WO2012175796A1 - Installation de bioraffinage intégrée pour la production de biocombustible - Google Patents

Installation de bioraffinage intégrée pour la production de biocombustible Download PDF

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Publication number
WO2012175796A1
WO2012175796A1 PCT/FI2012/050600 FI2012050600W WO2012175796A1 WO 2012175796 A1 WO2012175796 A1 WO 2012175796A1 FI 2012050600 W FI2012050600 W FI 2012050600W WO 2012175796 A1 WO2012175796 A1 WO 2012175796A1
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Prior art keywords
black liquor
conveying
heat
biofuel
transfer medium
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PCT/FI2012/050600
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English (en)
Inventor
Petri Kukkonen
Pekka Jokela
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Upm-Kymmene Corporation
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Publication of WO2012175796A1 publication Critical patent/WO2012175796A1/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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0035—Introduction of compounds, e.g. sodium sulfate, into the cycle in order to compensate for the losses of pulping agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0042—Fractionating or concentration of spent liquors by special methods
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C10J2300/092—Wood, cellulose
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
    • 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
    • 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 invention relates to refining biomass in an integrated biorefinery plant for producing at least pulp and crude biofuel.
  • the crude biofuel may be refined to biofuel in the plant.
  • the efficiency of the refinery plant may be increased.
  • the homogeneity requirements of the raw biomass for the plant may be decreased.
  • Biomass is commonly refined in many ways.
  • pulp or paper may be made of wood
  • energy may be produced by burning biomass, e.g. agricultural waste or wood-based waste
  • biofuel such as biogasoline, biodiesel or ethanol
  • wood or regional waste e.g. by gasification.
  • Pulp is produced from stem wood. Pulp may be produced by e.g. by chemical pulping, such as kraft pulping from wood chips. The kraft pulping produces also black liquor. Black liquor is conventionally burned in a recovery boiler to recover pulping chemicals and to produce heat, which may be converted to e.g. electricity. Pulp may be used for making paper. The pulp production process is optimized on one hand for producing pulp and on the other hand for producing energy (heat and/or electricity).
  • Biomass in general may be utilized also to produce liquid or gaseous biofuel.
  • Liquid biofuel may be used in many areas of human life including heating, transportation and producing power, such as electricity.
  • Gasification is a promising process for converting solid biomass to gaseous or liquid fuel.
  • solid biomass such as wood or regional waste
  • a synthesis gas which can be further processed to produce liquid fuel or gaseous fuel or both liquid and gaseous fuels.
  • the process produces also heat, which may be converted to e.g. electricity.
  • the gasification process is optimized on one hand for producing biofuel and on the other hand for producing energy (heat and/or electricity) .
  • a black liquor treating unit is integrated to pulp production process equipment. At least part of the black liquor recovered from the pulp production is treated in a black liquor treating unit where black liquor is treated with at least one additive in an elevated pressure and an elevated temperature.
  • crude biofuel is produced, which may further be refined to biofuels.
  • This has the advantage that some of the organic substances of the black liquor are converted to biofuel, and further, the respective capacity of a recovery boiler is freed. In the case that the recovery boiler is a bottleneck in the pulping process, this increases the overall yield of the pulping process. More advantages of the invention are discussed later in the specification.
  • cooking chemicals are recovered in the black liquor treatment and they are recycled to the pulp production process, e.g. to the evaporator or the recovery boiler.
  • the cooking chemicals recovered in the black liquor treatment are recycled to the pulp production process, to the evaporator arranged to evaporate water from black liquor.
  • gasification equipment can be further integrated to integrated pulping process equipment to form a single integrated biorefinery plant.
  • the output of the plant may be optimized with more flexibility.
  • the bark obtained from debarking may be used for biofuel production instead of energy production.
  • both pulping and gasification may use chips of wood, one chipper may be used for both processes. Therefore, the overall investment costs of an integrated biorefinery plant are reduced.
  • the homogeneity requirements for the raw material, i.e. biomass are loosened.
  • any one of many black liquor refining processes can be integrated with a process for producing pulp.
  • the integration can be further extended to hydroprocessing of crude biofuel or gasification of biomass.
  • Figure 1 shows schematically a process for making screened chips of wood
  • Figure 2 shows schematically a pulping process for making pulp and paper from screened chips
  • Figure 3a shows schematically a process for making biofuel from black liquor
  • Figure 3b shows schematically a batch process for making biofuel from black liquor
  • Figure 3c shows schematically another batch process for making biofuel from black liquor
  • Figure 3d shows schematically a continuous process for making biofuel from black liquor
  • Figure 3e shows schematically an integrated process of producing pulp and making biofuel from black liquor
  • Figure 3f shows schematically another integrated process of producing pulp and making biofuel from black liquor
  • Figure 4 shows schematically a gasification process for making a second biofuel from biomass
  • Figure 5 shows an embodiment of an integrated biorefinery plant, especially the material flow in the process
  • Figures 6-1 1 show embodiments of processing the products of an integrated biorefinery plant.
  • Stem wood may be used to produce paper.
  • pulp is used to make paper
  • screened chips of wood are used to make pulp.
  • Figure 1 shows a process for making screened chips 108 of wood from stem wood 100.
  • stem wood 100 is debarked to produce bark 102 and clean logs 104.
  • Clean logs 104 are chipped to produce chips 106 of wood, and these chips 106 are further screened to produce the screened chips 108.
  • small chips 1 10 and large chips 1 12 are removed from the chips 106, while the other chips are considered the screened chips 108.
  • large chips 1 12 are recycled for chipping. Chipping in itself may be a multistage process, and large chips 1 12 may be fed to the chipping process in another stage than the clean logs 104.
  • the bark 102 and the small chips 1 10 are used for energy production e.g. by burning them in a power boiler 1 15.
  • the reference number 101 refers to a wood pre- treating unit, which may comprise any one or any combination of
  • the screened chips 108 are used in pulp production to produce pulp 200. Further, pulp 200 is used in papermaking to produce paper 202.
  • the pulp production process comprises cooking and washing; evaporating, burning, and causticizing. In cooking and washing, the screened chips 108 are cooked with white liquor 210 in a digester 205 to produce pulp 200 and black liquor 220.
  • White liquor 210 comprises e.g. sodium hydroxide.
  • Black liquor 220 which comprises water, organic substances such as lignin, and chemicals, is conveyed to an evaporator 222, where water is evaporated from the black liquor to produce concentrated black liquor 223.
  • the concentrated black liquor 223 is conveyed to a recovery boiler 225, where organic substances are burned and chemicals are recovered.
  • Chemicals are recovered as smelt from the recovery boiler 225. By mixing water with the smelt, green liquor 230 is obtained. In addition, because of burning lignin, heat 240 is recovered in the process. Heat is recovered to water running in the boiler tubes, and it is further heated to produce superheated steam, which may be transformed to electricity e.g. by gas turbines. Green liquor 230 is causticized in a causticizer 235 to produce white liquor 210.
  • the process steps of producing pulp are known for the person skilled in the art. In this description the term pulp production refers to the process comprising cooking and washing; evaporating, burning, and causticizing, as discussed above.
  • a process for producing biofuel from black liquor is integrated with a process for the production of at least pulp. Pulp may be used to produce paper.
  • an intermediate product is obtained. This intermediate product is referred to as crude biofuel.
  • Crude biofuel is an oil with high-molecular-weight. Crude biofuel can be refined to biofuel, as will be discussed later.
  • concentrated black liquor 223 can be used to produce biofuel 500.
  • the process which will be referred to as BLF (Black Liquor to bioFuel) process, comprises treating concentrated black liquor 223 with at least one treatment agent 300, 301 in an elevated temperature and an elevated pressure for a treatment time to produce a solution 307 comprising crude biofuel 310.
  • the substances are preferably mixed or agitated so that the active surface area for chemical reactions is increased.
  • the solution 307 further comprises cooking chemicals 312.
  • the process produces gases (not shown in the figure).
  • the cooking chemicals 312 comprise water.
  • the cooking chemicals 312 further comprise compounds similar to those formed in the chemical recovery cycle of black liquor, e.g. NaOH and NaHS.
  • the cooking chemicals 312 may also comprise compounds such as NaCO 3 , Na 2 CO 3 , and NaS 2 . These compounds are dissolved in the water comprised by the cooking chemicals 312.
  • the crude biofuel 310 is separated from the solution 307, leaving the cooking chemicals 312.
  • crude biofuel 310 is hydroprocessed (i.e. treated with hydrogen) in a hydroprocessing unit 320 to produce biofuel 500.
  • the product of the process may as well be the crude biofuel 310, which will be hydroprocessed or otherwise refined in a separate process, possibly in a separate biofuel refinery.
  • a first treatment agent 300 may be used as the at least one treatment agent.
  • a second treatment agent 301 may be used as the at least one treatment agent
  • the first treatment agent 300 may comprise at least one of hydrogen (H 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ), and nitrogen (N 2 ). In a preferred embodiment the first treatment agent 300 consists essentially of hydrogen (H 2 ) and carbon monoxide (CO). In this embodiment the first treatment agent forms an inert atmosphere.
  • the second treatment agent 301 may comprise at least one of water, wood oil distillate, sodium hydroxide (NaOH), calcium oxide (CaO), sodium carbonate (Na 2 CO 3 ), and sodium sulfide (Na 2 S).
  • alkali is used as the second treatment agent 301 , wherein the alkali consists essentially of water and sodium hydroxide (NaOH). Sodium carbonate is also known as disodium carbonate.
  • the elevated temperature may be in the range of 250 - 350 °C. In an embodiment, the elevated temperature was about 300 °C.
  • the elevated pressure may be in the range of 50 - 220 bar, preferably in the range of 100 - 170 bar. In an embodiment, the elevated pressure was about 150 bar.
  • the treatment time was 15 minutes (min). A shorter treatment time may also suffice, such as 10 min or 5 min, depending on the elevated temperature and the elevated pressure. Also, depending on the elevated temperature and the elevated pressure, the treatment time 15 min may not suffice, but a longer time is needed, such as 20 min or 30 min. Thus, the treatment time may be 5 - 30 min. Proper treatment time may be selected to comply with the elevated temperature, the elevated pressure, and the composition of the at least one treatment agent 300, 301 .
  • the BLF process may be a batch process or a continuous process.
  • Fig. 3b shows a first batch BLF process.
  • the first batch BLF process comprises:
  • the heating of the vessel may also be done after conveying the at least one treatment agent to the vessel.
  • the gases may be released from the vessel 350 e.g. from a valve.
  • the conveying means 355 or the other conveying means may comprise a pipe.
  • the vessel 350 comprises the conveying means 355.
  • the means is inserted to the vessel from above, and the products are conveyed from the vessel 350 using suction.
  • the low pressure is of the order of the pressure in the recovery boiler, e.g. close to atmospheric pressure.
  • the pressure in the vessel 350 is increased to the elevated pressure by conveying the first treatment agent to the vessel.
  • the alkali 301 is fed to the black liquor stream 223 entering the vessel 350.
  • the pressure in the vessel 350 may be increased by controlling the black liquor flow to the vessel.
  • the process equipment shown in Fig. 3b are collectively referred to as black liquor treating unit 305.
  • Fig. 3c shows a second batch BLF process.
  • the second batch BLF process comprises:
  • the system of Fig. 3c comprises means 356 for conveying the solution from the first vessel 350 to the second vessel 352.
  • the system comprises also a valve 354 to control the treatment time in the first vessel.
  • the valve When the valve is opened, the solution in the first vessel is conveyed to the second vessel, since the pressure in the second vessel is lower.
  • a pump may be utilized.
  • the low pressure is of the order of the pressure in the recovery boiler, e.g. close to atmospheric pressure.
  • the second vessel 352 comprises the conveying means 358.
  • the means is inserted to the second vessel from above, and the products are conveyed from the second vessel 352 using suction.
  • the pressure in the vessel 350 is increased to the elevated pressure by conveying the first treatment agent to the vessel.
  • the alkali 301 is fed to the black liquor stream 223 entering the vessel 350.
  • the pressure in the vessel 350 may be increased by controlling the black liquor flow to the vessel.
  • the process equipment shown in Fig. 3c are collectively referred to as black liquor treating unit 305.
  • Fig. 3d shows a continuous BLF process.
  • the continuous BLF process comprises:
  • the elevated pressure in the BLF reactor is controlled by the conveying of the first treatment agent 300. In an embodiment the elevated pressure in the BLF reactor is controlled by the conveying of the concentrated black liquor 223. In an embodiment the elevated pressure in the BLF reactor is controlled by the conveying of the alkali 301 .
  • the process equipment shown in Fig. 3d are collectively referred to as black liquor treating unit 305.
  • the BLF process as described in above in Figs. 3a- 3d, may be integrated to the pulp production process, as described in Fig. 2.
  • a method for producing pulp 200 and crude biofuel 310 from screened chips 108 has been invented.
  • the screened chips are made of stem wood. Referring to Fig. 2, the method comprises:
  • the method further comprises:
  • the crude biofuel 310 may be refined, e.g. by hydroprocessing to produce biofuel 500.
  • the hydroprocessing may be optimized for the production of at least one of biogasoline and biodiesel.
  • the hydroprocessing may be realized by a catalytic process comprising the steps of hydrotreating and isomerizing of the crude biofuel. Also single step processes for catalytic hydroprocessing of the crude biofuel may be employed. After hydroprocessing, the resulting hydrocarbon compounds are fractionated according to their boiling point.
  • the crude biofuel 310 may also be refined in a separate process, possibly in a separate biofuel refinery.
  • the product of the process may as well be the crude biofuel 310, which will be as such used in heating applications replacing fossil heavy and light fuel oils. Crude biofuel may be subjected to purification before it is used in heating applications.
  • the integration of the BLF process to the pulping process means that the equipment for different process steps are located physically close to each other.
  • the pulping process equipment comprises
  • the BLF process equipment comprises a black liquor treating unit 305, such as the vessel 350 or the BLF reactor 360, to treat concentrated black liquor 223 to produce cooking chemicals 312 and crude biofuel 310.
  • a black liquor treating unit 305 such as the vessel 350 or the BLF reactor 360, to treat concentrated black liquor 223 to produce cooking chemicals 312 and crude biofuel 310.
  • the integrated biorefinery plant comprises
  • a black liquor divider 525 arranged to divide the concentrated black liquor 223 to a first part 223a and a second part 223b,
  • a black liquor treating unit 305 arranged to produce cooking chemicals 312 and crude biofuel 310 from the second part 223b of the concentrated black liquor, and - means for conveying the second part 223b of the concentrated black liquor to the black liquor treating unit 305.
  • the means for conveying the second part 223b of the concentrated black liquor is preferably stationary, such as a pipe, but may also be a movable container.
  • the distance between the evaporator 222 and the black liquor treating unit 305 is preferably small.
  • the distance between the evaporator 222 and the black liquor treating unit 305 may be for example less than 100 m, less than 50 m, or less than 25 m.
  • the black liquor divider 525 is arranged to divide the concentrated black liquor 223 to a first part 223a and a second part 223b such that the first part has a first mass flow rate m and the second part has a second mass flow rate m 2 , both measured in kg/s.
  • the black liquor divider 525 may be arranged to divide the concentrated black liquor 223 such that the ratio m 2 :m of the mass flow m 2 of the second part 223b (flowing to the BLF process) to the total concentrated black liquor flow m is between 15 - 35 %.
  • the ratio m 2 :m is between 20 - 30 % and in an embodiment the ratio m 2 :m is approximately 25 %. It is noted that regardless of the ratio, essentially all pulping chemicals are recycled to the process with the cooking chemicals 312.
  • the integrated biorefinery plant of Fig. 3e also comprises means for conveying the cooking chemicals 312 from the from the black liquor treating unit 305 to the pulp production process (e.g. the recovery boiler 225 in Fig. 3e).
  • the cooking chemicals 312 may be conveyed to the pulping process also in another phase of the pulping process. Referring to the embodiment disclosed in Fig. 3f, the method comprises:
  • the BLF part of the integrated process may be a batch process, or a continuous process, as discussed above.
  • the integrated biorefinery plant of Fig. 3f comprises means for conveying the cooking chemicals 312 from the black liquor treating unit 305 to the evaporator.
  • Part of the organic content (i.e. lignin) of the black liquor can be utilized to produce biofuel rather than producing heat in the recovery boiler 225.
  • the economical value of the biofuel may be greater than that of the heat. Therefore, the value of the products obtained in the process is greater than the value of a pulping process.
  • the integrated process uses stem wood to produce crude biofuel 310 and pulp 200.
  • Liquid or gaseous biofuel can be produced also from other types of biomass in a process comprising gasification.
  • the process comprising gasification will be referred to as BTL (Biomass-To- Liquid) process.
  • biomass 520 is processed to produce liquid biofuel 505 (second biofuel).
  • Biomass 520 comprises at least one of agricultural waste, wood residues, stumps, branches, and waste wood such as bark, wooden construction debris, and wood product residuals.
  • the BTL process comprises:
  • a first high temperature e.g.
  • All the processes are not necessarily performed at the described sequence, e.g. reforming may be done before cleaning. Moreover, all process steps are not necessarily performed to all synthesis gas, e.g. part of the synthesis gas may be conveyed to bypass the gas shifting step. At least gasification, reforming, and Fischer-Tropsch (FT) processing are performed in elevated temperatures, as described above. Therefore, heat 420 is obtained from cooling, heat 435 is obtained from scrubbing, and heat 446 from FT . Heats 420 and 446 may be stored in steam, e.g. superheated steam for power generation, and heat 435 may be stored in water, e.g. for district heating.
  • FT Fischer-Tropsch
  • the heat 420 obtained from cooling is stored in saturated steam, and the steam pressure is between 15 - 18 bar (i.e. the temperature is between 198 - 207 °C).
  • the heat 446 obtained from FT is stored in saturated steam, and the steam pressure is about 18 bar (i.e. the temperature is about 207 °C).
  • the heat 435 obtained from scrubber is stored in water, and the temperature of the water is between 60 - 100 °C).
  • the term "second biofuel” is used only to distinct the product of the BTL process from the product "biofuel" of the BLF process.
  • the biomass 520 In preprocessing, the biomass 520, such as stubs or stumps are be cleaned from impurities (metal pieces and rocks), and chipped or crushed to smaller particles to produce processed biomass 400. Preprocessing may be done in a pretreating unit 401 . Alternatively, the biomass 520 may consists of preprocessed biomass 400, in which case preprocessing is not needed, or preprocessing is done elsewhere.
  • chips 106 As chips 106 (Fig. 1 ) are produced for pulp production process, and processed biomass 400 (Fig. 4) may comprise chips, the same chipper(s) may be used both in pulping and in BTL. The chipper(s) may be used subsequently or in turns for pulping and for BTL, as sorting of the chips would be an extremely difficult process.
  • the chips produced from stem wood may be used in both processes (pulping and BTL), or mainly in one of the processes, depending on the need of the products of different processes. On one hand, e.g. when the business cycle has driven the pulp price high, most of the chips may be needed for pulping. On the other hand, when the pulp demand in low, most of the chips may be utilized for producing at least one of energy and biofuel.
  • the barks 102 and small chips 1 10 (Fig. 1 ) are conventionally burned to produce energy in the boiler 1 15. However, in an integrated plant, the barks 102 and the small chips 1 10 may be utilized in the BTL process. This reduces the amount of burned biomass in the boiler 1 15. Thus, the boiler 1 15 needs not to be running continuously, which enables better maintenance. Alternatively, a smaller boiler 1 15 may suffice, reducing the investment costs.
  • the chips 108 for pulping are produced from stem wood (Fig. 2).
  • the biomass 520 for BTL may comprise stubs or stumps.
  • the integrated biorefinery plant may be able to receive all types of raw biomass, e.g. wood based biomass comprising logs and stubs.
  • the received raw biomass may be divided to two parts.
  • the first part may comprise stem wood for pulping, e.g. logs.
  • the second part may comprise other biomass for biofuel production.
  • the logistics of raw biomass may thus be significantly simplified compared to separated biofuel and pulp plants.
  • Heat is produced both the BTL process, in the recovery boiler and in the boiler 1 15.
  • the heat is stored in at least one of water, steam, and superheated steam.
  • Superheated steam may be used to produce electricity in steam turbines.
  • superheated steam from BTL, from the recovery boiler and from the boiler 1 15 are conveyed to the same power generating unit. Therefore, investment costs are reduced, as the same turbines are used to produce electricity from the heat of both processes.
  • the BTL-process may be used to preheat the water for the recovery boiler.
  • the scrubber 432 may produce heat 435 but only at a relatively low temperature. Utilization of the heat may be difficult. District heating is possible in some cases. However, a pulp plant may be located away from a settlement, in which case the utilization for district heating would require large investments. However, the heat
  • the heat 435 may also be utilized to preheat the water that is later heated in the recovery boiler 225.
  • the heat 435 may also be utilized to preheat the water that is later heated in the cooler 417. This diminishes the cooling capacity of the cooler.
  • biomass may be used to produce biofuel in the BTL process and to produce heat and electricity in the boiler 1 15.
  • the use of biomass may be optimized at the integrated biorefinery plant with great flexibility, also apart from pulping.
  • Figure 5 shows a principle view of an embodiment of the process in an integrated biorefinery plant. As compared to Fig. 1 , some process steps are omitted for clarity. The BTL process of FIG. 4 is shown only very briefly.
  • the integrated biorefinery plant of Fig. 5 is arranged to receive raw biomass 510.
  • Raw biomass 510 comprises at least one of stem wood and biomass 520. Therefore, raw biomass 510 comprises at least one of stem wood, stumps, branches, chipped wood, crushed wood, hay, straw, agricultural waste, bark, wooden construction debris, and wood product residuals.
  • Raw biomass 510 is first divided to two parts. The first part, the biomass 520, is used as energy biomass in at least one of the BTL process and the boiler 1 15.
  • the second part consists of stem wood 100 and it is used in pulp production. The first part is preprocessed to processed biomass 400. The second part is be pre-treated as described above, to produce screened chips 108, bark 102 and small chips 1 10. Bark 102 and small chips 1 10 are combined with processed biomass 400 and used as energy biomass in at least one of the BTL process and the boiler 1 15.
  • the energy biomass i.e. processed biomass 400, bark 102, and small chips 1 10 is divided to two parts.
  • the first part is be processed with a BTL process to obtain at least one of: liquid biofuel, gaseous biofuel, heat, and electricity.
  • the second part is burned in the boiler 1 15 to produce at least one of heat and electricity.
  • the process may also have been optimized such the either the BTL process or the burning process is omitted, in which case the energy biomass is conveyed to only one of the processes.
  • the screened chips 108 are conveyed to the digester 205 for cooking.
  • the details of the cooking process were shown in Fig. 2, and the integration to BLF in Figs. 3e and 3f.
  • Figure 5 shows on one hand the embodiment of Fig 3e integrated to the BTL process.
  • the cooking chemicals 312 are conveyed to the to the pulp production process, e.g. to the recovery boiler 225.
  • Figure 5 shows on the other hand the embodiment of Fig 3f. integrated to the BTL process.
  • the cooking chemicals 312 are conveyed to the evaporator 222.
  • Cooking chemicals 312 could be conveyed both partly to the evaporator and partly to the recovery boiler.
  • the lignin concentration of the concentrated black liquor 223 can be optimized in such a process.
  • the integrated biorefinery plant may be arranged to receive many types of biomass.
  • the integrated biorefinery plant may be used to produce from the raw biomass 510 at least one of products: biofuel, heat, electricity, pulp, and paper.
  • the process yield may be optimized based on the need of any one or any combination of the products.
  • the pre-treating equipment for pulping comprises a first wood pre-treating unit 101 .
  • the BTL process equipment comprises a gasifier 402 to gasify the processed biomass 400 to synthesis gas 405.
  • the integrated biorefinery plant comprises means for conveying at least one product of the first wood pre-treating unit 101 to the gasifier 402.
  • the at least one product comprises at least one of bark 102 and small chips 1 10.
  • the means for conveying may be a conveyor, such a belt conveyor or a screw conveyor.
  • the distance between first wood pre- treating 101 unit and the gasifier 402 is preferably small.
  • the distance between the first wood pre-treating unit 101 and the gasifier 402 may be for example less than 100 m, less than 50 m, or less than 25 m.
  • the equipment for pulping comprises a boiler 1 15 for burning bark 102 and small chips 1 10.
  • the BTL process equipment may comprise a second pretreating unit 401 , to clean raw biomass from impurities and to chip or crush raw biomass to smaller particles to produce processed biomass 400.
  • the integrated biorefinery plant may comprise means for conveying the product of the second pre-treating unit 401 to the boiler 1 15.
  • the means for conveying may be a conveyor, such a belt conveyor or a screw conveyor.
  • the distance between the second pre- treating unit 401 and the boiler 1 15 is preferably small.
  • the distance between the second pre-treating 401 unit and the boiler 1 15 may be for example less than 100 m, less than 50 m, or less than 25 m.
  • energy biomass comprises at least one of processed biomass 400, bark 102 and small chips 1 10.
  • the integrated biorefinery plant of Fig. 5 comprises:
  • an energy biomass divider 530 arranged to divide energy biomass into two parts, a first energy biomass and a second energy biomass
  • heat may be recovered from several units, such as the scrubber 432 and the cooler 417 of the BTL process (Fig. 4), from the boiler 1 15 (Fig. 1 ) and from the recovery boiler 225 (Fig. 2). From the cooler 417, boiler 1 15, and recovery boiler 225, heat may be obtained in the form of steam or superheated steam, which are referred collectively to as steam.
  • the steam may be conveyed to a common power station 610 to generate electricity from the steam.
  • the integrated biorefinery plant of Fig. 6 comprises:
  • the integrated biorefinery plant may also comprise:
  • second biofuel from BTL process and biofuel from BLF process may be conveyed to a common storage for storing the biofuel.
  • the storage may be located on a vehicle for transportation.
  • the integrated biorefinery plant of Fig. 6 comprises:
  • the integrated biorefinery plant may comprise only one of the storage unit 620 and the power station 610.
  • the integrated biorefinery plant of Fig. 7 comprises a collector 710 arranged to receive steam from at least the recovery boiler 225 and the cooler 417.
  • the integrated biorefinery plant comprises means to convey steam from the collector 710 to the power station 610.
  • the integrated biorefinery plant may comprise a common storage unit 620 (not shown).
  • the integrated biorefinery plant of Fig. 8 comprises a heat exchanger 810 in connection with the scrubber 432 to preheat water for the recovery boiler 225 by using the heat from the scrubber 432.
  • the integrated biorefinery plant shown in the figure 8 comprises:
  • the heat transfer medium 850 may comprise water, or it may consist essentially of water.
  • the integrated biorefinery plant may comprise a common storage unit 620 (not shown).
  • the integrated biorefinery plant may also comprise a collector 710 (not shown).
  • the integrated biorefinery of Fig. 9 produces heat for both district heating and for preheating water for the recovery boiler.
  • the integrated biorefinery plant the figure 9 comprises:
  • a first heat exchanger 810 in connection with the scrubber, arranged to heat the first heat transfer medium 850 using heat of a synthesis gas
  • the integrated biorefinery plant may comprise a common storage unit 620 (not shown).
  • the integrated biorefinery plant may also comprise a collector 710 (not shown).
  • Figure 10 shows another integrated biorefinery.
  • the heat of the BTL process is utilized in the evaporator 222 arranged to evaporate water from the black liquor 220 to produce the concentrated black liquor 223.
  • the heat 420 is obtained from the cooler 417 via a heat exchanger 880, and as discussed previously, may be initially stored in steam having a temperature of about 200 °C.
  • the integrated biorefinery of Fig. 10 comprises
  • an evaporator 222 arranged to evaporate water from black liquor 220 to produce concentrated black liquor 223,
  • the first heat transfer medium comprises water, which may be also in the form of steam or superheated steam. Water is heated in the first heat exchanger 870 in connection with the cooler 417 to produce steam having a temperature of 198 - 207 °C. Steam is circulated to the second heat exchanger 880, Where the steam is used to heat the second heat transfer medium.
  • the second heat transfer medium comprises oil.
  • the heated second heat transfer medium is conveyed to evaporator 222.
  • the second heat transfer medium heats the black liquor 220. Water is thus evaporated from the black liquor 220 to produce concentrated black liquor 223.
  • the concentrated black liquor 223 is conveyed partly to the recovery boiler 225 and partly to the black liquor treating unit 305 as discussed above.
  • FIG. 1 1 shows another integrated biorefinery.
  • the heat of the BTL process is utilized in the evaporator 222 arranged to evaporate water from the black liquor 220 to produce the concentrated black liquor 223.
  • the heat 446 is obtained from the Fischer- Tropsch unit 442 of the BTL process (cf. Fig. 4) via a heat exchanger 890, and as discussed previously, may be initially stored in steam having a temperature of about 200 °C.
  • the integrated biorefinery of Fig. 1 1 comprises
  • a second heat exchanger 900 arranged to heat the second heat transfer medium 905 by cooling the first heat transfer medium 895, - means for conveying the first heat transfer medium 895 from the first heat exchanger 890 to the second heat exchanger 900, and
  • the first heat transfer medium comprises water, which may be also in the form of steam or superheated steam. Water is heated in the first heat exchanger 890 in connection with the Fischer-Tropsch unit 442 to produce steam having a temperature of about 200 °C. Steam is circulated to the second heat exchanger 900, Where the steam is used to heat the second heat transfer medium.
  • the second heat transfer medium comprises oil.
  • the heated second heat transfer medium 905 is conveyed to evaporator 222.
  • the second heat transfer medium 905 heats the black liquor 220. Water is thus evaporated from the black liquor 220 to produce concentrated black liquor 223.
  • the concentrated black liquor 223 is conveyed partly to the recovery boiler 225 and partly to the black liquor treating unit 305 as discussed above. Cooking chemicals 312 are recycled to the process.
  • black liquor can be processed to produce gaseous biofuel also in a supercritical water gasification (SCWG) process.
  • SCWG supercritical water gasification
  • the SCWG process may be employed in an elevated pressure (220 - 440 atm) and elevated temperature (375 - 650 °C) using a residence time of 5 - 120 s.
  • the product of the SCWG process comprises hydrogen (H 2 ), carbon monoxide (CO), and methane (CH 4 ).
  • cooking chemicals 312 may be obtained from or before the SCWG process.
  • black liquor can be gasified to produce gaseous biofuel. Cooking chemicals can be recovered from the gasification process or before the gasification process.
  • any process for producing (a) crude biofuel 310 or biofuel 500 and (b) cooking chemicals 312 from black liquor 220 or concentrated black liquor 230 can be integrated with kraft pulp production process as discussed above.
  • the process for producing (a) crude biofuel 310 or biofuel 500 and (b) cooking chemicals 312 from black liquor 220 or concentrated black liquor 230 is referred to as a black liquor refining process.
  • the described BLF process, the SCWG process, and the black liquor gasification process are embodiments of the black liquor refining process.
  • the process equipment for the black liquor refining process is referred to as the black liquor treating unit. In case of BLF, an embodiment of the black liquor treating unit 305 was described.
  • the black liquor refining process may be used to refine black liquor 220 or concentrated black liquor 230.
  • the result of the integration process is an integrated process for the production of
  • the integration can also be applied to further integrate the hydroprocessing process the process for producing pulp and refining black liquor.
  • the hydroprocessing can be integrated to the black liquor refining process that produces crude biofuel 310.
  • the hyrdoprocessing itself produces biofuel 500 as shown in Fig. 3a.
  • the integration process itself comprises providing means for conveying the crude biofuel 310 from the black liquor treating unit 305 to the hydroprocessing unit 320.
  • the integration can also be applied to further integrate the biomass gasification (BTL) process to the process for producing pulp and refining black liquor.
  • the process for producing pulp comprises the pulp production steps: cooking and washing; evaporating, burning, and causticizing, and further comprises debarking stem wood 100 in a wood pre- treating unit 101 to produce bark 102.
  • the biomass gasification (BTL) process comprises gasifying biomass in the gasifier 402.
  • the integration process itself comprises providing means for conveying the bark 102 from the wood pre-treting unit 101 to the gasifier 402.
  • the integrated system for performing the integrated process is an integrated biorefinery plant.
  • the integrated biorefinery plant comprises
  • the integrated biorefinery plant further comprises
  • a black liquor divider 525 arranged to divide the black liquor 220 or the concentrated black liquor 223 to a first part and a second part,
  • the means for conveying black liquor or concentrated black liquor to the black liquor divider 525 is arranged to convey black liquor 220 from the digester 205 to the black liquor divider 525.
  • the means for conveying black liquor or concentrated black liquor to the black liquor divider 525 is arranged to convey concentrated black liquor 223 from the evaporator 222 to the black liquor divider 525.
  • the BTL (biomass to liquid) gasification process as discussed in this application, may be integrated to the described integrated biorefinery plant.

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Abstract

L'invention porte sur un procédé pour la fabrication de pâte (200) et de biocombustible brut (310) à partir de copeaux (108) de bois criblés. Le procédé comprend la production de pâte (200) et de liqueur noire (220) à partir des copeaux criblés (108) dans un procédé de production de pâte et l'évaporation de l'eau de la liqueur noire (220) dans un évaporateur (222) pour produire de la liqueur noire concentrée (223). Le procédé comprend en outre le traitement d'une partie (223d) de la liqueur noire concentrée avec au moins un agent de traitement (300, 301) à une température élevée et une pression élevée pour produire du biocombustible brut (310) et des produits chimiques de cuisson (312) et le transport des produits chimiques de cuisson (312) vers le procédé de production de pâte. L'agent de traitement peut être essentiellement constitué d'hydrogène et de monoxyde de carbone. L'agent de traitement peut être essentiellement constitué d'eau et d'hydroxyde de sodium. L'invention porte également sur un système pour la mise en œuvre du procédé. De plus, l'invention porte sur un procédé pour l'intégration d'un procédé de raffinage de liqueur noire avec un procédé pour la production de pâte.
PCT/FI2012/050600 2011-06-23 2012-06-14 Installation de bioraffinage intégrée pour la production de biocombustible WO2012175796A1 (fr)

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EP3207108A4 (fr) * 2014-10-15 2018-05-09 Licella Pty Ltd Lessives de réduction en pâte et utilisations de ceux-ci
US11834783B2 (en) 2014-10-15 2023-12-05 Canfor Pulp Ltd. Integrated kraft pulp mill and thermochemical conversion system
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WO2016141432A1 (fr) * 2015-03-09 2016-09-15 Leaf Sciences Pty Ltd Appareil, système et procédé de traitement de matière ligno-cellulosique
WO2017048164A1 (fr) * 2015-09-16 2017-03-23 Sca Forest Products Ab Procédé discontinu de production de bio-huile à partir d'une liqueur noire usée
WO2017048163A1 (fr) * 2015-09-16 2017-03-23 Sca Forest Products Ab Procédé continu de production d'huile biologique à partir d'une liqueur noire épuisée
US10920622B2 (en) 2017-12-13 2021-02-16 Valmet Technologies Oy Method and a system for recovering thermal energy in a system comprising a chemical recovery boiler and a lime kiln
WO2022234180A1 (fr) * 2021-05-06 2022-11-10 Valmet Technologies Oy Procédé et système de production d'une fraction de produit à partir de biomasse

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