VAN WALSUM, G., Peter (5 Allen Road, #54Orono, ME, 04473, US)
WHEELER, M., Clayton (15 Sunrise Terrace, Orono, ME, 04473, US)
PENDSE, Hemant, P. (11 Page Place, Orono, ME, 04473, US)
VAN WALSUM, G., Peter (5 Allen Road, #54Orono, ME, 04473, US)
WHEELER, M., Clayton (15 Sunrise Terrace, Orono, ME, 04473, US)
| What is claimed is: 1. An integrated suite of processes to make jet fuel from wood. 2. The processes of claim 1 which are located within a wood products processing facility such as an operating pulp mill or repurposed pulp mill. 3. The processes of claim 1 which make jet fuel and associated hydrocarbon products. 4. A central process platform which uses thermal deoxygenation (TDO) of mixed organic acids to produce a predominately hydrocarbon mixture. 5. The process platform of claim 4 wherein the mixed organic acids come from one or more of the following sources: a) chemical conversion of whole wood chips; b) chemical conversion of cellulose separated from wood chips; c) chemical conversion of hemicellulose separated from wood chips; d) biological conversion (pure or mixed cultures) of whole wood chips; e) biological conversion (pure or mixed cultures) of cellulose separated from wood chips; and f) biological conversion (pure or mixed cultures) of hemicellulose separated from wood chips. 6. The process platform of claim 4 which tailors a combination of organic acids from different sources and processes to change yield and composition of the TDO product. 7. The process platform of claim 4 which is useful with mixtures of organic acids that are not pure. 8. The process platform of claim 4 wherein the recovery of the metal cations used in TDO is integrated with pulp mill recovery cycles. 9. A process platform in which tri-decane or other alkanes are produced by aldol condensation using furfural and ketones, the furfural produced from wood hemicellulose or hemicellulose separated from wood chips. 10. The process platform of claim 9 wherein the ketones are produced from TDO of organic acids from one or more of the sources of claim 5. 11. A process platform in which tri-alkylglycerides (TAGs) are produced from cellulosic pulp or hemicellulose extracted from wood prior to pulping. 12. Products from the process platforms of claims 4, 9, 10 or 11 that are hydrotreated either separately or in appropriate mixtures to vary the yield and composition of the hydrocarbon product which includes jet fuel and other associated hydrocarbon fractions. |
JET FUEL PROCESSES IN AN INTEGRATED FOREST BIOREFINERY
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001 ] This application claims the benefit of United States Provisional Application No. 61/357,280, filed June 22, 2010, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates in general to processes for producing fuels, and in particular to a renewable technology for producing jet fuels.
[0003] The market for jet fuel is very large. Jet fuel is currently derived from petroleum resources. Increasing worldwide use of air travel and leveling production of petroleum are likely to result in high prices for jet fuel into the foreseeable future. Unlike other uses for liquid fuels, such as home heating or ground transportation, there are no renewable alternatives available for fueling jet-powered air transportation. For reasons of increased sustainability and national security, it would be desirable to produce jet fuel from renewable resources.
[0004] The wood processing industry is primarily concerned with the production of forest products, such as wood pulp, paper and construction materials. For example, owners of wood pulping facilities rely exclusively on the pulp market for their business. It would be desirable for the wood processing industry to be able to diversify their products and increase their profitability. In particular, it would be advantageous to achieve increased diversification and profitability while utilizing existing equipment and business infrastructure.
[0005] Consequently, it would be desirable to provide a process for producing jet fuel from a woody biomass feedstock. SUMMARY OF THE INVENTION
[0006] This invention relates to an integrated suite of processes to make jet fuel from wood. In preferred embodiments, the processes are located within a wood products processing facility.
[0007] The invention also relates to a central process platform which uses thermal deoxygenation (TDO) of mixed organic acids to produce a predominately
hydrocarbon mixture.
[0008] The invention further relates to products from the process that are hydrotreated to vary the yield and composition of the hydrocarbon product which includes jet fuel and other associated hydrocarbon fractions. The products may be mixed with tri-decane or other alkanes or hydrotreated tri-acylglycerides to improve fuel quality.
[0009] Various aspects of this invention will become apparent to those skilled in the art from the following detailed description of the preferred embodiment, when read in light of the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Fig. 1 is a schematic of a process for producing jet fuel according to the invention.
[0011 ] Fig. 2 is a graph showing the reaction products of brown stock hydrolysis and dehydration.
[0012] Fig. 3 is a graph showing relative levels of consumed sugars, consumed acids, produced cell density and final cell yield on consumed sugars and acid.
[0013] Fig. 4 is a graph showing accumulation of acetic acid in four wood extract conditions.
[0014] Fig. 5 is a graph showing accumulation of C3-C7 carboxylic acids in four wood extract fermentation conditions.
[0015] Fig. 6 is a graph showing accumulation of lactic acid in four wood extract fermentation conditions. [0016] Fig. 7 is a graph showing accumulation of lactic acid in four wood extract fermentation conditions.
[0017] Fig. 8 shows sequencing batch fermentation at 50 gallon scale. After initial batch growth, fermented extract was removed and replaced with fresh extract at a rate of 20% volume once per week. On day 94 the extract was increased to 50% volume once per week.
[0018] Fig. 9 shows a chromatogram for products of the thermal deoxygenation of fermentation-derived carboxylic acids.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] This invention provides a process, including several alternate processing schemes, for producing jet fuel quality liquid fuels from renewable woody biomass resources. The process can enable the adaptation of existing infrastructure of the wood processing industry to produce biofuels with only minor changes to existing technical and business practices.
[0020] The process includes several technologies that convert forestry or wood processing waste to jet fuels. In certain embodiments, these technologies are scalable down to the scale of a mobile unit capable of converting woody biomass feedstock into high energy-density liquid intermediates suitable for making HRJ (hydrotreated renewable jet) fuels.
[0021 ] Any suitable woody or other lignocellulosic feedstock can be used in the process. In certain embodiments, specific feedstocks of interest include (1) forest residue available as low quality whole tree chips often used for direct combustion in wood-fired boilers and (2) raw wood extracts rich in hemicelluloses that otherwise would have been burned as a part of spent black liquor in recovery boilers at pulp mills. These two feedstocks are potentially available at existing wood processing facilities. Pulp mill facilities can include both producing facilities and repurposed facilities that are no longer producing pulp.
[0022] Fig. 1 is a schematic of a process for producing jet fuel according to the invention. The process may be called an "Integrated Forest BioRefinery" (IFBR) for producing jet fuel. The Jet Fuel IFBR incorporates flexible configurations and sequences of the following technologies:
[0023] · A pre-pulping extraction step is used to produce wood extract (rich in C5 sugars like xylan) and brownstock (rich in C6 cellulose), which is currently used to make market pulp, but can be converted to levulinic acid. Extraction can be optimized for pulp vs. levulinic acid production.
[0024] · Two acid-catalyzed dehydration processes are involved for converting C6 and C5 sugars to intermediate compounds levulinic acid and furfural, respectively.
[0025] · Thermal deoxygenation (TDO) upgrades carboxylic acids by increasing carbon numbers and removing oxygen.
[0026] · Defined culture fermentation converts conditioned extracts into organic acids, solvents, or triglycerides. Organic acids (i.e. acetic acid, butyric acid) can be upgraded through TDO, hydrogenation and further hydroprocessing. Solvents (i.e. acetone, butanol, ethanol (ABE)) serve as material feeds for hydroprocessing or aldol condensation. Triglycerides can be hydrotreated into jet fuel constituents.
[0027] · Non- sterile mixed culture fermentation (acidogenic digestion) converts raw, unconditioned extract into mixed organic acids (acetic, lactic, propionic, etc. up to C 7 acids) that can be upgraded to jet fuel range alkanes through TDO,
hydrogenation and further hydroprocessing.
[0028] · Aldol condensation is used to increase carbon chain length.
[0029] · Hydroprocessing involves hydrogenation and hydroisomerization aimed at producing an appropriate mix of high carbon number alkanes and branched or cyclo alkanes.
[0030] More generally, as shown in Fig. 1, the invention provides an integrated suite of processes to make jet fuel and associated hydrocarbon products from wood. In certain embodiments, the processes are located within a wood products processing facility such as a pulp mill.
[0031 ] The invention also provides a central process platform which uses thermal deoxygenation (TDO) of mixed organic acids to produce a predominately hydrocarbon mixture. The mixed organic acids can come from multiple sources such as, but not limited to:
i. chemical conversion of whole wood chips;
ii. chemical conversion of cellulose separated from wood chips;
iii. chemical conversion of hemicellulose separated from wood chips;
iv. biological conversion of whole wood chips;
v. biological conversion of cellulose separated from wood chips; and vi. biological conversion of hemicellulose separated from wood chips.
[0032] The mixed organic acids can be a combination of organic acids from different sources and processes that can be tailored to change yield and composition of the TDO products.
[0033] The mixtures of organic acids used in the process need not be pure. This saves the cost and time of purification procedures.
[0034] In certain embodiments, the recovery of the metal cations used in TDO can be synergistically integrated with pulp mill recovery cycles.
[0035] In certain embodiments, the products of the process platform are
hydrotreated to vary the yield and composition of hydrocarbon product which includes jet fuel and other associated hydrocarbon fractions.
[0036] Further, in certain embodiments, the above-mentioned products are mixed with tri-decane or other alkanes in order to improve fuel qualities. The tri-decane or other alkanes can be produced by an aldol condensation pathway using furfural derived from wood extracts or from chemical conversion of hemicellulose from wood chips. Ketones for aldol condensation could be produced through TDO from any suitable organic acids mentioned above.
[0037] Also, in certain embodiments, the above-mentioned products are mixed with try-acylglycerides (TAGs) to improve fuel yields and qualities. The TAG can be produced by fermenting cellulose and or hemicellulose from wood with lipid accumulating microbes such as algae or bacteria. [0038] The following Table 1 lists eight process subsystems shown in Fig. 1 that can be included in one or more alternate embodiments of the process for producing jet fuels. Certain of the subsystems will be described in more detail below.
[0039] Table 1 List of Subsystems in IFBR for Wood to Jet Fuels
SUB 1 Extraction and extract conditioning if needed
SUB 2 DHP: Dehydration Process for Cellulose to Mixtures of Levulinic
Acid (HLev) and Formic Acid Conversion
SUB 3 XDHP: Dehydration Process for Xylan to Furfural Conversion
SUB 4 Pure Culture Fermentation of Conditioned Extract to Lipids or
Carboxylic Acids
SUB 5 Mixed Culture Fermentation of Raw extract to Mixed Acids
SUB 6 TDO: Thermal Deoxygenation of Carboxylate Salts
SUB 7 ACP: Aldol Condenstion Process for Furfural to Tridecane
Conversion
SUB 8 Hydroprocessing, Distillation & Blending
[0040] Wood Handling, On-site Steam, Power & Hydrogen Generation, and other co-products recovery processes are not shown in Fig. 1 for convenience of
simplification of graphical illustration.
[0041 ] The IFBR wood-to-jet fuel process scheme provides great flexibility in processing of woody biomass to liquid hydrocarbons and jet fuel. This flexibility can improve the capability of implementing a suitable pathway into an existing mill operation. The pathway flexibility is illustrated with the following aspects of the technology that allow processing choices to be made:
(1) incorporation of four pathways to provide input to hydroprocessing step,
(2) incorporation of two pathways to produce furfural,
(3) wood extracts can go to three different processing steps,
(4) levulinic acid can come from two sources (brownstock & whole tree chips),
(5) define culture fermentation can produce two different products for different processes,
(6) TDO can take in three different carboxylic acid input streams, and (7) several intermediate products can also be purified and marketed as value-added co- products.
[0042] These aspects of the technology can provide unique synergy, added flexibility, opportunities to optimize, and efficient use of two major types of woody feedstocks (pulpwood chips and whole tree chips) that come to existing pulp mills, allowing conversion of a pulp mill into jet fuel producing facility.
[0043] As mentioned above, the IFBR wood-to-jet fuel process scheme shown in
Fig. 1 includes eight process subsystems listed in Table 1. Certain of the subsystems are described in more detail and exemplified below.
[0044] SUB 1 : Extraction and Extract Conditioning if Needed
[0045] Processes for the extraction of wood chips before pulping are described in more detail in U.S. Patent No. 7,824,521, issued Nov. 2, 2010, and No. 7,842,161, issued Nov. 30, 2010, both of which are incorporated by reference herein.
[0046] SUB 2: DHP— Dehydration Process for Cellulose to Mixtures of Levulinic
Acid (HLev) and Formic Acid Conversion
[0047] Source of the cellulose
[0048] Brownstock which had been produced from wood chips in which much of the hemicellulose had been removed by hot water extraction.
[0049] Experiment
[0050] The brown stock was dried and then refined using a blender to make loose fibers. Five grams of the refined solids were mixed with 95 grams of water and 9.3 grams of sulfuric acid in a 300 mL reactor. The mixture was heated to 150°C and agitated. Liquid samples were collected periodically and analyzed by HPLC. Figure 2 shows the composition of the liquid mixture as a function of reaction time.
[0051 ] The results are consistent with batch dehydration of pure cellulose in literature. We have conducted TDO experiments which demonstrate residual sulfate and furfural in levulinic acid TDO feedstocks don't negatively affect oil production. [0052] SUB 4: Pure Culture Fermentation of Conditioned Wood Extracts to Lipid Accumulating Microbes
[0053] Source of the Culture:
[0054] Rodococcus Opacus was kindly provided by Dr. Anthony Sinsky in the department of biology at MIT.
[0055] Sugar Source:
[0056] The sugar source for the experiment was wood extract, produced by the University of Maine FBRI. The green liquor extract was a concentrated by
evaporation, hydrolyzed with sulfuric acid, evaporated and diluted three times to remove acetic and formic acids through volatilization and finally resin extracted with NR6 resin to reduce sodium content. The extract was passed through the resin three times with a resin to liquid ratio of 2: 1. After resin extraction the resin was washed with water three times to recover the sugars that had been bound to the resin. The samples used for fermention included: the resin filtered extract; the wash liquid from the resin wash; and a 50/50 blend of the resin filtered extract and the wash liquid.
[0057] The concentrations of the different sugars and acids present in the extract and wash water are presented in table SUB4.1 :
Table SUB4.1: Composition of conditioned wood extract and resin wash water
[0058] Fermentations:
[0059] Four different sets of duplicate fermentations were done using the R. opacus cultures. The fermentations were done with water and nutrients as a control, and then blends of nutrients with resin treated extract, resin washed liquid and the 50/50 blend of wash and extract liquids.
[0060] Procedure:
[0061 ] Aliquots of 2X concentrated LB broth medium were prepared in 8 different shake flasks and sterilized. The 3 different combinations of sugar extracts were sterilized separately. After sterilization, the nutrient broth and sugar solutions (water in the case of the control) were blended together prior to inoculation. The extract and the LB broth were sterilized separately so as to avoid any intermediate reactions formation during the sterilization process. Care was taken that the final volume in each fermentation flask would have equal volumes of LB broth and sugar extract.
[0062] Results:
[0063] Physical Observations:
[0064] The lag phase of the fermentation took about 2 days and the fermentation was continued for approximately 2 weeks, which was more time than required to complete the fermentation. Attempts were made to detect the optical density of the sample so as to construct a microbial growth curve, but after 2 days the cultures were too dense to make accurate measurements.
[0065] After fermentation the samples were refrigerated and centrifuged to separate the cells from the liquid. The supernatant thus collected was sent for analysis by HPLC for remaining sugars ( Biorad HPX-87H column) and the cells were further washed to remove any sugars bound to the cell wall. Thus separated cells were then freeze-dried using a lyophilizer. Finally, the weight of the samples were recorded and tabulated.
[0066] Fermentation:
[0067] The results show that the R. Opacus was able to grow on the conditioned extract samples, which included xylose and the primary sugar source. The equal volumes of extract and wash liquid showed a better growth of the culture than the control, to which no additional sugar was added. Total sugars fed to the Microbial cultures are listed in table SUB4.2. Final cell mass of the cultures are tabulated in table SUB4.3. Table SUB4.4 presents the final sugar content in the fermentations. IT can be seen that not all fermentations consumed the majority of sugar available.
Finally, Figure 3 presents comparative sugar and organic acid consumption, cell production and cell yield on consumed sugars. It can be seen that the cells achieve up to 6)% mass yield on consumed sugars (metabolic yield). The results showed conclusively that xylose is consumed by the R. Opacus. [0068] In addition to this study, a separate study found that R. opacus can tolerate acetate concentrations of up to 30 g/L when grown in a simple water + nutrients medium.
Table SUB4.2: Feed composition for fermentation experiment
Table SUB 4.3: Final cell mass collected at the end of fermentation
Table SUB4.4: Final sugar amounts remaining after fermenting the R. Opacus cultures
[0069] SUB 4: Pure Culture Fermentation of Conditioned Wood Extracts to Carboxylic Acids
[0070] Wood extracts can be fermented to carboxylic acids using a pure culture of microbes. For example, lactic acid has been produced from wood extracts. Please refer to the patent application entitled: "Production of Lactic Acid from Hemicellulose Extracts", United States Utililty Application No. 12/912,283, filed October 26, 2010, which is incorporated by reference herein.
[0071 ] SUB 5: Fermentation of Raw Wood Extracts to Mixed Carboxylic Acids
[0072] Fermentation of wood extracts to accumulate mixed acids has been demonstrated at the bench (100 mL) and floor ( 50 gal) scales.
[0073] Substrates:
[0074] For small scale experiments, wood extracts were collected from wood chip digesters located in the process development pilot plant in the Department of
Chemical and Biological Engineering at the University of Maine. For the floor scale experiments, extract was generated from mixed hardwood either in the Department of Chemical and Biological Engineering at the University of Maine or was kindly supplied by Old Town Fuel and Fiber, of Old Town ME. The extracts were used raw, without conditioning. The extracts used for this study were prepared by carrying out relatively mild condition extractions on hardwoods using either hot water or water mixed with green liquor.
[0075] Hot water extracts were obtained by cooking aspen wood strands in water. The small scale green liquor extract was a blended 1.44% green liquor hemicellulose extract from mixed hard wood chips. The total sugar content in the green liquor extract was measured to be around 10.25g/L and the acetic acid content was around 11.8g/L. The total sugar content in the hot water extract was measured to be around 27g/L and the acetic acid was about 9.6g/L. The large scale green liquor extracts were generated under similar but not identical conditions.
[0076] Media and Nutrients:
[0077] Nutrient sources used included corn steep liquor or dried chicken manure. Corn steep liquor was purchased from the Sigma- Aldrich. It was blended into the wood extracts at a concentration of 5g/L. For large scale fermentations, chicken manure was added at 20% by weight of carbohydrate in the extract. Ammonium bicarbonate, or lime and calcium carbonate were used as a buffering agents. The buffer was added in its solid form so as to maintain an optimum pH between 6.5 and 7.3. Ammonium bicarbonate dissolves completely upon addition and was added when the fermentation pH dropped below 5.8. For a green liquor extract the solution was already well buffered by the pulping salts and it did not require any buffer addition at the initiation of the experiment.
[0078] Inoculum:
[0079] Inocula for this experiment were obtained from various sources, including secondary clarifier sludge from the waste water treatment facility at a kraft pulp mill, saline sediments from The Great Salt Lake in Utah and salt water sediment collected from tidal flats near Rockland or Friendship, ME. To minimize the exposure to oxygen, these were collected in tightly sealed containers with the solids content having microbes covered with sea water. [0080] Methanogen Inhibitor:
[0081 ] Iodoform (CHI 3 ) was used as an inhibitor to prevent or diminish the production of methane. In several cases, methane production was low and no inhibitor was required. Excessive use of this chemical may harm the growth of the other microbes present in the mixed culture, and so should be used sparingly. The concentration required for effective methane inhibition is about 10 mg/L.
[0082] Fermentation Process:
[0083] The small scale experiments were carried out in duplicate or triplicate batch mode to determine reproducibility of results. The batch fermentations were performed in 250 ml serum bottles (Wheaton science products # 223950). The bottles were filled with approximately 100ml of the wood extract in each bottle, which left sufficient head space for accumulation of produced gasses. These bottles were placed in a shaking incubator (Sartorius Certomat BS-1) with continuous shaking at about 200 rpm and constant temperature maintenance. Two different temperatures are investigated for the process: one at 37°C and the other at 55°C.
[0084] The floor scale fermentations took place in a single 50 gallon fermentor. One experiment was carried out in sequencing batch mode, in which 20 to 50% of the volume of the fermentor was exchanged once per week with fresh wood extract. This sequencing batch fermentation converted the extract sugar oligomers to organic acids without need of added enzymes or extract conditioning.
[0085] The gas and liquid samples were taken at regular intervals of time so as to determine the total acid productivity, carboxylic acid concentration, total yield, available sugar concentrations and to check for any methane production during the process.
[0086] Analytical Methods
[0087] Gas Measurement and Analysis:
[0088] Gas samples were taken on a daily basis to measure volume (bench scale) and composition ( bench and floor scale) The total gas volume in the serum vial was measured by connecting it to a gas volume measuring device and noting down the total liquid displacement in the device. Methane and carbon dioxide concentrations in the produced gas were measured using a SRI multiple gas analyzer #2.
[0089] Liquid Samples:
[0090] Liquid samples were collected on a daily basis after the gas volume was measured. A total volume of approximately 1 ml was collected and was diluted with an appropriate volume of water so as to measure the products within the prescribed range of values. The samples were stored in a freezer in 1.5ml micro- centrifuge tubes. These collected samples were run through the HPLC and GC for determination of total acid production.
[0091 ] HPLC Analysis for Sugars and Acids:
[0092] The samples from the batch cultures were collected at regular intervals of time— typically on the order of once every 24 hours. The samples were analyzed to measure the total sugar concentrations in the reactor and also the total volatile solids present within the system. The measurement of the total sugars was analyzed on a Shimadzu Prominence HPLC system (Shimadzu scientific instruments, Columbus. MD.) which was equipped with an Aminex HPX-87H column supplied by the Bio- Rad Laboratories. For determinationof oligomer concentration, the liquid samples were acid hydrolyzed and the sugar concentration compared to the non-hydrolyzed samples. Lactic acid was also quantified by HPLC.
[0093] Gas Chromatography for Measuring Acids:
[0094] The liquid samples collected from the batch cultures are also analyzed on a GC system. C3- C7 acids in the sample were analyzed on a Shimadzu GC-2010 gas
chromatograph with a capillary column "Stebilwax-DA" supplied by Restek Corporation.
[0095] pH Analysis:
[0096] The pH analysis is performed using the Orion pH probe, calibrated using the known pH standards of pH 7.0 and pH 10.01. This helped to provide accurate results.
[0097] Results:
[0098] Bench scale scale fermentations were completed at four conditions: hot water extract at 37 and 55°C and green liquor extract at 37 and 55°C. A summary of results is presented in table SUB5.1. Floor scale fermentations were carried out at 37 C with calcium carbonate and lime as buffers. In general, higher temperature fermentation favors production of acetic acid whereas mesophilic temperature fermentation produces a broader spectrum of longer chain aliphatic acids.
Fermentation at thermophiUic temperature also tended to accumulate lactic acid, while at mesophilic temperature, the lactic acid was produced but then consumed again and converted into simple aliphatic acids. Time trends for bench scale accumulation of acetic acid, C3 - C7 acids, lactic acid, and formic acid are shown in Figures 4-7. A time trend for the sequenced batch floor scale fermentation is shown in Figure 8. At the time of this submission, this experiment was on going and not all data (such as C3- C7 acids after day 56) had been analyzed and recorded yet. It can be seen that the fermentation has operated for over 100 days with relatively steady performance.
Individual points far above or below the general trend lines represent the composition of the feed added on weekly intervals.
Table SUB5.1: Hot water and green liquor extract fermentations at thermophilic and mesophilic temperatures using ammonium bicarbonate as buffering agent.
[0099] SUB 6: TDO— Thermal Deoxygenation of Fermentation-Derived
Carboxylic Salts
[00100] Processes for thermal deoxygenation of fermentation-derived carboxylic salts, and more generally for energy densification of biomass-derived organic acids, are described in U.S. utility patent application serial no. 12/912,387, filed October 26, 2010, which is incorporated by reference herein. Also related is a provisional application that expands on the thermal deoxygenation of levulinic acid and covers effects of mixtures of organic acids, in particular formic acid: U.S. provisional patent application serial no. 61/438,419, filed Feb. 1, 2011, which is incorporated by reference herein. Following is a description of a particular example of a thermal deoxygenation process. [00101 ] Materials and Methods:
[00102] Dried residues from a fermentation of algefiber was ground up and inserted into a 300 mL Parr reactor. Thermal conversion was carried out by ramping up the temperature to 450 C while agitating the salts in the reactor in the presence of stainless steel ball bearings, which provide heat transfer to the solid salts. Volatile product was condensed with a chilled condenser and analyzed by GC-MS. Figure 9 shows the chromatogram for these products.
[00103] Results and Discussion:
[00104] The carboxylate components present in the dried residues included calcium salts of acetate, propionate and butyrate. Upon the thermal deoxygenation reaction, all of the anticipated ketones deriving from these salts were observed, including acetone, MEK and 2-pentanone. Other, larger and more oxygen reduced ketones were alswo identified, indicating an increasing degree of deoxygenation with the more complex starting material.
[00105]
[00106] SUB 7: Aldol Condensation Process for Furfural to Tridecane
[00107] An example of an aldol condensation process for furfural to tridecane is described in a publication by Xing et al. entitled "Production of jet and diesel fuel range alkanes from waste hemicellulose-derived aqueous solutions", Green Chem., 2010, 12, 1933-1946, which is incorporated by reference herein. Other aldol condensation processes are known in the art.
[00108] The principle and mode of operation of this invention have been explained and illustrated in its preferred embodiments. However, it must be understood that this invention may be practiced otherwise than as specifically explained and illustrated without departing from its spirit or scope.
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