ES2395162B2 - PROCESS FOR THE USE OF BY-PRODUCTS OF THE AGRO-FOOD INDUSTRY FOR THE OBTAINING OF BIOFUEL PRECURSORS, FUNCTIONAL FOODS AND COSMETICS. - Google Patents

Abstract

Process for the use of by-products from the agri-food industry to obtain precursors for biofuels, functional foods and cosmetics. # The present invention aims to obtain products with high added value from by-products from the agri-food industry, being a reference material beer bagasse. # The products obtained as a result of this process are oil and molasses, each of which can be used in different applications.

Description

PROCESS FOR THE USE OF BY-PRODUCTS OF THE AGRO-FOOD INDUSTRY FOR THE OBTAINING OF BIOFUEL PRECURSORS, FUNCTIONAL FOODS AND COSMETICS.

TECHNICAL SECTOR TO WHICH THE INVENTION REFERS. The present invention relates to the sectors of biofuel production, agri-food and beer production sector.

STATE OF THE TECHNIQUE PRIOR TO THE DATE OF PRESENTATION. The agri-food industry generates a series of waste that, treated conveniently, they can be used to obtain precursors of biofuels and high added value products. The latter can be reused in the food industry itself or in food processing functional and cosmetic. The residual biomass of the agri-food industry contains lipids, carbohydrates, proteins and compounds of industrial interest. The only limitation its use as biofuel precursors lies in the economic profitability of the process of obtaining the different precursors and their quality. For him process described below it is estimated that the minimum content of lipids and carbohydrates that would make the process profitable stands at 5% and 20% respectively.

Next, we will describe the particularized global process for the case of residue from the beer industry.

The brewing process requires four main ingredients, water, yeast, hops and malt. The malt comes from the malting process of cereal (usually barley). Brewing consists of several stages. The first is the grinding of the malt, followed by the maceration stage where the ground malt comes in contact with water, allowing enzymes (formed during germination) degrade malt constituents (carbohydrates and proteins) to soluble forms and then the liquid that leaves

to ferment, called must. Subsequently, the must is removed by pressing and filtering, and the solid residue from this stage is called beer bagasse. Basically it is formed by the remains of grain and husk of the cereal. (Source: Industrial Microbiology, Alicia Hemández, Ileana Alfaro and Ronald Arrieta, First edition, Editorial Universidad Estatal a Distancia, San José, Costa Rica, 2003).

Bagasse is a wet product with a dry matter content of 20-25%. There are no significant differences in the chemical composition correlated with the dry matter content, although this is variable. In the market it receives other names such as that of beer fat, and it is the equivalent term to what the Anglo-Saxon world knows as quot; wetbrewers' s grainsquot ;.

Beer bagasse is a by-product rich in protein, with an average protein content of 24-26% on dry matter. The ether extract represents 6%. It is a by-product also rich in fiber, with an FND content of 44% and F AD of 20%, although it is a very ineffective fiber (18%). The lignin content is 5% and the ash content is 7%. In the mineral residue its phosphorus content stands out (6 glkg), being the Ca content lower (3 glkg).

(Sources: Spanish Foundation for the development of animal nutrition. Http: // www 1.etsia. Upm.es/fedna/Subp _humedos / bagazocerveza.htm

Animal husbandry, Animal production bases, Volume III, Food and rationing, Page 72, Carlos Buxadé, Grupo Mundi-Prensa, 1995, ISBN 84 7114-565-0).

Beer bagasse is considered as a waste with little commercial interest. Currently it is sold to the livestock sector to be used as feed for cattle and sheep mainly. This commercial outlet is common for all beer companies. The bagasse selling price varies by company. There are some that give a symbolic price, provided that the bagasse is removed in the shortest possible time. Others give you a sale price that is intended to cover the cost of transportation. In short, we must say that bagasse is not a source of income and that the reason for its sale is to avoid having to carry out waste management with the consequent cost.

(Sources: Animal Husbandry, Animal production bases, Volume III, Food and rationing, Page 141, Carlos Buxadé, Grupo Mundi-Prensa, 1995, ISBN 84 7114-565-0).

Another possible use of it is contained in the Chyba et al. Patent (US patent, 4,197,321. 1980) in which beer bagasse is used to obtain an extract that serves to increase the nutritional value of beer.

Biodiesel is a compression ignition fuel made from mostly vegetable oils or animal fats. The fuel can be used pure or mixed in different formulations (blending) with gas oils obtained from petroleum. Before being used as fuel, vegetable oil is first chemically reacted with an alcohol (usually methanol) through a process called transesterification. This chemical process produces an oil made up of fatty acid esters and glycerol. Glycerol is removed before fatty acid esters are used as fuels. Esterified oil can be used in most diesel engines without engine modifications, however it is usually mixed with other different oils obtained by the same process and with diesel from petroleum in order to improve its properties as fuel. In general, biodiesel is considered a biodegradable, clean burning and safe resource. (Sources: Chemical and Bioassay Analyzes of Dieseland Biodiesel Particulate Matter: Pilot Study FINAL REPORT. Norman Y. Kado, Robert A. Okamoto and Paul A. Kuzmicky.

Department of Environmental Toxicology, University of California, Davis, California 95616 November 1996).

As raw material for the transesterification process, the following sources are usually used:

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Animal fats.

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Unused oils. Among the most used are rapeseed, soybean, flax, sunflower, palm, coconut, hemp, cotton, and peanut oils.

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Used vegetable oil.

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Algae.

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Raw materials and crops with high cellulose content (lignocellulosic), whose carbohydrates are found in more complex forms (wood, agricultural and forest residues, lignocellulosic crops, herbaceous material, etc.).

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Halophyte oil like salicornia.

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Bioethanol or ethyl alcohol of vegetable origin is obtained by fermentation of sugary musts that give rise to "wines". of variable alcoholic degree (normally between 10 and 15%). This alcohol can later be concentrated by distillation until obtaining the so-called hydrated alcohol (4-5% water) or it can reach absolute alcohol after a specific dehydration process.

Hydrated ethanol (CzHsOH) can be used directly in conventional explosion engines with slight modifications, with similar performances to those obtained with gasoline.

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Absolute (dehydrated) ethanol can be used in admixture with regular gasoline (up to 22% today), to increase the octane number and produce "unleaded superfuels," which reduce pollutant emissions. These fuels are known as gasohols and are being used in around 35 countries (especially in the United States and Brazil). Absolute ethanol can also be added to diesel for use in diesel engines (typically in 10-15% ethanol blends) for the same purpose of reducing pollution. This is done, for example, in Tours (France) and Stockholm (Sweden).

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Bioethanol is also used for the synthesis of ETBE (5-ethyl-tert-butyl ether), an additive to gasoline that increases the number of octanes. It is normally used in 10-15% mixtures. (Source: Company and renewable energy, what your company should know about renewable energy, energy efficiency and Kyoto. Pepa Mosquera Martínez, Luis Merino Ruesga. Edited by: Fundación Confemetal, Madrid ISBN: 84-96169-70-7).

Bioethanol can be obtained from three types of raw materials:

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• Crops and materials with a high content of sucrose, such as sugar cane, sugar beets, sweet sorghum and molasses, among others.

•

Starchy crops with high starch content, such as cereals (corn, grain sorghum, wheat and barley) or roots and tubers (potato, cassava, sweet potato, etc.) or inulin (topinambur, agave, yam, etc.).

(Source: Biofuels Manual, regional association of oil and natural gas companies in Latin America and the Caribbean).

Bioethanol is produced from lignocellulosic residues, by microbial fermentation of soluble sugars released from cellulose and hemicellulose, by chemical (acidic or basic), enzymatic or microbial hydrolysis. It is estimated that the amount of plant residues, potentially usable for this purpose, in the world is 1,51015g / year (dry weight) whose production of bioethanol, together with that which could be obtained from other crop residues could replace up to 32% of current gasoline consumption (Kim and Dale, 2004). (Source: Compostaje, Moreno Casco, J and Moral Herrero, R (Edit. Cient.) Madrid; Ediciones Mundi-Prensa, 2008, ISBN: 9-346-8).

The processes for obtaining ethanol from lignocellulosic biomass using acid catalysts allow, under suitable conditions of pressure and temperature, a hydrolysis of hemicellulose and cellulose, leaving lignin practically unchanged. At temperatures above 200 ° C, decomposition products of sugars appear, therefore very high yields cannot be obtained. In addition, these substances are inhibitors of the fermentation process, so they must be removed from the hydrolyzate before fermentation. Industrial methods of acid hydrolysis of the cellulosic fraction are grouped into two types: those using concentrated acids and low temperatures, and those using dilute acids at higher temperatures. Despite the high hydrolysis yields obtained with processes that use concentrated acids, there is no industrial plant operating with this system, due to its lack of profitability. Among the cellulose hydrolysis processes using dilute acids, the most widely used is the percolation method, in which the acid is passed through the material. (Source: http: // www. Virtual. Unal.edu.co/cursos/sedes/arauca/87061/docs _curso / C8 _ L2.ht m)

There are alternatives to acid hydrolysis that employ mixed processes in which, after a first stage of acid hydrolysis, enzymes are used to complete the degradation of the residual oligosaccharides and polysaccharides. The inclusion of enzymatic hydrolysis steps entails a significant increase in costs associated with the enzymatic reactor and the procedures associated with it, in addition to increasing the degree of difficulty of operation of the installation. For this reason, the present proposal opts for acid hydrolysis, which can be carried out in multiple stages.

(Sources: Lyons, M ~ Hoskins, B. Composition and Methods for conversion10n of lignocellulosic material to fermentable sugars and products produced therefrom. W02010 / 107944 Al. Charilaos X. et al. Hydrolisis and fermentation ofbrewer's spent grains by Neurospora crassa. 2008. Bioresource Technology. 99, 5427-5435.)

EXPLANATION OF THE INVENTION The present invention aims to obtain high value-added products from by-products of the agri-food industry that have a content of lipids and dietary fiber equal to or greater than 5% and 20% by weight, respectively, based on Dried, beer bagasse being a reference material. In this way, it is possible to give a more efficient commercial outlet to many residues in the agri-food industry, among which is beer bagasse. From this point on, beer bagasse will be taken as reference material and we will refer to it as "bagasse".

The process aims to obtain two products. The first is a substance made up of as many of the fats contained in the bagasse as possible, from this point on we will refer to this product in memory as "oil". The second is a substance rich in sugars whose water content will depend on the different purposes that you want to give it, from this point we will refer to this product in memory as "melazaquot ;.

The process consists of a common line, which from this point we will call the main line and two secondary lines. Each secondary line has the purpose of obtaining one of the two products, from this point we will call them: line

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secondary for obtaining oil and secondary line for obtaining molasses depending on the end product of the line. The mode of operation can be continuous or discontinuous (batch or load), also the stages of which it consists, as well as the purposes and conditions of operation will be the same. The most efficient mode of operation is continuous.

The main line will consist of the following stages:

Stage 1 Dosage. The amount of bagasse deemed appropriate to process, per unit of time or cycle, previously loaded in a hopper or other storage system, is entered in the process.

1st

Stage 2 Elimination of water. Bagasse is introduced directly or through a transport system into a unit that will make you lose most of the water it contains.

Stage 3 Grinding. The partially dehydrated bagasse is introduced into a particle size reduction system in order to increase its contact surface.

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Stage 4 Lipid extraction. At this stage, the bagasse, partially dehydrated and ground, is contacted with an organic solvent that allows the solid-liquid extraction of the fats contained in the bagasse. If any of the final products is intended for food use, the use of potentially dangerous solvents in the human body will be ruled out, as is the case with chlorinated solvents. For this stage it will be necessary an extraction equipment that works continuously, semi-continuously or discontinuously. The extraction percentage on the dry bagasse mass will vary according to the solvent used.

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Two secondary currents are obtained. The first one will be made up of most of the solvent and the largest amount of oil (which will be called the secondary stream that contains the oil). The second stream will consist of the solid residues from the extraction stage and part of the solvent with dissolved lipids (which will be called the secondary stream that contains the lignocellulosic residue).

Stage 5 Separation of solids. The solvent containing the dissolved oil is separated by filtration from the solid residue.

In this way, the separation of the two previous secondary streams is achieved.

Both streams will be processed on the corresponding secondary lines mentioned above.

The secondary oil collection line will process the secondary stream containing the solvent with the oil in solution, coming from the main line and will have the purpose of removing the solvent. Depending on the type of solvent, the most appropriate procedure for its separation will be applied.

In turn, in this line two new currents are obtained. The first stream contains the solvent already separated and which will be recirculated for reuse in Stage 4 of the main line (Lipid Extraction). The second stream will be composed of the oil contained by the bagasse. This current will be that of the final product that we have defined as oil.

In all the proposed alternatives mentioned above, solvent losses will be experienced that must be compensated by adding new solvent in the solvent inlet stream from Stage 4 of the main one.

The secondary molasses line will process the solids contained in the secondary stream containing the lignocellulosic residue from Step 5, from the main line (Solids Separation). It will aim to transform this stream of solids into usable sugars. It will consist of the following stages.

Stage 1 Acid hydrolysis. Solids are introduced into one or more reactors together with water and dilute sulfuric acid. A solid residue will be obtained that will be discarded and a liquid stream made up of water, acid residues and sugar.

The solid residues of the lipid extraction stage may contain solvent residues, even having recovered as much of them as possible. Depending on the solvent used and the use to be made of the products, their complete elimination may be necessary. For this reason, it is proposed to remove the solvent residues by adding the necessary amount of acetic acid or another agent before being introduced into the reactors. In this way, this agent will react with the solvent residues, transforming it into other components that do not interfere with the use that will be given to the final product.

Stage 2 Neutralization. The liquid stream from Stage 1 (Acid hydrolysis) is introduced into a decanter with a suitable base for its neutralization. A solid residue will be obtained that will be discarded and a liquid stream made up of water and sugar.

Stage 3 Elimination of water and formulation. The current of Stage 2 (Neutralization) is introduced into a device where the amount of water necessary for its use will be removed. If the product from this line is going to be used to produce bioethanol, the inlet current from this stage will be introduced into a concentrator where the necessary water will be removed until the required concentration is obtained. If the product of this line is going to be used as sugar used for different purposes, the input stream will be introduced into a crystallizer to obtain crystalline sugar. If the product of this line is going to be used as a sugar supplement in the fermentation of beer, both a concentrator and a crystallizer can be used, depending on the concentration of water necessary for the process.

The products obtained are oil and molasses and have the following uses.

The oil obtained in the secondary line for obtaining oil is characterized by being a vegetable oil obtained from beer bagasse and by its high degree of unsaturation.

The molasses obtained in the secondary molasses production line is characterized by being a mixture of sugars obtained by acid hydrolysis of beer bagasse. Mainly containing glucose and xylose.

BRIEF DESCRIPTION OF THE FIGURES.

Fig. 1: General diagram of the process.

METHOD OF CARRYING OUT THE INVENTION. The process specifications are as follows:

The temperatures of the stages of the main line and the secondary line for obtaining molasses should not exceed 90 ° C and 1 05 ° C respectively, to avoid the degradation of the bagasse components.

Stage 2 of the main line (Water Elimination) will eliminate between 75% and 90% of the water contained in the bagasse.

Stage 3 of the main line (Grinding) must provide a material with a particle size between 0.5 and 5 millimeters.

Stage 4 of the main line (Lipid Extraction) will last between 15 and 60 minutes. This time will be determined by the chosen solvent, the inlet temperature, the particle size and the residual humidity.

Stage 5 of the main line (solids separation) should leave the solid with the least amount of solvent possible. This can be done by washing with water or dragging with steam.

The secondary oil collection line should separate the solvent from the oil until the solvent concentration is low enough to be used for the chosen purpose. The thermal processes used may not exceed 150 ° C to avoid lipid cracking.

Stage 1 of the secondary line for obtaining molasses (Acid hydrolysis) will use sulfuric acid or another strong acid that allows the hydrolysis of sugars. The acid used must be in a concentration that allows hydrolysis to occur but does not degrade the sugars.

Stage 2 of the secondary line for obtaining molasses (Neutralization) will use a slight excess over the stoichiometric amount of base to ensure complete neutralization. The base used will be selected to help remove the conjugate base from the acid used for hydrolysis.

Stage 3 of the secondary line for obtaining molasses (Elimination of water and formulation) must not exceed a temperature of 105 ° C to avoid caramelization processes. The desired formulation of the final product will determine the amount of water to be removed.

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WAY IN WHICH THE INVENTION IS SUSCEPTffiLE OF INDUSTRIAL APPLICATION. The oil can be used for different purposes as shown below.

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The oil can be used as a raw material for the production of biodiesel through the transesterification process.

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The oil can be used as an additive to other oils that are going to be used for the production of biodiesel. The utility of the oil will be to correct the viscosity of the biodiesel obtained, thus obtaining adequate parameters for its use as fuel. These parameters will be determined by the standard values of the fuel legislation.

The oil can also be used as an extraction made with hexane.

additive food forever than the

Molasses can be used for different purposes as shown below.

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Molasses can be used as a raw material to obtain bioethanol through fermentation. Bioethanol can be used to obtain biofuels among other purposes.

Molasses can be formulated as sugar once it has undergone the crystallization process. This sugar can be used for food purposes.

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Molasses or sugar obtained through the concentration or crystallization stages can be used as a sugar supplement for beer production. Being a sugar obtained from bagasse, being this in turn obtained from barley, it would not constitute a "added sugar".

Claims (11)

l.- Process for the use of by-products from the agri-food industry with a content of lipids and dietary fiber equal to or greater than 5% and 20%, respectively, on a dry basis, characterized in that it comprises the following stages: Conditioning stage of the main line, which consists of the dosing, water removal and milling operations of said by-products. Solid-liquid extraction stage in continuous, semi-continuous or discontinuous lipid regimen using an organic solvent, from the main line. Solids separation stage from the main line, two secondary streams are obtained by filtration, the first, consisting mainly of solvent, containing the oil in solution, and the second, consisting of a solid lignocellulosic residue, and containing traces of the solvent with dissolved oil. Stage of treatment of the secondary stream containing the oil that consists of an operation of removing the solvent from this secondary stream to obtain the oil by thermal processes whose temperature may not exceed 150 o C to avoid cracking of the same. Treatment stage of the secondary stream containing the lignocellulosic residue consisting of the operations:

o Acid hydrolysis of this secondary stream for the degradation of the polysaccharides present in the solid residue, from the dietary fiber, for the production of sugars and obtaining lignin as a by-product.

o Neutralization of the acid used in the hydrolysis stage, by adding a base.

o Concentration and / or crystallization of sugars obtained by elimination of water by thermal methods, at temperatures below 105 ° C to avoid caramelization of sugars.

2.-Use of the process according to claim 1 where the by-product used is beer bagasse. 3.-Use of the products obtained by the process described in claim 1 to obtain biofuel precursors, functional foods, cosmetics and food consumption. 4.-Use of the product obtained from the secondary stream treatment stage that contains the oil according to claim 1, as a precursor to biodiesel production. 5.-Use of the product obtained from the secondary stream treatment stage containing the oil according to claim 1, for the correction of biodiesel properties obtained from other sources. 6.-Use of the product obtained from the secondary stream treatment stage containing the lignocellulosic residue, according to claim 1, to complement the sugars used in beer production, thus not constituting an additive. 7.-Use of the product obtained from the secondary stream treatment stage containing the lignocellulosic residue, according to claim 1 as a precursor to the production of bioethanol. 8.-Use of the products obtained by the process described in claims 1 and 2 to obtain biofuel precursors, functional foods, cosmetics and food consumption. 9.-Use of the product obtained from the secondary stream treatment stage that contains the oil according to claims 1 and 2, as a precursor to biodiesel production. s 10.-Use of the product obtained from the secondary stream treatment stage containing the oil according to claims 1 and 2, for the correction of biodiesel properties obtained from other sources. 11.-Use of the product obtained from the secondary stream treatment stage that 10 contains the lignocellulosic residue, according to claims 1 and 2, to complement the sugars used in beer production, thus not constituting an additive. 12.-Use of the product obtained from the secondary stream treatment stage that contains the lignocellulosic residue, according to claims 1 and 2 as a precursor to the production of bioethanol.