EP2021438A2 - Microreactor process for making biodiesel - Google Patents
Microreactor process for making biodieselInfo
- Publication number
- EP2021438A2 EP2021438A2 EP07795499A EP07795499A EP2021438A2 EP 2021438 A2 EP2021438 A2 EP 2021438A2 EP 07795499 A EP07795499 A EP 07795499A EP 07795499 A EP07795499 A EP 07795499A EP 2021438 A2 EP2021438 A2 EP 2021438A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- microreactor
- biodiesel
- alcohol
- oil
- soybean oil
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
Classifications
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- 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
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- 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
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- 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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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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
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00835—Comprising catalytically active material
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00837—Materials of construction comprising coatings other than catalytically active coatings
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00844—Comprising porous material
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00858—Aspects relating to the size of the reactor
- B01J2219/0086—Dimensions of the flow channels
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00891—Feeding or evacuation
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00905—Separation
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00905—Separation
- B01J2219/00907—Separation using membranes
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
- B01J2219/00952—Sensing operations
- B01J2219/00954—Measured properties
- B01J2219/00959—Flow
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- 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
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
- B01J2219/00984—Residence time
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- 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
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- 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
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- 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 concerns embodiments of a process for making biodiesel, particularly a process that utilizes at least one microreactor device.
- Biodiesel is registered with the U.S. Environmental Protection Agency as a pure fuel or as a fuel additive, is a legal fuel for commerce, and meets clean diesel standards established by the California Air Resources. Its physical and chemical properties as they relate to operation of diesel engines are similar to petroleum-based diesel fuel as per the ASTM fuel tests shown in Table 1.
- Biodiesel can be used most effectively as a supplement for other energy liquid fuels such as diesel fuel. It is biodegradable and non-toxic, has low pollutant emission and therefore is environmentally beneficial.
- Biodiesel has been considered as a fuel or fuel additive since the late 1970's.
- the oil embargo by the Organization of Petroleum Exporting countries of 1973 resulted in significant biodiesel research by various universities, government agencies, and research organizations.
- the general conclusion is that biodiesel is a technically acceptable substitute, replacement, or blending stock for conventional petroleum diesel. It can be used at a 100-percent level (BlOO) or mixed with diesel in any proportion.
- BlOO 100-percent level
- the most common mixtures are B2 containing 2 percent biodiesel and B20 containing 20 percent biodiesel.
- biodiesel is the renewable fuel of choice in the European Union. Nearly 40 percent of the cars in Europe have diesel engines. Some cars are even fueled by BlOO, pure biodiesel. Germany uses the most biodiesel: 200 million gallons in 1991; 500 million gallons in 2001; and an estimated 750 million gallons in 2002. Most of Germany's biodiesel is made from rapeseed oil.
- Biodiesel become the only alternative fuel to have successfully completed the EPA-required Tier I and Tier II healthy effects testing under the clean air act. These independent tests conclusively demonstrated biodiesel's significant reduction of virtually all regulated emissions and showed that biodiesel does not pose a threat to human health.
- Biodiesel contains no sulfur or aromatics, and using biodiesel in a conventional diesel engine substantially reduces unburned hydrocarbons, carbon monoxide and particulate matter.
- the EPA has surveyed biodiesel emissions studies and compared them with the testing results obtained in major studies of conventional fuels. The results are shown in Table 2. Table 2
- Lubricity additives will have to be added to this new ultra-low sulfur diesel fuel to provide satisfactory protection for engines and high-pressure fuel injection equipment.
- Using biodiesel as a blending stock may help refineries meet future sulfur specifications. Biodiesel also has excellent lubricity characteristics and improves lubricity, even with a blend as low as 2% in conventional diesel fuel.
- Biodiesel has been produced in different ways, including microemulsification, pyrolysis and transesterification.
- Microemulsification forming a colloidal equilibrium dispersion of optically isotropic fluid microstructure with dimensions generally in the 1-150 nm range
- solvents such as methanol, ethanol and ionic or nonionic amphiphiles.
- Microemulsions form spontaneously from two normally immiscible liquids. Short term performances of both ionic and nonionic microemulsions of aqueous ethanol in soybean oil were found to be similar to # 2 diesel fuel, in spite of the lower cetane number and energy content. In longer term testing (200 hours), no significant deteriorations in performance were observed.
- Pyrolysis converts one substance into another using heat, or heat and a catalyst, typically in the absence of air or oxygen.
- SiO 2 and Al 2 O 3 are typical pyrolysis catalysts.
- Animal fats can be pyrolyzed to produce many smaller chain compounds, and fat pyrolysis has been investigated for over a hundred years, especially in regions that lack petroleum deposits.
- Thermal decomposition of triglycerides produces compounds of several classes, including alkanes, alkenes, alkadienes, carboxylic acids, aromatics and small amounts of gaseous products.
- Pyrolyzed oils are unacceptable in terms of ash content, carbon residues, and pour point. Additionally, oxygen removal during thermal processing eliminates any environmental benefits of using an oxygenated fuel.
- Transesterification also called alcoholysis
- Transesterification reaction is the reaction of a fat or oil with an alcohol to form esters and glycerol.
- the physical properties of chemicals related to the transesterification reaction are summarized in Table 3.
- Biodiesel also has been produced using supercritical methanol [350 0 C and 45 MPa] to produce methyl esters (biodiesel) by transesterification without using any catalyst.
- supercritical methanol 350 0 C and 45 MPa
- a study of rapeseed oil transesterification in supercritical methanol found that transesterification proceeds very effectively and produces the same methyl esters as those obtained in the conventional method using an alkali catalyst.
- the methyl ester yield in the supercritical methanol reaction is higher because the free fatty acids contained in crude oils and fat also are efficiently converted to methyl esters.
- a reaction temperature of 350 0 C and a methanol-to-rapeseed oil molar ratio of 42:1 produced the best reaction conditions.
- Increasing the reaction temperature increased ester conversion, but thermal degradation of hydrocarbons occured at a temperature above 400 0 C.
- Embodiments of a method for producing biodiesel are disclosed.
- One embodiment of the method comprise providing a microreactor, and then using the microreactor to produce biodiesel.
- Reactants suitable for producing biodiesel are flowed to the microreactor.
- the method may comprise flowing a first fluid comprising an alcohol and a second fluid comprising an oil to the microreactor.
- process steps such as purification of products produced, can be accomplished "on chip” using a microseparator, for example, or "off chip,” such as by using conventional purification techniques, such as precipitation, crystallization, distillation, chromatography, etc., and any and all combinations of such techniques.
- Alcohols useful for producing biodiesel typically, but not necessarily, are lower aliphatic alcohols, such as alcohols having 10 or fewer total carbon atoms and including alkyl, alkenyl or alkynyl alcohols. Specific examples of suitable alcohols include methanol, ethanol, propanol, butanol, amyl alcohol or combinations thereof. Suitable sources of oil products include soy, inedible tallow and grease, corn, edible tallow and lard, cotton, rapeseed, sunflower, canola, peanut, safflower, and combinations thereof.
- Catalysts can be used to facilitate biodiesel production.
- suitable catalysts include metals, such as Pt, Pd 5 Ag, Ni, Zn, Fe etc., metal oxides, such as FeO, Fe 2 Cb, Fe 3 O 4 , NiO, ZnO, SnO etc., metal hydroxides, metal carbonates, alcoholic metal oxides, alcoholic metal hydroxides, alcoholic metal carbonates, alkoxides, mineral acids and enzymes. Any and all combinations of such catalysts also can be used.
- Working embodiments typically used Group I metal hydroxides or alkoxides as catalysts, such as sodium or potassium hydroxides or alkoxides.
- the conditions used to produce biodiesel can vary.
- pressure and temperature both can be substantially ambient conditions, or can be elevated.
- the temperature useful for producing biodiesel according to disclosed embodiments typically varies from about ambient (e.g. about 25 0 C) to about the degradation temperature of either reactants or products, which typically is less than about 350 °C, more typically less than about 250 0 C.
- pressure can be substantially ambient, or can be substantially greater than ambient.
- Particular working embodiments for producing biodiesel also can be conducted at supercritical conditions, typically supercritical conditions relative to any alcohol component used. These conditions will vary, as will be understood by a person of ordinary skill in the art, based on the reactants used.
- Relative reactant amounts also can be varied, but reactants typically were used in at least a 3: 1 molar ratio of alcohol-to-oil, and more typically a larger excess of alcohol.
- the method may result in forming two phases.
- the method can include separating two phases produced by the reaction, such as by using a distillation process, a centrifugation process, or combinations thereof.
- Rj, R 2 and R 3 independently are fatty acids.
- Suitable fatty acids typically have carbon chain lengths ranging from at least as few as 10 carbon atoms to at least as many as 20 carbon atoms, and more typically chain lengths range from about 12 carbon atoms to about 18 carbon atoms.
- Examples of particular fatty acids include, without limitation, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid. These fatty acids can be saturated or unsaturated, and can include at least one site of unsaturation other than a carbon-carbon double bond.
- microreactors for the production of biodiesel.
- Various microreactor structures are suitable for making biodiesel according to the present invention, and the structures described herein are exemplary.
- microreactors can be used that vary the oil and alcohol fluid layer thicknesses, such as thicknesses that range from about 10 ⁇ m to about 500 ⁇ m.
- microreactors having microchannels with variable surface-to- volume ratios can be used, such as microchannels having surface-to-volume ratios that range from about 10,000 m 2 /m 3 to about 50,000 m 2 /m 3 .
- Microreactors having a single microchannel might be used to make biodiesel, but increasing output may require using (1) devices having plural microchannels, (2) plural microreactors, or (3) both.
- Typical working embodiments of microreactors had plural laminae with at least one lamina defining at least one microchannel for receiving fluid.
- Microreactors useful for producing biodiesel also can include a manifold, or manifolds, for distributing fluid flow to individual microchannels. Commercial implementations of the disclosed method likely will use plural microreactors to provide suitable quantities of biodiesel.
- Biodiesel can be blended with other materials.
- certain embodiments of the present invention include blending biodiesel produced by the method with petroleum-based products.
- the biodiesel produced by the method can be blended with greater than zero weight percent petroleum product to less than 100 weight percent petroleum product.
- a particular embodiment of the disclosed method for producing biodiesel comprises first providing a microreactor.
- a first fluid comprising a lower aliphatic alcohol is flowed to the microreactor, as is a second fluid comprising a triglyceride having a formula
- a reaction catalyst is then provided, such as an alcoholic solution comprising a reaction catalyst selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, alcoholic metal oxides, alcoholic metal hydroxides, alcoholic metal carbonates, alkoxides, mineral acids, enzymes, or combinations thereof.
- the microreactor is then used to produce biodiesel, which is blended with petroleum-based products in an amount greater than zero weight percent petroleum product to less than 100 weight percent petroleum product.
- working embodiments include using soybean oil, methanol or ethanol, and the method further comprises using a metal hydroxide catalyst, such as a metal hydroxide catalyst used in an amount of about 1.0 weight % of the soybean oil used for the transesterification reaction.
- Oil and alcohol fluids have been pumped to the microreactor using a pump volume flow rate ratio of oihalcohol of about 3.4, which resulted in a molar ratio of oil-to-alcohol of about 1 :7.2.
- Oil conversion to biodiesel typically increases with increasing mean microreactor residence time. So, for working embodiments that used a microchannel having a 100 ⁇ m thickness, soybean oil, and a transesterification processing temperature of about 25 0 C, conversion, of soybean oil to biodiesel ranged from about 12 % at about 0.4 MRT to about 91 % at 10 minutes MRT, and total methyl ester concentration ranged from about 0.3 mole/1 at about 0.4 minute MRT to about 2.5 moles/1 at about 10 minutes MRT.
- conversion of soybean oil to biodiesel ranged from about 4% at about an 0.4 MRT to about 86% at about 10 minutes MRT, and total methyl ester concentration ranged from about 0.1 mole/1 at about 0.43 minute MRT to about 2.4 moles/1 at about 10.6 minutes MRT.
- FIG. 1 is a schematic diagram of one embodiment of a microreactor used to produce biodiesel according to the present invention.
- FIG. 2 is an exploded schematic view of a microreactor used in working embodiments of a process for making biodiesel.
- FIG. 3 is a digital image showing a plate patterned to define microchannels and apertures for receiving fluid flow.
- FIG. 4 is a digital image showing plural plates of FIG. 3 positioned adjacent end plates used to construct a working embodiment of the present invention.
- FIG. 5 is a schematic perspective drawing illustrating positioning plural plates defining microchannels to collectively define one embodiment of a microreactor for producing biodiesel.
- FIG. 6 is digital image of a working embodiment of a system comprising a microreactor useful for making biodiesel according to the present invention.
- FIG. 7 is a digital image of one embodiment of a disassembled microreactor useful for making biodiesel according to the present invention adjacent a penny for size comparison.
- FIG. 8 is a digital image providing a front perspective view of one embodiment of a microreactor useful for making biodiesel according to the present invention adjacent a penny for size comparison.
- FIG. 9 is a digital image providing a perspective view of one embodiment of an end plate, adjacent a penny for size comparison, used in one embodiment of a microreactor useful for making biodiesel according to the present invention.
- FIG. 10 is a digital image providing a side perspective view of one embodiment of a microreactor useful for making biodiesel according to the present invention adjacent a penny for size comparison.
- FIG. 11 is a digital image providing a top perspective view of dual syringe pump used with one embodiment of a microreactor useful for making biodiesel according to the present invention.
- FIG. 12 is a schematic diagram illustrating methanol and soybean oil flow through a microchannel.
- FIG. 13 is a cross sectional schematic drawing illustrating a microchannel without a catalyst and a microchannel having catalyst disposed therein.
- FIG. 14 is a schematic cross sectional drawing illustrating a microchannel having two fluids flowing therethrough.
- FIG. 15 is a graph of fluid layer thickness (m) versus velocity (m/s) comparing fluid flow velocities of methanol and soybean oil in a microchannel.
- FIG. 16 is a graph of soybean oil conversion (%) versus mean microchannel residence time (minutes) using a microreactor having a 100 ⁇ m microchannel thickness.
- FIG. 17 is a graph of ester concentration (mol/1) versus mean microchannel residence time (minutes) using a microreactor having a 100 ⁇ m microchannel thickness.
- FIG. 18 is a graph of methyl ester concentration (mole/1) versus mean microchannel residence time (minutes) using a microreactor having a 100 ⁇ m microchannel thickness.
- FIG. 19 is a graph of soybean oil conversion (%) versus mean microchannel residence time (minutes) using a microreactor having a 200 ⁇ m microchannel thickness.
- FIG. 20 is a graph of methyl ester concentration (mole/1) versus mean microchannel residence time (minutes) using a microreactor having a 200 ⁇ m microchannel thickness.
- FIG. 21 is a graph of methyl ester concentration (mol/1) versus mean microchannel residence time (minutes) using a microreactor having a 200 ⁇ m microchannel thickness.
- FIG. 22 is a graph of soybean oil conversion (%) versus time (minutes) providing a survey of the work of othes, as reported by Noureddini & Zhu, (1997), showing that the conversion of soybean oil to methyl esters in a batch reactor is a reaction process with changing mechanisms reflected in a sigmoidal conversion curve for soybean oil conversion.
- FIG. 23 is a graph of soybean oil conversion (%) versus time (minutes) comparing batch reactors to microreactors.
- FIG. 24 is a graph of soybean oil conversion (%) versus time (minutes) comparing batch reactors to microreactors.
- FIG. 25 is a graph of soybean oil conversion (%) versus time (minutes) comparing microreactors having 100 ⁇ m and 200 ⁇ m microchannels.
- FIG. 26 is a graph of methyl ester concentration (mol/1) versus time (minutes) comparing microreactors having 100 ⁇ m and 200 ⁇ m microchannels.
- FIG. 27 is a graph of methyl ester concentration (mol/1) versus mean residence time (minutes) comparing microreactors having 100 ⁇ m and 200 ⁇ m microchannels.
- FIG. 28 is a graph of soybean oil conversion (%) versus mean residence time (minutes) comparing production results to modeling results for a 100 ⁇ m microchannel.
- FIG. 29 is a graph of soybean oil conversion (%) versus mean residence time (minutes) comparing production results to modeling results for a 200 ⁇ m microchannel.
- Biodiesel, Fats, Oils and Alcohols is defined as a mixture of mono alkyl esters of long chain fatty acids derived from renewable lipid sources.
- Fats and oils also referred to as triglycerides, are primarily water-insoluble, hydrophobic substances in the plant and animal kingdom comprising one mole of glycerol and three moles of fatty acids.
- Natural vegetable oils and animal fats are extracted or pressed to obtain crude oil or fat. These usually contain free fatty acids, phospholipids, sterols, water, odorants and other impurities. Even refined oils and fats may contain small amounts of free fatty acids and water.
- Vegetable oils generally are liquids at room temperature while fats typically are solids at room temperature because they contain a larger percentage of saturated fatty acids. Table 4 summarizes the fatty acid compositions found in common sources of vegetable oils and fat.
- Rj 3 R 2 and R 3 independently are fatty acids.
- Fatty acids vary in carbon chain length and in the number of sites of unsaturation.
- the fatty acids may have carbon chain lengths ranging from at least as low as 10 carbon atoms to at least 20 carbon atoms, and more typically about 12 carbon atoms, such as with lauric acid, up to at least 18 carbon atoms, such as with stearic, oleic, linoleic or linolenie acid.
- Sites of unsaturation typically are double bonds, although compounds having different sites of unsaturation, such as triple bonds, also potentially are useful fuel sources.
- Numerical indications used herein adjacent fatty acids, e.g. 18:2 for linoleic acid indicate the number of carbon atoms (18 in this example), and the number of sites of unsaturation (2, in this example).
- saturated fatty acids include, but are not limited to:
- oils and fats for use in biodiesel production are soy, inedible tallow and grease, corn, edible tallow and lard, cotton, sunflower, canola, peanut, rapeseed and safflower. Soy oil accounts for about 58% of the total oil and fat production, and is by far the largest available product for biodiesel production. Much of the research and promotion for biodiesel production has come from national and state soybean associations.
- Scheme 1 illustrates one embodiment of a method for making biodiesel according to the present invention. This embodiment involves transesterification of vegetable oil or animal fat with an alcohol. Transesterification can be accomplished according to the present invention using a microreactor and any suitable process, such as by using a catalyst or not, and/or using supercritical conditions, to yield glycerin and biodiesel according to Scheme 1.
- Scheme 1 illustrates one embodiment of a method for making biodiesel according to the present invention. This embodiment involves transesterification of vegetable oil or animal fat with an alcohol. Transesterification can be accomplished according to the present invention using a microreactor and any suitable process, such as by using a catalyst or not, and/or using supercritical conditions, to yield glycerin and biodiesel according to Scheme 1.
- Scheme 1 also illustrates the use of an alcohol, ROH, for transesterifi cation.
- Any alcohol suitable for performing the transesterification reaction can be used to practice embodiments of the present invention.
- the alcohol generally is a lower aliphatic alcohol, i.e. an alcohol having 10 or fewer total carbon atoms.
- R typically is a Cl-ClO aliphatic chain, more typically an alkyl, alkenyl and/or alkynyl group.
- suitable alcohols include, but are not limited to, methanol, ethanol, propanol, butanol and amyl alcohol. Methanol and ethanol are used most frequently.
- Ethanol is a useful alcohol, at least in part, because it is derived from agricultural products, is renewable and less environmentally objectionable than other commonly used alcohols.
- methanol is primarily used because of its low cost and its physical and chemical advantages (polar and shortest chain alcohol). Methanol quickly reacts with triglycerides, and typical catalysts, such as metal hydroxides, are more readily soluble in methanol than other alcohols.
- a catalyst may be used to improve the reaction rate and yield. Any suitable catalyst can be used. Exemplary classes and species of catalysts include metals, such as Pt, Pd 5 Ag 5 Ni, Zn 5 Fe etc.; metal oxides, such as FeO 5 Fe 2 Os, F ⁇ 3 ⁇ 4 , NiO 5 ZnO, SnO etc.; alkaholic metal hydroxides and carbonates, particularly methanolic or ethanolic NaOH or KOH; sodium and potassium alkoxides, such as sodium methoxide, which is more effective than sodium hydroxide, although sodium hydroxide is cheaper; zeolites; Lewis bases generally; acidic catalysts, such as sulfuric acid (H2SO 4 ); enzymatic catalysts; and combinations thereof.
- metals such as Pt, Pd 5 Ag 5 Ni, Zn 5 Fe etc.
- metal oxides such as FeO 5 Fe 2 Os, F ⁇ 3 ⁇ 4 , NiO 5 ZnO, SnO etc.
- alkaholic metal hydroxides and carbonates particularly
- alkali-catalyzed transesterif ⁇ cation proceeds approximately 4,000 times faster than that catalyzed by the same amount of an acidic catalyst; thus, alkali-catalyzed transesterification is a preferred embodiment.
- a triglyceride has a higher free fatty acid content (> 0.5 %) and more water, acid-catalyzed transesterification is preferred.
- the triglycerides and alcohol must be substantially anhydrous to avoid soap production, which lowers the yield of esters.
- separating ester and glycerol, and the water washing steps are performed with difficulties.
- the product stream of the transesterification reaction consists mainly of esters, glycerol and traces of alcohol, catalyst and tri-, di-, and monoglycerides.
- Transesterification can occur at different temperatures, depending on the oil. Typically, higher temperatures increase the reaction rate and yield of esters.
- the temperature at which the transesterification reaction is conducted can vary from at least as low as ambient (about 25 0 C) to at least as high as the degradation temperature of reactants and/or products, typically less than about 400 0 F, more typically less than about 350 0 F, and even more typically less than about 250 0 F, and any temperature within this range.
- Certain embodiments also can be conducted at supercritical conditions relative to the alcohol component.
- transesterification can be conducted using supercritical methanol at a temperature of about 350 0 C.
- pressure also can influence supercritical conditions, and further that there is a relationship between the temperature and pressure and whether a fluid is supercritical.
- the pressure can be at least as high as 45 MPa.
- the conditions resulting in supercritical fluid depend on the fluid itself. Hence if an alcohol other than methanol is used for supercritical fluid transesterification, then the supercritical conditions will be other than that stated for methanol to exemplify this process.
- Supercritical conditions can be determined by consulting a phase diagram for particular compounds.
- Microreactors are usually defined as miniaturized reaction vessels fabricated, at least partially, by methods of microtechnology and precision engineering.
- the characteristic dimensions of the internal structure of microreactor fluid channels can vary substantially, but typically range from the sub-micrometer to the sub-millimeter range.
- Microreactors most often are designed with microchannel architecture. These structures contain a large number of parallel channels, often with common inlet/outlet flow regions. Each microchannel is used to convert a small amount of material.
- Increased fluid throughput using microreactors is facilitated usually by a numbering-up approach, rather than by scale-up approach, although both numbering up and/or scale up processes can be used to increase throughput. Numbering-up guarantees that desired features of a basic unit remain unchanged when increasing the total system capacity.
- miniaturized systems designed with dimensions similar to microreactors, compared to a large-scale process include, but are not limited to: large-scale batch process can be replaced by a continuous flow process; smaller devices need less space, fewer materials, less energy and often shorter response times; cost per device can be kept low by parallel microfabrication and. automated assembly; and system performance is enhanced by decreasing the component size, which allows integration of a multitude of small functional elements.
- Smaller linear dimensions of microreactors increase the respective gradient for a given difference in some important physical properties in the chemical reactor such as temperature, concentration, density and pressure. Consequently, microreactors significantly intensify heat transfer, mass transport, and diffusional flux per unit volume or unit area.
- Typical thickness of the fluid layer in a microreactor can be set to few tens of micrometers (typically from about 10 to about 500 ⁇ m) in which diffusion plays a major role in the mass/heat transfer process. Due to a short diffusional distance, the time for a reactant molecule to diffuse through the interface to react with other molecular species is reduced to milliseconds and, in some cases, to nanoseconds. Therefore, the conversion rate is significantly enhanced and the chemical reaction process appears to be more efficient. Diffusion is no longer a rate determining step.
- microreactors include earlier production start at lower costs and safer operation; easier production scale-up; smaller plant size for distributed production; lower transportation, materials and energy costs; and more flexible response to market demands.
- FIG. 1 A particular working embodiment of a microreactor system 110 used to produce biodiesel according to the present invention is illustrated schematically in FIG. 1.
- System 110 includes a fluid delivery system 112 and a microreactor system 114.
- Certain working embodiments of the present invention used a dual syringe pump 116 for fluid delivery to microreactor system 1 14, such as mechanical syringe pump model 975 from Harvard Apparatus Company.
- This pump has a 30-speed mechanical gear box with a positive locking mechanism.
- the pump's syringe holder can hold either one or two syringes of any size from 5 milliliters to 100 milliliters.
- System 110 has been used to deliver an alcohol and soybean oil to microreactor system 114.
- a first syringe 118 typically a 10 milliliter syringe
- a second syringe 120 typically a 60 milliliter syringe
- Alcohol was delivered by syringe 118 to the microreactor system 114 through a fluid conduit 122 having an in-line stop valve 124.
- soybean oil was delivered by syringe 120 to the microreactor system 114 through a fluid conduit 126 having an in-line stop valve 128.
- the illustrated microreactor 110 had three channels in a rectangular cross section — one 100 mm wide by 0.8 mm deep, another 100 mm wide by 1.7 mm deep, and the third 135 mm wide by 135 mm deep. Alcohol and soybean oil were mixed in the microreactor for varying mean residence times, as discussed further below in the working examples. Transesterif ⁇ cation produced biodiesel and glycerol, collected in cold trap 132, which allowed effective separation of the two phases.
- FIG. 2 is a schematic, exploded view of one embodiment of a microreactor 210 used in working embodiments of the present invention for making biodiesel. FIG. 2 also illustrates that the microreactors typically are assembled using plural laminae that, when appropriately assembled, collectively define the working microreactor.
- microreactor 210 includes a front plate 212 and a back plate 214.
- Working embodiments of plates 212 and 214 were sealed liquid cells (model SL-3) having two 304 stainless steel plates (front plate 212 and back plate 214). Plates 212 and 214 allow accurate visual alignment of the other cell (microreactor) components.
- Each plate 212, 214 has an inlet 216a (inlet 216b of plate 214 is not shown) and an outlet 218a, 218b having lure type connectors.
- Microreactor 210 also includes two gaskets 40 and 42.
- a working embodiment of microreactor 210 included two viton gaskets 220, 222, each 38.5 x 19.5 x 4 mm. Gaskets 220 and 222 cushion and form seals with metal and optic components.
- Microreactor 210 also includes two optic windows 224 and 226.
- a working embodiment of microreactor 210 included two polished crystal optics (CAF2), each 38.5 x 19.5 x 4 mm, which serve as windows.
- CAF2 polished crystal optics
- Microreactor 210 also includes spacers 228 and 230.
- a working embodiment included two teflon spacers, each 38.5 x 19.5 mm.
- Each spacer 228, 230 had different thicknesses (50 ⁇ m or 100 ⁇ m each).
- Spacers 228, 230 create space between windows 220, 224 of the microreactor 210 for the reactant liquids and to enable assembly of microreactor 210 with accurate pathlengths.
- FIGS. 3-6 are digital images illustrating microchannels formed in individual lamina.
- FIG. 3 is an end perspective view of a single lamina 300 having plural microchannels 302 extending axially along the long axis of the lamina.
- Plural fluid ports 304 also are illustrated, with each microchannel 302 having a fluid port through which fluid, such as an alcohol or an oil, flows for reaction in the microreactor 300.
- FIG. 4 is a digital image illustrating a dissembled view of a microreactor 400 comprising plural laminae 402, each of which defines plural fluid microchannels 404 and plural fluid ports 406 for delivering fluid to the microchannels, as described for the single lamina illustrated by FIG. 3.
- FIG. 4 also indicates that plural such laminae can be used, each having the same microfeatures, so that increased fluid throughput, and hence increased biodiesel production, is realized by a numbering up approach, as opposed to a feature-size scale up approach.
- FIG. 4 also illustrates two end plates 408, 410 positioned adjacent the plural microchannel laminae 402. The two end plates 408, 410 also include a manifold portion 412 formed therein for distributing fluid flow to the individual microchannels 404.
- FIG. 5 is a schematic perspective exploded view illustrating positioning plural laminae, each defining microchannels, to collectively define one embodiment of a microreactor 510 for producing biodiesel as with the embodiment of FIG. 4.
- Microreactor 510 includes end plates 512 and 514, and plural laminae 516, 518, 520, 522 and 524, each defining plural microchannels.
- Microreactor 510 also includes plural manifolds, such as manifolds 526 and 528 for end plate 512, and manifolds 530 and 532 in end plate 514. Fluids enter and exit the manifolds through fluid ports. For example, fluids may enter or exit manifold 532 through fluid port 534.
- FIGS. 6-12 are digital images of working embodiments of microreactor systems useful for making biodiesel according to the present invention.
- microreactors suitable for biodiesel synthesis can operate with and without solid catalysts.
- the reaction conditions can be operated either under subcritical or supercritical operating conditions.
- the reaction also can be accomplished using co- solvents.
- microreactors can be used that operate at supercritical conditions with addition of a cosolvent.
- a suitable cosolvent for supercritical conditions is CO 2 .
- CO 2 is added as co-solvent to mediate the temperature and/or pressure of the reaction mixture, whereas the supercritical conditions otherwise are determined by the alcohol component used in the reaction mixture.
- FIG. 13 illustrates a first microchannel 1300 and a second microchannel
- MicroChannel 1302 having a single phase reaction mixture 1304, either under subcritical or supercritical conditions, therein.
- MicroChannel 1300 does not include a catalyst.
- microchannel 1302 does include a catalyst 1305 positioned effectively for catalyzing the production of biodiesel.
- MicroChannel 1302 includes both a first wall 1306 and a second wall 1308.
- the illustrated embodiment includes catalyst 1305 associated with both walls.
- the catalyst 1305 may be deposited at the reactor walls for use in subcritical or supercrital operating conditions.
- the illustrated embodiment of microchannel 1302 has catalyst substantially uniformly distributed along the length of walls 1306, 1308. A person of ordinary skill in the art will appreciate that it may not be necessary to have catalyst associated with both walls of a microchannel, nor that the catalyst be substantially uniformly distributed on a wall, or walls.
- Oil and alcohol are hydrophobic/hydrophilic respectively to each other and are immiscible for all practical purposes.
- One way to control the interface between oil and alcohol in a reaction mixture is to use inserts that have a relative small size, such as from about 20 ⁇ m to about 60 ⁇ m thick with micrometer size openings.
- This interface material can be made from a variety of materials, such as polymers, metals, and combinations thereof. Wicking material, woven fabrics or otherwise mashed fiber-like materials also can be used for this purpose. Without being limited to a theory of operation, such interface materials use natural surface tension effects to create a stable interface.
- FIG. 14 is a schematic drawing of a microchannel 1400.
- MicroChannel 1400 has a first oil phase 1402 and a second alcohol phase 1404 flowing therethrough.
- MicroChannel 1400 also includes an interface supporting material 1406.
- Interface mesh 1406 can also serve as a substrate for solid catalyst.
- Mesh material for example metals, with stainless steel being one example, can be coated with solid catalyst materials, such as catalysts particularly useful for supporting biodiesel synthesis. These materials typically are used as relatively small particles, such as nanometer-scale particles. Also the mesh material may have nanoparticles incorporated into its structure even before the mesh is produced.
- FIG. 15 illustrates the velocity profile of the two immiscible reactants, such as methanol and soybean oil, in a microchannel.
- the thickness of each fluid layer depends on the volumetric ratio and the ratio of viscosities of the two substances.
- the thickness of the oil layer may be important for modeling and for determining process rate.
- B a 168.75 *10 '6 m (168.75 ⁇ m)
- B b 31.25 * 10 "6 m (31.25 ⁇ m).
- This example concerns transesterification of soybean oil at room temperature (25 0 C) and at atmospheric pressure using a working embodiment of a microreactor as described above.
- a 10-milHliter syringe was filled with a stock solution comprising dried sodium hydroxide dissolved in 10 milliliters of methanol.
- Two steps were required to prepare a stock solution of methanolic sodium hydroxide (NaOH).
- NaOH methanolic sodium hydroxide
- the amount of NaOH used for transesterification represented 1.0 wt% of the soybean oil used for the transesterification reaction.
- the amount of sodium hydroxide to be used was calculated according to the following formula:
- NaOH amount (g) 1% * volume of soybean oil in 60 milliliter syringe * sp gr.
- the molar ratio of soybean oil/methanol provided by using a 60 milliliter syringe and a 10 milliliter syringe was 1:7.2. Both the 10-milliliter and the 60-milliliter syringes were installed in the syringe pump.
- the syringe pump delivered the two solutions to the microreactor at a constant volumetric flow rate ratio of soybean oil-to-methanol of 3.4:1, which corresponds to the calculated 1 :7.2 soybean oil/alcohol molar ratio.
- Six syringe pump flow positions were used. Flow position numbers 20, 22, 24, 26, 28 and 30 were used for the 100 ⁇ m ⁇ -channel thickness.
- Fluids from both syringes were pumped into a microreactor ⁇ -channel, where they formed two layers with different thicknesses as shown in the soybean oil/methanol laminar velocity profile, FIG. 15.
- the layer thicknesses of the soybean oil and methanol inside the microreactor were determined by their viscosities and flow rate ratios as calculated above.
- the microreactor reaction channel dimensions were 2.33 cm length, 1.05 cm width, and 100 or 200 ⁇ m in height, depending on the spacer thickness used. Fluid flowed out of the microreactor as a two-phase stream and was collected in a cold trap (0 C), mainly to stop any further reaction in the test tube. The two phases in the test tube were further separated by centrifuge.
- methyl ester standards Five compounds were used as methyl ester standards: methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, and methyl linolenate. These standards were used to identify biodiesel (methyl ester) peaks in the recorded chrornatographs. Identifications were established by comparing retention times of both reference standards with eluted sample peaks. The biodiesel peaks were eluted in the following retention times: methyl palmitate (9 minutes), methyl stearate (16.3 minutes), methyl oleate (17.5 minutes), methyl linoleate (20.5 minutes), methyl linolenate (25.3 minutes).
- each methyl ester standard Five methyl ester concentrations were prepared from standard methyl ester samples having a minimum purity of 99%. 5 ⁇ l or equivalent weight from each methyl ester standard was diluted into 6,000 ⁇ l of hexane to give a 0.000833 ⁇ l mole ester/ ⁇ l hexane concentration. These five methyl ester standards were analyzed in the GC twice, before and after running the biodiesel samples, to check for any inconsistencies or shifts over the duration of the analysis. The differences in the GC standard areas for both runs (before and after analyzing the experimental samples) ranged from 1% to 4.7%. The RRF (concentration over GC standard area) for each methyl ester standard was calculated and was used to determine the corresponding methyl ester concentration in the biodiesel phase. RRFs are provided below in Table 7.
- RRFs Methyl Ester Relative Response Factors
- the overall transesterif ⁇ cation reaction showed that three moles of methyl esters were obtained for each soybean oil (triglyceride) milliliter reacted.
- soybean oil triglyceride
- soybean oil moles entered in the reaction at each MRT 77.27 % of the total product sample volume (biodiesel phase + glycerol phase) was assumed to be originally soybean oil and the rest to be methanol. This assumption was based on the syringes' flow rate volume ratio of soybean oil-to-methanol, which was 3.4:1 or 77.27%:22.72%.
- the conversion of soybean oil in the transesterification reaction was calculated by dividing the reacted soybean oil by the soybean oil which entered the reaction.
- Example 2 This example concerns biodiesel production using a microreaction process, and one embodiment of a microreactor having an adjustable ⁇ -channel thickness (100 ⁇ m or 200 ⁇ m) as previously described.
- a microreactor having an adjustable ⁇ -channel thickness 100 ⁇ m or 200 ⁇ m
- two sets of soybean oil transesterification procedures were performed in the microreactor.
- a first production run used a microreactor having a 100 ⁇ m ⁇ -channel thickness (spacers) and the other run was with a 200 ⁇ m ⁇ -channel thickness (spacers). This was done to assess the effect of ⁇ -channel thickness on biodiesel production.
- a 10-milliliter syringe was filled with a stock solution of dried sodium hydroxide dissolved in methanol.
- Another 60-milliliter syringe was filled with 34 milliliters of soybean oil.
- the syringe pump delivered the two solutions from both syringes to the microreactor at a constant volumetric flow rate ratio.
- the ratio of the flow rates of soybean oil to methanol was 3.4:1 which corresponds to a 1:7.2 molar ratio.
- the reaction products flowed from the microreactor in two phases: a biodiesel phase and a glycerol phase. Both phases were collected in a single container. Part of the biodiesel phase was diluted and injected into the GC to obtain peak records of the methyl esters. Using the methyl esters standards, the recorded chromatographic values were converted into methyl esters concentrations at different MRT.
- FIG. 16 shows that soybean oil conversion increases with MRT. Soybean oil conversion ranges from 12.33 % at 0.41 MRT to 91.1% at 10 minutes MRT. Remaining unconverted reactant is not pure soybean oil but it instead contains some intermediate reactants, such as diglycerides and monoglycerides. However, the remaining percentage was considered to be pure soybean oil due to lack of an analytical method useful for measuring the concentrations of these intermediates. Therefore, the conversions of soybean oil in reality may be higher than stated.
- FIG. 17 provides the total methyl ester concentration as a function of MRT.
- the methyl esters concentration ranges from 0.355 mol/1 at 0.41 minute MRT to 2.56 moles/1 at 10 minutes MRT.
- FIG. 18 shows individual methyl ester concentrations at different MRTs. The differences in the concentration of each methyl ester at a given MRT depend on the original composition of fatty acids in the soybean oil.
- volumetric flow rates (0.107, 0.0559, 0.02915, 0.01363, 0.00760 and 0.004328 milliliter/min) were used. These volumetric flow rates corresponded to MRTs of 0.43, 0.82, 1.58, 3.37, 6.05 and 10.63 min. Each production run corresponds to one MRT.
- FIG. 19 shows that soybean oil conversion increases with the MRT.
- the soybean oil conversion ranged from 4.75 % at 0.43 MRT to 86.36% at 10.63 minutes MRT.
- FIG. 20 shows that the total methyl esters concentration is a function of MRT.
- the methyl esters concentration ranges from 0.136 mol/1 at 0.43 minute MRT to 2.45 moles/1 at 10.63 minutes MRT.
- FIG. 21 shows individual methyl ester concentrations at different MRTs.
- the transesterification reaction process in the batch reactor clearly exhibits three different rates: a) an initial mass-transfer-controlled region (slow rate) followed by b) a kinetically controlled region (fast rate) and c) a final slow region when equilibrium is approached.
- soybean oil and methanol are not miscible and form two liquid phases upon their initial introduction into the reactor.
- the reaction process is diffusion-controlled. Slowly diffusing reactants in two different phases results in a slow reaction rate.
- Mechanical mixing increases the contact between the reactants, resulting in an increase in the mass transfer rate.
- the duration of the slow rate region decreases as the mixing intensity increases. The mixing effect is most significant during the slow rate region of the reaction. As a single phase is established, increased mixing intensity becomes insignificant and the reaction rate primarily is influenced by the reaction temperature.
- One benefit of using a microreactor for producing biodiesel is the mass transfer intensification. Eliminating the mass transfer-controlled regime in the transesterification reaction process is one of the main reasons for applying microreactor technology to biodiesel production. Setting the thickness of soybean oil and methanol layers in a microreactor to a few tens of micrometers (100 ⁇ m and 200 ⁇ m in disclosed working embodiments) allows diffusion to play a major role in the mass transfer-controlled region. Because there is a short diffusion distance, the time required for a reactant molecule to diffuse through the interface to react with other molecular species is reduced to seconds and in some cases to milliseconds. The conversion rate therefore is significantly enhanced and the transesterification reaction process appears to be more efficient.
- FIGS. 23 and 24 compare the soybean oil conversions obtained in a microreactor (100 ⁇ m and 200 ⁇ m; 25 0 C) and the conversions obtained in a batch reactor (30 0 C, 50 0 C and 70 0 C) as reported by Noureddini & Zhu, 1997. Noureddini, H. (University of Kansas); Zhu, D. Kinetics of transesterification of soybean oil, JAOCS, Journal of the American Oil Chemists' Society, V. 74, n i l, Nov, 1997, p 1457-1463. In the batch reactor, 90% conversion is achieved after 90 minutes at 70 0 C.
- FIGS. 25 and 26 show these process improvements.
- the soybean oil conversion increases from 86% to 91% and total methyl esters concentrations increase from 2.45 to 2.59 moles/1.
- FIG. 27 shows the increase in concentrations for each methyl ester between 100 ⁇ m and 200 ⁇ m. Again, this emphasizes the advantage of the microreaction process in processes requiring mechanical mixing to improve mass transfer.
- the microreactor process is faster than processes performed in conventional reactors if mass transfer is an important step in the chemical process rate.
- the characteristic diffusion length may be reduced to a size that is often much smaller than the characteristic droplet size attained in a conventional mixing.
- the characteristic diffusion length is approximately 100 ⁇ m, which is the thickness of the film obtained in the microreactor.
- this diffusion length is maintained approximately uniformly throughout the reactor, and it is achieved without mixing or power consumption.
- the microreactor type used for certain working embodiments may be used to predict soybean oil conversion and biodiesel concentration under a variety of operating conditions.
- microreactors can be used to produce biodiesel, such as by transesterification of soybean oil.
- Reducing microreactor ( ⁇ -channel) thickness from 200 ⁇ m to 100 ⁇ m improved the overall process performance.
- a 91% soybean oil conversion (2.59 moles/1 biodiesel concentration) was achieved.
- an 86% conversion (2.45 moles/1 biodiesel concentration) was achieved.
- microreactor residence time based on the oil phase since it had higher flow rate than methanol. Residence time was calculated according to the following equation: microreactor chanal volume (cm 3 )
- the microreactor channel area includes a rectangular area and a triangle area.
- Table 9 provides the residence time for a 100 ⁇ m microreactor thickness.
- Methyl ester ratio factors were determined using the following formula:
- each methyl ester was multiplied by 4,000 ⁇ l of hexane to determine the concentration in a 5 ⁇ l biodiesel sample.
- the moles of each methyl ester were calculated in 5 ⁇ l followed by calculating the moles of each methyl ester in the biodiesel phase of the sample.
- the reacted soy bean oil was calculated by dividing the total moles of methyl esters in the biodiesel phase by three.
- the soybean oil moles entered in the reaction was calculated by assuming 77.27 % of the total products sample volume (biodiesel phase + glycerol phase) was originally soybean oil and the rest was methanol. This assumption was based on the syringe flow rate volume ratio of soybean oil to methanol, which is 3.4: 1 or 77.27%:22.72%.
- the percent conversion of soybean oil in the transesterification reaction was calculated by dividing the amount of soybean oil reacted by the soybean oil entering the reaction.
- Table 12 provides the areas of methyl esters sample analysis, 100 ⁇ m thickness, with a 1- minute mean residence time. Table 12
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Also Published As
Publication number | Publication date |
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EP2021438A4 (en) | 2010-09-29 |
WO2007142983A2 (en) | 2007-12-13 |
US20090165366A1 (en) | 2009-07-02 |
WO2007142983A3 (en) | 2008-01-24 |
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