WO2015196243A1 - Fabrication de biodiesel - Google Patents

Fabrication de biodiesel Download PDF

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Publication number
WO2015196243A1
WO2015196243A1 PCT/AU2015/000367 AU2015000367W WO2015196243A1 WO 2015196243 A1 WO2015196243 A1 WO 2015196243A1 AU 2015000367 W AU2015000367 W AU 2015000367W WO 2015196243 A1 WO2015196243 A1 WO 2015196243A1
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Prior art keywords
degrees
tube
process according
fatty acid
catalyst
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PCT/AU2015/000367
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English (en)
Inventor
Colin Llewellyn Raston
Joshua BRITTON
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Flinders University Of South Australia
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Priority claimed from AU2014902456A external-priority patent/AU2014902456A0/en
Application filed by Flinders University Of South Australia filed Critical Flinders University Of South Australia
Publication of WO2015196243A1 publication Critical patent/WO2015196243A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00189—Controlling or regulating processes controlling the stirring velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/187—Details relating to the spatial orientation of the reactor inclined at an angle to the horizontal or to the vertical plane
    • 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
    • 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

Definitions

  • the present disclosure relates to processes for the production of saturated or unsaturated fatty acid ester mixtures that are suitable for use as fuels, such as biodiesel, fuel additives and lubricants.
  • the present invention also relates to fuels, such as biodiesel, produced using the processes.
  • Biofuels are an alternative to fossil fuels that do not have the same negative environmental impacts as fossil fuels because they are derived from atmospheric carbon dioxide, and thus do not increase the net amount of carbon dioxide in the atmosphere. Furthermore, the use of biofuels may not require substantive changes to existing infrastructure and machinery as may be required from some other alternative energy sources.
  • Biodiesel is a biodegradable transportation fuel for use in diesel engines that is produced from plant- or animal -derived oils or fats. Biodiesel is used as a component of diesel fuel or as a replacement for diesel fuel. Biodiesel can be readily used in diesel-engine vehicles, which distinguishes biodiesel from the straight vegetable oils (SVO) or waste vegetable oils (WVO) used as fuels in some modified diesel vehicles. Biodiesel is biodegradable and non-toxic, and has significantly fewer emissions than petroleum-based diesel when burned and, therefore, its use can result in substantial environmental benefits.
  • SVO straight vegetable oils
  • WVO waste vegetable oils
  • Biodiesel is comprised of a mix of mono-alkyl esters of long chain fatty acids, and is typically produced by transesterification of vegetabl e oil or animal fat with methanol using acid or basic catalysts.
  • International patent application WO03/022961 describes a method for producing biofuel from waste oil or oil by-products by transeterification with methanol in the presence of sulfuric acid.
  • International patent application WO2006/128881 describes a method for producing biodiesel from rapeseed oil or sunflower oil by transesterification with methanol in the presence of sodium hydroxide.
  • biodiesel can be produced from vegetable oils by an enzyme (Candida cylindracea) catalysed transesterification reaction (for example see published United States patent application 2005/0084941 ).
  • VFD thin film vortex fluid device
  • a process for producing CpQ, alkyl fatty acid esters comprising: providing a reactant fluid comprising a fatty acid, fatty acid glyceride or mixture thereof; providing a catalyst fluid comprising a C] -C 6 alkyl alcohol and an acid or base catalyst; contacting the reactant fluid and the catalyst fluid in a thin film tube reactor comprising a tube having a longitudinal axis, wherein the angle of the longitudinal axis relative to the horizontal is between about 0 degrees and about 90 degrees; rotating the tube about the longitudinal axis under conditions to produce Ci-C 6 alkyl fatty acid esters; and recovering the Ci-C 6 alkyl fatty acid esters from the reactor.
  • the process can be used to produce biodiesel from readily available oils and solid fats.
  • a process for producing biodiesel comprising: providing a reactant fluid comprising a fatty acid, fatty acid glyceride or mixture thereof; providing a catalyst fluid comprising a Ci -C 6 alkyl alcohol and an acid or base catalyst; contacting the reactant fluid and the catalyst fluid in a thin film tube reactor comprising a tube having a longitudinal axis, wherein the angle of the longitudinal axis relative to the horizontal is between about 0 degrees and about 90 degrees; rotating the tube about the longitudinal axis under conditions to produce biodiesel; and recovering biodiesel from the reactor.
  • the angle of the longitudinal axis relative to the horizontal is between about 10 degrees and about 90 degrees.
  • the thin film tube reactor comprises an inner cylindrical surface and a hemispherical base.
  • the thin film tube reactor comprises a hemispherical base.
  • the process is carried out without the need for heating.
  • the reactant fluid comprises substantially no solvent.
  • the catalyst fluid comprises substantially no solvent other than the C r C 6 alkyl alcohol.
  • the recovered Ci-C 6 alkyl fatty acid esters or biodiesel are substantially free of glycerol.
  • the process is a continuous process.
  • the thin film tube reactor comprises a plurality of thin film tube reactors.
  • a C r C 6 alkyl fatty acid ester produced according to the process of the first aspect.
  • biodiesel produced according to the process of the second aspect.
  • FIG. 1 shows a schematic of the transesterification process occurring within the vortex fluidic device (VFD). This shows the catalytic conversion of oil to biodiesel (Fatty Acid Methyl Ester (FAME)) and a photograph of a VFD;
  • VFD vortex fluidic device
  • FIG. 2 is a plot of % acetone co-solvent vs % conversion to biodiesel.
  • the figure shows the effect of a co-solvent (acetone) on the conversion of pure oil into biodiesel; for single feed experiments, 0.50 g of triolein (99.5 % purity) was used with 20 mL of 10 % KOH (in methanol) with different ratios of acetone. When two separate feeds were used, 2 mL of triolein was used with an equi- volume of 10 % KOH (in methanol) with different volumes of acetone. A rotational speed of 5250 rpm was used, at an angle of incline, 0, of 45° relative to the horizontal position.
  • Figure 3 is a plot of concentration of KOH vs % conversion into biodiesel. The plot shows a variation in concentration of KOH biodiesel production from sunflower oil; 10 mL samples were used in a 1 : 1 ratio (oil: methanol), a rotational speed of 5250 rpm, o 45° relative to the horizontal position. Three separate experiments were carried out per data point;
  • Figure 4 is a plot of flow rate vs % conversion into biodiesel. The plot shows the effect of change in flow rate for the generation of biodiesel from sunflower oil; a rotational speed of 5250 rpm, 0 45° relative to the horizontal position, 1.0 M KOH. Three separate experiments were carried out per data point;
  • Figure 5 shows: (a) a three-phase separation; (b) colour change from using pure 1 M KOH (left) and the recycled catalyst three times (right), which arises from impurities; and (c) a plot of catalyst turnover vs % conversion into biodiesel showing the effect on conversion of sunflower oil to biodiesel versus the number of times of recycling the catalyst. Three separate experiments were carried out per data point;
  • Figure 6 is a plot of methanol/oil ratio vs free fatty acid conversion.
  • the plot shows the effect of volumetric ratio of methanol to oil on the conversion of FFA to the corresponding methyl ester using the VFD for different flow rates of the lipid oil. Results are in triplicate.
  • Optimum conditions are 1 :6 volume ratio of oil feedstock to methanol and 0.2 molar equivalents of sulphuric acid catalyst loading for a combined flow rate of 3.5 ml/min in a 17. 7 ID tube rotating at 7500 rpm;
  • Figure 7 is a plot of rotational flow rate vs % free fatty acid showing the flow rate of oil into the VFD for both five and six volumetric ratios of methanol to oil. Results are in triplicate and the average is taken;
  • Figure 8 is a plot of flow rate vs free fatty acid conversion showing the residence time of methanol in the rotating tube at 6950 rpm, tilted 45 degree relative to the horizontal position. Results are in triplicate and the average taken;
  • Figure 9 is a plot of molar ratio of sulphuric acid to free fatty acid vs free fatty acid conversion. Results are in triplicate and the average taken;
  • Figure 10 is a plot of rotational speed vs free fatty acid conversion. The plot shows the effect of tube rotation speed on the conversion of FFA into FAME. Results are in triplicate. DESCRIPTION OF EMBODIMENTS
  • a process for producing Ci -C 6 alkyl fatty acid esters comprises providing a reactant fluid comprising a fatty acid, fatty acid glyceride or mixture thereof and a catalyst fluid comprising a C r C 6 alkyl alcohol and an acid or base catalyst.
  • the reactant fluid and the catalyst fluid are contacted in a thin film tube reactor comprising a tube.
  • the angle of the longitudinal axis relative to the horizontal is between about 0 degrees and about 90 degrees.
  • the tube is rotated about the longitudinal axis under conditions to produce Ci-C 6 alkyl fatty acid esters which are then recovered from the reactor.
  • the process is particularly useful for the production of biodiesel from readily available oils.
  • the tube comprises an inner cylindrical surface. In embodiments, the tube comprises a hemispherical base.
  • the reactor is a vortex fluidic device (VFD).
  • VFD vortex fluidic device
  • the reactant fluid and catalyst fluid mix in the thin film tube, thereby triggering a reaction between them to produce the biodiesel and glycerol.
  • the mixing is convection-enhanced by shear stress induced circulation occurring within each of the reactants with intense micro-mixing. Separation of glycerol from the biodiesel occurs simultaneously post processing using the vortex fluidic device.
  • the reactor can be a continuous throughput reactor and a number of reactors can be connected in parallel to improve throughput.
  • the thin film tube reactor 10 comprises a tube 12 rotatable about its longitudinal axis by a motor 14.
  • the tube 12 is substantially cylindrical or comprises a portion that is tapered.
  • the motor 14 can be a variable speed motor for varying the rotational speed of the tube 12 and can be operated in controlled set frequency and set change in speed.
  • a generally cylindrical tube 12 is shown in the accompanying drawings but it is contemplated that the tube could also take other forms and could, for example, be a tapered tube, a stepped tube comprising a number of sections of different diameter, and the like.
  • the tube 12 can be made of any suitable material including glass, metal, plastic, ceramic, and the like.
  • the tube 12 is made from borosilicate.
  • the inner surface of the tube can comprise surface structures or aberrations.
  • An optional jacket 16 can be used to partially or wholly surround the circumference of the tube 12 for heating and/or cooling and/or insulating the tube 12.
  • the jacket 16 may also insulate the tube 12 from the external environment.
  • the tube 12 is situated on an angle of incline 18 relative to the horizontal 20 of above 0 degrees and less than 90 degrees. In certain embodiments, the tube 12 is situated on an angle of incline 1 8 relative to the horizontal 20 of between 10 degrees and 90 degrees.
  • the angl e of incline 18 can be varied. In the embodiment illustrated in Figure 1 , the angle of incline 18 is 45 degrees.
  • angles of incline 1 8 can be used including, but not limited to, 1 degree, 2 degrees, 3 degrees, 4 degrees, 5 degrees, 6 degrees, 7 degrees, 8 degrees, 9 degrees, 10 degrees, 1 1 degrees, 12 degrees, 13 degrees, 14 degrees, 15 degrees, 16 degrees, 17 degrees, 18 degrees, 19 degrees, 20 degrees, 21 degrees, 22 degrees, 23 degrees, 24 degrees, 25 degrees, 26 degrees, 27 degrees, 28 degrees, 29 degrees, 30 degrees, 31 degrees, 32 degrees, 33 degrees, 34 degrees, 35 degrees, 36 degrees, 37 degrees, 38 degrees, 39 degrees, 40 degrees, 41 degrees, 42 degrees, 43 degrees, 44 degrees, 46 degrees, 47 degrees, 48 degrees, 49 degrees, 50 degrees, 51 degrees, 52 degrees, 53 degrees, 54 degrees, 55 degrees, 56 degrees, 57 degrees, 58 degrees, 59 degrees, 60 degrees, 61 degrees, 62 degrees, 63 degrees, 64 degrees, 65 degrees, 66 degrees, 67 degrees, 68 degrees, 69 degrees, 70 degrees, 71 degrees, 72 degrees, 73 degrees, 74 degrees, 75 degrees,
  • the angle of incline 18 can be adjusted so as to adjust the location of the vortex that forms in the rotating tube 12 relative to the closed end of the tube.
  • the angle of incline 18 of tube 12 can be varied in a time-dependent way during operation for dynamic adjustment of the location and shape of the vortex. This also leads to a dynamic adjustment of the mechanical induced shear within the thin liquid film.
  • a spinning guide 22 assists in maintaining the angle of incline 18 and a substantially consistent rotation around the longitudinal axis of the tube 12.
  • the reactant fluid and the catalyst fluid are supplied to the inner surface of the tube 12 by way of at least one feed tube 24.
  • Any suitable pump can be used to pump the reactant fluid and the catalyst fluid from a reactant fluid source and a catalyst fluid source to the feed tube(s) 24.
  • Separate pumps may be used for the reactant fluid and the catalyst fluid so that each component can be introduced into the feed tube(s) 24 at different flow rates, as required.
  • the tubes 24 may be of different lengths to supply fluids to variable locations on the inner surface of the tube 12 with controlled flow rates.
  • Solid reactants can also be added to the tube 12 so that heterogeneous reactions can be carried out in the tube 12.
  • Solid reactants can be added via feed tube 24 or they may be added directly to the tube 12 which may be the case when solid catalysts are used in the tube 12, for example.
  • a further gas feed tube 70 can supply gas to the tube 1 10 as is required for processes using the thin film tube reactor 100.
  • One or more clamps 80 may be employed to hold feed tubes 60 and gas feed tubes 70 in position either externally or within tube 1 10.
  • a collector 26 positioned substantially adjacent to the opening of the tube 12 can be used to collect product exiting the tube 12. Fluid product exiting the tube 12 may migrate under centrifugal force to the wall of the collector where it can exit through a product outlet.
  • the VFD has several features which enhance the generation of biodiesel, compared to the prior art horizontally aligned rapid thermal processing (RTP). This includes high shear rates associated with the angle of incline 18 of the tube, reduction in the relative amount of solvent required, finer control of the residence time, and reduced capital outlay.
  • RTP rapid thermal processing
  • the reactant fluid can be a liquid, solution, suspension or emulsion comprising one or more fatty acid(s) or one or more fatty acid glyceride(s), or mixtures of these.
  • fatty acid means a carboxylic acid with a long saturated or unsaturated aliphatic tail, or with an aromatic component.
  • Fatty acids that are particularly suitable for the production of biodiesel include, but are not limited to palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures of these.
  • glyceride means a mono-, di- or triglyceride glycol ester.
  • the source of the one or more fatty acid(s) or one or more fatty acid glyceride(s) in the reactant fluid is one or more plant oils and/or an animal fats.
  • Glyceride containing plant oils or animal fats can be any oil or fat product of plant or animal origin that contains glycerides. Plant oils and animal fats contain mostly triglycerides, although they typically also contain some monoglycerides and diglycerides.
  • the glyceride containing plant oil or animal fat may be selected from the group including, but not limited to, animal tallow, plant oils, used cooking oils and fats, seeds, seed residue feedstocks, and grease trap oils.
  • Suitable plant oils that may be used in the production of biodiesel include: rapeseed oil, soybean oil, palm oil, mustard oil, castor oil, coconut oil (copra oil), corn oil, cottonseed oil, false flax oil, hemp oil, peanut oil, radish oil, ramtil oil, rice bran oil, safflower oil, sunflower oil, tung oil, algae oil, copaiba oil, honge oil, jatropha oil, jojoba oil, milk bush oil, petroleum nut oil, walnut oil, sunflower oil, dammar oil, linseed oil, poppyseed oil, stillingia oil, vernonia oil, amur cork tree fruit oil, apple seed oil, balanos oil, bladderpod oil, bruceajavanica oil, burdock oil (bur oil), candlenut oil (kukui nut oil), carrot seed oil, chaulmoogra oil, crambe oil, cuphea oil, lemon oil, orange oil, mango oil, mowrah butter, nee
  • the plant oils may be used "as is” (ie without further purification and/or treatment) in the process of the invention, but the invention is not limited to these embodiments.
  • Animal fats are fats obtained from animal sources. Suitable animal fats that may be used in the production of biodiesel include: tallow (beef fat), lard (pork fat), schmaltz (chicken fat), blubber, cod liver oil, yellow grease, and the by-products of the production of omega-3 fatty acids from fish oil. Some animal fats may be solid or gelatinous at room temperature and, in those cases, it is contemplated that the reactant fluid will contain a solvent or heated using dissipated heat from the motor used for spinning the tube, or other sources. However, the solvent is preferably a C] -C 6 alcohol and more preferably the C C 6 alcohol used in the catalyst fluid.
  • the catalyst fluid can be a liquid, solution, suspension or emulsion comprising a Ci-C 6 alcohol and an acid or base catalyst.
  • the Ci-C 6 alcohol may be selected from one or more of the group consisting of: methanol, ethanol, n-propanol, i-propranol, n-butanol, s-butanol, and t-butanol.
  • Methanol is an alcohol that is commonly used in biodiesel production and we have found it to be suitable for use in the processes described herein. However, it is contemplated that ethanol may also be particularly suitable.
  • the catalyst fluid also comprises an acid or base transesterification catalyst.
  • the acid catalyst may be any suitable mineral acid, such as hydrochloric acid, sulphuric acid, nitric acid, etc.
  • the base catalyst may be potassium hydroxide, sodium hydroxide, sodium methoxide, etc.
  • Other transesterification catalysts, including metal or enzyme catalysts can also be included in the catalyst fluid.
  • the transesterification catalyst is potassium hydroxide (KOH).
  • KOH potassium hydroxide
  • the transesterification catalyst is sodium hydroxide which is less expensive than potassium hydroxide.
  • the transesterification catalyst is sulphuric acid.
  • a second catalyst can be bound to an internal surface of the tube 12.
  • the catalyst may be a solid acid, base, metal or enzyme catalyst. These embodiments may be particularly effective when the VFD is operated in confined mode and the reactant fluid and catalyst fluid are in contact with the solid catalyst for a sufficient time.
  • the flow rate of reactant fluid and catalyst fluid into the VFD affects the purity of the biodiesel product, with an almost l inear decline in biodiesel purity for increasing flow rate.
  • the flow rate of the reactant fluid and the catalyst fluid is less than 2 mL/min, and in certain embodiments it is less than 1 mL/min.
  • the liquid produced according to the processes described herein spontaneously separates into three layers.
  • the lower level is glycerol with the highest density, ⁇ 1 .26 g/mL, and can be readily removed, for use in a wide range of commercial applications.
  • the middle layer is biodiesel.
  • the upper layer contains methanol and the catalyst.
  • the upper layer ie. a used catalyst fluid comprising methanol, around 10 % FAME and catalyst
  • the resultant catalyst fluid can then be introduced back into the system for further biodiesel generation without any further purification. Greater than 95 % conversion to biodiesel can be maintained for a number of cycles. However, in our system we found that the conversion decreased at the fourth cycle.
  • the reactant fluid and the catalyst fluid are supplied to the inner surface of the tube by way of feed tube which is fed through a flow control device from an injection pump.
  • feed tube which is fed through a flow control device from an injection pump.
  • the fatty acid and/or fatty acid glyceride and the alkoxide of the C] -C 6 alcohol react to form a mixture of methyl ester, glycerol, and residual methanol and catalyst.
  • the tube is spun at high speeds
  • the VFD can be operated in a batch mode in which the reactor is configured to retain a finite amount of liquid in the tube 12.
  • the VFD is advantageously operated in continuous flow mode wherein the reactant fluid and catalyst fluid are introduced continuously into the reactor via the feed tube and the products are removed from the top of the reactor continuously.
  • the continuous flow mode of operation imparts additional shear relative to the confined mode (angle of incline > 0°) arising from the viscous drag as the fluid whirls along the tube prior to exiting at the top.
  • glycerol has enough translational energy to overcome the viscous drag and exit the system, thus enhancing the position of equilibrium in favour of the desired products.
  • the size and the diameter of the tube can be increased and/or a plurality of VFD reactors can be connected in parallel in order to increase throughput, as can multiple passes of the liquid through a number of VFD reactors.
  • the processes described herein have a number of desirable features such as high volume, low capital and operating costs, short residence times, compact and modular process equipment design, moderate process conditions, and low energy usage.
  • Ci -C 6 alkyl fatty acid ester or biodiesel produced according to the described processes.
  • the VFD was equipped with a 20 mm external diameter glass tube (borosilicate glass, as a standard NMR tube). The tube was rotated at 5250 rpm at a tilt angle ⁇ of 45 ° relative to the horizontal position.
  • the reactants were injected via automated pumps at a flow rate of 0.50 mL/min.
  • a 10 mL solution of 1 M base (KOH, NaOH, or NaOMe in methanol) was injected through one jet feed whilst 10 ml of untreated oil was injected in via another parallel aligned jet feed, at the same flow rate.
  • Products were collected in a separating funnel via an exit tube, which resulted in instantaneous separation into three layers.
  • the lower layer (glycerol) was removed first, followed by the middle layer (biodiesel) then the top layer (catalyst, methanol , impurities and - 10 % of the synthesised FAME).
  • the oil layer was washed with 50 °C water (3 x 25 mL), 2 M NaHC0 3 ( 1 x 25 mL) and 2 M HC1 ( 1 x 25 mL), to remove any possible free fatty acids (FFA), impurities and remaining catalyst. Yields were calculated based on the maximum amount of transesterification product possible when using a 10 mL sample of commercial sunflower oil sample. All biodiesel was subjected to a typical "shake" test with water and a pH test to make sure that the catalyst and any possible FFA had been removed
  • the catalyst was introduced back into the system for further biodiesel generation without any purification on the above removal of the solvent.
  • the percent conversion remained high at 95 % until the fourth cycle, whereupon there was a dramatic reduction in conversion to ca 22 %, Figure 5. This possibly arises from a build up in contaminants, which is evident with a change in colour (which does not change colour when neutralised with 2 M HCl), disrupting the transesterification of the sunflower oil.
  • Sodium hydroxide is less expensive than potassium hydroxide, and is another common catalyst used in the production of biodiesel. Indeed, repl acing the KOH with NaOH in the methanol was equally effective in biodiesel production using the VFD, and heightens the cost-effectiveness of the process, with the less hygroscopic and safer nature of NaOH improving the green chemistry metrics of the process. Unlike previous studies, there is no need to use anhydrous solvents to eliminate water from the system. To further highlight this, the same experiment was undertaken with water as the solvent rather than methanol. There was no hydrolysis or modification of the sunflower oil at 1.0 M or 3.0 M KOH/NaOH in water, thus establishing that we have a rather unique system.
  • Stearic acid (Ci 8 H3 6 0 2 ), a free fatty acid of solid composition at room temperature can also be esterified with methanol using a sulphuric acid catalyst. This was achieved by firstly dissolving the solid acid ( 1 .00 g) in methanol (30.0 mL), and this solution was then passed through the vortex fluidic device at a speed of 0.50 mL/min at a tilt angle of 45 degrees relative to the horizontal position, as described in Example 1. The resultant solution was taken to dryness by reduced pressure removal of the residual methanol. The residue was washed with sodium carbonate and the solid filtered off. The white solid compound was spectroscopically identified as the steric acid methyl ester, with no indication of any free fatty acid present by ⁇ NMR or 13 C NMR.
  • the VFD was set at a tilt angle, ⁇ , of 45 degrees relative to the horizontal position.
  • the oil was again centrifuged at a reduced temperature to allow the water to separate. The oil was then removed, dried under vacuum and then weighed. A sample of 10 mL of oil was used each time, and the results were carried out in triplicate.
  • the oil used was purchased from Sigma ( ⁇ 90 % technical grade Oleic acid) and was used as received for modelling a high FFA system.
  • M ba mass of benzoic acid (g), V 0 - Volume of KOH titrant used (mL) , V t - Volume of titrant used (mL), V n - Volume of titrant required to naturalise 50 mL propan-2-ol (mL), C - Concentration of titrant (moles L 1 ), M 0ll - mass of oil sample (g), AVi - Initial acid value (mg KOH g "1 ), AV f - Final acid value (mg KOH g "1 ).
  • the catalyst loading significantly influences biodiesel processing, and this is even more important in flow chemistry systems, as in using the VFD.
  • the VFD operates under plug flow conditions, and thus the catalyst has limited time (47 seconds) to recycle to other parts of the tube, with the effectiveness of the VFD relating to a system not governed by diffusion control.
  • the catalyst loading of the system is a direct molar ratio between the FFA present and the moles of sulphuric acid used.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un procédé de production d'esters alkyliques d'acides gras en C1-C6 ou biodiesel. Le procédé consiste à utiliser un fluide réactif comprenant un acide gras, un glycéride d'acide gras ou leur mélange ; à utiliser un fluide catalyseur comprenant un alcool d'alkyle en C1-C6 et un catalyseur de type acide ou base ; à mettre en contact le fluide réactif et le fluide catalyseur dans un réacteur tubulaire à couche mince comprenant un tube ayant un axe longitudinal, où l'angle de l'axe longitudinal par rapport à l'horizontale est compris entre environ 0 degrés et environ 90 degrés ; à faire tourner le tube autour de l'axe longitudinal dans des conditions permettant de produire des esters alkyliques d'acide gras en C1-C6 ; et à récupérer les esters alkyliques d'acide gras en C1-C6 ou biodiesel du réacteur.
PCT/AU2015/000367 2014-06-26 2015-06-26 Fabrication de biodiesel WO2015196243A1 (fr)

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AU2014902456 2014-06-26
AU2014902456A AU2014902456A0 (en) 2014-06-26 Biodiesel production

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070219340A1 (en) * 2006-03-20 2007-09-20 Lichtenberger Philip L Esterification and transesterification systems, methods and apparatus
WO2009075762A1 (fr) * 2007-12-11 2009-06-18 Cargill, Incorporated Procédé de fabrication de biodiesel et d'esters d'acides gras
US20090293346A1 (en) * 2008-05-28 2009-12-03 Birdwell Jr Joseph F Integrated reactor and centrifugal separator and uses thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070219340A1 (en) * 2006-03-20 2007-09-20 Lichtenberger Philip L Esterification and transesterification systems, methods and apparatus
WO2009075762A1 (fr) * 2007-12-11 2009-06-18 Cargill, Incorporated Procédé de fabrication de biodiesel et d'esters d'acides gras
US20090293346A1 (en) * 2008-05-28 2009-12-03 Birdwell Jr Joseph F Integrated reactor and centrifugal separator and uses thereof

Non-Patent Citations (2)

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Title
LODHA, H. ET AL.: "Intensified Biodiesel Production Using a Rotating Tube Reactor.", ENERGY FUELS, vol. 26, 4 October 2012 (2012-10-04), pages 7037 - 7040, XP055246226 *
LYZU, Y. ET AL.: "Optimising a Vortex Fluidic Device for Controlling Chemical Reactivitv and Selectivitv.", SCIENTIFIC REPORTS 3, 25 July 2013 (2013-07-25), XP055246222 *

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