 of the Drawings ). For it:

Stage II 2. Esterijicacion proper.

For the development of this example, since the starting raw material is refined, and contains an FFA value of less than 50%, the test is carried out as described in example 2, with the proviso that the system is used of impurity extraction described in example 1 as a homogenization and mixing system for the dosage of methanol acidified with methanesulfonic acid. Thus, the homogenization tank consists of a multi-mouth glass flask (6), with a capacity of 2000 ml. By pumping, UCO (1) is dosed into the homogenization tank (6) by one of the mouths available in the upper lid thereof, at a rate of approximately 8.5 g / min (the device discharged into the container at the bottom of the same). In order to bring the fat stream to the required temperature (65 ° C), prior to entering the tank, a system consisting of a serpentine-shaped pipe is available, which is submerged in a maintained glycerin bath at 120 ° C (heating and continuous stirring by magnetic stirrer provided with temperature controller through a Pt-100 probe) (3). In line with the previous dosage, an amount of methanol acidified with methanesulfonic acid (in a methanol / acid ratio of 96/4) (4) at a rate of 2,189 g / min (the point was fed through another of the upper mouths of the reactor) downloading of the same also took place at the bottom). Subsequently, the resulting mixture is kept in continuous movement inside the reactor, by means of a mechanical stirrer at a speed of 1000 rpm. To avoid cooling the mixture during the contact time; through the outer lining ("jacket") of the reactor, a fluid stream was passed at a temperature slightly above 70 ° C.

The residence time of the mixture in the homogenization vessel is about 3 h (residence time of the product in the 2000 ml tank, at a flow rate of 8.5 g / min). For another of the upper mouths of the container, the continuous output of the product takes place, whose current, at the rate of 10,689 g / min, forks in two fractions (10) and (11) of 5,345 g / min each, and they pass in parallel through two special multistage reactors (16) and (17). Subsequently, the reaction mixtures obtained in both esterification reactors (18) and (19) are attached to the outlet thereof (20), and deposited in a special gravimetric decanter (multilayer separator) (21). After a period of residence in the decanter, of approximately 3 h (equivalent to the residence time), to

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through the two outputs of the separator the separated phases are collected: on the one hand the light phase (23) at a rate of 2,007 g / min and on the other the heavy phase (22) at the rate of 8,682 g / min.

At regular time intervals, (every 3 h) samples were taken of the two outputs of the reactors (18) and (19), and after centrifugation, the content of free fatty acids of each of the heavy phases was determined, to assess the degree of reaction that took place. Likewise, at the same time, samples were also taken of the heavy phase output of the decanter to proceed to the analytical determination of the water content by Karl-Fischer and the content of free fatty acids (FFA) by titulometry. Table 6 collects the effects of the continuous esterification system of free fatty acids according to the invention by comparison with the input parameters of the refined raw material (FFA content, ash, unsaponifiable and water content).

Phase III: Recovery of Solvent (Methanol).

It is developed in the same way as example 1, 2, 3, 4 and 5.

Obtaining biodiesel according to UNE EN-14214 regulations

To assess the effects of the invention on the final quality of the FAME that can be obtained, biodiesel was obtained from the esterified global oil phase (29 + 39). It is obtained by a conventional transesterification process.

According to this, a batch of 22518.11 g of esterified oil obtained according to the invention is subjected to two successive stages of transesterification with methanol (in the presence of potassium methylate as a catalyst). After the separation of the phases (biodiesel and glycerin), water washing and acid washing of the biodiesel phase is performed, according to the usual FAME purification technique. Then, to remove the traces of methanol and the moisture that the biodiesel may contain, the vacuum is distilled from the previous mixture. Subsequently, this fluid stream is cooled, filtered and sent to the final polishing vessel. Finally, biodiesel is centrifuged and filtered before storage as final biodiesel. The amount of biodiesel obtained from the mass fed to the transesterification inlet is 20102.78 g. On the product obtained, the parameters of the standard UNE EN 14214: 2013 of interest were determined, which are presented summarized in table 4. Likewise, in this table the same parameters are presented for a biodiesel obtained according to traditional technologies for a raw material with similar characteristics.

(Table 6 goes to next page)

ES 2 585 706 A1

 TABLE 6.- Pardmetos determined in the different fuses obtained in the procedure according to the invention. (Example 6 of CASE B). Data in% (ni / m).

 Sample / Stage

 Amount (g) FFA (%) WATER (%) CEMZAS (%) INSAPONIFICABLE (%) METHANOL (%) FAME (%) pH OIL (%)% PHASE'11

 RAV Original (l)

 25315.20 13.50 0.52 0.01 0.98 0.00 0.00 3.80 84.99 100.00

 Stage IV RAV Stage II.2 (22)

 25856.93 0.19 0.32 0.00 0.48 3.42 12.43 3.42 83.14 102.14

 MeOH-Acid Water Stage 11.2 (23)

 6039.87 0.30 6.55 0.01 2.05 83.63 5.03 0.62 0.28 23.86

 MeOH-Neutralized Water Stage III. 1 (31)

 5637.95 0.05 16.83 2.81 U0 79.02 0.16 6.36 0.08 22.27

 Oil Phase Stage III. 1 (32)

 1020.75 1.49 3.50 0.02 6.08 58.40 29.17 5.12 1.19 4.03

 Recovered MeOH Stage III.3 (40)

 4490.76 0.00 0.80 0.00 0.00 99.20 0.00 7.0 0.00 17.74

 Cola Water Stage III.3 (41)

 1021.94 0.29 89.90 3.30 6.11 0.00 0.57 4.99 0.46 4.04

 Oil Phase to Transestenficar (22 + 32)

 26877.63 0.24 0.44 0.01 0.69 5.51 13.06 4.08 80.03 106.17

 Biodiesel from traditional technology with inclusion of the mvencion

 25375.97 0.16 0.02 0.00 0.72 0.04 98.30 4.90 0.66 100.24

 Biodiesel from traditional technology

 23796.29 0.42 0.05 0.00 0.98 0.05 93.89 3.80 0.80 94.01

 (1) This percentage expresses the amount of phase in relation to the original quantity of raw material input.

Claims (44)

5 10 fifteen twenty 25 30 35 1. A process for the continuous refining and esterification of fatty materials without acidity limit (FFA), regardless of the type of raw material, comprising: I. A refining phase, characterized by: 1.1. a stage in which the fatty material to be refined is filtered and heated to a temperature sufficient to reach the desired degree of refinement 1.2. a stage of extraction of impurities that accompany the fatty material, in the course of which the fraction of these components are separated from the free fatty acids and acylglycerides; by physical separation (decantation or centrifugation) after a concentrated acid treatment. II. A continuous esterification phase, characterized by: 11.1. a stage in the course of which the fatty material refined in I, is subjected to a process of partial extraction of free fatty acids by physical separation (decantation) after contacting with acidified methanol with any strong acid suitable for use as catalyst in an acid esterification process. 11.2. an esterification stage proper, characterized in that: to. the heavy phase obtained in II.1 (fatty material partially extracted from FFA), is esterified in a special multistage continuous reactor, after dosing an additional fraction of acidified methanol (with the same acid as in II.1), b. the light phase obtained in II.1, (acid methanol with fraction of FFA extracted) is esterified in parallel in a second continuous multistage special reactor, C. the reaction mixture obtained in (a) and (b), are unified at their output, and the resulting current is fed to a multilayer separator where the physical separation by gravity of the heavy phase takes place (low fat material FFA, suitable for its transesterification or final industrial application) of the light phase (methanol-water-acid-oil, which feeds the next phase of the process of the invention). III. A Methanol Recovery Phase, characterized by: 111.1. a neutralization stage (alkaline phase dosing) and polarity change (water dosing), or vice versa, of the light phase obtained in II.2.c, in the course of which the fatty material dissolved in the methanol phase is Recovered by decantation. 111.2. a stage of filtering and heating of the methanol-neutralized water phase. III.3 a rectification stage of the methanol-neutralized water phase obtained in III.2, whereby pure methanol and an aqueous glue phase are recovered. 2. A process according to claim 1, characterized in that the methanol recovered in Phase III can be reused in Phase II of the process; determined because all Phases are carried out continuously. 5 10 fifteen twenty 25 30 35 3. A method according to claim 1, characterized in that the aqueous tail phase recovered in Phase III.3 can be reused in Phase III.1 of the process; determined because all Phases are carried out continuously. 4. A method according to claim 1, characterized in that the Phase I can be carried out at the temperature that allows the fatty material to have fluid; determined because all operations (Phases I to III) are carried out continuously. 5. A method according to claim 1, characterized in that the Phase I can be carried out at a temperature of 85 ° C; determined because all operations (Phases I to III) are carried out continuously. 6. A method according to claim 1, characterized in that Phase I can be carried out using a concentrated acetic acid solution; determined because all operations (Phases I to III) are carried out continuously. 7. A method according to claim 1, characterized in that Phase I can be carried out using a solution of concentrated methanesulfonic acid; determined because all operations (Phases I to III) are carried out continuously. A method according to claim 1, characterized in that Phase II can be carried out using concentrated methanesulfonic acid as esterification catalyst; determined because all Phases are carried out continuously. 9. A process according to claim 1, characterized in that Phase II can be carried out using concentrated sulfuric acid as the esterification catalyst; determined because all Phases are carried out continuously. 10. A method according to claim 1, characterized in that Phase III can be carried out using a sodium hydroxide solution as an alkaline neutralization phase; determined because all Phases are carried out continuously. 11. A method according to claim 1, characterized in that Phase III can be carried out using a basic catalyst solution used in oil transesterification as an alkaline neutralization phase; determined because all Phases are carried out continuously. 12. A process for the continuous refining and esterification of fatty materials without acidity limit (FFA), regardless of the type of raw material, comprising: I. A refining phase, characterized by: 1.1. a stage in which the fatty material to be refined is filtered and heated to a temperature sufficient to reach the desired degree of refinement 1.2. a stage of extraction of impurities that accompany the fatty material, in the course of which the fraction of these components are separated from the free fatty acids and acylglycerides; by physical separation (decantation or centrifugation) after a concentrated acid treatment. 5 10 fifteen twenty 25 30 35 II. A continuous esterification phase, characterized by: a unique stage of esterification proper, characterized in that: to. The fatty material refined in I, is subjected to an esterification process in two special continuous multistage reactors, after contact with acidified methanol with any strong acid suitable for use as a catalyst in an acid esterification process. b. the reaction mixture obtained in the two reactors is unified at the outlet thereof, and the resulting current is fed to a multilayer separator where the physical separation by gravity of the heavy phase takes place (fatty material under FFA, suitable for its transesterification or final industrial application) of the light phase (methanol-water-acid-oil, which feeds the next phase of the process of the invention). III. A Methanol Recovery Phase, characterized by: 111.1. a neutralization stage (alkaline phase dosing) and polarity change (water dosing), or vice versa, of the light phase obtained in II.b, in the course of which the fatty material dissolved in the methanol phase is recovered by decantation 111.2. a stage of filtering and heating of the methanol-neutralized water phase. III.3 a rectification stage of the methanol-neutralized water phase obtained in III.2, whereby pure methanol and an aqueous glue phase are recovered. 13. A process according to claim 12, characterized in that the methanol recovered in Phase III can be reused in Phase II of the process; determined because all Phases are carried out continuously. 14. A method according to claim 12, characterized in that the aqueous tail phase recovered in Phase III.3 can be reused in Phase III. 1 of the procedure; determined because all Phases are carried out continuously. 15. A method according to claim 12, characterized in that Phase I can be carried out at the temperature that allows the fatty material to have fluid; determined because all operations (Phases I to III) are carried out continuously. 16. A method according to claim 12, characterized in that Phase I can be carried out at a temperature of 85 ° C; determined because all operations (Phases I to III) are carried out continuously. 17. A method according to claim 12, characterized in that Phase I can be carried out using a concentrated acetic acid solution; determined because all operations (Phases I to III) are carried out continuously. 18. A method according to claim 12, characterized in that Phase I can be carried out using a concentrated methanesulfonic acid solution; determined because all operations (Phases I to III) are carried out continuously. 5 10 fifteen twenty 25 30 35 19. A process according to claim 12, characterized in that Phase II can be carried out using concentrated methanesulfonic acid as esterification catalyst; determined because all Phases are carried out continuously. 20. A process according to claim 12, characterized in that Phase II can be carried out using concentrated sulfuric acid as the esterification catalyst; determined because all Phases are carried out continuously. 21. A method according to claim 12, characterized in that Phase III can be carried out using a sodium hydroxide solution as an alkaline neutralization phase; determined because all Phases are carried out continuously. 22. A method according to claim 12, characterized in that Phase III can be carried out using a basic catalyst solution used in oil transesterification as an alkaline neutralization phase; determined because all Phases are carried out continuously. 23. A procedure for the continuous esterification of fatty materials that do not need to be refined, without acidity limit (FFA), regardless of the type of raw material, which includes: I. A continuous esterification phase, characterized by: 1.1. a stage in which the refined or crude fatty material without the need for refining is optionally subjected to a partial extraction process of free fatty acids by physical separation (decantation) after contacting with acidified methanol with any strong acid Suitable for use as a catalyst in an acid esterification process. 1.2. an esterification stage proper, characterized in that: to. the heavy phase obtained in I.1 (fatty material partially extracted from FFA), is esterified in a special multistage continuous reactor, after dosing an additional fraction of acidified methanol (with the same acid as in I.1), b. the light phase obtained in I.1, (acid methanol with extracted FFA fraction) it is esterified in parallel in a second special multistage continuous reactor, C. the reaction mixture obtained in (a) and (b), are unified at the outlet thereof, and the resulting current is fed to a multilayer separator where the physical separation by gravity of the heavy phase takes place (low fatty material FFA, suitable for its transesterification or final industrial application) of the light phase (methanol-water-acid-oil, which feeds the next phase of the process of the invention). II. A Methanol Recovery Phase, characterized by: II.1. a neutralization stage (alkaline phase dosing) and polarity change (water dosing), or vice versa, of the light phase obtained in I.2.c, in the course of which the fatty material dissolved in the methanol phase is Recovered by decantation. 5 10 fifteen twenty 25 30 35 II.2. a stage of filtering and heating of the methanol-neutralized water phase. II.3 a rectification stage of the methanol-neutralized water phase obtained in II.2, whereby pure methanol and an aqueous glue phase are recovered. 24. A process according to claim 23, characterized in that the methanol recovered in Phase II can be reused in Phase I of the process; determined because all Phases are carried out continuously. 25. A process according to claim 23, characterized in that the aqueous tail phase recovered in Phase II.3 can be reused in Phase II.1 of the process; determined because all Phases are carried out continuously. 26. A method according to claim 23, characterized in that Phase I can be carried out using concentrated methanesulfonic acid as esterification catalyst; determined because all Phases are carried out continuously. 27. A method according to claim 23, characterized in that Phase I can be carried out using concentrated sulfuric acid as the esterification catalyst; determined because all Phases are carried out continuously. 28. A method according to claim 23, characterized in that Phase II can be carried out using a sodium hydroxide solution as an alkaline neutralization phase; determined because all Phases are carried out continuously. 29. A method according to claim 23, characterized in that Phase II can be carried out using a basic catalyst solution used in oil transesterification as an alkaline neutralization phase; determined because all Phases are carried out continuously. 30. A procedure for the continuous esterification of fatty materials that do not need to be refined, without acidity limit (FFA), regardless of the type of raw material, which comprises: I. A continuous esterification phase, characterized by: a unique stage of esterification proper, characterized in that: to. The refined or crude fatty material, if it does not need to be refined, is subjected to an esterification process in two special multistage continuous reactors, after contacting with acidified methanol with any strong acid suitable for use as a catalyst in an acid esterification process. . b. the reaction mixture obtained in the two reactors is unified at the outlet thereof, and the resulting current is fed to a multilayer separator where the physical separation by gravity of the heavy phase takes place (fatty material under FFA, suitable for its transesterification or final industrial application) of the light phase (methanol-water-acid-oil, which feeds the next phase of the process of the invention). 5 10 fifteen twenty 25 30 II. A Methanol Recovery Phase, characterized by: 11.1. a neutralization stage (alkaline phase dosing) and polarity change (water dosing), or vice versa, of the light phase obtained in I.b, in the course of which the fatty material dissolved in the methanol phase is recovered by decantation. 11.2. a stage of filtering and heating of the methanol-neutralized water phase. II.3 a rectification stage of the methanol-neutralized water phase obtained in II.2, whereby pure methanol and an aqueous glue phase are recovered. 31. A method according to claim 30, characterized in that the methanol recovered in Phase II can be reused in Phase I of the process; determined because all Phases are carried out continuously. 32. A method according to claim 30, characterized in that the aqueous tail phase recovered in Phase II.3 can be reused in Phase II.1 of the process; determined because all Phases are carried out continuously. 33. A method according to claim 30, characterized in that Phase I can be carried out using concentrated methanesulfonic acid as esterification catalyst; determined because all Phases are carried out continuously. 34. A method according to claim 30, characterized in that Phase I can be carried out using concentrated sulfuric acid as the esterification catalyst; determined because all Phases are carried out continuously. 35. A method according to claim 30, characterized in that Phase II can be carried out using a sodium hydroxide solution as an alkaline neutralization phase; determined because all Phases are carried out continuously. 36. A method according to claim 30, characterized in that Phase II can be carried out using a basic catalyst solution used in oil transesterification as an alkaline neutralization phase; determined because all Phases are carried out continuously.