WO2014007898A1 - Procédés d'élimination de sulfate dans une gazéification hydrothermale catalytique en phase liquide d'une biomasse - Google Patents

Procédés d'élimination de sulfate dans une gazéification hydrothermale catalytique en phase liquide d'une biomasse Download PDF

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Publication number
WO2014007898A1
WO2014007898A1 PCT/US2013/034552 US2013034552W WO2014007898A1 WO 2014007898 A1 WO2014007898 A1 WO 2014007898A1 US 2013034552 W US2013034552 W US 2013034552W WO 2014007898 A1 WO2014007898 A1 WO 2014007898A1
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WO
WIPO (PCT)
Prior art keywords
feedstock
wet
sulfate
contaminants
wet biomass
Prior art date
Application number
PCT/US2013/034552
Other languages
English (en)
Inventor
Douglas C. Elliott
James R. Oyler
Original Assignee
Battelle Memorial Institute
Genifuel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/541,003 external-priority patent/US8608981B2/en
Application filed by Battelle Memorial Institute, Genifuel Corporation filed Critical Battelle Memorial Institute
Priority to EP13813442.4A priority Critical patent/EP2870224A4/fr
Priority to IN9147DEN2014 priority patent/IN2014DN09147A/en
Publication of WO2014007898A1 publication Critical patent/WO2014007898A1/fr

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Classifications

    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/086—Hydrothermal carbonization
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • This document describes methods for treating wet biomass by liquid-phase catalytic hydrothermal gasification that address the problem of poisoning and fouling of the catalyst, especially by sulfate contaminants that are soluble in the liquid portion of the wet biomass feedstock.
  • the methods involve operations at temperatures and pressures that maintain the wet biomass feedstock in the liquid phase without forming a critical or supercritical fluid.
  • the wet biomass feedstock comprises solid and/or soluble biomass, soluble sulfate contaminants, and sub- critical liquid water.
  • Some biomass feedstocks can also comprise inorganic wastes that can cause plugging and poisoning of the catalyst. These sulfate contaminants and inorganic wastes can be precipitated out before gasification by heating the wet biomass feedstock prior to exposure to the catalyst according to embodiments of the present invention.
  • treatment of the wet biomass feedstock comprises heating 100 the wet biomass with a heating unit to a pre-treatment temperature sufficient for organic constituents in the feedstock to decompose, for precipitates of inorganic wastes to form, for preheating the wet feedstock in preparation for removal of the soluble sulfate contaminants, or combinations thereof.
  • the process further comprises reacting 101 the soluble sulfate with cations present in the feedstock in order to yield sulfate-containing precipitates and separating 102 the precipitates of inorganic wastes and the sulfate-containing precipitates out the wet biomass feedstock.
  • the liquid of the wet biomass feedstock can have a decreased sulfate content.
  • the feedstock can have less than 20 ppm sulfate content. Having removed much of the inorganic wastes and the soluble sulfate contaminants that can cause poisoning and fouling, the wet biomass feedstock can be exposed to the heterogeneous metal catalyst for gasification 103.
  • biomass refers to biological material that can be used for fuel or for industrial production.
  • Exemplary biomass can include, but is not limited to, biosludge from wastewater treatment facilities, sewage sludge from municipal treatment systems, wet byproducts from biorefinery operations, wet byproducts/residues from food processing, animal waste and waste from centralized animal raising facilities.
  • biomass can also refer to various organic wastes. Examples include, but are not limited to organic chemical manufacturing wastewater streams, and industrial wastewater containing organics.
  • Biomass commonly comprises organic matter that can be treated in a continuous reactor, according to embodiments of the present invention, to yield a gas containing hydrogen or useful for hydrogen production (e.g., methane).
  • Common inorganic contaminants which can poison and/or foul the catalyst, can include, but are not limited to minerals comprising Ca, Mg, P, and/or Fe.
  • Sulfur-containing contaminants can occur in two different forms, reduced and oxidized.
  • the reduced sulfur contaminants can occur in protein structures.
  • the oxidized sulfur contaminants can occur as soluble sulfate contaminants.
  • the sulfate contaminants can arise, for example, from oxidation of protein structures.
  • the biomass can further comprise at least a partial source of the cations that react with the soluble sulfate contaminants to yield sulfate-containing precipitates.
  • the biomass can comprise certain compounds that yield cations in the feedstock at processing conditions.
  • the cations can be provided by adding 104 a salt to the feedstock.
  • cations can include, but are not limited to, barium and calcium.
  • the salt added to the feedstock can be substantially water-soluble.
  • An example of a water-soluble salt comprising calcium can include, but is not limited to, calcium ascorbate.
  • the salt can be only partially water-soluble.
  • Examples of calcium salts can include, but are not limited to, calcium oxide, calcium hydroxide, and calcium carbonate.
  • the heterogeneous catalysts comprise Ru, Ni, and/or Ni with added Na.
  • the Na can be in the form of a sodium carbonate co-catalyst.
  • the catalyst comprises Ru on a carbon support. Furthermore, the catalyst can be configured to gasify the organic constituents into a hydrogen-containing feedstock for subsequent catalytic reformation.
  • Separation of solids, including the sulfate-containing precipitates, from the heated wet biomass feedstock can be achieved using a solids separation unit, which can include, but is not limited to, a gravity separation unit, a hydrocyclonic separation unit, and/or a filtration unit.
  • a solids separation unit which can include, but is not limited to, a gravity separation unit, a hydrocyclonic separation unit, and/or a filtration unit.
  • Removal of reduced sulfur can be achieved using a sulfur separation unit comprising, for example, an adsorbent bed with a metal or metal oxide.
  • Embodiments of the catalytic hydrothermal process occur at conditions in which water is below its critical point (i.e., sub-critical) and remains in the liquid phase.
  • the wet biomass feedstock is heated to a pre-treatment temperature of at least 300 °C.
  • a catalytic reactor containing the heterogeneous catalyst is heated to a temperature between 250 °C and 374 °C.
  • the pressure in the catalytic reactor can be up to 23 MPa without transitioning into a critical or supercritical fluid.
  • the catalytic reactor is operated at temperatures between 340 °C and 360 °C and pressures between 18 MPa and 21 MPa.
  • sub-critical liquid refers to the liquid of the feedstock that is below the effective critical point and not just below the standard critical point of water.
  • the solubility of the sulfate-containing precipitate is low enough at the operating conditions described herein for hydrothermal gasification (i.e., at elevated temperatures) that the cations can facilitate removal of the otherwise soluble sulfate contaminants by reaction to form precipitates.
  • the cations were too soluble to be useful in removing soluble sulfate contaminants.
  • a surprising result was that the cations and the soluble sulfate contaminants were soluble in the feedstock at conventional temperatures and pressures (i.e.
  • the process further comprises capturing the soluble, reduced sulfur contaminants in an adsorbent bed by reaction with a metal or a metal oxide.
  • This document also describes an embodiment encompassing a catalytic hydrothermal process for treating a wet biomass feedstock comprising biomass, inorganic contaminants, soluble sulfate contaminants, and sub-critical liquid water.
  • the process operates at temperatures and pressures that maintain the wet biomass feedstock in liquid phase without forming a supercritical fluid and is characterized by adding a salt comprising a calcium cation to the feedstock.
  • the process further comprises heating under pressure the wet biomass feedstock to a pre-treatment temperature, which is at least 300 °C and is sufficient for organic constituents in the feedstock to decompose, for precipitates of inorganic wastes to form, and for preheating the wet feedstock in preparation for removal of the soluble sulfate contaminants and reacting the soluble sulfate contaminants with calcium cations from the salt to yield a sulfate-containing precipitate.
  • the precipitates of inorganic wastes and the sulfate-containing precipitates are separated out the wet biomass feedstock to yield a liquid of the wet biomass feedstock having a decreased sulfate content, which can then be gasified.
  • FIG. 1 is a block diagram depicting removal of soluble sulfate contaminants according to embodiments of the present invention.
  • FIG. 2 is a diagram depicting system for hydrothermal gasification of biomass according to one embodiment of the present invention.
  • the wet biomass feedstock typically comprises at least two types of solids that can clog, plug, and/or poison the catalyst - organic matter and mineral materials.
  • proper preheating of the biomass feedstock can transform the solid organic matter to liquid and/or gas, both of which can pass into the catalytic reactor without causing plugging and/or poisoning. Furthermore, there is little solid char formation. In the prior art, char can be a major product at lower temperature ( ⁇ 300C), sub-critical conditions.
  • the present invention also calls for sub-critical liquid-phase operating conditions and provides approaches for the minerals to be precipitated and separated from the liquid stream while allowing the liquefied biomass organics to pass on to the catalytic reactor. With the solids separated, a sulfur scrubber bed could also be used without plugging, as well as the catalytic bed for gasification.
  • heating of the feedstock can also concurrently cause precipitation of inorganic material that might otherwise deactivate the catalyst by plugging and/or poisoning.
  • a continuous- flow reactor system comprises a wet biomass feedstock heater 201, a sulfur removal unit 203, a solids separation unit 202, a catalytic reactor 204, and a gas-liquid separator 205.
  • the large bore head, valve, and tubing allowed suctioning and pumping of the viscous slurries while still allowing the pump to operate at 3500 psi max. All valves and valve trim (except the pressure-control valve) were made of SS. The feeding rates were measured directly by the screw drive of the positive displacement syringe pump.
  • the preheater was a 1 -liter 316 SS vessel that functioned as a continuous-flow, stirred- tank reactor in which the feedstock was brought to the reaction temperature. In the process of heat up, the organics in the biomass were pyrolyzed and liquefied while inorganic components, such as calcium phosphates, formed and precipitated as solids. Furthermore, as described elsewhere herein, cations present in the feedstock can react with the soluble sulfate contaminants to form sulfate- containing precipitates, which can be removed to ultimately reduce the content of sulfate contaminants in the feedstock.
  • the catalytic reactor was constructed of 304 SS and had an inner diameter of one inch with a length of 72 inches.
  • the reactor had bolted-closure endcaps with metal o-rings on each end. Catalyst pellets were supported in the reactor on a circle of fine screen.
  • the reactor furnace was a 6-kWe resistance heater split into three separately controllable zones. The pressure was controlled with a dome-loaded diaphragm back-pressure regulator.
  • a solid separations unit was placed in the process line between the preheater and the reactor to capture and remove the solids before they reached the catalyst bed, where, in previous tests, they have collected and caused flow plugging.
  • These solids can comprise precipitates of the inorganic contaminants and/or the sulfate-containing precipitates.
  • a sulfur scrubber trap incorporating a chemical trap for reduced sulfur forms was also used.
  • the reduced sulfur components reacted with the trap material to form insoluble sulfide, which prevented their passing into the catalyst bed where they could react with the metal of the catalyst and destroy its catalytic capability.
  • Phosphate in the feedstock at about 940 ppm was found to be absent, ⁇ lppm, following the processing. Sulfate was also present in the feed at 35 ppm but was found in the range of 2 to 10 ppm in the effluent.
  • a feed comprising sulfate and a feed comprising sulfate along with calcium ascorbate as a calcium material were compared to specifically determine the effectiveness of reducing sulfate contaminants from a wet biomass feedstock.
  • solutions of sodium sulfate and calcium ascorbate were brought to 350C in a stirred tank reactor and the solid precipitate (calcium sulfate) separated by settling in a subsequent vessel.
  • the sulfate content in the remaining liquid solution was monitored as a function of time.
  • the source was switched to the feed comprising calcium ascorbate.
  • the sulfate content drops from a value greater than 300 ppm to a value of about 20 ppm.
  • Table 1 A summary of sulfate content in a feedstock with and without calcium ascorbate providing Ca cations.
  • cations are present in the feedstock without having added a salt.
  • salt addition may not be needed because there are sufficient cations present such that a stoichiometric amount can react with the soluble sulfate contaminants and form insoluble sulfate precipitates. If there is an insufficient amount of cations, then a salt can be added to the feedstock.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un traitement de charge de départ de biomasse humide par gazéification hydrothermale catalytique en phase liquide qui doit s'attaquer à l'encrassement et à l'empoisonnement du catalyseur. Une solution peut mettre en jeu le chauffage de la biomasse humide par une unité de chauffage à une température de prétraitement suffisante pour que les constituants organiques dans la charge de départ se décomposent, pour que des précipités de déchets inorganiques se forment, pour préchauffer la charge de départ humide en préparation pour une élimination ultérieure de contaminants sulfates solubles, ou des combinaisons de ceux-ci. Le traitement comprend en outre la réaction des contaminants sulfates solubles avec des cations présents dans la matière de charge de départ pour fournir un précipité contenant du sulfate et la séparation des précipités inorganiques et/ou des précipités contenant du sulfate hors de la charge de départ humide. Ayant éliminé beaucoup des déchets inorganiques et des contaminants sulfates qui peuvent provoquer un empoisonnement et un encrassement, la charge de départ de biomasse humide peut être exposée au catalyseur hétérogène pour une gazéification.
PCT/US2013/034552 2012-07-03 2013-03-29 Procédés d'élimination de sulfate dans une gazéification hydrothermale catalytique en phase liquide d'une biomasse WO2014007898A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP13813442.4A EP2870224A4 (fr) 2012-07-03 2013-03-29 Procédés d'élimination de sulfate dans une gazéification hydrothermale catalytique en phase liquide d'une biomasse
IN9147DEN2014 IN2014DN09147A (fr) 2012-07-03 2013-03-29

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/541,003 2012-07-03
US13/541,003 US8608981B2 (en) 2008-01-31 2012-07-03 Methods for sulfate removal in liquid-phase catalytic hydrothermal gasification of biomass

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WO2014007898A1 true WO2014007898A1 (fr) 2014-01-09

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EP (1) EP2870224A4 (fr)
IN (1) IN2014DN09147A (fr)
WO (1) WO2014007898A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10688464B2 (en) 2017-06-05 2020-06-23 General Atomics Corrosion inhibition in hydrothermal processing
CN114891545A (zh) * 2022-05-07 2022-08-12 深圳市沃尔奔达新能源股份有限公司 一种超临界水反应器及有机废气物燃气化利用系统

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US5630854A (en) * 1982-05-20 1997-05-20 Battelle Memorial Institute Method for catalytic destruction of organic materials
US20070000177A1 (en) * 2005-07-01 2007-01-04 Hippo Edwin J Mild catalytic steam gasification process
US20090126274A1 (en) * 2005-10-04 2009-05-21 Frederic Vogel Process for Generating Methane and/or Methane Hydrate From Biomass
US20100154305A1 (en) * 2008-01-31 2010-06-24 Battelle Memorial Institute Methods and apparatus for catalytic hydrothermal gasification of biomass
US20120094879A1 (en) * 2010-12-13 2012-04-19 Exxonmobil Research And Engineering Company Hydrothermal treatment of biomass with heterogeneous catalyst

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
JP4074071B2 (ja) * 2001-06-29 2008-04-09 株式会社東芝 有機化合物の処理方法
WO2009015358A2 (fr) * 2007-07-26 2009-01-29 The Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno Procédés, systèmes et appareil pour obtenir du biocarburant à partir de café et carburants ainsi produits
US20090165383A1 (en) * 2007-12-28 2009-07-02 Greatpoint Energy, Inc. Catalytic Gasification Process with Recovery of Alkali Metal from Char

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US5630854A (en) * 1982-05-20 1997-05-20 Battelle Memorial Institute Method for catalytic destruction of organic materials
US20070000177A1 (en) * 2005-07-01 2007-01-04 Hippo Edwin J Mild catalytic steam gasification process
US20090126274A1 (en) * 2005-10-04 2009-05-21 Frederic Vogel Process for Generating Methane and/or Methane Hydrate From Biomass
US20100154305A1 (en) * 2008-01-31 2010-06-24 Battelle Memorial Institute Methods and apparatus for catalytic hydrothermal gasification of biomass
US20120094879A1 (en) * 2010-12-13 2012-04-19 Exxonmobil Research And Engineering Company Hydrothermal treatment of biomass with heterogeneous catalyst

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10688464B2 (en) 2017-06-05 2020-06-23 General Atomics Corrosion inhibition in hydrothermal processing
CN114891545A (zh) * 2022-05-07 2022-08-12 深圳市沃尔奔达新能源股份有限公司 一种超临界水反应器及有机废气物燃气化利用系统

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EP2870224A1 (fr) 2015-05-13
EP2870224A4 (fr) 2016-03-02
IN2014DN09147A (fr) 2015-05-22

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