EP0718392A1 - Procédé d'amélioration d'huiles de pyrolyse comme combustibles et comme produit de départ pour produits chimiques par réaction avec des alcools - Google Patents

Procédé d'amélioration d'huiles de pyrolyse comme combustibles et comme produit de départ pour produits chimiques par réaction avec des alcools Download PDF

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Publication number
EP0718392A1
EP0718392A1 EP95309400A EP95309400A EP0718392A1 EP 0718392 A1 EP0718392 A1 EP 0718392A1 EP 95309400 A EP95309400 A EP 95309400A EP 95309400 A EP95309400 A EP 95309400A EP 0718392 A1 EP0718392 A1 EP 0718392A1
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pyrolysis
alcohol
ethanol
liquid products
steps
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EP0718392B1 (fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C5/00—Production of pyroligneous acid distillation of wood, dry distillation of organic waste

Definitions

  • This invention relates to a method of upgrading liquid products freshly obtained from the pyrolysis of biomass to chemically and thermally stabilize said products.
  • a method is provided for modifying the liquid products from the pyrolysis of biomass by removing water therefrom and for converting aldehydic, ketonic and carboxylic compounds present therein to acetals, ketals and esters, respectively.
  • the said liquid product is referred to variously as the pyrolysate, pyrolytic oil or pyrolytic tar.
  • An object of this invention is to provide an economical method for improving the liquid products from the pyrolysis of lignocellulosic materials and other biomass for the purposes of their use as liquid fuels in boilers, turbines and internal combustion engines.
  • Another object of this invention is to provide a method for reducing the corrosivity of the said biomass pyrolysis oils to minimize problems with their storage and handling.
  • Yet another object of this invention is to provide a method for enhancing the chemical and thermal stability of the said pyrolysis oils so as to prevent aging and thus to avoid the consequent problems of viscosity increases with time and deposition in fuel lines.
  • a further object of this invention is to provide a method for enhancing the specific heating value of the said pyrolysis oils by chemical combination of these oils with a suitable alcohol and further by reducing the water content of the oils.
  • a method of upgrading liquid products freshly obtained from the pyrolysis of biomass to chemically and thermally stabilize said products comprising:
  • Figure 1 is a graph comparing the overall material balance initially after the ethanol is added and after the completion of the reaction.
  • the viscosity of the said pyrolysis oils are substantially reduced which facilitates the pumping and atomization of these oils in combustion apparatus and improves their filterability which could be relevant for removing cation contaminants.
  • This invention is based on the discovery that, under appropriate conditions, pyrolysis oils obtained in the manner described will chemically combine with substantial quantities of various alcohols and that compared with the original pyrolysis oil, this modified product is of lower acidity, contains reduced amounts of aldehydic groups, is of lower viscosity, contains less water and has a higher specific heating value. These enhancements are expected to minimize most of the problems associated with the use of these oils as fuels.
  • the alcohol combined is ethanol.
  • a hardwood pyrolysis oil was mixed at room temperature with an excess of ethanol, a small quantity of a mineral acid and a suitable dehydrating agent (for example, Molecular Sieve 3A), astonishingly up to 40 wt% of the alcohol on the basis of the organic fraction of the oil became chemically combined with the oil.
  • the resulting mixture had the desirable properties previously outlined.
  • Molecular Sieve 3A was used as a desiccant to remove water of reaction and thereby to drive any reversible reactions to completion.
  • This sieve has a sufficiently small pore size that only water should be absorbed within the pores though adsorption of organic species may be expected to occur on the external surfaces.
  • Fifteen grams of the activated molecular sieve were added to 40.6 g of the solution and the mixture was allowed to stand at room temperature. Within a few minutes, ester and acetal peaks began to appear in the gas chromatographic trace of the solution. After two hours, the solution was again analyzed quantitatively. In addition, the ethanol content was determined to be 35.9 wt% and the water content was 0.28 wt%.
  • the hardwood pyrolysis tars typically contain 52 wt% carbon and 6 wt% hydrogen on a moisture-free basis so the initial heating value is estimated to be 25.7 MJ/kg.
  • the calorific value of the tar after chemical combination with ethanol by making use of the same assumptions made in calculating the mass balance. The result is that the final elemental composition on an ethanol and water-free basis is 57 wt% carbon and 7.7 wt% hydrogen giving an estimated calorific value of 29.7 MJ/kg, an increase of about 16%.
  • Example 1 The extent of chemical combination of methanol with the organic fraction of the pyrolysate can be estimated using the calculational scheme outlined in Example 1. The result is that the uptake was only 0.0533 kg of methanol/kg of organic material originally present in the pyrolysis tar. This is much less than that obtained with ethanol in Example 1.
  • Example 3 a mixture of two alcohols was tested.
  • the hardwood pyrolysate used in Example 3 was dissolved in a mixture of methanol and n-propanol so that the initial concentrations of the alcohols were 18.72 and 28.01 wt% respectively.
  • the initial water content of this mixture was 4.31 wt% and the mass fraction of organics from the pyrolytic tar amounted to 48.96 wt% of it.
  • To this solution was added 3.34 wt% sulfuric acid as catalyst and the whole mixture placed over an amount of Molecular Sieve 3A equivalent to 80 wt% of it.
  • Example 1 After five hours on standing at room temperature, the mixture was analyzed and found to contain 12.32 wt% and 17.76 wt% of methanol and n-propanol respectively. The final water concentration was small (less than 0.2 wt%).
  • a pyrolytic tar obtained by flash pyrolysis of Eucalyptus wood.
  • This tar contained a high proportion of pyrolytic lignin (36.4 wt% of the organic fraction of the liquid) with a correspondingly low concentration of low molecular weight carbonyl compounds.
  • hydroxyacetaldehyde was only 7.1 wt% of the organic fraction of the tar.
  • hydrochloric acid was used as an alternative catalyst for the reaction.
  • esters of acetic and formic acids are known commercial chemicals, while the acetals of hydroxyacetaldehyde and glyoxal may have value as solvents, fuel additives or as flavour chemicals.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Fats And Perfumes (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Processing Of Solid Wastes (AREA)
EP95309400A 1994-12-22 1995-12-22 Procédé d'amélioration d'huiles de pyrolyse comme combustibles et comme produit de départ pour produits chimiques par réaction avec des alcools Expired - Lifetime EP0718392B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9426066 1994-12-22
GBGB9426066.8A GB9426066D0 (en) 1994-12-22 1994-12-22 Method of upgrading biomass pyrolysis liquids for use as fuels and as a source of chemicals by reaction with alcohols

Publications (2)

Publication Number Publication Date
EP0718392A1 true EP0718392A1 (fr) 1996-06-26
EP0718392B1 EP0718392B1 (fr) 1999-09-01

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Application Number Title Priority Date Filing Date
EP95309400A Expired - Lifetime EP0718392B1 (fr) 1994-12-22 1995-12-22 Procédé d'amélioration d'huiles de pyrolyse comme combustibles et comme produit de départ pour produits chimiques par réaction avec des alcools

Country Status (4)

Country Link
EP (1) EP0718392B1 (fr)
AT (1) ATE184045T1 (fr)
DE (1) DE69511832D1 (fr)
GB (1) GB9426066D0 (fr)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001094498A1 (fr) * 2000-06-08 2001-12-13 Valtion Teknillinen Tutkimuskeskus Procede et appareil de production d'huile pyrolytique
CN101812376A (zh) * 2010-04-20 2010-08-25 浙江大学 一种微波条件下酯化生物油催化提质的方法
US7998315B2 (en) 2006-08-16 2011-08-16 Aston University Biomass pyrolysis
WO2012035410A2 (fr) 2010-09-14 2012-03-22 IFP Energies Nouvelles Procédés de valorisation d'huile biologique en hydrocarbures de transport
CN101531922B (zh) * 2009-04-10 2012-05-23 中国林业科学研究院林产化学工业研究所 反应萃取提质生物质热解油的方法
US8323456B2 (en) 2010-08-26 2012-12-04 Kior, Inc. Removal of bound water from bio-oil
US8377152B2 (en) 2010-10-29 2013-02-19 Kior, Inc. Production of renewable bio-distillate
WO2013135986A1 (fr) 2012-03-12 2013-09-19 IFP Energies Nouvelles Procede optimise pour la valorisation de bio-huiles en carburants hydrocarbones
US8628589B2 (en) 2011-02-11 2014-01-14 Kior, Inc. Renewable heating oil
US8636888B2 (en) 2011-08-18 2014-01-28 Kior, Inc. Process for improving the separation of oil/water mixtures
US8669405B2 (en) 2011-02-11 2014-03-11 Kior, Inc. Stable bio-oil
US9039790B2 (en) 2010-12-15 2015-05-26 Uop Llc Hydroprocessing of fats, oils, and waxes to produce low carbon footprint distillate fuels
US9062264B2 (en) 2010-10-29 2015-06-23 Kior, Inc. Production of renewable bio-gasoline
US9187444B2 (en) 2013-03-08 2015-11-17 Upm-Kymmene Corporation Process for converting bio-oil
US9193926B2 (en) 2010-12-15 2015-11-24 Uop Llc Fuel compositions and methods based on biomass pyrolysis
US9387415B2 (en) 2011-08-18 2016-07-12 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
US9617489B2 (en) 2011-02-11 2017-04-11 Inaeris Technologies, Llc Liquid bio-fuels
US9631145B2 (en) 2007-11-20 2017-04-25 Ensyn Renewables, Inc. Rapid thermal conversion of biomass
US9809564B2 (en) 2006-04-03 2017-11-07 Pharmatherm Chemicals, Inc. Thermal extraction method and product
US9951278B2 (en) 2010-05-20 2018-04-24 Ensyn Renewables, Inc. Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas
US9969942B2 (en) 2011-12-12 2018-05-15 Ensyn Renewables, Inc. Systems and methods for renewable fuel
US10041667B2 (en) 2011-09-22 2018-08-07 Ensyn Renewables, Inc. Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same
US10337726B2 (en) 2015-08-21 2019-07-02 Ensyn Renewables, Inc. Liquid biomass heating system
US10400175B2 (en) 2011-09-22 2019-09-03 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
US10400176B2 (en) 2016-12-29 2019-09-03 Ensyn Renewables, Inc. Demetallization of liquid biomass
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
US10633606B2 (en) 2012-12-10 2020-04-28 Ensyn Renewables, Inc. Systems and methods for renewable fuel
US11028325B2 (en) 2011-02-22 2021-06-08 Ensyn Renewables, Inc. Heat removal and recovery in biomass pyrolysis

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8864999B2 (en) 2009-12-23 2014-10-21 Uop Llc Methods for regenerating acidic ion-exchange resins and reusing regenerants in such methods
US8524087B2 (en) 2009-12-23 2013-09-03 Uop Llc Low metal, low water biomass-derived pyrolysis oils and methods for producing the same
US8499702B2 (en) 2010-07-15 2013-08-06 Ensyn Renewables, Inc. Char-handling processes in a pyrolysis system
US9382489B2 (en) 2010-10-29 2016-07-05 Inaeris Technologies, Llc Renewable heating fuel oil
US9447350B2 (en) 2010-10-29 2016-09-20 Inaeris Technologies, Llc Production of renewable bio-distillate
US9315739B2 (en) 2011-08-18 2016-04-19 Kior, Llc Process for upgrading biomass derived products
US9347005B2 (en) 2011-09-13 2016-05-24 Ensyn Renewables, Inc. Methods and apparatuses for rapid thermal processing of carbonaceous material
US9044727B2 (en) 2011-09-22 2015-06-02 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 96, no. 18, 3 May 1982, Columbus, Ohio, US; abstract no. 96146001, POLK M. B.: "development of methods for the stabilization of pyrolytic oils." page 198; column right; XP002000127 *
POLK M.B., REPORT 1981 EPA600/2-81.201 *

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001094498A1 (fr) * 2000-06-08 2001-12-13 Valtion Teknillinen Tutkimuskeskus Procede et appareil de production d'huile pyrolytique
US9809564B2 (en) 2006-04-03 2017-11-07 Pharmatherm Chemicals, Inc. Thermal extraction method and product
US7998315B2 (en) 2006-08-16 2011-08-16 Aston University Biomass pyrolysis
US9631145B2 (en) 2007-11-20 2017-04-25 Ensyn Renewables, Inc. Rapid thermal conversion of biomass
US10544368B2 (en) 2007-11-20 2020-01-28 Ensyn Renewables, Inc. Rapid thermal conversion of biomass
CN101531922B (zh) * 2009-04-10 2012-05-23 中国林业科学研究院林产化学工业研究所 反应萃取提质生物质热解油的方法
CN101812376A (zh) * 2010-04-20 2010-08-25 浙江大学 一种微波条件下酯化生物油催化提质的方法
US10563127B2 (en) 2010-05-20 2020-02-18 Ensyn Renewables, Inc. Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas
US9951278B2 (en) 2010-05-20 2018-04-24 Ensyn Renewables, Inc. Processes for controlling afterburn in a reheater and for controlling loss of entrained solid particles in combustion product flue gas
US8323456B2 (en) 2010-08-26 2012-12-04 Kior, Inc. Removal of bound water from bio-oil
WO2012035410A2 (fr) 2010-09-14 2012-03-22 IFP Energies Nouvelles Procédés de valorisation d'huile biologique en hydrocarbures de transport
US9062264B2 (en) 2010-10-29 2015-06-23 Kior, Inc. Production of renewable bio-gasoline
US9850440B2 (en) 2010-10-29 2017-12-26 Inaeris Technologies, Llc Production of renewable bio-gasoline
US8377152B2 (en) 2010-10-29 2013-02-19 Kior, Inc. Production of renewable bio-distillate
US8454712B2 (en) 2010-10-29 2013-06-04 Kior, Inc. Production of renewable bio-distillate
US8506658B2 (en) 2010-10-29 2013-08-13 Kior, Inc. Production of renewable bio-distillate
US9039790B2 (en) 2010-12-15 2015-05-26 Uop Llc Hydroprocessing of fats, oils, and waxes to produce low carbon footprint distillate fuels
US9193926B2 (en) 2010-12-15 2015-11-24 Uop Llc Fuel compositions and methods based on biomass pyrolysis
US8628589B2 (en) 2011-02-11 2014-01-14 Kior, Inc. Renewable heating oil
US8669405B2 (en) 2011-02-11 2014-03-11 Kior, Inc. Stable bio-oil
US9617489B2 (en) 2011-02-11 2017-04-11 Inaeris Technologies, Llc Liquid bio-fuels
US11028325B2 (en) 2011-02-22 2021-06-08 Ensyn Renewables, Inc. Heat removal and recovery in biomass pyrolysis
US8636888B2 (en) 2011-08-18 2014-01-28 Kior, Inc. Process for improving the separation of oil/water mixtures
US9387415B2 (en) 2011-08-18 2016-07-12 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
US10427069B2 (en) 2011-08-18 2019-10-01 Inaeris Technologies, Llc Process for upgrading biomass derived products using liquid-liquid extraction
US10041667B2 (en) 2011-09-22 2018-08-07 Ensyn Renewables, Inc. Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same
US10400175B2 (en) 2011-09-22 2019-09-03 Ensyn Renewables, Inc. Apparatuses and methods for controlling heat for rapid thermal processing of carbonaceous material
US10794588B2 (en) 2011-09-22 2020-10-06 Ensyn Renewables, Inc. Apparatuses for controlling heat for rapid thermal processing of carbonaceous material and methods for the same
US9969942B2 (en) 2011-12-12 2018-05-15 Ensyn Renewables, Inc. Systems and methods for renewable fuel
US10975315B2 (en) 2011-12-12 2021-04-13 Ensyn Renewables, Inc. Systems and methods for renewable fuel
US10570340B2 (en) 2011-12-12 2020-02-25 Ensyn Renewables, Inc. Systems and methods for renewable fuel
WO2013135986A1 (fr) 2012-03-12 2013-09-19 IFP Energies Nouvelles Procede optimise pour la valorisation de bio-huiles en carburants hydrocarbones
US10633606B2 (en) 2012-12-10 2020-04-28 Ensyn Renewables, Inc. Systems and methods for renewable fuel
US9187444B2 (en) 2013-03-08 2015-11-17 Upm-Kymmene Corporation Process for converting bio-oil
US10640719B2 (en) 2013-06-26 2020-05-05 Ensyn Renewables, Inc. Systems and methods for renewable fuel
US10948179B2 (en) 2015-08-21 2021-03-16 Ensyn Renewables, Inc. Liquid biomass heating system
US10337726B2 (en) 2015-08-21 2019-07-02 Ensyn Renewables, Inc. Liquid biomass heating system
US10400176B2 (en) 2016-12-29 2019-09-03 Ensyn Renewables, Inc. Demetallization of liquid biomass
US10982152B2 (en) 2016-12-29 2021-04-20 Ensyn Renewables, Inc. Demetallization of liquid biomass

Also Published As

Publication number Publication date
DE69511832D1 (de) 1999-10-07
EP0718392B1 (fr) 1999-09-01
ATE184045T1 (de) 1999-09-15
GB9426066D0 (en) 1995-02-22

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