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WO2012015635A2 - Procédés de fabrication d'huiles de pyrolyse dérivées de biomasse à teneur réduite en acide et de phase stable - Google Patents

Procédés de fabrication d'huiles de pyrolyse dérivées de biomasse à teneur réduite en acide et de phase stable Download PDF

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Publication number
WO2012015635A2
WO2012015635A2 PCT/US2011/044595 US2011044595W WO2012015635A2 WO 2012015635 A2 WO2012015635 A2 WO 2012015635A2 US 2011044595 W US2011044595 W US 2011044595W WO 2012015635 A2 WO2012015635 A2 WO 2012015635A2
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WO
WIPO (PCT)
Prior art keywords
biomass
derived pyrolysis
pyrolysis oil
base
mixing
Prior art date
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Ceased
Application number
PCT/US2011/044595
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English (en)
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WO2012015635A3 (fr
Inventor
Mark B. Koch
Timothy A. Brandvold
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Honeywell UOP LLC
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UOP LLC
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Application filed by UOP LLC filed Critical UOP LLC
Publication of WO2012015635A2 publication Critical patent/WO2012015635A2/fr
Publication of WO2012015635A3 publication Critical patent/WO2012015635A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/04Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention generally relates to methods for producing biofueis, and more particularly relates to methods for producing phase stable, reduced acid biomass- derived pyrolysis oils.
  • 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 biofueis 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.
  • 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 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.
  • 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. DETAILED DESCRIPTION
  • 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 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 0 +
  • hydroxide ions OH "
  • 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 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 C0 3 ), and calcium carbonate (CaC0 3 ).
  • Exemplary suitable metal hydroxides comprise lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide ( OH), 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 phase stable, reduced acid biomass-derived pyrolysis oil has a water content no greater than 30 weight percent (wt.%).
  • the terms "30 weight percent” and “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).
  • 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 30 wt.%, at least a portion of the water is removed from the water-containing biomass- derived pyrolysis oil, the base, or both.
  • x the concentration of water in the phase stable, reduced acid biomass-derived pyrolysis oil expressed as g H 2 0/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 0/g starting oil (as determined by Karl Fischer Reagent Titration Method (ASTM D 1364), 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);
  • g 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, lOOmL) solution to 1.00 liters (L) in isopropanol.
  • TnBAH 0.05N tetra-n-butylammonium hydroxide solution
  • the solution is mixed thoroughly before transferring the solution to a Dosimat bottle. lmL of concentrated HC1 is added to lOOmL of deionized water and mixed thoroughly. 4mL of this solution is added to 140mL of DMF ( ⁇ , ⁇ -dimethylformamide) (available from, for example, Burdick & Jackson of Muskegon, MI (USA)) for titration of samples. To standardize the titrant, 0.15-0.20g of dried benzoic acid is weighed into a titration beaker and the weight recorded to the nearest 0.1 mg. 120mL of the DMF solution is added to the benzoic acid and titrated with the TnBAH solution. The standardization should be done in duplicate. The Normality is calculated to three significant figures and the standardization repeated every three hours.
  • the titration beaker is blanketed with nitrogen and stirred for 5 minutes before titration.
  • the selected base is added to the water-containing biomass-derived pyroiysis oil to produce reduced acid biomass-derived pyroiysis 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 pyroiysis 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 40°C.
  • the base is added at a temperature from 20°C to 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 ( 40% to 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.
  • the water content of the reduced acid biomass-derived pyrolysis oil to be produced (“x" in equation (I) above) is determined to be greater than 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.
  • phase stable, reduced acid biomass-derived pyrolysis oil having a water content no greater than 30 wt% is substantially homogenous, with an acidity (as measured by pH) reduced from that of conventional biomass-derived pyrolysis oil.
  • energy density of the phase stable, reduced acid biomass-derived pyrolysis oil is higher than that of conventional biomass-derived pyrolysis oil.
  • the increased pH, phase homogeneity, and higher energy density of the phase stable, reduced acid biomass-derived pyrolysis oil produced in accordance with exemplary embodiments as described herein improve its suitability as a fuel and biofuel.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

L'invention concerne des procédés de fabrication d'huiles de pyrolyse dérivées de biomasse à teneur réduite en acide et de phase stable. Une huile de pyrolyse dérivée de biomasse ayant une teneur en eau déterminée inférieure ou égale à 30 % en poids est décrite. Une base est mélangée avec l'huile de pyrolyse dérivée de biomasse pour fabriquer une huile de pyrolyse dérivée de biomasse à teneur réduite en acide. Une base est choisie parmi une base inorganique ou une base contenant de l'azote.
PCT/US2011/044595 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 Ceased WO2012015635A2 (fr)

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US12/845,519 2010-07-28
US12/845,519 US20120023809A1 (en) 2010-07-28 2010-07-28 Methods for producing phase stable, reduced acid biomass-derived pyrolysis oils

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WO2012015635A2 true WO2012015635A2 (fr) 2012-02-02
WO2012015635A3 WO2012015635A3 (fr) 2012-05-24

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US20120023809A1 (en) 2012-02-02
WO2012015635A3 (fr) 2012-05-24

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