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US20120023809A1 - Methods for producing phase stable, reduced acid biomass-derived pyrolysis oils - Google Patents

Methods for producing phase stable, reduced acid biomass-derived pyrolysis oils Download PDF

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Publication number
US20120023809A1
US20120023809A1 US12/845,519 US84551910A US2012023809A1 US 20120023809 A1 US20120023809 A1 US 20120023809A1 US 84551910 A US84551910 A US 84551910A US 2012023809 A1 US2012023809 A1 US 2012023809A1
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pyrolysis oil
derived pyrolysis
biomass
base
water
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US12/845,519
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Mark B. Koch
Timothy A. Brandvold
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Honeywell UOP LLC
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UOP LLC
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Assigned to UOP LLC reassignment UOP LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BRANDVOLD, TIMOTHY A., KOCH, MARK B.
Priority to PCT/US2011/044595 priority patent/WO2012015635A2/fr
Priority to ARP110102704A priority patent/AR082386A1/es
Publication of US20120023809A1 publication Critical patent/US20120023809A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention generally relates to methods for producing biofuels, and more particularly relates to methods for producing phase stable, reduced acid biomass-derived pyrolysis oils.
  • Fast pyrolysis is a thermal process during which solid carbonaceous biomass feedstock, i.e., “biomass”, such as wood waste, agricultural waste, etc., is rapidly heated to pyrolysis temperatures of about 300° C. to about 900° C. in the absence of air using a pyrolysis reactor. Under these conditions, solid and gaseous pyrolysis products are formed. A condensable portion (vapors) of the gaseous pyrolysis products is condensed into biomass-derived pyrolysis oil.
  • biomass feedstock i.e., “biomass”, such as wood waste, agricultural waste, etc.
  • Biomass-derived pyrolysis oil can be burned directly as fuel for certain boiler and furnace applications, and can also serve as a potential feedstock in the production of biofuels in petroleum refineries or in stand-alone process units.
  • Biomass-derived pyrolysis oil has the potential to replace up to 60% of transportation fuels, thereby reducing the dependency on conventional petroleum and reducing its environmental impact.
  • biomass-derived pyrolysis oil is a complex, highly oxygenated organic liquid having properties that currently limit its utilization as a fuel/biofuel, particularly for diesel applications.
  • biomass-derived pyrolysis oil has high acidity (with a low pH and high total acid number (TAN)) making it corrosive to storage, pipes, and downstream equipment, with low energy density and susceptibility to increased viscosity over time.
  • Conventional biomass-derived pyrolysis oil typically has a pH of ⁇ 3 and a TAN >150.
  • the high acidity and low energy density of the biomass-derived pyrolysis oil is attributable in large part to oxygenated hydrocarbons in the oil, particularly carboxylic acids such as formic acid, acetic acid, etc.
  • Oxygenated hydrocarbons as used herein are organic compounds containing hydrogen, carbon, and oxygen. The oxygenated hydrocarbons in the oil are derived from oxygenated hydrocarbons in the gaseous pyrolysis products produced during pyrolysis.
  • phase instability results in phase separation, viscosity increases, and often, solids formation. Such phase instability reduces utilization of the biomass-derived pyrolysis oil as a biofuel.
  • phase stable, reduced acidity biomass derived pyrolysis oils it is desirable to provide methods for producing phase stable, reduced acidity biomass derived pyrolysis oils. It is also desirable to produce phase stable, reduced acid biomass-derived pyrolysis oils having increased energy density. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the and the appended claims, taken in conjunction with the accompanying drawings and this background of the invention.
  • a method for producing phase stable, reduced acid biomass-derived pyrolysis oil comprises providing a biomass-derived pyrolysis oil having a determined water content no greater than about 30% by weight.
  • a base is mixed with the biomass-derived pyrolysis oil.
  • Methods are provided for producing phase stable, reduced acid biomass-derived pyrolysis oil from water-containing biomass-derived pyrolysis oil, in accordance with yet another exemplary embodiment of the present invention.
  • the method comprises selecting a base comprising either an inorganic base or a nitrogen-containing base. At least a portion of the water is removed from the water-containing biomass-derived pyrolysis oil, the base, or both.
  • the base is added to the water-containing biomass-derived pyrolysis oil to produce reduced acid biomass-derived pyrolysis oil.
  • Methods are provided for producing phase stable, reduced acid biomass-derived pyrolysis oil in accordance with yet another exemplary embodiment of the present invention.
  • the method comprises providing water-containing biomass-derived pyrolysis oil.
  • a base adapted to be added to the water-containing biomass-derived pyrolysis oil to produce reduced acid biomass-derived pyrolysis oil is selected.
  • the water content of the reduced acid biomass-derived pyrolysis oil is determined. If the reduced acid biomass-derived pyrolysis oil is determined to have a water content greater than about 30 wt %, at least a portion of the water is removed from the water-containing biomass-derived pyrolysis oil, the base, or both.
  • the selected base is added to the water-containing biomass-derived pyrolysis oil.
  • FIG. 1 is a flow chart of a method for producing phase stable, reduced acid biomass-derived pyrolysis oils, according to exemplary embodiments of the present invention.
  • phase stable, reduced acid biomass-derived pyrolysis oils are directed to a method for producing phase stable, reduced acid biomass-derived pyrolysis oils.
  • oil produced according to exemplary embodiments of the present invention is generally described herein as a “reduced acid biomass-derived pyrolysis oil”, this term generally includes any oil produced having a lower acidity than the conventional biomass-derived pyrolysis oil from which it is derived.
  • phase stability as used herein means the ability of the oil to resist changes in chemical composition and maintain homogeneity. Phase instability results in phase separation, viscosity increases and often, solids formation.
  • the phase stable, reduced acid biomass-derived pyrolysis oil has higher energy density than conventional biomass-derived pyrolysis oil.
  • Higher energy density as used herein means that the phase stable, reduced acid biomass-derived pyrolysis oil has an increased heat of combustion as compared to conventional biomass-derived pyrolysis oil. An increased heat of combustion increases the suitability of the oil as fuel and biofuel.
  • a method 10 for producing phase stable, reduced acid biomass-derived pyrolysis oil begins by providing conventional biomass-derived pyrolysis oil from a source such as a feed tank or other source operative to provide such oil (step 100 ).
  • Biomass-derived pyrolysis oil is available from, for example, Ensyn Technologies Inc., of Ontario, Canada.
  • the composition of biomass-derived pyrolysis oil is somewhat dependent on feedstock and processing variables.
  • the biomass-derived pyrolysis oil may be produced, for example, from fast pyrolysis of wood biomass in a pyrolysis reactor. However, virtually any form of biomass can be considered for pyrolysis to produce biomass-derived pyrolysis oil.
  • biomass-derived pyrolysis oil may be derived from biomass material such as bark, agricultural wastes/residues, nuts and seeds, algae, grasses, forestry residues, cellulose and lignin, or the like.
  • the biomass-derived pyrolysis oil may also be obtained by different modes of pyrolysis, such as fast pyrolysis, vacuum pyrolysis, catalytic pyrolysis, and slow pyrolysis (also known as carbonization) or the like.
  • Biomass-derived pyrolysis oil typically contains about 20-33% by weight water with a high acidity (TAN >150).
  • the water content in the starting water-containing biomass-derived pyrolysis oil may be measured, for example, by Karl Fischer Reagent Titration Method (ASTM D1364), as known to one skilled in the art.
  • biomass-derived pyrolysis oil may alternatively be referred to herein as “water-containing biomass-derived pyrolysis oil.”
  • method 10 continues by selecting a base to neutralize the carboxylic acids in the water-containing biomass-derived pyrolysis oil, thereby reducing the acidity of the water-containing biomass-derived pyrolysis oil (step 200 ).
  • neutralization is a chemical reaction whereby the acids in the water-containing biomass-derived pyrolysis oil and the selected base react to form water and a salt.
  • solvated hydrogen ions hydroonium ions, H 3 O +
  • hydroxide ions OH ⁇
  • water is not always formed; however, there is always a donation of protons.
  • Neutralization in accordance with exemplary embodiments raises the pH and lowers the TAN of water-containing biomass-derived pyrolysis oil.
  • the target pH levels are in the range of about 4.5 to about 4.9.
  • the base may be in an aqueous solution or a solid base. The selected base is adapted to be added to the water-containing biomass-derived pyrolysis oil as hereinafter described.
  • the base comprises either an inorganic base or a nitrogen-containing base.
  • the inorganic bases are strong bases.
  • a strong base is a basic chemical compound that is able to deprotonate weak acids in an acid-base reaction. Compounds with a pK a of more than about 13 are considered strong bases. Very strong bases are even able to deprotonate very weakly acidic C—H groups in the absence of water.
  • Suitable exemplary inorganic bases include metal oxides, metal alkoxides, metal carbonates of the alkali and alkaline earth metals, alkali and alkaline earth exchanged zeolites (e.g., Ca—X zeolite), mixed metal oxides (e.g., hydrotalcite), metal hydroxides, and combinations thereof.
  • Exemplary suitable metal oxides comprise calcium oxide, magnesium oxide, and combinations thereof.
  • Exemplary suitable metal alkoxides comprise sodium ethoxide, potassium tert-butoxide, and combinations thereof.
  • Exemplary suitable metal carbonates comprise potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), and calcium carbonate (CaCO 3 ).
  • Exemplary suitable metal hydroxides comprise lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), caesium hydroxide (CsOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ), strontium hydroxide (Sr(OH) 2 ), barium hydroxide (Ba(OH) 2 ), and combinations thereof.
  • the metal hydroxides generate water when neutralizing carboxylic acids, with the essential reaction being the combination of hydrogen ions with hydroxyl ions to form water.
  • the maximum amount of water produced during neutralization with a metal hydroxide comprises 1 mole eq water to 1 mole eq of neutralized acid. The exact amount of the water produced depends on the selected base.
  • the nitrogen-containing base can be a tetraalkylammonium hydroxide, an amine, or combinations thereof.
  • Suitable tetraalkylammonium hydroxides include tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, and combinations thereof.
  • Amines suitable for use herein include dialkyl amines, trialkyl amines, or combinations thereof.
  • the amine may also comprise pyrrolidine, morpholine, piperidine, N-methylpyrrolidine, and NR 1 R 2 X wherein R 1 and R 2 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec. butyl, pentyl, hexyl, cyclohexyl, and benzyl groups; and X is selected from the group consisting of hydrogen, R 1 , and R 2 . Neutralization with non-hydroxyl bases do not generate water.
  • the phase stable, reduced acid biomass-derived pyrolysis oil has a water content no greater than about 30 weight percent (wt. %).
  • the terms “about 30 weight percent” and “about 30% by weight” as used herein means +/ ⁇ 3 weight percent of 30 weight percent.
  • the water content of the reduced acid biomass-derived pyrolysis oil after the selected base is added to the water-containing biomass-derived pyrolysis oil is determined (the “determined water content”) (step 300 ). If the water content of the reduced acid biomass-derived pyrolysis oil to be produced is determined to be less than about 30 wt.
  • the selected base is added to the water-containing biomass-derived pyrolysis oil to produce reduced acid biomass-derived pyrolysis oil.
  • the water content of the reduced acid biomass-derived pyrolysis oil to be produced is determined to be greater than about 30 wt. %, at least a portion of the water is removed from the water-containing biomass-derived pyrolysis oil, the base, or both.
  • the water content is determined by the following equation (I) (which takes into account the water in the water-containing biomass-derived pyrolysis oil and the water associated with the base (water in the base and the water produced during neutralization)):
  • x the concentration of water in the phase stable, reduced acid biomass-derived pyrolysis oil expressed as g H 2 O/g oil;
  • a the amount of the starting water-containing biomass-derived pyrolysis oil to be treated in grams
  • b the concentration of water in the starting water-containing biomass-derived pyrolysis oil expressed as g H 2 O/g starting oil (as determined by Karl Fischer Reagent Titration Method (ASTM D1364), as noted previously);
  • c the concentration of carboxylic acids in the starting water-containing biomass-derived pyrolysis oil expressed as mol acid/gram oil (determined by the method as hereinafter described);
  • d the concentration of free water in the neutralizing base in gH 2 O/gram of base (as determined, for example, by Karl Fischer Reagent Titration Method (ASTM D1364);
  • e the concentration of neutralizing base in mol base/gram as provided by the manufacturer or determined using methods known by those skilled in the art (i.e., dilution of a more concentrated base solution and/or titration against a standard acid);
  • g an amount of water in grams produced by neutralization of the pyrolysis oil acids. This is dependent on the nature of the neutralizing base such that for:
  • the concentration of carboxylic acids in the starting water-containing biomass-derived pyrolysis oil (“c” in equation (I) above), is determined by the following method adapted from Dence, C. W., Determination of carboxyl groups [in lignin], Methods Lignin Chem. (1992), p. 458-464:
  • a solution of 0.05N tetra-n-butylammonium hydroxide solution (TnBAH) is prepared by diluting 50.0 milliliters (mL) of 1.0N TnBAH (Aldrich, SAP#1014519, 100 mL) solution to 1.00 liters (L) in isopropanol. The solution is mixed thoroughly before transferring the solution to a Dosimat bottle.
  • N g ⁇ ⁇ Benzoic ⁇ ⁇ Acid ( mL ⁇ ⁇ titrant ) ⁇ ( 0.12212 )
  • 0.05-0.08 g of p-hydroxybenzoic acid is weighed into a titration beaker.
  • the DMF/HCl solution is added to the p-hydroxybenzoic acid.
  • the resultant solution is titrated through the 3 rd inflection. This is the blank used to calculate the HCl correction, and can be used as a QC for the phenolic hydroxyl titrations.
  • 0.3-0.4 g of lignin and 0.05-0.08 g of p-hydroxybenzoic acid are weighed into a titration beaker.
  • the DMF/HCl solution is added to the titration beaker.
  • the titration beaker is blanketed with nitrogen and stirred for 5 minutes before titration.
  • the solution is titrated with 0.05N TnBAH to the 3 rd inflection.
  • the theoretical titer of the internal standard used in the blank or sample titration is calculated according to the following equation:
  • a ⁇ ⁇ ( mL ) g ⁇ ⁇ pHBA 0.13812 ⁇ ( N )
  • c (mL) [(measured volume to reach 2 nd inflection of blank) ⁇ (measured 1 st inflection)] ⁇ ( a (mL, calculated above))
  • the selected base is added to the water-containing biomass-derived pyrolysis oil to produce reduced acid biomass-derived pyrolysis oil (step 400 ).
  • the amount of the selected base (f in equation (I) above and equation (II) below) to be added to the water-containing biomass-derived pyrolysis oil to neutralize the starting carboxylic acid content is determined according to the following equation (II):
  • a the amount of the starting water-containing biomass-derived pyrolysis oil to be treated in grams
  • c the concentration of carboxylic acids in the starting water-containing biomass-derived pyrolysis oil expressed as mol acid/gram oil (as determined above).
  • e the concentration of neutralizing base in mol base/gram as provided by the manufacturer or determined using methods known by those skilled in the art (i.e., dilution of a more concentrated base solution and/or titration against a standard acid).
  • the base is added at an effective rate to maintain the temperature of the mixture at less than about 40° C.
  • the base is added at a temperature from about 20° C. to about 40° C.
  • a solid base may be dissolved in an organic solvent (thereby producing a base solution) prior to addition of the base to the water-containing biomass-derived pyrolysis oil.
  • Suitable exemplary organic solvents comprise methanol, ethanol, and combinations thereof.
  • the addition of the solvent (about 40% to about 95% by volume) allows the base to be added gradually in a controlled manner, without raising the water content of the resultant phase stable, reduced acid biomass-derived pyrolysis oil above the threshold value.
  • the solvent raises the solubility of the components in the mixture. Less solvent is needed when the water produced in the titration (during neutralization) does not exceed the solubility level of the biomass-derived pyrolysis oil. If an excess of base is added, a precipitate may form that may be removed by filtration.
  • water content of the reduced acid biomass-derived pyrolysis oil to be produced (“x” in equation (I) above) is determined to be greater than about 30 weight percent, at least a portion of the water is removed from the water-containing biomass-derived pyrolysis oil, the base, or both (step 500 ) prior to addition of the selected base as described above (step 400 ).
  • Water may be removed from the water-containing biomass-derived pyrolysis oil, the base, or both by methods known to one skilled in the art, for example, distillation, evaporation, or the like.
  • a base may be selected specifically because it does not generate water during the neutralization reaction, for example, the non-hydroxide bases and the nitrogen-containing bases, and therefore little or no water may have to be removed to produce the reduced acid biomass-derived pyrolysis oil with a water content below the threshold value, i.e., a phase stable, reduced acid biomass-derived pyrolysis oil.
  • the water-containing biomass-derived pyrolysis oil has a water content below the threshold value and the selected base does not generate water during neutralization, the removal of water from the reduced acid biomass-derived pyrolysis oil is unnecessary to produce a phase stable, reduced acid biomass-derived pyrolysis oil because the water content thereof has been maintained below the threshold value.
  • the reduced acid biomass-derived pyrolysis oil may be inspected (step 600 ) to verify that there is no phase separation. Phase separation typically occurs, if at all, within 48 hours after the base is added to the water-containing biomass-derived pyrolysis oil. If phase separation occurs, additional water may be removed from the reduced acid biomass-derived pyrolysis oil (step 700 ) by methods known to one skilled in the art, for example distillation and evaporation, until no phase separation is observed on inspection.
  • the phase stable, reduced acid biomass-derived pyrolysis oil having a water content no greater than about 30 wt % is substantially homogenous, with an acidity (as measured by pH) reduced from that of conventional biomass-derived pyrolysis oil.
  • the energy density of the phase stable, reduced acid biomass-derived pyrolysis oil is higher than that of conventional biomass-derived pyrolysis oil.

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PCT/US2011/044595 WO2012015635A2 (fr) 2010-07-28 2011-07-20 Procédés de fabrication d'huiles de pyrolyse dérivées de biomasse à teneur réduite en acide et de phase stable
ARP110102704A AR082386A1 (es) 2010-07-28 2011-07-27 Metodos de produccion de aceites de pirolisis derivados de biomasa con reduccion de la acidez de fase estable

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