WO2016203301A1 - Procédé de production de biodiesel à partir d'huiles végétales - Google Patents

Procédé de production de biodiesel à partir d'huiles végétales Download PDF

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Publication number
WO2016203301A1
WO2016203301A1 PCT/IB2015/057787 IB2015057787W WO2016203301A1 WO 2016203301 A1 WO2016203301 A1 WO 2016203301A1 IB 2015057787 W IB2015057787 W IB 2015057787W WO 2016203301 A1 WO2016203301 A1 WO 2016203301A1
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WO
WIPO (PCT)
Prior art keywords
reactor
biodiesel
transesterification
vegetable oils
oil
Prior art date
Application number
PCT/IB2015/057787
Other languages
English (en)
Inventor
Giovanni Santilli
Pasquale PERRI
Maria Concetta SORIANO
Sergio SENATORE
Donato SABATELLA
Original Assignee
Varat Srl
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Varat Srl filed Critical Varat Srl
Publication of WO2016203301A1 publication Critical patent/WO2016203301A1/fr

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Classifications

    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a process for producing biodiesel from vegetable oils.
  • the present invention relates to a process for producing biodiesel from vegetable oils, the virgin or exhausted ones, of the type realized in small size plants .
  • biodiesel is today the source of renewable energy more widely available on the European market, as well as the biofuel that can satisfy the principles of sustainability currently debated.
  • biofuels such as, ethanol, bio-methanol , biodesel and bio-hydrogen appear to be attractive alternatives for the future in the transport sector and thus a significantly increase of their production is expected in the coming decades.
  • trans-esterification in which a triglyceride molecule reacts with a short-chain alcohol at the presence of a catalyst. More in detail, the reaction of trans-esterification is the reaction between a triglyceride and an alcohol leading to the formation of a mixture of fatty acids and glycerin, and is the process that leads to the formation of biodiesel.
  • the reaction of trans-esterification is an equilibrium reaction that is carried out by means of reagent mixing and requires an excess of alcohol to get high conversions.
  • glycerol is obtained, which is insoluble in the methyl ester, thus causing the formation of two phases, which must be separated. Being this reaction reversible, high amounts of alcohol are required to obtain maximum conversion, but that makes difficult the final separation of the biodiesel and of the glycerol from alcohol .
  • the steps for production of biodiesel from vegetable oils are numerous. First of all it is necessary to verify the content of free fatty acids in the origin oil, for example by titration: if this content is less than about 2,5% wt (by weight), then it's possible to carry out the trans-esterification, otherwise a previous acid esterification is performed. Then, a pre-treatment step follows, namely the oil refining to obtain a raw material with constant characteristics. Obviously if the origin oil is a refined oil there is no pre-treatment need; otherwise the oil must be refined by a process of preliminary purification to remove impurities and possibly the water present in oil. This process is critical when oil from waste frying and recycling is used.
  • the third step is the mixing of alcohol and catalyst (almost always KOH, potassium hydroxide) , realized in a suitable container in a controlled environment to obtain a homogeneous mixture.
  • the catalyst (KOH) is supplied from a storage tank and added in a predetermined amount to the methanol.
  • the next step is the mixing reaction of oil with the alcohol / catalyst, normally using a 1:6 ratio of alcohol with respect to oil, by reacting the mixture oil / methanol at a temperature of 50-60 0 C for about 90-120 min.
  • the separation step is the next one: the methylester-glycerin mixture is transferred to a unit for decanting or centrifuging where, the glycerine phase is separated and transferred to the storage tank for its eventual neutralization with water and phosphoric acid.
  • the purification step of the methyl ester follows to eliminate the traces of the hydrophilic phase (traces of glycerol remained in suspension, excess of methanol, catalyst), performing washing the product with water (liquid-liquid extraction), which is then dried and finally stored. In a later step a vacuum distillation is performed to remove the water. Dry cleaning are also made using special filters with ion exchange resins. It's possible to delete the methanol from the crude biodiesel using a vacuum distillation.
  • the aqueous phase coming from the washing of biodiesel and the aqueous phase coming from the eventual neutralization of the glycerine are separately transferred to dedicated distillation columns.
  • the methanol, which is recovered for subsequent trans- esterification, and the glycerin with required purity originate from the distillation columns.
  • Purpose of the present invention is to provide a process for producing biodiesel from vegetable oils that is economical and efficient, thus overcoming the limitations of previously described process with reference to the known technique.
  • FIG. 1 shows a scheme of a process for producing biodiesel from vegetable oils, according to the invention.
  • a process for producing biodiesel from vegetable oils comprises: - An initialization step, or Start-up;
  • the startup step comprises:
  • the step of providing vegetable oil, virgin or exhausted one comprises the step of filtering the oil, through a filter plates pump, to remove carbonaceous residues and small percentages of water, so as to obtain an oil with moisture, ability to be unsaponifiable and insoluble products (MIU) to the maximum of 3% and an acidity of 5% and the absence of impurities.
  • the start-up step involves a trans- esterification in a single step where the filtered oil is pumped into the second secondary trans-esterification reactor RT2, inside of which it is heated and recirculated via a pump.
  • the mixing step of the catalyst with the alcohol comprises mixing potassium hydroxide with methanol to obtain a mixture, improperly called "methoxide", which is added to the heated oil, as soon as the oil temperature reaches 55 °C - 60 °C.
  • methanol is in the ratio of 6:1 with respect to oil and the potassium hydroxide is about 1% w/w with respect to the oil and mixing is deemed complete after about 5 - 10 minutes.
  • the step for preparing the methoxide, as described, is followed by the single step transesterification, and, more specifically, the methoxide is sent into the reactor RT2 by means of the suction circuit of said pump.
  • the line of methoxide is inserted in the suction circuit of said pump by means of a beveled nozzle, defined as a "whistle" system.
  • a beveled nozzle defined as a "whistle” system.
  • the mixing of methoxide with oil thus realized allows oil and methoxide intimately blend both thanks to the "whistle” system that at the passage of the mixture in the pump helping to create a high turbulence in the fluid and reacting to form the mixture of methyl esters.
  • the reagent mixture continues to be mixed by means of a circulation pump in the reactor RT2 for about 90-120 minutes, at the reaction temperature.
  • the purification step of the crude biodiesel from the glycerin is made by means of decantation inside the reactor RT2, and is favored by the conformation of the reactor RT2 which has a conical bottom.
  • the glycerin is removed by means of a drain valve on the bottom of the reactor.
  • the glycerin is transferred to the storage tank.
  • the crude biodiesel is present in the reactor RT2 with a high percentage of methanol that will be recovered by means of a stripping step simultaneously with the step of production of biodiesel in two steps.
  • the alcohol stripping step and the simultaneous primary transesterification step at room temperature in a first transesterification reactor RT1 comprises the steps of:
  • the methoxide in proportions from 3 ⁇ 4 to 3 ⁇ 4 to let occur the primary transesterification step that will last at least for the time required for stripping.
  • the methoxide once prepared as already described above, is sent into the reactor RT1 through the suction circuit of the pump that is recirculating oil in the reactor RT1.
  • the line of methoxide also in this case is grafted onto the suction circuit of said pump through the "whistle" system.
  • the ejector ET1 provides to lower the pressure, lowering the vapor pressure inside the packed column thus favoring the evaporation of the methanol.
  • an optimal mixing between methoxide and oil is obtained in the reactor RT1 thanks to the strong speed present inside the tubes connected to the ejector and to the good turbulence that is generated inside the ejector to ensure a high degree of vacuum in the packed column, such as to promote trans-esterification at lower temperatures and lower reaction times.
  • the oil is used as motor fluid recirculating from the reactor RT1 to the ejector ET1, thus retrieving the stripped methanol, which is recovered from the top of the stripping column CS1, condensed through double threaded tube water cooled condensers, aspirated from the ejector ET1 through its suction nozzle, which sends the methanol in the diffuser where it mixes with the oil for finally relapsing in the reactor RT1.
  • the primary is carried out at a temperature inferior compared to the secondary transesterification .
  • the process according to the invention advantageously improves the mixing between the oil and other reagents (methoxide added to the aspirated methanol) .
  • the stripping step ends when the pressure indicator placed on the reactor RT2 doesn't detect pressure changes and is below 0.2 bara. At this point by means of an opening and closing valves system, the flow is blocked in the ejector ET1 and the reactor RT2 is brought to atmospheric pressure.
  • the purification step of the crude biodiesel in the reactor RT2 comprises the steps of:
  • the filtering of biodiesel takes place by sending the biodiesel from a tower of filtration FP1 to another battery of filters designed to remove any suspended solids (of the order of microns) and traces of water present in the biodiesel, and, more specifically, a mechanical filter FS1, which holds particles of diameter greater than 0.7 microns, and a water filter cartridge FW1.
  • the primary transesterification reaction proceeds in the reactor RT1.
  • the mixture will continue the transesterification inside the reactor RT1.
  • the biodiesel produced in the primary transesterification is separated from the glycerine by means of decantation inside the reactor RT1 and the separation is favored by the conformation of the conical bottom of the reactor RT1.
  • the glycerin is removed through a drain valve on the bottom of the reactor.
  • the secondary transesterification step at the reaction temperature in the second transesterification reactor RT2 comprises the steps of:
  • the steps of preparation of methoxide and of mixing are identical to those of the primary transesterification .
  • the step of secondary transesterification comprises the steps of bringing the mixture to the reaction temperature and of injecting the methoxide continuing to mix for about 90 -120 minutes .
  • the step of secondary transesterification is followed by:
  • the whole process is calibrated taking into account that the process is suitable for small plants with capacity between 0.15 to 5 ton/day.
  • the process for producing biodiesel from vegetable oils allow to realize the transesterification reaction in two different steps contemporary purifying biodiesel, using a single reactor for the purification and for the first trans- esterification.
  • Another advantage of the process for producing biodiesel from vegetable oils according to the invention consists in the saving of reactors, time, cost of plant and operating costs.
  • Another advantage of the process for producing biodiesel from vegetable oils according to the invention consists in the possibility of working with excess of methanol allowing to maximize the reaction.
  • Another advantage of the process for producing biodiesel from vegetable oils according to the invention consists in the possibility to completely recover the reagent and transfer it directly to the oil avoiding the inclusion of an intermediate step, such as washing with water which determines most losses, both in terms of reagent and in terms of energy to be used to retrieve the methanol .

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un procédé de production de biodiesel à partir d'huiles végétales comprenant : - une étape d'initialisation ; - une étape de réextraction de l'alcool et une étape simultanée de transestérification primaire à température ambiante à l'intérieur d'un premier réacteur de transestérification RT1 ; - une étape de décantation secondaire ; - une étape de purification et de stockage du biodiesel brut ; - une étape de transestérification secondaire à la température de réaction à l'intérieur d'un second réacteur de transestérification RT2 ; et - une étape de décantation, de purification et de stockage du biodiesel brut.
PCT/IB2015/057787 2015-06-17 2015-10-12 Procédé de production de biodiesel à partir d'huiles végétales WO2016203301A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITUB2015A001458 2015-06-17
ITUB20151458 2015-06-17

Publications (1)

Publication Number Publication Date
WO2016203301A1 true WO2016203301A1 (fr) 2016-12-22

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050204612A1 (en) * 2002-09-20 2005-09-22 Joosten Connemann Method and device for producing biodiesel
US20080282606A1 (en) * 2007-04-16 2008-11-20 Plaza John P System and process for producing biodiesel
US20120142953A1 (en) * 2008-11-10 2012-06-07 Jean-Francois Devaux Method for the transesterification of hydroxylated oils
US20150031097A1 (en) * 2012-02-02 2015-01-29 Revolution Fuels, Inc. Mobile processing systems and methods for producing biodiesel fuel from waste oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050204612A1 (en) * 2002-09-20 2005-09-22 Joosten Connemann Method and device for producing biodiesel
US20080282606A1 (en) * 2007-04-16 2008-11-20 Plaza John P System and process for producing biodiesel
US20120142953A1 (en) * 2008-11-10 2012-06-07 Jean-Francois Devaux Method for the transesterification of hydroxylated oils
US20150031097A1 (en) * 2012-02-02 2015-01-29 Revolution Fuels, Inc. Mobile processing systems and methods for producing biodiesel fuel from waste oils

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