Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23K—FODDER
  • A23K10/00—Animal feeding-stuffs
  • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
  • A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
  • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1014—Biomass of vegetal origin
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
  • Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
  • Y02P60/87—Re-use of by-products of food processing for fodder production

Definitions

• the present invention relates to a new process for the preparation of fatty acid esters which can be used especially as biodiesel from oleaginous seeds.
• Biodiesel is a fuel obtained from a vegetable or animal oil transformed by a chemical process called transesterification, in order to obtain Vegetable Oils Methyl Esters (VOMEs) obtained with methanol, or Ethyl Esters of Vegetable Oils ( EEHV) obtained with ethanol.
• VOMEs Vegetable Oils Methyl Esters
• EEHV Ethyl Esters of Vegetable Oils
• the subject of the present invention is a process for preparing fatty acid esters from oleaginous seeds whose yield is excellent and which at the same time makes it possible to overcome the disadvantages of the processes described in the prior art.
• the present invention firstly relates to a process for preparing fatty acid esters which can be used as biodiesel from whole oil seeds, characterized in that it comprises the following successive stages: a. Preheating unshelled whole seeds b. Flattening of oilseeds with their hull; vs. Drying of the flattened seeds so as to obtain a water and volatile matter content of between 0.5 and 2.5%, preferably between 1.5% and 2%
• % d Transesterification by contacting the dried flattened seeds with an alcoholic medium in the presence of a catalyst; e. Separation of liquid and solid phases resulting from transesterification; f. Neutralization of the liquid phase resulting from step e); and g. Elimination of alcohol and separation of glycerin from fatty acid esters.
• oil seeds all plant seeds containing fat, preferably rich in triglycerides. Thus, germs, pips, nuts and cores also fall into this category. Oleaginous seeds also contain proteins, fibers and minerals.
• the seeds are preferably selected from the seeds of cultivable plants.
• rapeseed, jatropha, peanut, castor, sesame, sunflower, safflower, soybean, lupine, camelina and cotton can be used.
• the Preferred seeds are rapeseed, sunflower and jatropha seeds. Even more preferably, the seeds are preferably rapeseeds.
• seeds chosen from rapeseed, peanut, castor, sesame, sunflower, safflower, soybean, lupine, camelina and cotton seeds.
• the seeds can be used with all or a large part of their shell.
• "oleaginous seeds” refers to the whole seed or seed partially freed from its shell.
• the seed is preferably used essentially whole, that is to say, retaining at least 80% of its shell. This constitutes an advantageous fibrous support to avoid the disintegration of the flattened seed when placed in contact with the alcoholic medium during step d) of transesterification.
• the shell is too large compared to the almond of the seed (eg for macadamia nuts, Brazil nuts, andiroba nuts, coconut, shea nuts, or cupuacu)
• the oleaginous seeds are flattened. They are then generally in the form of a thin elongated sheet, a flake or a shell.
• the seeds are preferably cleaned, that is to say freed from their solid impurities, such as pebbles, rags, sticks, metal parts, dust.
• the thickness of the flattened seeds is preferably between 10 ⁇ m and 1 mm. According to a particularly preferred embodiment, the thickness of the flattened seeds is between 0.1 and 0.3 mm, and even more preferably, the thickness of the flattened seeds is less than 0.2 mm, especially in the case of rapeseeds.
• the size of the flattened seeds is preferably between 3 and 5 mm, especially in the case of rapeseed and other seeds of similar size, where it is about 4 mm.
• the oleaginous seeds may be preheated to a temperature of between 40 ° C. and 60 ° C., preferably 50 ° C., before carrying out the flattening step b) in order to increase their plasticity.
• the seeds are brought to this temperature just the time necessary to achieve the desired plasticity. It is indeed preferable to avoid drying the seeds which causes them to split at the time of flattening. Seeds should never be cooked or dried before flattening.
• the oleaginous seeds can be preheated to a temperature between 50 and 55 0 C for 5 to 60 min, preferably 30 minutes, before carrying out step b) flattening, optionally under steam.
• the flattening of the oleaginous seeds is advantageously carried out by means of rollers which may be of any type, in particular smooth or corrugated, preferably smooth. Their diameter can go up to 80 cm.
• the spacing of the rollers is preferably less than 0.2 mm, more preferably less than 0.1 mm.
• the speed of the rollers is determined so as to avoid the splitting of the seeds during flattening.
• the diameter and the speed of the rollers are identical so as to avoid tearing phenomena and therefore the breaking up of the seeds.
• the flattening of the oleaginous seeds is carried out by means of smooth rollers, preferably in a single pass.
• Step b) of flattening is an essential step of the process because it makes it possible to obtain a significantly higher yield than that obtained without flattening, that is to say a better transesterification yield and a better extraction yield. ethyl esters.
• the seeds After the flattening step, the seeds must be dried as quickly as possible in order to stop the enzymatic activity and thus prevent the degradation of the materials they contain.
• the drying step c) is thus carried out immediately after the flattening step b), not later than 24 hours after the flattening step b), preferably less than 2 hours after the step a). flattening, at best within one hour after flattening.
• the drying of the flattened seeds is carried out so as to obtain a water and volatile matter content of between 0.5 and 2.5%, preferably between 1.5% and 2%.
• the water and volatile matter content of the dried seeds is determined according to the method NF V 03-909.
• the drying step c) is carried out at a temperature of between 50 and 100 ° C., preferably between 70 ° C. and 90 ° C.
• a transesterification step is carried out by contacting the dried flattened seeds with an alcoholic medium in the presence of a catalyst.
• the catalyst is basic or acidic, preferably basic.
• the alcoholic medium may comprise one or more alcohols chosen from C1-C6 alcohols, such as methanol or ethanol, optionally admixing one or more aliphatic hydrocarbons, such as hexane.
• the alcoholic medium is preferably ethanol containing a quantity of water less than 5000 ppm, preferably 3000 ppm.
• the basic catalyst is preferably anhydrous and homogeneous and may be selected from sodium hydroxide, potassium hydroxide, sodium or potassium carbonate or hydrogen carbonate, sodium or potassium carbonate, sodium or potassium methoxide or ethanolate.
• the acid catalyst may be, for example, sulfuric acid.
• the transesterification step Before starting the transesterification step, it may be advantageous, in the context of a discontinuous regime, to put the flattened seeds in prior contact with the alcoholic medium, so as to impregnate them with this alcoholic medium and then to promote the transesterification.
• the pre-impregnation can take place for a period of between 10 and 30 minutes, preferably 30 minutes, at a temperature of between 40 and 80 ° C., preferably 75 ° C. This step is to be avoided if the reaction takes place continuously.
• the mass ratio catalyst / flattened seeds is preferably between 0.5 / 100 and 2/100 and / or the weight ratio alcohol / flattened seeds is preferably between 100/100 and 100 and 500/100.
• the transesterification reaction is advantageously carried out at a temperature of between 45 and 55 ° C., preferably approximately 50 ° C., for a period ranging from 10 minutes to 2 hours, preferably between 20 and 40 hours. min.
• the bringing into contact of the flattened seeds with the alcoholic medium during step d) transesterification is carried out with slow stirring or by watering and percolation. It is preferably carried out by percolation of the alcoholic medium containing the catalyst through the flattened seeds.
• the percolation can be carried out by watering a bed of flattened seeds, the height of which is preferably about 80 cm.
• the liquid and solid phases resulting from said transesterification are separated, preferably by dewatering.
• the recovered liquid phase is rich in fatty acid esters produced by the transesterification reaction.
• the residual fat content in the solid phase i.e. the cake, is less than 1% by weight of the total dry matter.
• the grouped liquid phases resulting from stage e) can be filtered, for example on a fabric with a pore diameter of between 10 and 50 ⁇ m, in order to eliminate all the fine particles.
• the extraction step h) is preferably carried out by percolation, countercurrently, with ethanol, with a weight ratio of alcohol to flattened seeds of between 100/100 and 200/100.
• the alcohol used in the extraction step h) may be chosen from C1-C6 alcohols, such as ethanol containing a quantity in water of less than 5000 ppm, preferably less than 3000 ppm.
• the liquid phase resulting from the transesterification step e), optionally added with the liquid phase resulting from the extraction step h), is then neutralized. either with the aid of an acid if the catalyst of the reaction is basic, or with the aid of a base if the catalyst of the reaction is acidic.
• the acid is preferably selected from sulfuric acid, hydrochloric acid, phosphoric acid, citric acid or acetic acid.
• the base may be for example soda.
• the amount of acid added to the liquid phase is determined such that the fatty acid content in the ethyl esters of fatty acids remains below 0.25% (equivalent to an acid number ⁇ 0.5 mg KOH /boy Wut).
• the neutralization of the liquid phase is carried out partially so as not to increase the quantity of soaps in it.
• the neutralization acid is added in an amount leading to a pH close to 10, especially in an amount of less than 0.04% of the total amount of fatty acid esters present in said liquid phase. .
• step f) of neutralization the alcohol phase is then removed from the liquid phase and the glycerine is separated from the fatty acid esters.
• the elimination of the alcohol is preferably carried out by evaporation at a temperature of between 50 and 100 ° C. under a pressure of between 200 and 1000 mbar, preferably at approximately 80 ° C. under atmospheric pressure, until a residual alcohol content less than 1%.
• the separation of the glycerin from the fatty acid esters is preferably carried out by centrifugation at a temperature of between 60 and 80 ° C. It can also be carried out by static decantation. Glycerine carries with it a large part of impurities such as catalyst, soaps, phosphoric derivatives or sodium sulfate.
• the fatty acid esters are then advantageously washed with water, preferably at about 80 ° C., in order to completely remove the impurities, and then separated from the washing water, in particular by decantation or centrifugation, preferably about 80 0 C, then dried, preferably by evaporation at a temperature between 90 and 100 0 C under a pressure of the order of 200 mbar, to obtain a residual water content of less than 500 ppm relative to the total dry matter.
• the fatty acid esters thus obtained can then be packaged under nitrogen after having been cooled.
• the subject of the present invention is a process for the preparation of cakes for animal feed from the solid phase resulting from stage e) or i) of the process for the preparation of fatty acid esters as described previously , comprising the following steps:
• the solid phase resulting from step 1) may be further added to the washings described above in the process for the preparation of fatty acid esters.
• the solid phase from step e) or i) of said process for preparing fatty acid esters contains between 50 and 65% by weight of alcohol.
• the elimination of the alcohol from this solid phase can be carried out mechanically, in particular by pressing or spinning, then thermally, by steam stripping, until a residual water content of less than 500 ppm is obtained with respect to the total dry matter.
• the final cake obtained in step 2) can then be packaged in powder form or extruded.
• the removed alcohol can be recovered and dehydrated for reuse in the process for the preparation of fatty acid esters.
• the objective of this first series of tests is to highlight the importance of the preheating step of the undried seed before it is flattened.
• the procedure comprises the following steps:
• the ethanol passing through the seed bed is then recovered downstream of the fixed bed in a glass recipe.
• the amount of fat extracted and the time of percolation are then measured.
• Table 1 Influence of the preheating temperature on the amount of fat extracted from the flattened seeds and the rate of percolation.
• the seed may dry before flattening, which would make it harder, which would induce the production of fine materials at the time of flattening.
• the preparation of the flattened and dried seeds is a very important step in the process that is the subject of the present invention. It consists of :
• Seeds prepared according to Method 1 Three series of rapeseeds were prepared and tested: Seeds prepared according to Method 1, Seeds prepared according to Method 2, Seeds prepared according to Method 3.
• the flattened seeds were characterized by the measurement of the following parameters: fat content accessible by extraction with hexane (soxlhet) - THR 105 - Residual moisture content at 105 0 C
• the dry seeds do not support the flattening and the percolation of ethanol is weaker with these seeds because of the fines, the drying of the seeds prevents the degradation of the fat.
• the dry fat content of the fat is much lower than that of fresh seeds, the fluted rollers produce more fines than the smooth rolls, the desired spacing of the rolls is 0.1 mm maximum.
• the flattening is carried out under the following conditions:
• the total oil content of the seed is 50%.
• the calculation of the grinding defect is:
• the spacing of the rollers may be between 0.05 mm and 0.1 mm.
• the thickness of the flattened seed must be less than 0.2mm.
• the fat of the flattened wet seeds can be degraded by enzymatic hydrolysis with the storage time. Its acid number increases.
• the work in this section is aimed at determining the appropriate conditions for the conservation of flattened rapeseeds.
• the rapeseeds were flattened and then treated immediately on the spot.
• the rapeseeds (6-7% in water) were flattened under the following conditions, without preheating:
• the flattened seeds are then dried in a Turbétuve dryer either at 80 0 C or at 90 0 C to obtain a residual water content between 1 and 2%.
• the drying conditions are:
• Drying baskets 4 quarters with perforated bottom, - Quantity of flakes: 4 X 5 kg,
• Dry seeds are packaged in sealed plastic bags and stored at room temperature. The quality of the seeds was followed by measurements of: Volatile Content (%), accessible fat content (% DM), yield - Soxlhet extraction with hexane for 10 h, acid value of the material fat extraction (mg KOH / g) - NF T 60-204, - peroxide number, percolation.
• the flattened unseasoned seed sees the acidity of its oil rise very rapidly: thus, after one week, the acidity can reach a value of 17 mg KOH / g.
• This acidity is equivalent to 10% of the hydrolysed oil in free fatty acids.
• the free fatty acids thus produced will have a negative impact on the reaction in basic medium, they will be saponified (consumption of NaOH catalyst). Thus the yield of the ester will be even lower than the hydrolysis will be important.
• seeds dried immediately after manufacture have a stable oil acidity over time.
• flattened and dried rapeseed can be stored for at least 35 days in an airtight plastic bag.
• the objective of this series of tests is to highlight the importance of the step of alcoholic impregnation of previously flattened and dried seeds and in particular, its impact on the extractive and reactive power of ethanol vis-à-vis -vis the oleaginous fat.
• the procedure comprises the following key steps:
• This step may be used in the batch process to improve the fat extraction and the purity of the ester thus converted.
• this step is undesirable because a precipitate has been observed which is found at the head of the bed when the catalyst is added after impregnation for 30 min and even on an impregnation of 5 min. This precipitate then causes a very rapid and very significant decrease in percolation. Out, industrially, it is not possible to work with weak percolations, at the risk of clogging the extractor.
• Prepreg has a positive advantage over extraction (90-92%) whereas percolation rates are greatly reduced when the catalyst is added.
• the flow rate drops from 10 to 5 or 1 m3 / hm 2 depending on the pre-impregnation time.
• the final esters represent about 40% of the starting seeds. They have a very good purity.
• a 0.05 mm roll gap makes it possible to produce a larger quantity of esters than a gap of 0.1 mm.
• the yield of the transesterification reaction is therefore better with a gap of 0.05 mm than with a gap of 0.1 mm.
• the pre-impregnation is preferable for a good extraction and conversion of the fat.
• the duration of 30 minutes of impregnation can be decreased to increase the productivity of the installations.
• the ratio "Catalyst / Ethanol / Seeds" can be set at "17.5g / 1500g / 1000g".
• the test conditions F4, F5, F6 are the best.
• the ratio "Ethanol / Seeds" can be between 1.3 / 1 in the stirred and discontinuous regime of the reaction. For a continuous and fixed bed, this ratio must be adjusted.
• the water content of ethanol can be from about 3000 ppm for the reaction.
• the cakes from the first filtration underwent 4 co-current extractions with ethanol at different water contents.
• Triglycerides % 98.7 4.9
• the liquid resulting from the transesterification was prepared under the following conditions:
• Seed prepared according to method 3a two aplatissages: 1 spacing 0.4 mm and 2nd gauge 0.04 mm,
• the liquid phase (LO) was neutralized with sulfuric acid solution at different concentrations in 97% ethanol.
• Table 11 shows that the esters obtained without neutralization have the lowest acid number. On the other hand, the quantity of recovered esters is also the lowest.
• the Partial neutralization makes it possible to obtain more esters. We can neutralize the liquid phase with a 10% sulfuric acid solution.
• a production of rapeseed oil ethyl esters is carried out from 20 kg of whole seeds.
• the conditions of implementation of the batch mode process are as follows:
• preheating temperature before flattening 50 ° C.
• the esters thus prepared are analyzed on the basis of the main criteria of the European standard NF EN 14214 applicable to methyl esters intended for a fuel application.
• the results obtained demonstrate that the ethyl esters produced are of high purity (> 97%), free of contaminants and other by-products in quantities greater than the standards (total glycerol, water, ethanol, phosphorus, free fatty acids, mono, di and triglycerides). They also have a cetane number well above the specifications of the standard (> 51), all of these results confirming that these ethyl esters can be used as fuels.
• Table 12 Analysis of the Composition of the Esters Obtained from Rape Seeds According to the Process of the Invention

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• Polymers & Plastics (AREA)
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