WO2011009056A1

WO2011009056A1 - Miscible bio-oil fuels and production thereof

Info

Publication number: WO2011009056A1
Application number: PCT/US2010/042294
Authority: WO
Inventors: Christopher Churchill; William Kolker
Original assignee: Tolero Energy LLC
Current assignee: Tolero Energy LLC
Priority date: 2009-07-16
Filing date: 2010-07-16
Publication date: 2011-01-20
Anticipated expiration: 2012-01-16

Abstract

Improved miscible bio-oil fuels described herein include petroleum diesel or at least one first fluid as an agent when obtaining a bio-oil. The ratio of the first fluid to bio-oil as a mixture in the fuel ranges from 95:05 to 05:95. Improved miscible bio-oil fuels are generally not highly acidic. The process of producing said improved fuels includes providing a first fluid as a quenching agent when obtaining a bio-oil vapor during biomass pyrolysis. The improved miscible bio-oil fuels comprise a mixture that may be further processed and/or filtered prior to storage or use. The improved miscible bio-oil fuels may thus, in some forms, undergo an acid esterification reaction that raises pH of the mixture and provides oxidative stability. Additional processes to raise pH of the mixture and/or provide oxidative stability are also suitable. In one or more forms, improved miscible bio-oil fuels as described comply with at least ASTM D975 and/or other comparable tests for use. Said fuels provided herein do not contain biodiesel or in a quantity that requires testing, thus testing of said under ASTM 6751 is not necessary or required.

Description

TITLE [0001] Miscible Bio-Oil Fuels and Production Thereof

CROSS-REFERENCES TO RELATED APPLICATION

[0002] This application claims the benefit of U.S. Provisional Application No. 61/226,042 filed on July 16, 2009, and U.S. Provisional Application No. 61/243,461 filed on September 17, 2009. The entirety of each of these applications is hereby incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0003] Not applicable.

BACKGROUND

[0004] The description herein relates generally to the field of bio-oil production and improved formulations as well as the process and formation of such improved formulations into improved products.

[0005] There have been attempts to make bio-oil derived from the pyrolysis of biomass that may be miscible in petroleum diesel and distillates. For example, in International Publication No. WO 2008/066950, a pyrolysis system is used to create bio-oil products after biomass conversion in a condensation process. Biodiesel is used and defined as a mono alkyl ester of fatty acid. A bio-oil/biodiesel mixture is then treated (fractionated and dewatered) prior to being mixed with petroleum-based diesel fuel to produce a miscible, multi-component diesel fuel. Thus, while miscibility is shown as possible, the high acidity of the bio-oil component that is mixed with the biodiesel renders compliance with biodiesel test methods very problematic if not improbable. High acidity (e.g., low pH) is an indication of an excessively high oxidative reactivity measured by ASTM 6751 and the high acidity of bio-oil provided by WO 2008/066950 means the fuel that is formed must be tested under ASTM 6751. Fuel that is formed by WO 2008/066950 is not suitable for metal components (e.g., engines, engine gaskets) because it is excessively corrosive to metal components. Biodiesel is considerably more expensive than petroleum diesel and miscible bio-oil. Biodiesel is also not as readily available as petroleum diesel in locations that bio-oil is being produced. The use of biodiesel as a condensate to render bio-oil miscible is not only problematic, it may be economically unfeasible.

SUMMARY

[0006] The invention described provides improved miscible bio-oil fuels. An improved miscible bio-oil fuel described herein includes a first fluid as an agent when obtaining the bio- oil. The first fluid may include petroleum diesel (petrodiesel), a petroleum product and/or its distillate and may also include but is not limited to one or more of No. 2 fuel oil, No. 4 fuel oil, No. 6 fuel oil, kerosene, jet fuel and the like as well as one or more of algal bio fuel, ethanol (produced from cellulose or other means), non-ester renewable diesel (produced from cellulose or other means), butanol, biobutanol, oils from plants such as palm oil, jatropha oil, and the like, including plants such as switchgrass and the like. The ratio of first fluid to bio-oil in a fuel mixture may range from 95:05 to 05:95. Depending on the choice of first fluid, the improved miscible bio-oil fuel described herein may not be highly acidic. In one or more forms, improved miscible bio-oil fuels described herein will comply with ASTM D975 (or various other tests required for use or for application of the improved fuel). In one or more forms, a fuel described herein, such as one complying with ASTM D975, does not contain biodiesel; thus, testing under ASTM 6751 is not necessary or required.

[0007] In one or more embodiments is an improved miscible bio-oil fuel comprising a mixture of bio-oil, a first fluid and optionally a second fluid, wherein the mixture is formed after the first fluid is provided as a quenching agent when obtaining a bio-oil vapor via biomass pyro lysis.

[0008] In one or more further embodiments is an improved miscible bio-oil fuel comprising a mixture of bio-oil, a first fluid and optionally a second fluid, wherein the mixture obtained with the use of the first fluid has a final ratio of first fluid to bio-oil from 95:05 to 05:95. [0009] In one or more additional embodiments is an improved miscible bio-oil fuel comprising a mixture of bio-oil, a first fluid and optionally a second fluid, wherein the mixture obtained with use of the first fluid is filtered using an acid esterification reaction that raises pH of the mixture and provides oxidative stability.

[0010] One or more embodiments further include an improved miscible bio-oil fuel comprising a bio-oil, a first fluid and optionally a second fluid, wherein diesel fuel is less than about 5% by total volume.

[0011] Additional embodiments include an improved miscible bio-oil fuel wherein the fuel is in compliance with ASTM D975 or an equivalent test for use of the improved fuel.

[0012] Still further embodiments include an improved miscible bio-oil fuel wherein the fuel does not contain biodiesel.

[0013] Yet further embodiments include an improved miscible bio-oil fuel wherein the fuel does not require testing under ASTM 6751.

[0014] Those skilled in the art will further appreciate the above-noted features and advantages of the invention together with other important aspects thereof upon reading the detailed description that follows in conjunction with the drawings.

DESCRIPTION

[0015] The invention, as defined by the embodiments, may be better understood by reference to the following detailed description. The description is meant to be read with reference to any figures that may be contained herein. This detailed description relates to examples of the subject matter for illustrative purposes, and is in no way meant to limit the scope of the invention. The specific aspects and embodiments discussed herein are merely illustrative of ways to make and use the invention, and do not limit their scope.

[0016] As described herein a first fluid is heated to an elevated temperature, such as about 60 degrees C or greater and used as a condensate for bio-oil vapors. Methanol or a chemical component of similar activity and/or structure is a downstream by-product of biomass pyrolysis. As described herein, this downstream by-product may be added as a second fluid to the first fluid (at an amount generally up to about 5% mass weight; however, in some forms the amount may be greater than 5%). The addition of the second fluid may occur prior to use of the first fluid as the bio-oil vapor condensate or may occur as a separate step, e.g., via addition as a spray at the time of vapor condensation, and provided as a co-condensate with the first fluid. The resultant mixture will include a first fluid and bio-oil and optionally a downstream by-product of biomass pyrolysis, which is a second fluid such as methanol.

[0017] The first fluid may include petrodiesel, a petroleum product and/or its distillate and may also include but is not limited to one or more of No. 2 fuel oil, No. 4 fuel oil, No. 6 fuel oil, kerosene, jet fuel and the like as well as one or more of algal bio fuel, ethanol (produced from cellulose or other means), non-ester renewable diesel (produced from cellulose or other means), butanol, biobutanol, oils from plants such as palm oil, jatropha oil, and the like, including plants such as switchgrass and the like.

[0018] In one form, alkanes and aromatic hydrocarbons (also referred to as petrodiesel) are heated to an elevated temperature, such as about 60 degrees C or greater and used as a condensate for bio-oil vapors. Methanol or a chemical component of similar activity and/or structure is a downstream by-product of biomass pyrolysis. This downstream by-product may be added in one or more embodiments to the petroleum diesel (at an amount generally up to about 5% mass weight). The addition may occur prior to petroleum diesel use as the bio-oil vapor condensate or may occur as a separate step, e.g., via addition as a spray at the time of vapor condensation, and provided as a co-condensate with the petroleum diesel. The resultant mixture will include petrodiesel and bio-oil and optionally a downstream by-product of biomass pyrolysis, such as methanol.

[0019] The ratio of the first fluid to bio-oil in the fuel ranges from 95:05 to 05:95. The mixing ratio of the first fluid to bio-oil is generally provided at a ratio from about 95:05 or from about 90:10 or from about 80:20 or from about 70:30 or from about 60:40 or from about 40:60 or from about 30:70 or from about 20:80 or from about 10:90 or from about 05:95. Such mixing ratios may be met by taking advantage of the condensate reaction and quenching properties of the first fluid when the first fluid is used as the condensate for the bio-oil vapor. The ratio of bio-oil may be increased as the temperature of the first fluid is raised, generally in a range from about 20 degrees Centigrade (C) to about 140 degrees C.

[0020] Prior to exposure to the bio-oil vapor, the first fluid is heated to a preferred temperature in an inert vessel, where is can be stored until use. The heat for the temperature gain may be obtained from the synthesis gas (syngas) produced by the pyrolysis reaction or by natural gas or by electricity. The temperature is controlled by a thermostat that controls the amount of heat directed to the heating vessel containing the first fluid.

[0021] After a bio-oil/first fluid mixture is obtained, it is generally cooled or kept at a temperature that is at or about 120 to 140 degrees C. In addition or as an alternative, the mixture may then be dewatered. Some improved fuel mixtures may not require further processing. These products may be stored in one or more storage containers until use. Some forms may be stored in one or more storage containers until further processing. As an alternative, other improved fuel mixtures will be further processed before storage and/or use, such as those useful as transportation fuels. Further processing may include one or more steps to modify pH of the mixture. In addition or as an alternative, the improved fuel mixture may undergo filtering. In addition or as an alternative, the described mixture, following dewatering and filtering, is passed through a filter encasing. An example of means for filtering as used herein is a polymer based catalyst and ion exchange resin, such as those prepared of functionalized styrene components, such as a divinylbenzene copolymer. Many standard grade resins or beads for alkylation reactions may be suitable, such as, for example, Amberlyst™ 15 or Amberlyst™ BD20 beads (Amberlyst™ is a trademark of Rohm and Haas Company). Catalytic filtration may be run online as the mixture is formed. Suitable polymers beads provide a catalytic effect for acid esterification which, in addition to some second fluids (that improves stability and cetane number of a resulting mixture, such as methanol), raises the pH of the mixture and, therefore, provides oxidative stability. At this point, a filtered mixture may be stored in one or more storage containers prior to further processing, shipping or use. After filtering, a filtered mixture may be tested for compliance with ASTM D975 or other suitable test for use. [0022] Because filtered mixtures as well as non-filtered mixtures provided herein do not contain mono-alkyl esters of fatty acids, it is not necessary to test the fuel mixture under ASTM 6751, which is specified for biodiesel fuel.

[0023] In some embodiments, filtered mixtures provided herein (e.g., bio-oil/petrodiesel or bio-oil/petrodiesel/methanol) may comprises about 5% or less diesel fuel by total volume. Accordingly, said fuels as described herein do not have a requirement for further labeling by the Federal Trade Commission as would be required for alternative fuels, such as transportation fuels having greater than 5% or less diesel fuel or other alternative fuel in the mixture.

[0024] While specific alternatives to steps of the invention have been described herein, additional alternatives not specifically disclosed but known in the art are intended to fall within the scope of the invention. Thus, it is understood that other applications of the present invention will be apparent to those skilled in the art upon reading the described embodiment and after consideration of the appended claims and drawing.

Claims

CLAIMS What is claimed is:

1. A miscible bio-oil fuel comprising a mixture, wherein the mixture includes:

bio-oil;

at least one first fluid; and

optionally at least one second fluid,

wherein the mixture is formed from one of a condensation reaction using the at least one first fluid as a quenching agent when obtaining a bio-oil vapor during biomass pyrolysis or after the at least one first fluid is provided as a quenching agent when obtaining a bio-oil vapor during biomass pyrolysis.

2. The miscible bio-oil fuel of claim 1, wherein the at least one first fluid is selected from the group consisting of petrodiesel, a petroleum product and/or its distillate, No. 2 fuel oil, No. 4 fuel oil, No. 6 fuel oil, kerosene, jet fuel, algal bio fuel, ethanol, fuel produced from cellulose, non-ester renewable diesel, butanol, biobutanol, and oils from plants.

3. The miscible bio-oil fuel of claim 1, wherein the at least one second fluid is a downstream by-product of biomass pyrolysis.

4. The miscible bio-oil fuel of claim 1, wherein the at least one second fluid is methanol.

5. The miscible bio-oil fuel of claim 1, wherein the mixture obtained has a final ratio of first fluid to bio-oil from 95:05 to 05:95.

6. The miscible bio-oil fuel of claim 1 , wherein the mixture is dewatered and filtered before one or more of shipping or storage.

7. The miscible bio-oil fuel of claim 1, wherein the mixture is filtered using an acid esterification reaction that raises pH of the mixture and provides oxidative stability.

8. The miscible bio-oil fuel of claim 1 , wherein fuel obtained contains diesel as less than about 5% or less by total volume.

9. The miscible bio-oil fuel of claim 1 , wherein the fuel is in compliance with ASTM D975.

10. The miscible bio-oil fuel of claim 1, wherein the fuel does not contain a mono-alkyl ester of fatty acid biodiesel.

11. The miscible bio-oil fuel of claim 1 , wherein the fuel does not require testing under ASTM 6751.

12. A method of making a miscible bio-oil fuel comprising

preparing a mixture, wherein the mixture is formed from one of a condensation reaction using a first fluid as a quenching agent when obtaining a bio-oil vapor during biomass pyrolysis or after the first fluid is provided as a quenching agent when obtaining a bio-oil vapor during biomass pyrolysis; wherein the mixture obtained has a final ratio of a first fluid to bio-oil from 95:05 to 05:95.

13. The method of claim 12, wherein the first fluid is selected from the group consisting of petrodiesel, a petroleum product and/or its distillate, No. 2 fuel oil, No. 4 fuel oil, No. 6 fuel oil, kerosene, jet fuel, algal biofuel, ethanol, fuel produced from cellulose, non-ester renewable diesel, butanol, biobutanol, and oils from plants.