WO2012178131A1 - Pyrolyse de biomasse dans la production de biocarburants - Google Patents

Pyrolyse de biomasse dans la production de biocarburants Download PDF

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Publication number
WO2012178131A1
WO2012178131A1 PCT/US2012/043906 US2012043906W WO2012178131A1 WO 2012178131 A1 WO2012178131 A1 WO 2012178131A1 US 2012043906 W US2012043906 W US 2012043906W WO 2012178131 A1 WO2012178131 A1 WO 2012178131A1
Authority
WO
WIPO (PCT)
Prior art keywords
feed
biomass
coking
solid biomass
feed material
Prior art date
Application number
PCT/US2012/043906
Other languages
English (en)
Inventor
John Daniel ELLIOTT
David Allan WEDLAKE
Original Assignee
Foster Wheeler Usa 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
Application filed by Foster Wheeler Usa Corporation filed Critical Foster Wheeler Usa Corporation
Priority to CA2840051A priority Critical patent/CA2840051A1/fr
Priority to EP12803300.8A priority patent/EP2723833A1/fr
Priority to BR112013032849A priority patent/BR112013032849A2/pt
Priority to CN201280031107.1A priority patent/CN103890145A/zh
Priority to ES201390104A priority patent/ES2482915B1/es
Priority to DE112012002578.4T priority patent/DE112012002578T5/de
Publication of WO2012178131A1 publication Critical patent/WO2012178131A1/fr
Priority to ZA2013/09579A priority patent/ZA201309579B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the invention relates to the production of a biofuel composition from a feedstock that includes a solid biomass material.
  • the present invention presents a process for the production of biofuels in a refinery thermal processing unit, by the co-processing of biomass together with distillates and residuals from a traditional refining process.
  • renewable feedstocks namely achieving the desirable characteristics of a specific fuel. Accordingly, there is desired a process in which renewable type feedstocks can be effectively used to make high quality fuels.
  • the process for production of biofuel by delayed coking of a feedstock is directed to the co-processing of a solid biomass with the fresh feed of hydrocarbon in a conventional delayed coking unit.
  • the feedstock of the conventional delayed coking unit comprises a feed of hydrocarbon such as petroleum residuals with or without distillates and a solid biomass material.
  • the solid biomass material is derived from aquatic plants. For example, aquatic plants such as pre-processed or whole lemna serve as a rich source of lipids, carbohydrates, residual proteins, cellulose and other organic materials that have the potential to be converted to hydrocarbons.
  • Pre-processing of lemna involves extraction of a protein rich stream prior to biomass conversion in a coker.
  • Other sources of solid biomass material that may be used in embodiments of the invention include materials of vegetable origin such as saw grass, woody materials, oil seeds and materials of animal origin such as fats. Biomasses of various types and origins may be used in embodiments of the invention.
  • the solid biomass is mixed with hydrocarbon residue in varying proportions and the resultant slurry is coked in a delayed coker.
  • the slurry can be formed in the fresh feed section of the unit or in the coke drum during the reaction stage.
  • the percentage by volume of said amount of solid biomass relative to the fresh feed is in a range from 0.1 % to 60%.
  • the proportion of biomass in the slurry can be increased depending upon the capacity of the coker unit and its ability to handle the biomass material.
  • FIG. 1 shows a schematic diagram of a delayed coking process
  • FIG. 2 shows a flowchart of a process for processing of biomass in accordance with an exemplary embodiment of the invention.
  • a hydrocarbon feed is fed into the coking process through the bottom liquid pool of a coker fractionator.
  • the fractionator serves as the point from where various liquid and gas products are withdrawn, for example fuel gas and LPG, light naphtha, heavy naphtha, light gas oil, medium gas oil and heavy gas oil.
  • the bottom product from the coker fractionator is fed into a coker heater so that the reactions of thermal cracking can begin.
  • the effluent from the coker heater is then sent to a coke drum, where the reactions of thermal cracking and coking or carbonization proceed to completion, producing coke and an effluent from the coke drum (coking vapor), composed of light hydrocarbons, which is sent to the coker fractionator.
  • a portion of the condensed liquids may be recycled and pumped to the coker heater with the feed.
  • the solid biomass material is mixed with a residual hydrocarbon feed and fed into a coker fractionator.
  • the solid biomass material may be added directly in the coke drum during the reaction or quenching stage.
  • the solid biomass material preferably in slurry form, may be added directly in the coker heater feed line or directly into the coke drum with prior heating. In other embodiments of the invention, the solid biomass material may be added to the coker heater feed line without prior heating.
  • Slurried biomass may be heated in stages and flashed following low temperature heating to reduce the load of produced water and acidic hydrocarbons that would otherwise need to be dealt with in the main section of the coker fractionator, coker heater, coke drums, fractionator recovery systems and refinery waste systems.
  • the percentage by weight of the amount of solid biomass material relative to the remainder of the slurry is in a range from 0.1 % to 60%. In an embodiment of the invention, a preferred weight on the amount of the solid biomass relative to the remainder of the slurry is in a range from 10% to 40%. In another embodiment of the invention, a preferred weight on the amount of the solid biomass relative to the remainder of the slurry is in a range from 20% to 40%.
  • the proportion of biomass in the slurry can vary depending upon the capacity of the coker unit. A small capacity unit may be able to accommodate between 5 and 20 wt% of biomass in petroleum residue, whereas a large capacity unit may be able to process between 40 and 50 wt% of solid biomass material in the slurry.
  • coking is carried out at normal temperatures and pressures.
  • the heavy oil feed e.g. vacuum residue is pumped to the coker heater at a pressure of about and preferably 300 to 4000 kPa (about 44 to 580 psig), where it is heated to a temperature from about 460°C to about 530°C. It is then discharged into the coker drum where a lower pressure prevails to allow volatiles to be removed overhead, typically from 65 to 1100 kPa (about 10 to 58 psig) and preferably in the range of 100 to 300 kPa (about 10 to 160 psig). Typical operating temperatures of the drum top are between about 405°C and 460°C.
  • FIG. 2 An embodiment of the process of the invention is set forth in FIG. 2.
  • FIG. 2 depicts a process for the pyrolysis of biomass.
  • a feedstock containing biomass is provided (Step 102).
  • the feedstock is subjected to thermal processing.
  • the thermal processing is carried out using a delayed coking process (Step 106).
  • the thermal processing is carried out using a fluidized bed coking process (Step 108).
  • the feed stream is heated to a temperature of 460 to 530° C at a pressure of 300 to 4000 kPa after which the heated stream is discharged into a delayed coker drum at a pressure of 65 to 1100 kPa and a top temperature of 405 to 460° C.
  • Step 108 the feed stream is discharged into a fluidized bed coking reactor at a pressure from atmospheric to 400 kPa and a temperature of 480 to 565° C.
  • the solid biomass typically starts to decompose at temperatures as low as 200°C.
  • the lower temperature biomass decomposition reactions produce reaction water and a number of potentially valuable chemical species including acetic acid.
  • the biomass decomposition reactions in the delayed coker at high temperatures in the coke drum impact the overall reacting mass.
  • the inlet reacting material needs to be at a temperature sufficiently high to overcome the decomposition endothermic reaction of the biomass. This temperature is significantly higher than the temperature that would be needed in a conventional coker and is dependent on the amount of biomass in the feed blend. This has an impact not only on the operation but on the specification of heat transfer equipment, typically a fired heater, to supply a higher than normal enthalpy.
  • An embodiment of the invention is directed to an alternative configuration for coprocessing biomass in a delayed coker, wherein a pre-reaction section that is either within or external to the coker.
  • a pre-reaction section either within or external to the coker would have the following advantages: a. Remove a significant amount of reaction water from the coker operation, simplifying processing of resultant products. b. It reduces the impact of the total enthalpy variance compared to non-biomass operations required in the coker. c. Remove and recover water soluble acid components for the coker. The components could be recovered separately if deemed commercially attractive. d.
  • the pre-reaction system can be configured a number of different ways. Some of these are: (1) Slurry with hot petroleum residue and flash off the water and light components using a simple vessel; and, (2) Slurry with hot petroleum residue and strip off the water and light components in a tower system.
  • compositions in wt%) as set forth in Table 1, which can vary depending on growth optimization and degree of pre-processing following protein extraction.
  • the lemna biomass is a light fluffy solid with a density of about 490 kg/m3. It may be pelletized for shipment to the refinery to minimize deliquescent water absorption and provides ease of handling with minimal dusting.
  • the biomass contains lipids, carbohydrates, residual proteins, cellulose and other organic materials of little or no interest to a typical petroleum refiner except as to the potential to convert it to
  • Hydrocarbons derived from mineral sources are composed mainly of organic compounds such as carbon and hydrogen with varying amounts of sulfurous and nitrogenous molecules and very minor amounts of oxygen, generally less than 0.5%, and metals.
  • the biomass assay above compared to typical delayed coker petroleum residue feedstock shows very low sulfur, high nitrogen and metals plus very high oxygen content.
  • the biomass carbon to hydrogen weight ratio (C:H) is 7.6 but it is only 52% by weight of the total.
  • a typical heavy petroleum residue fed to a commercial delayed coker might have a hydrogen content of 8.5 to 11 percent by weight with a C:H ratio on the order of 8.5 to 9.0. This ratio varies significantly by crude derivation and residue processing upstream of the delayed coker.
  • Table 2 shows the results of coking lemna biomass as a 10% blend with a light vacuum residue.
  • the lemna biomass mixes well with petroleum vacuum residue.
  • the biomass has a particle size averaging about 100 to about 150 microns and the bulk density is about 490 kg/m3. If the biomass is pelletized to provide environmentally low impact, more safe and convenient transportation, crushing and grinding would be used to produce the small particles for testing. Mixing will be improved by grinding to smaller particles, say 50 micron average size.
  • the gas produced is nearly all C0 2 with
  • a high percentage of light gas greater than
  • the high relative oxygen content of the biomass relative to petroleum delayed coker feedstock is shown to react mainly to gas as C02 and water with a relatively high amount of oxygen in the coke.
  • the liquid product has a high amount of oxygen relative to liquid product produced from coking petroleum residue feed. But the value is low compared to the total biomass oxygen content and when diluted in the operation with the liquid produced from the petroleum residue, the impact on other refinery processes such as hydrotreaters is mitigated.

Abstract

L'invention se rapporte à la production d'un biocarburant à partir d'une matière première qui comprend une biomasse solide telle que le lemna. Des plantes aquatiques telles que le lemna pré-traité ou le lemna entier servent de sources riche de lipides, d'hydrates de carbone, de protéines résiduelles, de cellulose et d'autres matières organiques possédant le potentiel d'être convertis en hydrocarbures. Une matière première hydrocarbure est introduite dans le procédé de cokéfaction et les produits de réaction générés par le procédé thermique sont recueillis. L'invention se rapporte en outre à un produit de coke qui présente une structure isotrope.
PCT/US2012/043906 2011-06-23 2012-06-23 Pyrolyse de biomasse dans la production de biocarburants WO2012178131A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA2840051A CA2840051A1 (fr) 2011-06-23 2012-06-23 Pyrolyse de biomasse dans la production de biocarburants
EP12803300.8A EP2723833A1 (fr) 2011-06-23 2012-06-23 Pyrolyse de biomasse dans la production de biocarburants
BR112013032849A BR112013032849A2 (pt) 2011-06-23 2012-06-23 pirólise de biomassa na produção de biocombustíveis
CN201280031107.1A CN103890145A (zh) 2011-06-23 2012-06-23 生物燃料制备中的生物质热解
ES201390104A ES2482915B1 (es) 2011-06-23 2012-06-23 Proceso para la producción de biocombustibles por coprocesamiento de biomasa en una unidad de procesamiento térmico en una refinería.
DE112012002578.4T DE112012002578T5 (de) 2011-06-23 2012-06-23 Pyrolyse von Biomasse bei der Herstellung von Biokraftstoffen
ZA2013/09579A ZA201309579B (en) 2011-06-23 2013-12-18 Pyrolysis of biomass in the production of biofuels

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161500250P 2011-06-23 2011-06-23
US61/500,250 2011-06-23

Publications (1)

Publication Number Publication Date
WO2012178131A1 true WO2012178131A1 (fr) 2012-12-27

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ID=47360803

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/043906 WO2012178131A1 (fr) 2011-06-23 2012-06-23 Pyrolyse de biomasse dans la production de biocarburants

Country Status (11)

Country Link
US (1) US20120325641A1 (fr)
EP (1) EP2723833A1 (fr)
CN (1) CN103890145A (fr)
BR (1) BR112013032849A2 (fr)
CA (1) CA2840051A1 (fr)
CL (1) CL2013003678A1 (fr)
DE (1) DE112012002578T5 (fr)
ES (1) ES2482915B1 (fr)
MY (1) MY177107A (fr)
WO (1) WO2012178131A1 (fr)
ZA (1) ZA201309579B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016100773A1 (fr) * 2014-12-19 2016-06-23 United States Of America, As Repressented By The Secretary Of Agriculture Procédés de production de coke calciné à partir d'une bio-huile et coke calciné ainsi obtenu
EP3636729A1 (fr) 2018-10-10 2020-04-15 BDI Holding GmbH Procédé de fabrication de charbon à coke

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110548879A (zh) * 2019-06-04 2019-12-10 北京化工大学 一种绿色合成新型铁炭材料的制备方法及其应用

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US6168709B1 (en) * 1998-08-20 2001-01-02 Roger G. Etter Production and use of a premium fuel grade petroleum coke
US20090031615A1 (en) * 2007-08-01 2009-02-05 General Electric Company Integrated method for producing a fuel component from biomass and system therefor
US20100256428A1 (en) * 2009-04-07 2010-10-07 Gas Technology Institute Hydropyrolysis of biomass for producing high quality liquid fuels
WO2010124030A1 (fr) * 2009-04-21 2010-10-28 Sapphire Energy, Inc. Procédés de préparation de compositions huileuses pour raffinage d'un combustible
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Publication number Priority date Publication date Assignee Title
WO2016100773A1 (fr) * 2014-12-19 2016-06-23 United States Of America, As Repressented By The Secretary Of Agriculture Procédés de production de coke calciné à partir d'une bio-huile et coke calciné ainsi obtenu
US10202557B2 (en) 2014-12-19 2019-02-12 The United States Of America, As Represented By The Secretary Of Agriculture Methods of producing calcined coke from bio-oil and calcined coke produced thereby
EP3636729A1 (fr) 2018-10-10 2020-04-15 BDI Holding GmbH Procédé de fabrication de charbon à coke

Also Published As

Publication number Publication date
DE112012002578T5 (de) 2014-08-07
EP2723833A1 (fr) 2014-04-30
ES2482915B1 (es) 2015-07-03
BR112013032849A2 (pt) 2017-02-21
CA2840051A1 (fr) 2012-12-27
MY177107A (en) 2020-09-07
US20120325641A1 (en) 2012-12-27
ZA201309579B (en) 2015-09-30
ES2482915A2 (es) 2014-08-05
CN103890145A (zh) 2014-06-25
ES2482915R1 (es) 2014-10-28
CL2013003678A1 (es) 2014-06-20

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