WO2012010223A1 - Système et procédé de conversion thermique de matériaux à base de carbone - Google Patents

Système et procédé de conversion thermique de matériaux à base de carbone Download PDF

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Publication number
WO2012010223A1
WO2012010223A1 PCT/EP2010/069881 EP2010069881W WO2012010223A1 WO 2012010223 A1 WO2012010223 A1 WO 2012010223A1 EP 2010069881 W EP2010069881 W EP 2010069881W WO 2012010223 A1 WO2012010223 A1 WO 2012010223A1
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WO
WIPO (PCT)
Prior art keywords
gas
reactor
bed reactor
outlet
fluid bed
Prior art date
Application number
PCT/EP2010/069881
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English (en)
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WO2012010223A8 (fr
Inventor
Jacob Hendrik Obbo Hazewinkel
Original Assignee
Rl Finance
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 PCT/NL2010/050464 external-priority patent/WO2012011803A1/fr
Priority claimed from PCT/NL2010/000111 external-priority patent/WO2012011801A2/fr
Priority claimed from PCT/NL2010/000109 external-priority patent/WO2012011799A2/fr
Priority claimed from PCT/NL2010/000110 external-priority patent/WO2012011800A1/fr
Priority claimed from PCT/NL2010/000112 external-priority patent/WO2012011802A2/fr
Application filed by Rl Finance filed Critical Rl Finance
Priority to US13/809,891 priority Critical patent/US20130118075A1/en
Priority to EP10803071.9A priority patent/EP2596083A1/fr
Priority to BR112013001461A priority patent/BR112013001461A2/pt
Publication of WO2012010223A1 publication Critical patent/WO2012010223A1/fr
Publication of WO2012010223A8 publication Critical patent/WO2012010223A8/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • 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
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • 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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • 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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • 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
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • 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
    • C10G2300/1003—Waste materials
    • 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
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • 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 present invention relates to a system for thermal conversion of carbon based materials. More
  • the present invention relates to a system for thermal conversion of carbon based materials into
  • the present invention relates to a method for thermal conversion of carbon based materials into combustible oil and/or gas.
  • the present invention also relates to the use of the present system for thermal conversion of carbon based materials into
  • One of the objectives of thermal conversion of carbon based, or carbon comprising matter for example biomass, wood, forestry waste products, organic waste, agricultural waste products, plastics, tires, tar sand, industrial waste, municipal waste, airport waste,
  • thermally disintegrating carbon based, or carbon comprising, materials under a reduced oxygen pressure is also designated as thermal cracking or pyrolysis .
  • Thermal cracking, or thermal disintegration or pyrolysis, of carbon comprising materials is a technique that can be used to convert these materials into valuable combustible oil and gas that subsequently can be used, for example, to power vehicles, generate electricity in turbines or as base products for chemical synthesis.
  • thermal cracking is cooling and cleaning of the hot synthesis gas. Due to a combination of tar and coke formation in practice, no coolers can be installed to recover heat and wet gas cleaning equipment is required. Therefore, the thermal efficiency of current thermal cracking processes is low and contaminated waste water is produced.
  • the current thermal cracking systems and processes are not suitable to integrate novel technologies such as oxygen membranes and fuel cells, due to the tar content and the presence of salt vapour. Therefore extra heating/cooling and gas treatment equipment is required.
  • a system for the thermal conversion of carbon based materials into combustible oil and/or gas said system comprises:
  • said first fluid bed reactor comprises at least one intake, said at least one intake
  • At least one inlet for receiving said carbon based materials comprises at least one inlet for receiving processed solid materials and at least one inlet for receiving solids and oil, at least one discharge end, said at least one discharge end comprises at least one outlet for carbon comprising solid material, at least one outlet for metals and minerals, and at least one outlet for
  • said first fluid bed reactor is operated at a temperature of 350°C to 450°C, preferably 375°C to 425°C , a hydrogen pressure of 200 to 300 mbar, preferably 225 to 275 mbar and an oxygen pressure of 10 ⁇ 5 to 10 ⁇ 9 mbar, preferably 10 ⁇ 6 to 10 "8 ;
  • a second vapour wash reactor connected to said outlet for effluent vapour and gas for washing effluent vapour and gas from said first fluid bed reactor, said second vapour wash reactor comprises at least one intake, said at least one intake comprises at least one inlet for receiving said effluent vapour gas and at least one discharge end, said at least one discharge end comprises at least one outlet for washed vapour and gas and at least one outlet for solids and oil connected to said inlet for solids and oil of said first fluid bed reactor for reintroducing said solids and oil into said first fluid bed reactor, and said second vapour wash reactor is operated at a temperature of 150°C to 300°C, preferably 200°C to 250°C, a hydrogen pressure of 200 to 300 mbar, preferably 225 to 275 mbar and an oxygen pressure of 10 ⁇ 5 to 10 "9 mbar, preferably 10 "6 to 10 "8 ;
  • a third reactor connected to said outlet for washed vapour and gas for fractioning of said vapour and gas, said third reactor comprises at least one intake, said at least one intake comprises at least one inlet for receiving said washed vapour and gas, at least one discharge end, said at least one discharge end comprises at least one outlet for
  • said third reactor is operated at a temperature of 30°C to 80°C, preferably 35°C to 60°C, a hydrogen pressure of 200 to 300 mbar, preferably 225 to 275 mbar and an oxygen pressure of 10 ⁇ 5 to 10 ⁇ 9 mbar, preferably 10 ⁇ 6 to 10 ⁇ 8 ;
  • a fourth moving bed reactor connected to said at least one outlet for carbon comprising solid material for stabilizing carbon in said solid material through conversion of gaseous materials, said fourth moving bed reactor comprises at least one intake, said at least one intake comprises at least one inlet for receiving said carbon comprising solid material and at least one discharge end, said at least one discharge end comprises at least one outlet for stabilized carbon comprising solid material, said fourth moving bed reactor is operated at a temperature of 550°C to 650°C, preferably 575°C to 625°C, a
  • a fifth fluid bed reactor connected to said at least one outlet for stabilized carbon comprising solid material
  • said fifth fluid bed reactor comprises at least one intake
  • said at least one intake comprises at least one inlet for receiving said stabilised carbon comprising solid material and at least one inlet for receiving processed gas from a sixth reactor
  • at least one discharge end comprises at least one outlet connected with said at least one inlet for receiving processed carbon comprising solid material for reintroducing processed solid materials into said first fluid bed reactor and at least one outlet for gas
  • said fifth fluid bed reactor is operated at a temperature of 700°C to 850°C
  • a sixth reactor connected to at least one outlet for non-condensed gas for gasification of non-condensed gas from said third reactor, said sixth reactor comprises at least one intake, said at least one intake comprises at least inlet for receiving said non-condensed gas and at least one discharge end, said at least one discharge end comprises at least one outlet for transporting processed gas to said at least one inlet for receiving processed gas, said sixth reactor is operated at a temperature of 1100°C to 1300°C, preferably 1150°C to 1250°C, a hydrogen pressure of 200 to 300 mbar, preferably 225 to 275 mbar and an oxygen pressure of 10 ⁇ 5 to 10 ⁇ 9 mbar, preferably 10 ⁇ 6 to 10 ⁇ 8 .
  • the present inventors have surprisingly discovered that a high quality oil and/or gas is obtained when thermal decomposition of carbon based materials is performed with the present system. Through using a series of separate reactors, in a specific order, the process conditions for each subprocess can be optimized. This results in an
  • Yet another advantage of the present system is that the gas produced, or synthesis gas, is practically tar free, thereby avoiding clogging in the various applications.
  • the present first fluid bed reactor for thermal cracking may also be designated as a reactor for thermal cracking or thermal cracker.
  • Thermal cracking is a refining process in which heat and pressure are used to break down, rearrange, or combine carbon molecules.
  • fuels and heavy oils were heated under pressure in large drums until they cracked into smaller molecules.
  • the advantage of using a fluid bed reactor is the ease of maintaining a uniform temperature through the cracking reactor. This uniform temperature avoids the appearance of hot spots.
  • the fluid bed reactor may comprise a Lewis acid.
  • the fluid bed reactor is heated by hot gas from said fourth moving bed reactor.
  • the present second vapour wash reactor may, in the present context, also be denoted as vapour washer.
  • a vapour washer washes the (hot) effluent vapour and gas and/or may separate heavy oil fractions.
  • the present vapour wash reactor is a packed washing column.
  • the vapour wash reactor is cooled directly by circulating product oil.
  • the present third reactor may also be denoted as fractionation reactor, or fractionation column.
  • Fractionation is a separation process in which a mixture is divided in a number of desired fractions, wherein the composition of the fraction changes according to their gradient.
  • the present third reactor separates and
  • fractionation reactor type is a packed column.
  • the present third reactor may be cooled directly by circulating product oil.
  • Carbon comprising solid material or “solid material” within the present context is a material which is solid after processing in the present first fluid bed reactor.
  • An example of such material is char or charred materials .
  • the present fourth moving bed reactor as used in the present context may also be denoted as a saturation reactor. This reactor stabilizes carbon in the solid
  • present fifth fluid bed reactor as used in the present context may also be denoted as quenching reactor or chemical quench.
  • the fifth fluid bed reactor has a double role: gasification of the stabilised carbon
  • Present sixth reactor may, according to the present invention, also be denoted as gasification reactor or gasifier.
  • Gasification is a process that converts carbon based materials into carbon monoxide and hydrogen. This resulting gas mixture is so called synthesis gas or syngas. Gasification is characterized by its high temperatures which distinguished from for example biological processes.
  • the sixth reactor according to the present invention is a pipe reactor.
  • the first fluid bed reactor is connected through at least one inlet for receiving the carbon based materials with a dryer.
  • the dryer comprises at least one inlet for receiving solid carbon based materials, at least one outlet for transporting dried solid carbon based materials into the first fluid bed reactor and at least one outlet for
  • the present dryer is preferably a fluid bed reactor.
  • the temperature in the dryer is preferably between 80°C to 120°C, more preferably between 90°C to 110°c.
  • the oxygen pressure within the dryer is between 10 to 40 mbar.
  • One advantage of the present dryer is that more carbon based materials can be processed. Accordingly, the applicability of the present system is increased.
  • the first fluid bed reactor is connected through at least one inlet for receiving said carbon based materials with an homogeniser.
  • the present homogeniser comprises at least one inlet for receiving liquid carbon based materials and at least one outlet for transporting homogenised liquid carbon based materials into the first fluid bed reactor.
  • the homogeniser is preferably a stirred tank reactor.
  • the temperature in the homogeniser is preferably between 80°C to 120°C, more preferably between 90°C to
  • the oxygen pressure within the homogeniser is between 1 to 10 mbar.
  • One advantage of the present homogeniser is that more carbon based materials can be processed or converted. For example, oil sludges or tar sand can be processed in the system according to the present invention .
  • the fifth reactor is connected through at least one outlet for gas with a gasfilter.
  • the present gasfilter comprises at least one inlet for receiving gas and at least one outlet for discharging combustible gas.
  • the present gasfilter is preferably a sediment filter, more preferably a bagfilter.
  • the gasfilter may be used for the removal from dust from the gas.
  • Preferably operating temperature is between 200°C and 240°C.
  • the hydrogen pressure of the gasfilter is 200 to 300 mbar, more preferably 225 to 275 and/or the oxygen pressure is 10 ⁇ 5 to 10 ⁇ 9 mbar, more preferably 10 ⁇ 6 to 10 ⁇ 8 mbar .
  • transport of solid material between the reactors is effected by fluming. More preferably the fluming is effected by pressurised gas. Through the use of fluming, hot process streams can be readily transported between the separate reactors. According to a preferred embodiment, the pressure in the reactors is higher than atmospheric pressure.
  • the present system comprises an oxygen membrane between the third reactor and the sixth reactor for oxygenation and/or oxidation of the non-condensed gas.
  • the present oxygen membrane may also be denoted as an oxygen transport membrane.
  • oxygen membranes exploit unique properties of mixed conducting ceramic materials, which transport both oxygen and electrons across a gas impermeable membrane.
  • the oxygen membrane is used for the selective transfer of oxygen ions to the present sixth reactor.
  • the oxygen membrane comprises hollow ceramic elements.
  • the temperature in the oxygen membrane is preferably of 850 °C to 1000°C.
  • the gas from the outlet for gas of the fifth fluid bed reactor is transported to the gasfilter through the fourth moving bed reactor and/or the first fluid bed reactor.
  • One advantage of this preferred embodiment is the thermal efficacy which is obtained by the using the heat of the gas of the fifth fluid bed reactor.
  • the present carbon based materials are selected from the group consisting of biomass, wood, forestry waste products, organic waste, agricultural waste products, plastics and tires, or any combination thereof.
  • the present invention relates to a method for the thermal conversion of carbon based materials . More specifically, the present invention relates to a method for the thermal conversion of carbon based materials into combustible oil and/or gas comprising
  • the residence time in the first fluid bed reactor is 30 to 90 minutes
  • the residence time in the second vapour wash reactor is 0.5 to 5 seconds
  • residence time in the third reactor is 1 to 5 seconds
  • the residence time in the fourth moving bed reactor is 180 to 240 minutes
  • the residence time in the fifth fluid bed reactor is 30 to 120 minutes
  • the residence time in the sixth reactor is 1 to 5 seconds.
  • the present invention relates to the use of the present system for thermal conversion of carbon based materials into
  • Figure 1 shows an example of a preferred system for the thermal conversion of carbon based materials into combustible oil and/or gas according to the present invention
  • Figure 2 shows a GCMS analysis of the combustible oil obtained with the system according to the present invention
  • Figure 3 shows a system for thermal cracking of a hydrocarbons comprising mass.
  • Figure 4 shows a system for thermal cracking of a hydrocarbons comprising mass.
  • Figure 5 shows a system for cracking a
  • Figure 6 shows a system for the treatment of
  • Figure 3 shows a system for the thermal cracking of a hydrocarbons comprising mass, comprising:
  • distillation device (3) connected with the discharge of the cracking device for the separation of a
  • a second cracking device connected with the discharge of the first cracking device (4) for the thermal separation of the charred product flow originating from the first cracking device in at least a heavy liquid fraction and a rest fraction, said second cracking device (4) comprising second heating means for heating the charred product flow,
  • At least one discharge of the distillation device (3) is adapted for discharging at least one light liquid fraction and at least one further discharge of the distillation device is equipped for discharging at least one gaseous fraction.
  • the synthesis gas may be lead as a heating gas through coils firstly the saturator (4) and secondly the thermal cracking process (2), before the synthesis gas preheats the air for the gasifier (5) .
  • the discharge of the distillation device adapted for discharging at said least one gaseous fraction is connected with an inlet of the first gasification device.
  • the distillation device (3) comprises third heating means for heating the product flow led in the distillation device.
  • first cracking device and the second cracking device are the same device (2) .
  • the system comprises an aerator connected to the inlet of the first gasification device for supplying air to the first gasification device.
  • the discharge of the second gasification device is connected with a thermally conducting discharge pipe for discharging the first gas fraction and the second gas fraction.
  • thermal conducting discharge pipe extends through the first cracking device, the second cracking device and/or the aerator.
  • the discharge of the second cracking device is connected with the inlet of the first cracking device for leading back to the first cracking device at least a part of the heavy liquid fraction originating from the second cracking device.
  • the separation device and the second gasification device are the same device (4)
  • the second gasification device is provided with means for causing the first gas fraction to flow through the rest fraction.
  • administration means connected to a discharge of the first gasification device for the administration of the first gas fraction to the second gasification device, whereby the means of administration extend to the lower zone of the second gasification device.
  • a discharge for at least a part of the first gas fraction and/or at least a part of the second gas fraction is arranged in a way such that the means of administration extend to the lowermost zone of the second gasification device.
  • the system reflects a method for the thermal cracking of a mass comprising hydrocarbons.
  • the process can be operated in three major reactors.
  • the first part is the saturator (1) where liquid hydrocarbons with a high condensing temperature are removed from the char.
  • the second part is the gasifier (2), an empty reactor providing a hold up time, where these liquid hydrocarbons, possible with other synthesis gas from the pyrolysis or gasification process, are gasified at a temperature of typically 1200 °C to 1400 °C.
  • the third part is the chemical quench (3), where the hot synthesis gas of the gasifier (2) is used for for the endothermic gasification of the char from the saturator (1) .
  • the process is characterized by leading hot synthesis gas from the second part of the process, the gasifier, to the third part of the process, the chemical quench (3) , where the hot synthesis gas gasifies the stablised char from the saturator (1) .
  • This reaction is endothermic and
  • the chemical quench (3) is a closed vessel fed with stabilised char that was treated in the saturator (1) . Because the stabilized char does not release liquid hydrocarbons, the synthesis gas practically does not contain any tar. The char is reduced to ashes and discharged from the vessel of the chemical quench.
  • said system comprises the steps of:
  • substantially gaseous fraction in the distillation device in at least a heavy liquid fraction and at least a light fraction
  • step B Further separating of the mass during step B) in a reducing atmosphere.
  • step H Further heating the mass during step H) to a temperature of between 500°C and 800°C, preferably between 500°C and 600°C.
  • step H Further pyrolysing the mass during step H) in a reducing atmosphere.
  • step C) in a time interval of between 1 and 10 seconds after step B) is initially
  • the heavy liquid fraction has a condensation temperature between 150°C and 600°C.
  • the light fraction has a condensation temperature lower than 150°C.
  • step L leading the first gas fraction during step L) through at least a part of the rest fraction.
  • step L fluidizing at least a part of the rest fraction during step L) by the first gas fraction flowing through the rest fraction.
  • step B heating the mass during step B) to a temperature of between 500°C and 800°C, preferably between 550°C and 650°C.
  • step D) during a time frame of between 0 to 10 seconds, preferably between 0 to 1 second.
  • the heavy liquid fraction having a condensation temperature of between 150°C en 600°C.
  • step D heating the heavy liquid fraction during step D) to a temperature of 1100°C and 1500°C, preferably between 1200°C and 1400°C.
  • step L performing the gasification according to step L) at a temperature of between 500°C and 900°C, preferably between 700°C and 800°C.
  • gas fraction comprises at least one substance selected from the group comprising: hydrogen, carbon monoxide, carbon dioxide, and steam.
  • Figure 4 shows a system for the thermal cracking of a hydrocarbons comprising mass, comprising:
  • a device (2) connected with the discharge of the separation to a first gasification device for gasification at least a part of the heavy liquid fraction from the separation device originating in a first gaseous fraction, said primary gasification device comprising second heating means, second gasification device a connected with the discharge of the first gasification device for gasification, using the first gaseous fraction, at least a part of rest fraction formed the in the separation device in a second gaseous fraction, said second gasification device being provided with a discharge for discharging at least a part of the first gaseous fraction and at least a part of the second gaseous fraction.
  • the separation device and the second gasification device are mirtually connected, and that the system
  • the separation device and the second gasification device are part of the same device.
  • the second gasification device is provided with means for causing the first gaseous fraction to flow through the rest fraction.
  • the system comprises administration means connected with the discharge of the first gasificaiton device for administrating the first gaseous fraction to the second
  • the discharge for the discharging of at least a part of the first gaseous fraction and at least a part of the second gaseous fraction is accommodated in the upper section of the second gasification device.
  • system of figure 5 reflects a method for the thermal cracking of a mass, comprising hydrocarbons, in particular using a system according to figure 5, comprising the steps of:
  • G discharging at least a part of the first gaseous fraction and least a part of the second gaseous fraction.
  • the second gasification device and the separation device form part of the same device.
  • step F leading the first gaseous fraction during step F) through at least a part of the rest fraction.
  • step B heating the mass during step B) to a temperature between 500 °C and 800 °C, preferably between 550 °C and 650 °C.
  • step D) within a time frame of 0 to 10 seconds, preferably within 0 to 1 second. Further, the condensation temperature of the heavy liquid, being between 150 °C and 600 °C.
  • step D the heating of the heavy liquid fraction during step D) to a temperature between 1100 °C and 1500 °C, preferably between 1200 °C and 1400 °C.
  • step G performing of the gasification according to step G) at a temperature between 500 °C and 900 °C, preferably between 700 °C and 800 °C.
  • gaseous fraction comprising at least one substance selected from the group comprising carbon monoxide, carbon dioxide, and steam.
  • Figure 5 shows a system for cracking a pyrolysable mass, particularly hydrocarbons, comprising:
  • distillation device (2) connected with a discharge of the cracking device (1) for the separation of a from the cracking device (1) originating substantially gaseous flow of a product in at least one heavy liquid fraction and at least one light fraction, whereby at least one discharge of the distillation device (2) is connected with the inlet of the cracking device for the leading back from the distillation device (2) to the cracking device (l)of at least one part of the heavy liquid fraction, and whereby the distillation device (2) comprises at least a second discharge for discharging at least one light
  • At least one second discharge of the distillation device (2) is equipped for the discharge of at least one light liquid fraction and that at least one other second discharge of the distillation device (2) is equipped for the discharge of at least one gaseous fraction.
  • the cracking device (1) comprises first heating means for the heating of the pyrolysable mass
  • the distillation device (1) comprises heating means for the heating of the in the distillation lead product flow.
  • the system comprises at least one closing device for closing the discharge of the cracking device from the inlet of the distillation device.
  • the system comprises at least one second closing device for closing the discharge of the distillation device from the inlet of the cracking device.
  • the figure reflects a method for cracking of a pyrolysable mass, particularly hydrocarbons, preferably using the device according to figure 6, comprising the following steps:
  • step B pyrolysing of the mass during step B) in a reducing atmosphere.
  • a reducing substance that is formed by at least one substance chosen from the group consisting of: hydrogen, carbon monoxide, and steam.
  • step C) within a timeframe of
  • step B 1 - 10 seconds after step B) initially is performed.
  • a heavy liquid fraction having a condensation temperature that amounts between 150 - 600 °C.
  • the light fraction having a condensation temperature being less than 150 °C.
  • steps B) , C) , D) being repeated at least one time after step F) is performed.
  • the thermal cracking is operated typically at 300 to 600 °C at elevated temperature. Whit this method the products from a thermal cracking process are, removed and then fed to a distillation process within a hold-up time of typically 1 to 10 second, preferably 2 seconds. In the distillation process the products of the thermal cracking process are separated into three fractions, a gaseous fraction, a light liquid fraction and a heavy liquid fraction. The residue is fed back to the thermal cracking process or can be tapped directly as a product if desirable. This fraction also contains dust particles, which are carried by the gas flow into the distillation process. Also these particles are returned to the thermal cracking process or are tapped.
  • the light liquid fraction is an oil fraction that does therefore not contain dust particles and can therefore be used as an engine or boiler fuel.
  • Figure 6 shows a system for the treatment of biomass, comprising:
  • the gasification device for the conversion of the combustible material in to a product gas and a rest fraction, in which the gasification device has at least one first discharge for the discharging of the product gas, and at least one second discharge for the discharging of the rest fraction,
  • At least one eductor connected with the second discharge of the gasification device for pumping at least one part of the rest fraction of the combustible material out of the gasification device, said eductor also being connected with the first discharge of the eductor for the leading of product gas through the eductor as a propellant for the purpose of pumping the rest fraction out of the
  • figure 7 reflects a method for treating combustible material, preferably by using the system
  • the product gas comprises at least one of the following components: flue gas, methane, water vapor, nitrogen, carbon monoxide, hydrogen, and/or carbon dioxide.
  • pneumatic transport is realized by an educator as a system to transport coal, coal products, charred material and ashes from one reactor to another using synthesis gas or flue gas as a drive gas.
  • bulk particles are driven through pipes by means of blowing a gas, in most cases air, through the pipes at high speed.
  • the drive gas is blown in to an educator placed in the middle of the pneumatic system, therefore creating a flow of drive gas in one direction.
  • This flow of drive gas creates a lower pressure in the pipe section before the joint where the educator is placed.
  • the lower pressure creates a flow of gas created by a pyrolysis or gasification process, carrying particles from one reactor to the other. Because drive gas is flue gas or synthesis gas, no (partial) combustion of the gas or particles take place.
  • Figure 1 shows a first fluid bed reactor (1) for thermal cracking of sludges, liquids and/or solids
  • the carbon based materials in the first fluid bed reactor (1) are subjected to the conditions:
  • the first fluid bed reactor (1) produces hot effluent vapour and gas which is transported to a second vapour wash reactor (2) .
  • the remaining carbon comprising solid materials are transported to a fourth moving bed reactor (4) and remaining metals and minerals are discharged from the system and collected.
  • the hot effluent vapour and gas are in the second vapour wash reactor (2) subjected to the conditions:
  • the second vapour wash reactor (2) produces washed vapour and gas which is transported (104) to a third reactor (3) .
  • the remaining solids and oil are transported (105) to the first fluid bed reactor (1) .
  • the third reactor (3) produces combustible oil and non-condensed gas.
  • the combustible oil is discharged (106) from the system and collected.
  • the non-condensed gas is transported (107) to an oxygen membrane (10) .
  • the non-condensed gas is in the oxygen membrane (10) subjected to the conditions:
  • the oxygen membrane (10) produces oxygenated gas which is transported (108) to a sixth reactor (6) for gasification .
  • the oxygenated gas is in the sixth reactor (6) subjected to the conditions:
  • the sixth reactor (6) produces processed gas which is transported (109) to a fifth fluid bed reactor (5) for cooling processed gas and gasification of stabilized carbon comprising solid material.
  • the processed gas is in the fifth fluid bed reactor (5) subjected to the conditions:
  • the fifth fluid bed reactor (5) produces cooled gas and gasified stabilized carbon comprising solid
  • the gas is transported (110) via a fourth moving bed reactor (4) and the first fluid bed reactor (1) to a gasfilter (9).
  • the gasified stabilized carbon comprising solid material is transported (111) to the first fluid bed reactor ( 1 ) .
  • the cooled gas is in the gasfilter (9) subjected to the conditions:
  • the gasfilter produces combustible gas and filter dust.
  • the combustible gas and filter dust are discharged (112 and 113 respectively) from the system and collected.
  • the remaining carbon comprising solid materials are in the fourth moving bed reactor (4) subjected to the conditions : Temperature 600°C
  • the fourth moving bed reactor (4) produces stabilized carbon comprising solid material which is transported (114) to the fifth fluid bed reactor (5)
  • the dryer (7) receives solid carbon based materials. These solid carbon based materials are in dryer subjected to the conditions:
  • the dryer (7) produces dried solid carbon based materials which are transported (115) to the first fluid bed reactor (1) and remaining metals and minerals are discharged (116) from the system and collected.
  • the homogeniser (8) receives liquid or semi-liquid carbon based materials. These liquid or semi-liquid carbon based materials are in the homogenizer (8) subjected to the conditions :
  • the homogenizer (8) produces homogenized liquid carbon based materials which are transported (117) to the first fluid bed reactor (1) .
  • the calorific value of the synthesis gas obtained by the system according to the example was 5.1 MJ/Nm 3 .
  • the combustible oil obtained in the above example has a good quality, as is further elucidated by Figure 2 which shows a GCMS analysis of the combustible oil obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Processing Of Solid Wastes (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un système de conversion thermique de matériaux à base de carbone en un gaz et/ou en une huile combustible. Ledit système comprend, plus précisément, un premier réacteur à lit fluidisé, un deuxième réacteur de lavage par la vapeur, un troisième réacteur de fractionnement, un quatrième réacteur à lit mobile, un cinquième réacteur à lit fluidisé et un sixième réacteur de gazéification.
PCT/EP2010/069881 2010-07-19 2010-12-16 Système et procédé de conversion thermique de matériaux à base de carbone WO2012010223A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/809,891 US20130118075A1 (en) 2010-07-19 2010-12-16 System And Method For Thermal Conversion Of Carbon Based Materials
EP10803071.9A EP2596083A1 (fr) 2010-07-19 2010-12-16 Système et procédé de conversion thermique de matériaux à base de carbone
BR112013001461A BR112013001461A2 (pt) 2010-07-19 2010-12-16 sistema e método para conversão térmica de materiais à base de carvão

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
NLPCT/NL2010/050464 2010-07-19
NLPCT/NL2010/000112 2010-07-19
NLPCT/NL2010/000110 2010-07-19
PCT/NL2010/050464 WO2012011803A1 (fr) 2010-07-19 2010-07-19 Système et procédé pour le craquage d'une masse pyrolysable, en particulier d'hydrocarbures
NLPCT/NL2010/000111 2010-07-19
PCT/NL2010/000111 WO2012011801A2 (fr) 2010-07-19 2010-07-19 Système et procédé de traitement de biomasse
PCT/NL2010/000109 WO2012011799A2 (fr) 2010-07-19 2010-07-19 Système et procédé de craquage thermique d'hydrocarbures comprenant une masse
PCT/NL2010/000110 WO2012011800A1 (fr) 2010-07-19 2010-07-19 Système et procédé de craquage thermique d'hydrocarbures comprenant une masse
NLPCT/NL2010/000109 2010-07-19
PCT/NL2010/000112 WO2012011802A2 (fr) 2010-07-19 2010-07-19 Dispositif et procédé pour la digestion anaérobie de matière organique en biogaz au moyen de micro-organismes

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US9353476B2 (en) 2014-04-18 2016-05-31 Georgia-Pacific Containerboard Llc Method for recycling waste material with reduced odor emission
CN105693055A (zh) * 2016-04-20 2016-06-22 陕西延长石油（集团）有限责任公司 一种油泥分质-气化资源化利用的方法

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CN107353936B (zh) * 2017-09-04 2019-12-24 东华工程科技股份有限公司 一种加氢气化合成气的净化分离系统及其工艺
NL2019552B1 (en) * 2017-09-14 2019-03-27 Torrgas Tech B V Process to prepare a char product and a syngas mixture
SE542564C2 (en) * 2017-10-13 2020-06-09 Cortus Ab Process and apparatus for hydrotreatment of pyrolysis oil

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US5849964A (en) * 1993-04-03 1998-12-15 Veba Oel Aktiengesellschaft Process for the processing of salvaged or waste plastic materials
US6084139A (en) * 1997-12-05 2000-07-04 Gibros Pec B.V. Method for processing waste or biomass material
US20090062581A1 (en) * 2003-03-28 2009-03-05 Appel Brian S Methods and apparatus for converting waste materials into fuels and other useful products
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US9353476B2 (en) 2014-04-18 2016-05-31 Georgia-Pacific Containerboard Llc Method for recycling waste material with reduced odor emission
CN105693055A (zh) * 2016-04-20 2016-06-22 陕西延长石油（集团）有限责任公司 一种油泥分质-气化资源化利用的方法
CN105693055B (zh) * 2016-04-20 2016-12-14 陕西延长石油（集团）有限责任公司 一种油泥分质‑气化资源化利用的方法

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US20130118075A1 (en) 2013-05-16
EP2596083A1 (fr) 2013-05-29
BR112013001461A2 (pt) 2016-05-31

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