US20060162245A1 - Microwave-enhanced process to maximize biodiesel production capacity - Google Patents
Microwave-enhanced process to maximize biodiesel production capacity Download PDFInfo
- Publication number
- US20060162245A1 US20060162245A1 US11/340,137 US34013706A US2006162245A1 US 20060162245 A1 US20060162245 A1 US 20060162245A1 US 34013706 A US34013706 A US 34013706A US 2006162245 A1 US2006162245 A1 US 2006162245A1
- Authority
- US
- United States
- Prior art keywords
- mixture
- biodiesel
- separation
- triglyceride
- biodiesel product
- 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.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- the present invention relates to an improved process for preparing biodiesel fuels wherein the feed stock preparation, reaction, and separation steps of the process are preceded by directing of radio frequency microwave energy into the mixtures prior to reacting and separating such mixtures to recover upgraded feed stocks and biodiesel products.
- Transesterification of triglycerides is a reaction that has been known for decades and has been practiced almost as long for the production of biodiesel fuels and fuel additives.
- the reaction uses feed stocks that contain triglycerides, such as various vegetable oils, rapeseed oil, soy oil, and even waste animal fats and cooking greases.
- the feed stocks In the case of waste fats and greases, the feed stocks must typically be pretreated in order to lower their free fatty acid (FFA) content.
- FFA free fatty acid
- the processes described in the art state an FFA limitation of less than 1% and carry out the reaction at temperatures up to 100° C. and pressures up to 10 bars.
- the reader is referred to U.S. Pat. Nos. 5,514,820, 5,578,090, and 6,174,501, for example.
- Triglycerides and their compositions are similarly described in U.S. Pat. No. 5,578,090, for example.
- the processes used in the art for the production of biodiesel fuels and fuel additives generally involve reacting a triglyceride with an alcohol, particularly a lower alcohol such as a C 1 -C 6 alcohol, more particularly methanol or ethanol.
- a catalyst for example, an alkaline catalyst such as potassium hydroxide or sodium hydroxide, these processes produce a fatty acid alkyl ester, glycerin, and unreacted alcohol in the reaction mixture.
- separation is required, often by settling, in order to remove the glycerin and the alcohol.
- Settling is typically performed in a settling tank, with the top phase of the reaction mixture being the biodiesel product.
- the biodiesel product is thereafter recovered (e.g., decanted) from the reaction mixture and is usually washed with water or an acid in order to neutralize any remaining catalyst.
- a separation is again required after the washing and is usually performed either in another settling tank, a static separator, or a centrifuge. Centrifuges are often used since separation in a static separator is imprecise and often incomplete.
- the present invention is an improvement over existing transesterification processes generally described above and in the prior art patents referred to previously.
- the improvement involves applying radio frequency microwave energy to the reaction mixture, including pre-preparation of suitable triglyceride-containing feed stocks, prior to the reaction and/or the separation step.
- the separation may then be performed using simple settling, centrifuging, or any other suitable technique for separating immiscible liquids.
- Application of radio frequency microwave energy allows the use of high FFA content feed stocks, including animal fats and used cooking oils, in existing transesterification processes by promoting the removal of the fatty acid.
- Application of radio frequency microwave energy also enhances the reaction rate for the conversion of triglycerides to biodiesel, and also drives the reaction equilibrium toward the production of biodiesel.
- radio frequency microwave energy further improves product recovery in the separation of the biodiesel product from alcohol and glycerin in the reaction mixture.
- application of radio frequency microwave energy to the reaction mixture before the separation of the wash water or acid solutions helps speed up the separation process and improves the yields.
- directing radio frequency microwave energy into the reaction mixture prior to at least one feed stock preparation, reaction, or separation step of the transesterification process may enhance the product yield and recovery, and directing radio frequency microwave energy into the reaction mixture prior to each feed stock preparation, reaction, and separation step may maximize the product yield, recovery, and overall biodiesel production capacity compared to a similar process without using radio frequency microwave energy.
- FIG. 1 and FIG. 2 are schematic flow sheets showing an arrangement of various elements and steps of the transesterification process according to embodiments of the invention.
- Biodiesel fuel or fuel additive is produced by subjecting a suitable triglyceride-containing feed stock (e.g., soy oil, virgin vegetable oil, used cooking oils, animal oils and other suitable triglyceride-containing feed stocks) to known transesterification or methyl- or ethyl-esterification processes.
- a suitable triglyceride-containing feed stock e.g., soy oil, virgin vegetable oil, used cooking oils, animal oils and other suitable triglyceride-containing feed stocks
- the processes result in an effluent stream of esterified triglycerides, also referred to as fatty acid esters, or esterified biodiesel product, and crude glycerol, where glycerol is a term that refers to a mixture of glycerin reaction byproduct and unreacted alcohol.
- Production capacity for producing biodiesel can be limited by separation processes because the crude glycerol is inherently insoluble in the esterified biodiesel product. Furthermore, the biodiesel is often washed with water (or an acid) to neutralize residual catalysts and remove impurities, forming a biodiesel/water emulsion. Gravity separation of the crude glycerol from the biodiesel and subsequently the biodiesel from the wash water causes the process to function as a semi-batch process, which constrains use of other process equipment and limits throughput for the entire system.
- Production yields of biodiesel can also be constrained by the reaction rate for converting triglycerides to the esterifed biodiesel product, and by the reaction equilibrium that constrains how much of the triglyceride will be converted to esterified biodiesel product.
- feeds that contain high levels of free fatty acids are particularly desirable because of their low cost and availability.
- FFA free fatty acids
- Embodiments of the invention provide a way to mitigate or overcome the above limitations by applying radio frequency microwave energy to the feed stocks, reactants, or product mixtures to be separated.
- the unique characteristics of radio frequency microwave energy specifically, the establishment of rapidly oscillating electric and magnetic fields that selectively energize strongly polar and strongly charged molecules relative to non-polar and neutral, or less polar and less charged, molecules—allow microwaves to facilitate certain physical and/or chemical reactions that are favorable to the biodiesel production process.
- Embodiments of the invention take advantage of the above-mentioned unique characteristics of radio frequency microwave energy to improve the biodiesel production process.
- the radio frequency microwave energy may be used to reduce the FFA content of high FFA triglyceride-containing feed stocks, such as animal fats and used cooking oils, by enhancing the conversion of free fatty acids and by enhancing the separation of the lower FFA triglyceride-containing feed stock from the treatment byproducts.
- radio frequency microwave energy may be used to enhance the rate of the transesterification reaction and the yield of biodiesel product.
- the radio frequency microwave energy helps drive the reaction to completion and facilitates separation of glycerin and unreacted alcohol (or glycerol) from other reaction products and intermediates, primarily biodiesel product composed of a blend of fatty acid esters and trace impurities.
- the radio frequency microwave energy may also be used to facilitate separation of both the biodiesel product from the glycerin byproduct and unreacted alcohol, and the biodiesel product from wash water or other washing agents that are used to neutralize and remove the trace impurities and any residual catalysts.
- Embodiments of the invention also provide a novel process and hardware for achieving the above benefits.
- microwave and radio frequency microwave energy refer to energy having a wavelength in the range of about 0.005 to 0.5 meters, although those having ordinary skill in the art will understand that higher or lower wavelength energy may also be used without departing from the scope of the invention.
- microwave and “radio frequency microwave energy,” as used herein, refer to energy having a wavelength in the range of about 0.005 to 0.5 meters, although those having ordinary skill in the art will understand that higher or lower wavelength energy may also be used without departing from the scope of the invention.
- temperature, residence time, flow rate, weight percentage, volume percentage, ratio, and so forth those having ordinary skill in the art will recognize that other values and ranges may also be used without departing from the scope of the invention.
- FIG. 1 shows a flow sheet 100 for a processing plant for operating a methyl-esterification process according to one embodiment of the invention.
- the triglyceride-containing feed stock is delivered from a raw feed tank 102 and mixed intensively with methanol and catalyst from a mix tank 104 .
- the reaction may take place in one or more mixers 106 , such as one or more static mixers, tube reactors, one or more heated, continuously stirred tank reactors, and the like.
- the reaction may occur at a temperature from about 20° to about 90° Celsius (C.) and a pressure from about 1 to about 200 atmospheres.
- the mole ratio of methanol to triglyceride-containing feed stock may be from about 1:1 to about 10:1.
- the flow rate of the reaction mixture may be from about 3 to about 120 gallons per minute (gpm).
- the reaction mixture then enters a microwave separation technology (MST) unit 108 where radio frequency microwave energy is applied to the reaction mixture.
- MST microwave separation technology
- Any suitable MST may be used for the reaction-driving MST unit 108 , including the MST shown and described in U.S. Pat. Nos. 5,914,014; 6,077,400; and 6,086,830, which patents are hereby incorporated by reference.
- the residence time in the reaction-driving MST unit 108 may be from about 0.2 to about 2 minutes, which should be sufficient to increase the temperature of the reaction mixture by about 50 to about 60° Fahrenheit (F.).
- reaction mixture may optionally proceed to a reaction mixture separation device 110 .
- the reaction mixture separation device 110 which may be any suitable separation device known to those having ordinary skill in the art, separates the reaction mixture into its constituent phases, glycerin plus unreacted alcohol, referred to as glycerol, and biodiesel product.
- Glycerol is the lower phase and is thereafter transferred to a glycerol methanol recovery unit 112 .
- the glycerol methanol recovery unit 112 separates the glycerol into glycerin and methanol and recycles the methanol for use in catalyst mix tank 104 . In some embodiments, however, it may not be desirable to recycle the methanol, depending on the particulars of the application. Indeed, in some embodiments, ethanol, propanol or any carbon chain length alcohol may be used instead of methanol.
- Biodiesel product which is the upper phase, is then mixed with wash water from a wash water tank 114 (and is sometimes acid neutralized) to produce a biodiesel product/wash water mixture.
- Mixing may be performed in one or more mixers 116 , such as one or more static mixers, one or more heated, continuously stirred tank reactors, and the like.
- the mixing may occur at a temperature from about 15 to about 80° C. and a pressure from about 1 to about 5 atmospheres.
- the flow rate of the biodiesel product/wash water mixture may be from about 3 to about 120 gallons per minute.
- the biodiesel product/wash water mixture is then transferred to another MST unit 118 where radio frequency microwave energy is applied to the mixture. Application of radio frequency microwave energy at this point assists in the subsequent separation of the biodiesel product/wash water mixture into its constituent phases, water and biodiesel product.
- the lower phase water may then be recycled to the wash water tank 114 , while the upper phase biodiesel product may be recovered.
- the water-washing MST unit 118 may be of a type similar to the reaction-driving MST unit 108 , although any suitable MST may be used without departing from the scope of the invention.
- the residence time in the water-washing MST 118 may be from about 0.2 to about 2 minutes, resulting in a temperature increase of the mixture by about 5° to about 60° F.
- one or more reactor units may be inserted into the process shown in FIG. 1 to further drive the transesterification reaction and/or improve the separation of the biodiesel product.
- a reactor unit may be inserted into the process of FIG. 1 between the mixer 106 and the reaction-driving MST unit 108 to provide additional reaction time before separating the biodiesel product from the glycerin.
- the reactor unit may be any suitable reactor unit known to those having ordinary skill in the art, including one or more static mixers, tube reactors, one or more heated, continuously stirred tank reactors, and the like.
- the reactor unit may be inserted into the process between the reaction-driving MST unit 108 and the reaction mixture separation device 110 to help drive the transesterification reaction.
- the reactor unit may be inserted into the process between the reaction-driving MST unit 108 and the reaction mixture separation device 110 to help drive the transesterification reaction.
- another MST unit between the reactor unit and the reaction mixture separation device 110 in order to both drive the reaction and improve the separation.
- the reaction-driving MST unit 108 and the water-washing MST unit 118 may include a radio frequency microwave energy applicator.
- the radio frequency microwave energy applicator may be used to direct radio frequency microwave energy into a chamber through which the mixture to be treated (i.e., high FFA feed stock, reaction mixture, biodiesel/glycerin mixture, or biodiesel/wash water mixture) passes.
- the radio frequency microwave energy is preferably reflected into one or more radio frequency terminal cavities, for example, by means of angled reflector plates located at the terminal end of a rectangular waveguide.
- the waveguide terminal reflector plates are sized and angled to minimize radio frequency losses and to prevent reflected energy from returning to and damaging the radio frequency transmitter.
- Low loss, radio frequency-transparent, flat plate windows may be used to prevent intrusion of the mixture into the waveguide.
- the mixture to be treated is then flowed through the chamber, preferably upward against gravity to prevent entrained solids from becoming trapped within the applicator cavities.
- the reentrant chamber dimensions may closely match the microwave standing wave patterns, based on the dielectric nature of the feed mixture flowing through the chamber.
- a three port circulator may be placed within the transmission path between the transmitter and the radio frequency microwave applicator to divert any reflected radio frequency microwave energy to a water-cooled dummy load.
- the inlet and outlet temperatures of the reaction-driving MST unit 108 and the water-washing MST unit 118 are monitored and the flow rate of the feed stock is controlled to maintain optimal residence times and exit temperatures. This helps ensure an optimum reaction performance and separation of the mixture components.
- An optimum temperature differential of the feed stock between the inlets and outlets of the microwave chamber may be fed back to the pump feed rate controller. Pumping rate may then be changed to maintain the proper temperature difference for optimum treatment.
- the temperature differential of the reaction-driving MST unit 108 between the inlets and outlets of the microwave chamber is from about 5° to about 60° F.
- the temperature differential of the water-washing MST unit 118 between the inlets and outlets of the microwave cavities is preferably from about 5° to about 60° F.
- Those having ordinary skill in the art may of course adjust the mixture flow rate or the intensity of the radio frequency microwave energy as needed to obtain the optimum operating parameters for each specific process.
- one or both of the MST units 108 and 118 may comprise a stand-alone microwave application system that is separate from the separation devices 110 and 120 . In other embodiments, however, one or both of the MST units 108 and 118 may be a microwave application system that also includes a separation device.
- the separation device may be any suitable separation device known to those having ordinary skill in the art, including gravity or mechanically enhanced devices (e.g., centrifuge, hydrocyclone, tank, etc.), or other commercially available separation devices. It is believed that the techniques for combining the MST and separation device into a single unit are well within the knowledge of those having ordinary skill in the art and is therefore not described here.
- Application of the MST units 108 and 118 whether alone or in combination with a separation device, helps make it possible to operate many biodiesel production plants in a continuous operation that can significantly enhance biodiesel production capacity.
- FIG. 2 shows a flow sheet 200 according to some embodiments of the invention where radio frequency microwave energy is used to enhance the reduction of free fatty acids in high FFA triglyceride-containing feed stocks, thereby making these feed stocks more suitable for biodiesel production.
- the high FFA triglyceride-containing feed stock is delivered from a raw feed tank 202 and mixed intensively with a carbonate or bicarbonate or other suitable reactant from a mix tank 204 .
- the reaction may take place in one or more mixers 206 , such as one or more static mixers, tube reactors, one or more heated, continuously stirred tank reactors, and the like. In some embodiments, the reaction may occur at a temperature from about 20° to about 100° C.
- the volume ratio of reactant to high FFA triglyceride-containing feed stock may be from about 0.1:1 to about 10:1.
- the flow rate of the reaction mixture may be from about 3 to about 120 gallons per minute.
- the high FFA reaction mixture then enters an MST unit 208 where radio frequency microwave energy is applied to the high FFA reaction mixture.
- Application of radio frequency microwave energy drives the reduction in FFA and enhances the separability of the resulting lower FFA triglyceride-containing feed stock and the byproduct waste emulsion.
- Any suitable MST may be used for the FFA-reducing MST unit 208 , including the MST shown and described in U.S. Pat. Nos. 5,914,014; 6,077,400; and 6,086,830 (incorporated previously by reference).
- the residence time in the FFA reducing MST unit 208 may be from about 0.2 to about 2 minutes, which should be sufficient to increase the temperature of the reaction mixture by about 50 to about 60° F.
- the reduced FFA reaction mixture may optionally proceed to a reaction mixture separation device 210 .
- the reduced FFA reaction mixture separation device 210 which may be any suitable separation device known to those having ordinary skill in the art, separates the reduced FFA reaction mixture into its constituent phases, a lower FFA triglyceride-containing feed stock, and a resulting byproduct waste emulsion.
- the byproduct waste emulsion is the lower phase and is thereafter transferred to a waste handling or disposal unit 212 .
- the lower FFA triglyceride-containing feed stock is transferred to a feed tank 214 for conversion into biodiesel.
- Example 1 a waste cooking oil brown grease was treated using a well-known bicarbonate-based procedure for reducing FFA content of high FFA feeds. A portion of the sample was then treated using radio frequency microwave energy applied using MST as described above. Samples not treated with MST were then separated using well-known gravity separation and centrifuge separation procedures. The MST treated samples were likewise separated using a well-known laboratory centrifuge procedure.
- MST-enhanced FFA treating (column D) significantly enhances the reduction in feed stock FFA content relative to conventional FFA treating without MST (columns B and C) for brown grease feed stock (column A).
- the feed stock undergoing MST-enhanced FFA reduction treatment showed significantly increased low FFA oil yield and/or rate of separation of emulsion and water byproducts from the low FFA oil (42% oil after 1 minute) relative to either the conventional gravity-based process without MST (21% oil after 60 minutes or 38% oil after 120 minutes) or the centrifuge process without MST (36% oil after 1 minute).
- Example 2 illustrates an improvement in the separation of the biodiesel product and the glycerin when the mixture is treated with radio frequency microwave energy as described above.
- Example 2 a soybean oil feed was treated with a well-known homogeneous catalyst prepared from methanol and potassium hydroxide (KOH) to produce biodiesel. A portion of the sample was also treated with MST. Samples not treated with MST were then separated using well-known gravity settling and laboratory centrifuge separation procedures. The MST-treated sample was similarly separated using a well-known centrifuge procedure.
- KOH potassium hydroxide
- MST-treated biodiesel/glycerin separation (column D) enhances the removal of glycerin from the biodiesel product phase relative to conventional separation without MST (columns B and C)
- MST-treated biodiesel/glycerin separation increases the rate and absolute percentage recovery of glycerin from the biodiesel (48% after 0.5 minutes and 89% after 12 minutes) relative to either the conventional gravity-based separation without MST (19% after 2 minutes and 77% after 12 minutes) or centrifuge-based separation without MST (29% after 0.5 minutes and 64% after 12 minutes).
- biodiesel product Following the conversion of triglycerides to fatty acid esters (biodiesel product) and the subsequent separation of biodiesel product from glycerin and residual methanol catalyst, it is generally necessary to water wash, and sometimes acid neutralize, the biodiesel product before it can be considered a finished product.
- Microwave enhancement is beneficial where an acid wash has been conducted as well as on the sample washed with water as described below.
- Example 3 a soybean oil feed was treated with a standard homogeneous catalyst prepared from methanol and KOH to produce biodiesel.
- the resulting biodiesel product and glycerin phases were separated using a well-known gravity-based separation procedure.
- the biodiesel product was then water washed using a 50/50 volumetric ratio of biodiesel and water using an in-line static mixer to insure complete mixing.
- a portion of the sample was also treated using radio frequency microwave energy applied by MST immediately downstream of the static mixer. Samples not treated with MST were then separated using a well-known gravity-based separation procedure.
- the MST-treated sample was separated using the same gravity-based separation procedure and also a well-known centrifuge separation procedure to simulate operation in a typical commercial MST configuration.
- MST-enhanced biodiesel product/wash water separation recovers a biodiesel product more quickly than a conventional separation without MST
- MST-enhanced biodiesel product/wash water separation reduces the amount of water retained in the separated biodiesel product
- use of microwave energy in a well-known commercial configuration that includes a centrifuge separator increases the rate of biodiesel product/wash water separation and reduces the amount of water retained in the biodiesel phase.
- biodiesel fuels Processes for production of biodiesel fuels are well known and are becoming increasingly common in commercial practice.
- the key reaction that characterizes biodiesel production involves conversion of an oil triglyceride feed stock into-a mixture of fatty acid esters (biodiesel product).
- Microwave heating increases the reaction rate for converting triglycerides to fatty acid esters (biodiesel product), and drives the ultimate reaction equilibrium toward the production of fatty acid esters (biodiesel product).
- Example 4 a soybean oil feed was treated with a standard homogeneous catalyst prepared from methanol and KOH to produce biodiesel product. A portion of the sample was also treated with microwave energy from an MST unit. Samples were then separated using a well-known centrifuge separation procedure. The volume of glycerin formed by the reaction and separated by the centrifuge separation procedure was recorded at centrifuge times from about 0.5 to about 8 minutes and the glycerin yield at each time was calculated as a percentage of the total final volume of glycerin produced.
- MST-enhanced biodiesel production yielded a higher final total volume of glycerin (16.8 v %) than production without MST (14.0 v %), where glycerin yield is directly proportional to and indicative of a higher yield of fatty acid ester (biodiesel product), and 2) MST-enhanced biodiesel production increased the reaction rate at which biodiesel was produced relative to production without MST, as indicated by the more rapid percentage production of glycerin and higher final yield, which is also directly proportional to and indicative of a higher rate and volume of biodiesel production.
Abstract
Description
- This application claims priority to, and hereby incorporates by reference, U.S. Provisional Application No. 60/647,332 entitled “Microwave-Enhanced Process to Maximize Biodiesel Production Capacity,” filed Jan. 26, 2005, with the United States Patent and Trademark Office.
- The present invention relates to an improved process for preparing biodiesel fuels wherein the feed stock preparation, reaction, and separation steps of the process are preceded by directing of radio frequency microwave energy into the mixtures prior to reacting and separating such mixtures to recover upgraded feed stocks and biodiesel products.
- Transesterification of triglycerides is a reaction that has been known for decades and has been practiced almost as long for the production of biodiesel fuels and fuel additives. The reaction uses feed stocks that contain triglycerides, such as various vegetable oils, rapeseed oil, soy oil, and even waste animal fats and cooking greases. In the case of waste fats and greases, the feed stocks must typically be pretreated in order to lower their free fatty acid (FFA) content. The processes described in the art state an FFA limitation of less than 1% and carry out the reaction at temperatures up to 100° C. and pressures up to 10 bars. For information regarding transesterification, the reader is referred to U.S. Pat. Nos. 5,514,820, 5,578,090, and 6,174,501, for example. Triglycerides and their compositions are similarly described in U.S. Pat. No. 5,578,090, for example.
- The processes used in the art for the production of biodiesel fuels and fuel additives generally involve reacting a triglyceride with an alcohol, particularly a lower alcohol such as a C1-C6 alcohol, more particularly methanol or ethanol. In the presence of a catalyst, for example, an alkaline catalyst such as potassium hydroxide or sodium hydroxide, these processes produce a fatty acid alkyl ester, glycerin, and unreacted alcohol in the reaction mixture. As a result, separation is required, often by settling, in order to remove the glycerin and the alcohol.
- Settling is typically performed in a settling tank, with the top phase of the reaction mixture being the biodiesel product. The biodiesel product is thereafter recovered (e.g., decanted) from the reaction mixture and is usually washed with water or an acid in order to neutralize any remaining catalyst. A separation is again required after the washing and is usually performed either in another settling tank, a static separator, or a centrifuge. Centrifuges are often used since separation in a static separator is imprecise and often incomplete.
- Thus, while transesterification is well known (and becoming increasingly important), there remains considerable inefficiencies in existing transesterification processes.
- The present invention is an improvement over existing transesterification processes generally described above and in the prior art patents referred to previously. The improvement involves applying radio frequency microwave energy to the reaction mixture, including pre-preparation of suitable triglyceride-containing feed stocks, prior to the reaction and/or the separation step. The separation may then be performed using simple settling, centrifuging, or any other suitable technique for separating immiscible liquids. Application of radio frequency microwave energy allows the use of high FFA content feed stocks, including animal fats and used cooking oils, in existing transesterification processes by promoting the removal of the fatty acid. Application of radio frequency microwave energy also enhances the reaction rate for the conversion of triglycerides to biodiesel, and also drives the reaction equilibrium toward the production of biodiesel. Application of radio frequency microwave energy further improves product recovery in the separation of the biodiesel product from alcohol and glycerin in the reaction mixture. Finally, application of radio frequency microwave energy to the reaction mixture before the separation of the wash water or acid solutions (used to remove impurities from the biodiesel fuel or additive) helps speed up the separation process and improves the yields.
- Accordingly, directing radio frequency microwave energy into the reaction mixture prior to at least one feed stock preparation, reaction, or separation step of the transesterification process may enhance the product yield and recovery, and directing radio frequency microwave energy into the reaction mixture prior to each feed stock preparation, reaction, and separation step may maximize the product yield, recovery, and overall biodiesel production capacity compared to a similar process without using radio frequency microwave energy.
-
FIG. 1 andFIG. 2 are schematic flow sheets showing an arrangement of various elements and steps of the transesterification process according to embodiments of the invention. - Biodiesel fuel or fuel additive is produced by subjecting a suitable triglyceride-containing feed stock (e.g., soy oil, virgin vegetable oil, used cooking oils, animal oils and other suitable triglyceride-containing feed stocks) to known transesterification or methyl- or ethyl-esterification processes. The processes result in an effluent stream of esterified triglycerides, also referred to as fatty acid esters, or esterified biodiesel product, and crude glycerol, where glycerol is a term that refers to a mixture of glycerin reaction byproduct and unreacted alcohol.
- Production capacity for producing biodiesel can be limited by separation processes because the crude glycerol is inherently insoluble in the esterified biodiesel product. Furthermore, the biodiesel is often washed with water (or an acid) to neutralize residual catalysts and remove impurities, forming a biodiesel/water emulsion. Gravity separation of the crude glycerol from the biodiesel and subsequently the biodiesel from the wash water causes the process to function as a semi-batch process, which constrains use of other process equipment and limits throughput for the entire system.
- Production yields of biodiesel can also be constrained by the reaction rate for converting triglycerides to the esterifed biodiesel product, and by the reaction equilibrium that constrains how much of the triglyceride will be converted to esterified biodiesel product.
- Furthermore, while a wide range of triglyceride-containing feed stocks can be used for the transesterification process, feeds that contain high levels of free fatty acids (FFA more than about 1 w %) are particularly desirable because of their low cost and availability. These feed stocks have heretofore been technically or economically undesirable, however, because the high FFA content inhibits the transesterification reaction and forms inseparable mixtures when treated by known methods for reducing the FFA content.
- Embodiments of the invention provide a way to mitigate or overcome the above limitations by applying radio frequency microwave energy to the feed stocks, reactants, or product mixtures to be separated. The unique characteristics of radio frequency microwave energy—specifically, the establishment of rapidly oscillating electric and magnetic fields that selectively energize strongly polar and strongly charged molecules relative to non-polar and neutral, or less polar and less charged, molecules—allow microwaves to facilitate certain physical and/or chemical reactions that are favorable to the biodiesel production process.
- Embodiments of the invention take advantage of the above-mentioned unique characteristics of radio frequency microwave energy to improve the biodiesel production process. For example, in some embodiments, the radio frequency microwave energy may be used to reduce the FFA content of high FFA triglyceride-containing feed stocks, such as animal fats and used cooking oils, by enhancing the conversion of free fatty acids and by enhancing the separation of the lower FFA triglyceride-containing feed stock from the treatment byproducts. In other embodiments, radio frequency microwave energy may be used to enhance the rate of the transesterification reaction and the yield of biodiesel product. The radio frequency microwave energy helps drive the reaction to completion and facilitates separation of glycerin and unreacted alcohol (or glycerol) from other reaction products and intermediates, primarily biodiesel product composed of a blend of fatty acid esters and trace impurities. In still other embodiments, the radio frequency microwave energy may also be used to facilitate separation of both the biodiesel product from the glycerin byproduct and unreacted alcohol, and the biodiesel product from wash water or other washing agents that are used to neutralize and remove the trace impurities and any residual catalysts. Embodiments of the invention also provide a novel process and hardware for achieving the above benefits.
- The terms “microwave” and “radio frequency microwave energy,” as used herein, refer to energy having a wavelength in the range of about 0.005 to 0.5 meters, although those having ordinary skill in the art will understand that higher or lower wavelength energy may also be used without departing from the scope of the invention. In addition, while a number of specific values and ranges are disclosed herein for temperature, residence time, flow rate, weight percentage, volume percentage, ratio, and so forth, those having ordinary skill in the art will recognize that other values and ranges may also be used without departing from the scope of the invention.
-
FIG. 1 shows aflow sheet 100 for a processing plant for operating a methyl-esterification process according to one embodiment of the invention. As can be seen, the triglyceride-containing feed stock is delivered from araw feed tank 102 and mixed intensively with methanol and catalyst from amix tank 104. The reaction may take place in one ormore mixers 106, such as one or more static mixers, tube reactors, one or more heated, continuously stirred tank reactors, and the like. In some embodiments, the reaction may occur at a temperature from about 20° to about 90° Celsius (C.) and a pressure from about 1 to about 200 atmospheres. The mole ratio of methanol to triglyceride-containing feed stock may be from about 1:1 to about 10:1. The flow rate of the reaction mixture may be from about 3 to about 120 gallons per minute (gpm). - The reaction mixture then enters a microwave separation technology (MST)
unit 108 where radio frequency microwave energy is applied to the reaction mixture. Application of radio frequency microwave energy drives the reaction rate higher and drives the reaction equilibrium toward higher production of transesterified biodiesel product. Any suitable MST may be used for the reaction-drivingMST unit 108, including the MST shown and described in U.S. Pat. Nos. 5,914,014; 6,077,400; and 6,086,830, which patents are hereby incorporated by reference. In one embodiment, the residence time in the reaction-drivingMST unit 108 may be from about 0.2 to about 2 minutes, which should be sufficient to increase the temperature of the reaction mixture by about 50 to about 60° Fahrenheit (F.). - From the reaction-driving
MST unit 108, the reaction mixture may optionally proceed to a reactionmixture separation device 110. The reactionmixture separation device 110, which may be any suitable separation device known to those having ordinary skill in the art, separates the reaction mixture into its constituent phases, glycerin plus unreacted alcohol, referred to as glycerol, and biodiesel product. Glycerol is the lower phase and is thereafter transferred to a glycerolmethanol recovery unit 112. The glycerolmethanol recovery unit 112 separates the glycerol into glycerin and methanol and recycles the methanol for use incatalyst mix tank 104. In some embodiments, however, it may not be desirable to recycle the methanol, depending on the particulars of the application. Indeed, in some embodiments, ethanol, propanol or any carbon chain length alcohol may be used instead of methanol. - Biodiesel product, which is the upper phase, is then mixed with wash water from a wash water tank 114 (and is sometimes acid neutralized) to produce a biodiesel product/wash water mixture. Mixing may be performed in one or
more mixers 116, such as one or more static mixers, one or more heated, continuously stirred tank reactors, and the like. The mixing may occur at a temperature from about 15 to about 80° C. and a pressure from about 1 to about 5 atmospheres. The flow rate of the biodiesel product/wash water mixture may be from about 3 to about 120 gallons per minute. - The biodiesel product/wash water mixture is then transferred to another
MST unit 118 where radio frequency microwave energy is applied to the mixture. Application of radio frequency microwave energy at this point assists in the subsequent separation of the biodiesel product/wash water mixture into its constituent phases, water and biodiesel product. The lower phase water may then be recycled to thewash water tank 114, while the upper phase biodiesel product may be recovered. In some embodiments, the water-washing MST unit 118 may be of a type similar to the reaction-drivingMST unit 108, although any suitable MST may be used without departing from the scope of the invention. The residence time in the water-washing MST 118 may be from about 0.2 to about 2 minutes, resulting in a temperature increase of the mixture by about 5° to about 60° F. - In some embodiments, one or more reactor units (not expressly shown) and/or one or more additional MST units may be inserted into the process shown in
FIG. 1 to further drive the transesterification reaction and/or improve the separation of the biodiesel product. For example, a reactor unit may be inserted into the process ofFIG. 1 between themixer 106 and the reaction-drivingMST unit 108 to provide additional reaction time before separating the biodiesel product from the glycerin. The reactor unit may be any suitable reactor unit known to those having ordinary skill in the art, including one or more static mixers, tube reactors, one or more heated, continuously stirred tank reactors, and the like. Alternatively, the reactor unit may be inserted into the process between the reaction-drivingMST unit 108 and the reactionmixture separation device 110 to help drive the transesterification reaction. For this configuration, is also possible to insert another MST unit between the reactor unit and the reactionmixture separation device 110 in order to both drive the reaction and improve the separation. These configurations and other similar configurations that serve to enhance the reaction rate and product yield and to facilitate separation of the resulting product mixture may be used without departing from the scope of the invention. - In accordance with the above-referenced U.S. Pat. Nos. 5,914,014; 6,077,400; and 6,086,830, the reaction-driving
MST unit 108 and the water-washing MST unit 118 may include a radio frequency microwave energy applicator. The radio frequency microwave energy applicator may be used to direct radio frequency microwave energy into a chamber through which the mixture to be treated (i.e., high FFA feed stock, reaction mixture, biodiesel/glycerin mixture, or biodiesel/wash water mixture) passes. The radio frequency microwave energy is preferably reflected into one or more radio frequency terminal cavities, for example, by means of angled reflector plates located at the terminal end of a rectangular waveguide. The waveguide terminal reflector plates are sized and angled to minimize radio frequency losses and to prevent reflected energy from returning to and damaging the radio frequency transmitter. Low loss, radio frequency-transparent, flat plate windows may be used to prevent intrusion of the mixture into the waveguide. - The mixture to be treated is then flowed through the chamber, preferably upward against gravity to prevent entrained solids from becoming trapped within the applicator cavities. The reentrant chamber dimensions may closely match the microwave standing wave patterns, based on the dielectric nature of the feed mixture flowing through the chamber. A three port circulator may be placed within the transmission path between the transmitter and the radio frequency microwave applicator to divert any reflected radio frequency microwave energy to a water-cooled dummy load.
- The inlet and outlet temperatures of the reaction-driving
MST unit 108 and the water-washing MST unit 118 are monitored and the flow rate of the feed stock is controlled to maintain optimal residence times and exit temperatures. This helps ensure an optimum reaction performance and separation of the mixture components. An optimum temperature differential of the feed stock between the inlets and outlets of the microwave chamber may be fed back to the pump feed rate controller. Pumping rate may then be changed to maintain the proper temperature difference for optimum treatment. In some embodiments, the temperature differential of the reaction-drivingMST unit 108 between the inlets and outlets of the microwave chamber is from about 5° to about 60° F. In some embodiments, the temperature differential of the water-washing MST unit 118 between the inlets and outlets of the microwave cavities is preferably from about 5° to about 60° F. Those having ordinary skill in the art may of course adjust the mixture flow rate or the intensity of the radio frequency microwave energy as needed to obtain the optimum operating parameters for each specific process. - In some embodiments, one or both of the
MST units separation devices MST units MST units -
FIG. 2 shows aflow sheet 200 according to some embodiments of the invention where radio frequency microwave energy is used to enhance the reduction of free fatty acids in high FFA triglyceride-containing feed stocks, thereby making these feed stocks more suitable for biodiesel production. As can be seen, the high FFA triglyceride-containing feed stock is delivered from araw feed tank 202 and mixed intensively with a carbonate or bicarbonate or other suitable reactant from amix tank 204. The reaction may take place in one ormore mixers 206, such as one or more static mixers, tube reactors, one or more heated, continuously stirred tank reactors, and the like. In some embodiments, the reaction may occur at a temperature from about 20° to about 100° C. and a pressure from about 1 to about 100 atmospheres. The volume ratio of reactant to high FFA triglyceride-containing feed stock may be from about 0.1:1 to about 10:1. The flow rate of the reaction mixture may be from about 3 to about 120 gallons per minute. - The high FFA reaction mixture then enters an
MST unit 208 where radio frequency microwave energy is applied to the high FFA reaction mixture. Application of radio frequency microwave energy drives the reduction in FFA and enhances the separability of the resulting lower FFA triglyceride-containing feed stock and the byproduct waste emulsion. Any suitable MST may be used for the FFA-reducingMST unit 208, including the MST shown and described in U.S. Pat. Nos. 5,914,014; 6,077,400; and 6,086,830 (incorporated previously by reference). In one embodiment, the residence time in the FFA reducingMST unit 208 may be from about 0.2 to about 2 minutes, which should be sufficient to increase the temperature of the reaction mixture by about 50 to about 60° F. - From the FFA-reducing
MST unit 208, the reduced FFA reaction mixture may optionally proceed to a reactionmixture separation device 210. The reduced FFA reactionmixture separation device 210, which may be any suitable separation device known to those having ordinary skill in the art, separates the reduced FFA reaction mixture into its constituent phases, a lower FFA triglyceride-containing feed stock, and a resulting byproduct waste emulsion. The byproduct waste emulsion is the lower phase and is thereafter transferred to a waste handling ordisposal unit 212. The lower FFA triglyceride-containing feed stock is transferred to afeed tank 214 for conversion into biodiesel. - Various embodiments of the invention may be better understood by reference to the following examples.
- Many processes for production of biodiesel fuels rely on the use of natural or food-grade oils (e.g., soybean, corn or palm oil) as feed stocks. It is often desirable to use lower quality, lower cost, waste oil feed stocks (e.g., waste cooking oils classified as yellow or brown grease, or animal fats), but such feed stocks are typically characterized by high FFA content (e.g., up to 40 w % or more). The high FFA inhibits the processing characteristics of these feed stocks due to the formation of water and soap that, in turn, inhibit the reaction of triglycerides to ester products and the separation of glycerin intermediates from the biodiesel product.
- In Example 1, a waste cooking oil brown grease was treated using a well-known bicarbonate-based procedure for reducing FFA content of high FFA feeds. A portion of the sample was then treated using radio frequency microwave energy applied using MST as described above. Samples not treated with MST were then separated using well-known gravity separation and centrifuge separation procedures. The MST treated samples were likewise separated using a well-known laboratory centrifuge procedure.
TABLE 1 (A) (B) (C) (D) Brown Gravity Centrifuge Centrifuge Grease Separation Separation Separation Feed (No MST) (No MST) (With MST) FFA (w %) 22.25 12.15 10.89 4.89 Sep'n Time (min) 60 120 1 4 1 4 Products (v %) Low FFA Oil 21 38 36 36 42 42 Emulsion 48 30 24 24 20 20 Water 31 32 40 40 38 38 - As can be seen from Table 1, MST-enhanced FFA treating (column D) significantly enhances the reduction in feed stock FFA content relative to conventional FFA treating without MST (columns B and C) for brown grease feed stock (column A). The feed stock undergoing MST-enhanced FFA reduction treatment showed significantly increased low FFA oil yield and/or rate of separation of emulsion and water byproducts from the low FFA oil (42% oil after 1 minute) relative to either the conventional gravity-based process without MST (21% oil after 60 minutes or 38% oil after 120 minutes) or the centrifuge process without MST (36% oil after 1 minute).
- The reaction of an oil triglyceride feed stock with methanol forms a mixture of fatty acid esters (biodiesel product) in which glycerin is generated as the major byproduct. Example 2 illustrates an improvement in the separation of the biodiesel product and the glycerin when the mixture is treated with radio frequency microwave energy as described above.
- In Example 2, a soybean oil feed was treated with a well-known homogeneous catalyst prepared from methanol and potassium hydroxide (KOH) to produce biodiesel. A portion of the sample was also treated with MST. Samples not treated with MST were then separated using well-known gravity settling and laboratory centrifuge separation procedures. The MST-treated sample was similarly separated using a well-known centrifuge procedure.
TABLE 2 (B) (D) (A) Gravity (C) Centrifuge Soybean Separation Centrifuge Separation Oil Feed (No Separation (With Stock MST) (No MST) MST) Total Glycerin (w %) Nil 2.58 5.51 2.16 (Biodiesel phase) Sep'n Time (min) 2 12 0.5 12 0.5 12 Products (v %) Biodiesel + Unreacted 98 92 96 91 92 85 Triglycerides Glycerin/Methanol 2 8 4 9 8 15 ˜% Glycerin Recovered 19 77 29 64 48 89 - As can be seen from Table 2, the results indicate: 1) MST-treated biodiesel/glycerin separation (column D) enhances the removal of glycerin from the biodiesel product phase relative to conventional separation without MST (columns B and C), and 2) MST-treated biodiesel/glycerin separation increases the rate and absolute percentage recovery of glycerin from the biodiesel (48% after 0.5 minutes and 89% after 12 minutes) relative to either the conventional gravity-based separation without MST (19% after 2 minutes and 77% after 12 minutes) or centrifuge-based separation without MST (29% after 0.5 minutes and 64% after 12 minutes).
- Following the conversion of triglycerides to fatty acid esters (biodiesel product) and the subsequent separation of biodiesel product from glycerin and residual methanol catalyst, it is generally necessary to water wash, and sometimes acid neutralize, the biodiesel product before it can be considered a finished product. The water wash—and more commonly, the acid wash—results in formation of emulsions that need to be separated. Microwave enhancement is beneficial where an acid wash has been conducted as well as on the sample washed with water as described below.
- In Example 3, a soybean oil feed was treated with a standard homogeneous catalyst prepared from methanol and KOH to produce biodiesel. The resulting biodiesel product and glycerin phases were separated using a well-known gravity-based separation procedure. The biodiesel product was then water washed using a 50/50 volumetric ratio of biodiesel and water using an in-line static mixer to insure complete mixing. A portion of the sample was also treated using radio frequency microwave energy applied by MST immediately downstream of the static mixer. Samples not treated with MST were then separated using a well-known gravity-based separation procedure. The MST-treated sample was separated using the same gravity-based separation procedure and also a well-known centrifuge separation procedure to simulate operation in a typical commercial MST configuration.
TABLE 3 Gravity-based Settling Water Content Biodiesel Resolution Sep'n Time (min) in Biodiesel (v % of Oil) 0.5 1 2 4 8 (w %) Without MST 72 84 92 92 96 0.3651 With MST 80 88 96 100 100 0.3432 With MST 100 100 100 100 100 0.2158 (Std. Centrifuge) Sep'n (Average of two tests) - As can be seen from Table 3, the results indicate: 1) MST-enhanced biodiesel product/wash water separation recovers a biodiesel product more quickly than a conventional separation without MST, 2) MST-enhanced biodiesel product/wash water separation reduces the amount of water retained in the separated biodiesel product, and 3) use of microwave energy in a well-known commercial configuration that includes a centrifuge separator increases the rate of biodiesel product/wash water separation and reduces the amount of water retained in the biodiesel phase.
- Processes for production of biodiesel fuels are well known and are becoming increasingly common in commercial practice. The key reaction that characterizes biodiesel production involves conversion of an oil triglyceride feed stock into-a mixture of fatty acid esters (biodiesel product). Microwave heating increases the reaction rate for converting triglycerides to fatty acid esters (biodiesel product), and drives the ultimate reaction equilibrium toward the production of fatty acid esters (biodiesel product).
- In Example 4, a soybean oil feed was treated with a standard homogeneous catalyst prepared from methanol and KOH to produce biodiesel product. A portion of the sample was also treated with microwave energy from an MST unit. Samples were then separated using a well-known centrifuge separation procedure. The volume of glycerin formed by the reaction and separated by the centrifuge separation procedure was recorded at centrifuge times from about 0.5 to about 8 minutes and the glycerin yield at each time was calculated as a percentage of the total final volume of glycerin produced.
TABLE 4 Total Glycerin Centrifuge Glycerin Content in Sep'n Time (min) Prod'd Biodiesel 0.5 1 2 4 8 (v %) (v %) Glycerin Yield (v %) Without MST 4 6 8 8 9 14.0 5.51 With MST 8 10 13 15 15 16.8 2.16 % of Final Glycerin Produced Without MST 29 43 57 57 100 With MST 48 59 77 89 100 - As can be seen from Table 4, the results indicate: 1) MST-enhanced biodiesel production yielded a higher final total volume of glycerin (16.8 v %) than production without MST (14.0 v %), where glycerin yield is directly proportional to and indicative of a higher yield of fatty acid ester (biodiesel product), and 2) MST-enhanced biodiesel production increased the reaction rate at which biodiesel was produced relative to production without MST, as indicated by the more rapid percentage production of glycerin and higher final yield, which is also directly proportional to and indicative of a higher rate and volume of biodiesel production.
- While the present invention has been described with reference to one or more particular embodiments, those skilled in the art will recognize that many changes may be made thereto without departing from the spirit and scope of the invention. Therefore, each of the foregoing embodiments and obvious variations thereof is contemplated as falling within the spirit and scope of the claimed invention, which is set forth in the following claims.
Claims (24)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/340,137 US20060162245A1 (en) | 2005-01-26 | 2006-01-26 | Microwave-enhanced process to maximize biodiesel production capacity |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US64733205P | 2005-01-26 | 2005-01-26 | |
US11/340,137 US20060162245A1 (en) | 2005-01-26 | 2006-01-26 | Microwave-enhanced process to maximize biodiesel production capacity |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060162245A1 true US20060162245A1 (en) | 2006-07-27 |
Family
ID=36741089
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/340,137 Abandoned US20060162245A1 (en) | 2005-01-26 | 2006-01-26 | Microwave-enhanced process to maximize biodiesel production capacity |
Country Status (2)
Country | Link |
---|---|
US (1) | US20060162245A1 (en) |
WO (1) | WO2006081457A2 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070017876A1 (en) * | 2005-07-21 | 2007-01-25 | Imperial Petroleum Recovery Corp. | Microwave-enhanced process to treat marine emulsion wastes |
US20070184962A1 (en) * | 2006-02-06 | 2007-08-09 | Battelle Energy Alliance, Llc | Microwave assisted oil-water analytical centrifuge |
US20080256845A1 (en) * | 2007-04-20 | 2008-10-23 | Meikrantz David H | Microwave-enhanced biodiesel method and apparatus |
US20090000941A1 (en) * | 2007-06-26 | 2009-01-01 | Kropf Matthew M | Ultrasonic and microwave methods for enhancing the rate of a chemical reaction and apparatus for such methods |
WO2009079019A1 (en) * | 2007-12-19 | 2009-06-25 | Auburn University | Fast biodiesel production from bio-substance with radio frequency heating |
US20090295509A1 (en) * | 2008-05-28 | 2009-12-03 | Universal Phase, Inc. | Apparatus and method for reaction of materials using electromagnetic resonators |
WO2009154437A1 (en) * | 2008-06-18 | 2009-12-23 | Echevarria Parres Antonio Jose | Process and apparatus for extracting biodiesel from algae |
US9095788B2 (en) | 2005-07-21 | 2015-08-04 | Ryan BOULWARE | Microwave-enhanced process and system to treat frac water |
US10315126B2 (en) | 2013-03-14 | 2019-06-11 | Donald W. Ramer | Apparatus for molecular targeting and separation of feedstock fluids |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007059783A1 (en) * | 2005-11-24 | 2007-05-31 | Scf Technologies A/S | Method and apparatus for converting organic material using microwave excitation |
CZ301958B6 (en) * | 2007-04-16 | 2010-08-11 | Univerzita Pardubice | Process for preparing biodiesel from vegetable oils, particularly from rapeseed oil |
CZ303071B6 (en) * | 2008-06-30 | 2012-03-21 | Univerzita Tomáše Bati ve Zlíne | Preliminary treatment process of waste oils and fats containing free fatty acids for alcoholytic preparation of biodiesel |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5514820A (en) * | 1989-09-29 | 1996-05-07 | Henkel Kommanditgesellschaft Auf Aktien | Continuous process for the production of lower alkyl esters |
US5578090A (en) * | 1995-06-07 | 1996-11-26 | Bri | Biodiesel fuel |
US5914014A (en) * | 1997-09-23 | 1999-06-22 | Kartchner; Henry H. | Radio frequency microwave energy apparatus and method to break oil and water emulsions |
US6077400A (en) * | 1997-09-23 | 2000-06-20 | Imperial Petroleum Recovery Corp. | Radio frequency microwave energy method to break oil and water emulsions |
US6086830A (en) * | 1997-09-23 | 2000-07-11 | Imperial Petroleum Recovery Corporation | Radio frequency microwave energy applicator apparatus to break oil and water emulsion |
US6174501B1 (en) * | 1997-10-31 | 2001-01-16 | The Board Of Regents Of The University Of Nebraska | System and process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
US20050274065A1 (en) * | 2004-06-15 | 2005-12-15 | Carnegie Mellon University | Methods for producing biodiesel |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6782875B2 (en) * | 2001-08-29 | 2004-08-31 | Hitoshi Yoshimoto | Systems and methods for conditioning or vaporizing fuel in a reciprocating internal combustion engine |
ES2201894B2 (en) * | 2002-01-18 | 2005-03-01 | Industrial Management, S.A | PROCEDURE TO PRODUCE BIODIESEL FUELS WITH IMPROVED PROPERTIES AT LOW TEMPERATURE. |
-
2006
- 2006-01-26 US US11/340,137 patent/US20060162245A1/en not_active Abandoned
- 2006-01-26 WO PCT/US2006/003001 patent/WO2006081457A2/en active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5514820A (en) * | 1989-09-29 | 1996-05-07 | Henkel Kommanditgesellschaft Auf Aktien | Continuous process for the production of lower alkyl esters |
US5578090A (en) * | 1995-06-07 | 1996-11-26 | Bri | Biodiesel fuel |
US5914014A (en) * | 1997-09-23 | 1999-06-22 | Kartchner; Henry H. | Radio frequency microwave energy apparatus and method to break oil and water emulsions |
US6077400A (en) * | 1997-09-23 | 2000-06-20 | Imperial Petroleum Recovery Corp. | Radio frequency microwave energy method to break oil and water emulsions |
US6086830A (en) * | 1997-09-23 | 2000-07-11 | Imperial Petroleum Recovery Corporation | Radio frequency microwave energy applicator apparatus to break oil and water emulsion |
US6174501B1 (en) * | 1997-10-31 | 2001-01-16 | The Board Of Regents Of The University Of Nebraska | System and process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
US20050274065A1 (en) * | 2004-06-15 | 2005-12-15 | Carnegie Mellon University | Methods for producing biodiesel |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070017876A1 (en) * | 2005-07-21 | 2007-01-25 | Imperial Petroleum Recovery Corp. | Microwave-enhanced process to treat marine emulsion wastes |
US10384960B2 (en) | 2005-07-21 | 2019-08-20 | Don B. Carmichael | Microwave-enhanced method for treating Frac water |
US9095788B2 (en) | 2005-07-21 | 2015-08-04 | Ryan BOULWARE | Microwave-enhanced process and system to treat frac water |
US8314157B2 (en) | 2005-07-21 | 2012-11-20 | Imperial Petroleum Recovery Corp. | Microwave-enhanced process to treat marine emulsion wastes |
US20070184962A1 (en) * | 2006-02-06 | 2007-08-09 | Battelle Energy Alliance, Llc | Microwave assisted oil-water analytical centrifuge |
US7775961B2 (en) | 2006-02-06 | 2010-08-17 | Battelle Energy Alliance, Llc | Microwave assisted centrifuge and related methods |
US20080256845A1 (en) * | 2007-04-20 | 2008-10-23 | Meikrantz David H | Microwave-enhanced biodiesel method and apparatus |
US8052848B2 (en) * | 2007-06-26 | 2011-11-08 | The Penn State Research Foundation | Ultrasonic and microwave methods for enhancing the rate of a chemical reaction and apparatus for such methods |
US20090000941A1 (en) * | 2007-06-26 | 2009-01-01 | Kropf Matthew M | Ultrasonic and microwave methods for enhancing the rate of a chemical reaction and apparatus for such methods |
WO2009079019A1 (en) * | 2007-12-19 | 2009-06-25 | Auburn University | Fast biodiesel production from bio-substance with radio frequency heating |
US20090165367A1 (en) * | 2007-12-19 | 2009-07-02 | Yifen Wang | Fast biodiesel production from bio-substance with radio frequency heating |
US20090295509A1 (en) * | 2008-05-28 | 2009-12-03 | Universal Phase, Inc. | Apparatus and method for reaction of materials using electromagnetic resonators |
US20110189741A1 (en) * | 2008-06-18 | 2011-08-04 | Echevarria Parres Antonio Jose De Jesus De San Jua | Process and apparatus for extracting biodiesel from algae |
WO2009154437A1 (en) * | 2008-06-18 | 2009-12-23 | Echevarria Parres Antonio Jose | Process and apparatus for extracting biodiesel from algae |
US8859270B2 (en) | 2008-06-18 | 2014-10-14 | Antonio Jose de Jesus de San Juan Bosco Echevarria Parres | Process and apparatus for extracting biodiesel from algae |
US10315126B2 (en) | 2013-03-14 | 2019-06-11 | Donald W. Ramer | Apparatus for molecular targeting and separation of feedstock fluids |
Also Published As
Publication number | Publication date |
---|---|
WO2006081457A2 (en) | 2006-08-03 |
WO2006081457A3 (en) | 2007-10-04 |
WO2006081457A9 (en) | 2006-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20060162245A1 (en) | Microwave-enhanced process to maximize biodiesel production capacity | |
AU2002224906B2 (en) | Method for pretreating crude oils and raw fats for the production of fatty acid esters | |
US8728177B2 (en) | Production of biodiesel and glycerin from high free fatty acid feedstocks | |
EP1444191B1 (en) | Improvements in or relating to a method for transesterifying vegetable oils | |
US7806945B2 (en) | Production of biodiesel and glycerin from high free fatty acid feedstocks | |
US8030505B2 (en) | Biodiesel production method | |
US9085547B2 (en) | Process for autocatalytic esterification of fatty acids | |
EP1849854A1 (en) | Biodiesel production process through transesterification/esterification reaction of vegetal oils or animal fats with alcohols induced by microwave radiation | |
EP3019580B1 (en) | Production of products from feedstocks containing free fatty acids | |
CN106675789A (en) | Method for preparing biodiesel with low sulfur content from gutter oil | |
US8188305B2 (en) | Method of producing biodiesel with supercritical alcohol and apparatus for same | |
Pruszko | Biodiesel production | |
AU2003267398A1 (en) | Method for improving the long term stability of biodiesel | |
CN103865639A (en) | Ultrasonic degumming technology of rice bran oil | |
US20170314047A1 (en) | Method for the production of alkyl esters | |
CN103374462B (en) | Preparation method of biodiesel | |
CA2561797A1 (en) | Continuous counter-current bio-diesel refining method | |
US10221375B2 (en) | Glycerol ester production from wastes containing organic oils and/or fats | |
US20230063878A1 (en) | Process for producing biodiesel from acidic charges | |
US8802878B2 (en) | Process for the production of fatty acid methyl esters from variable feedstock using heterogeneous catalysts | |
RU2717106C1 (en) | Method of producing monoglycerides of fatty acids | |
EP3299444B1 (en) | High efficiency method and catalyst for the production of alkyl esters from fatty acids with acid catalysis | |
CN206549626U (en) | A kind of reaction kettle of the esterification | |
WO2017192029A1 (en) | A method of producing biodiesel | |
PL199127B1 (en) | Method and system designed to obtain alkyl esters of fatty acids |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: IMPERIAL PETROLEUM RECOVERY CORP., TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PORTER, MARK J.;JENSEN, SCOTT;REEL/FRAME:017503/0442 Effective date: 20060125 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: EMMOTT, GARY, TEXAS Free format text: ASSIGNMENT: ASSIGNEE 1 DON B. CARMICHAEL- 83.12% INTEREST; ASSIGNEE 2 KK&PK FAMILY, L.P. - 10.39% INTEREST; ASSIGNEE 2 BARRY D. WINSTON - 5.19% INTEREST; ASSIGNEE 4 GARY EMMOTT - 1.30% INTEREST;ASSIGNOR:IMPERIAL PETROLEUM RECOVERY CORPORATION;REEL/FRAME:033473/0747 Effective date: 20140715 Owner name: CARMICHAEL, DON B., TEXAS Free format text: ASSIGNMENT: ASSIGNEE 1 DON B. CARMICHAEL- 83.12% INTEREST; ASSIGNEE 2 KK&PK FAMILY, L.P. - 10.39% INTEREST; ASSIGNEE 2 BARRY D. WINSTON - 5.19% INTEREST; ASSIGNEE 4 GARY EMMOTT - 1.30% INTEREST;ASSIGNOR:IMPERIAL PETROLEUM RECOVERY CORPORATION;REEL/FRAME:033473/0747 Effective date: 20140715 Owner name: KK&PK FAMILY, L.P., TEXAS Free format text: ASSIGNMENT: ASSIGNEE 1 DON B. CARMICHAEL- 83.12% INTEREST; ASSIGNEE 2 KK&PK FAMILY, L.P. - 10.39% INTEREST; ASSIGNEE 2 BARRY D. WINSTON - 5.19% INTEREST; ASSIGNEE 4 GARY EMMOTT - 1.30% INTEREST;ASSIGNOR:IMPERIAL PETROLEUM RECOVERY CORPORATION;REEL/FRAME:033473/0747 Effective date: 20140715 Owner name: WINSTON, BARRY D., TEXAS Free format text: ASSIGNMENT: ASSIGNEE 1 DON B. CARMICHAEL- 83.12% INTEREST; ASSIGNEE 2 KK&PK FAMILY, L.P. - 10.39% INTEREST; ASSIGNEE 2 BARRY D. WINSTON - 5.19% INTEREST; ASSIGNEE 4 GARY EMMOTT - 1.30% INTEREST;ASSIGNOR:IMPERIAL PETROLEUM RECOVERY CORPORATION;REEL/FRAME:033473/0747 Effective date: 20140715 |