[go: up one dir, main page]

WO2017050580A1 - Système et procédé pour le traitement de gaz dégagé par pyrolyse - Google Patents

Système et procédé pour le traitement de gaz dégagé par pyrolyse Download PDF

Info

Publication number
WO2017050580A1
WO2017050580A1 PCT/EP2016/071135 EP2016071135W WO2017050580A1 WO 2017050580 A1 WO2017050580 A1 WO 2017050580A1 EP 2016071135 W EP2016071135 W EP 2016071135W WO 2017050580 A1 WO2017050580 A1 WO 2017050580A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
pyrolysis
unit
hydrogen
plasma
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2016/071135
Other languages
English (en)
Inventor
François-Xavier Pascal Thierry CHIRON
Christian Wix
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of WO2017050580A1 publication Critical patent/WO2017050580A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/342—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • 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
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/046—Reducing the tar content
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/063—Refinery processes
    • C01B2203/065—Refinery processes using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1258—Pre-treatment of the feed
    • 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
    • C10J2300/093—Coal

Definitions

  • the invention relates to a system and a method for generating a hydrogen rich gas from pyrolysis of carbonaceous material.
  • the invention moreover relates to a system and a method for upgrading tar oil from pyrolysis of carbonaceous material.
  • Pyrolysis of carbonaceous material results in a pyrolysis gas which is rich in tar oil, water and a variety of hydrocarbons in vapor phase.
  • Any contaminant which was present in the carbonaceous material subject to pyrolysis, will be present in the pyrolysis gas.
  • Such contaminants may present problematic issues for downstream units, e.g. poisoning issues for catalysts (if present), fouling, corrosion. Cleaning steps may be necessary in case sensitive process, equipment or catalyst are used.
  • Tar oil has in the past been considered an undesirable by-product from pyrolysis of carbonaceous material, since there is cost and effort associated with the disposal of surplus tar. This has sparked an interest for an efficient conversion of the tar oil into products with an actual market demand.
  • pyrolysis shall be understood as a process in which a carbonaceous feedstock, such as coal or biomass, is heated either in the absence of oxygen or in the presence of sub-stoichiometric amounts of oxygen with respect to oxidation to C0 2 .
  • the products from pyrolysis consist of a solid phase, a gas phase and a liquid phase, i.e. tar oil.
  • pyrolysis differs from the term "gasification” due to the temperatures in a pyrolysis and a gasification reactor differ, the water content differs and the products differ.
  • the system comprises a pyrolysis reactor arranged to carry out pyrolysis on carbonaceous material fed into the pyrolysis reactor.
  • the pyrolysis reactor comprises a first output for outletting liquid and/or solid residue from the pyrolysis and a second output for outletting pyrolysis gas.
  • the system moreover comprises a quenching device comprising an input for inletting the pyrolysis gas and ar- ranged to separate the pyrolysis gas into liquid effluents and off gas.
  • the quenching unit comprises a first outlet for outletting the off gas and a second outlet for outletting liquid effluents from the quenching unit.
  • the system moreover comprises a hydrogen generation unit arranged for generating hydrogen from the off gas by facilitating reactions of hydrocarbons in the off gas into a reformed off gas comprising carbon monox- ide and hydrogen.
  • the system moreover comprises a gas separation unit comprising an input for inletting the reformed off gas from the hydrogen generation unit.
  • the gas separation unit being is arranged for separating the reformed off gas into a hydrogen rich gas and a hydrogen lean gas.
  • the system of the invention is a system where no recycle is necessary in order to obtain the required amount of hydrogen for the tar oil upgrading. Moreover, virtually no cleaning step is necessary, which provides for a less complex system, having fewer units, than a system with e.g. dedicated steam reforming equipment for hydrogen generation.
  • the system further comprises a preheating section downstream the quenching device and upstream the hydrogen generation unit.
  • the preheating section is arranged to preheat the off gas to a temperature in the range between about 500°C and about 800°C.
  • the system may also comprise a heat recovery section downstream hydrogen generation unit.
  • the carbonaceous material is coal and/or biomass.
  • the liquid effluents from the quenching device comprise tar oil and/or water.
  • system further comprising a water gas shift section downstream the hydrogen generation unit and upstream the gas separation unit. This provides for a further generation of hydrogen.
  • the hydrogen generation unit is a plasma unit comprising a plasma chamber, a plasma torch arranged to generate a plasma jet, a first input for inletting a torch feeding gas, a second input for inletting the off gas, a first output for outletting plasma treated gas and a second output for outletting solid and/or liquid residue.
  • the plasma torch is arranged to provide a plasma torch having a temperature of between about 3500°C and about 5000°C.
  • a plasma unit with a plasma torch mounted on a refractory lined reactor or chamber will be able to reform enough hydrocarbons to hydrogenate the tar oil in valuable product.
  • the plasma chamber is empty in the sense that no catalyst is present in the plasma chamber. The lack of catalyst in the hydrogen reforming unit provides for a hydrogen generation system that is robust against poisons in the off gas.
  • the plasma torch is arranged to raise the gas temperature so much that the C0 2 present in the gas will reform the hydrocarbons present in the gas.
  • Plasma is known to be insensitive to poisons in addition of having special properties to crack the
  • the plasma by nature dissociates the electrons from the pro- tons and creates extremely reactive radicals, boosting the cracking reactions.
  • the plasma unit requires electricity and only minor amounts of water and air or C0 2 .
  • the plasma unit typically comprises an empty (but refractory lined) plasma reactor with a conical section at the bottom. This way the plasma reactor can be function as a cy- clone. Carbonaceous residue in the form of deposits or particles will be removed at the bottom of the reactor, by gravity through an outlet in the bottom of the reactor.
  • the treated gas will contain less hydrocarbons (ethylene/ ethane/ propane) and more hydrogen and CO. This gas is suitable to enter a gas separation unit, such as a pressure swing absorption unit, where pure hydrogen or hydrogen rich gas is recovered. De- pending on the off gas pressure, compression of the hydrogen rich gas may also be advantageous.
  • the system is arranged to produce hydrogen from the off gas, with virtually no cleaning step and with very limited water consumption.
  • the system is flexible and works with a maximum load of the plasma unit of at least between 20% and 100%.
  • the start-up of the system is easy due to the easy start-up of the plasma unit.
  • No water gas shift unit is needed in the system with the plasma unit.
  • the hydrogen generation unit is a catalytic partial oxidation (CPO) unit comprising a reactor with a precious metal catalyst and optionally also a nickel based catalyst.
  • the catalytic partial oxidation unit comprising a first input for in- letting the off gas, a second input for inletting an oxidation gas, and an output for out- letting partially oxidized gas.
  • the amount of oxidation gas is adjusted so as to ensure that the temperature of the partially oxidized gas is in the range from about 700°C to about 1050°C.
  • This system also has a reduced water consumption compared to a system with a steam methane reforming unit.
  • the other advantages mentioned in relation to the system with the plasma unit in relation to easy start-up, load flexibility from 20% to 100% and no need of a water gas shift unit also apply to this embodiment.
  • the oxidation gas to the CPO unit may be air, oxygen enriched air or pure oxygen.
  • the hydrogen generation unit is a partial oxidation unit comprising a reactor with a reaction chamber.
  • the catalytic partial oxidation unit comprising a first input for inletting the off gas, a second input for inletting an oxidation gas, and an output for outletting partially oxidized gas.
  • the amount of oxidation gas is adjusted so as to ensure that the temperature of the partially oxidized gas is in the range from about 1200°C to about 1300°C.
  • This system also has a reduced water consumption compared to a system with a steam methane reforming unit.
  • the invention is also related to a system for upgrading tar oil from pyrolysis of carbonaceous material.
  • the tar upgrading system comprises a system for generating a hydrogen rich gas according to the invention and a sub-system for improving tar oil.
  • the system for improving tar oil comprises as least one tar hydro processing section.
  • the system for upgrading tar oil comprises a conduit from leading hydrogen rich gas from the system for generating a hydrogen rich gas to the tar hydro processing section of the sub-system.
  • the hydrogen obtained from the system for generating a hydrogen rich gas from pyrolysis is used to hydrogenate aromatic and poly-aromatic molecules in the tar oil during hydro processing.
  • the hydrogen rich gas is led into the feedstock, viz. the tar oil, which is to undergo hydro treatment or to one or more reactors arranged for carrying out hydro processing.
  • hydrogen rich gas may be added between reactor beds, mainly for temperature control.
  • the invention is also related to method of generating a hydrogen rich gas from pyrolysis off gas and to a method of upgrading tar oil from py- rolysis of carbonaceous material.
  • Figure 1 is a schematic drawing of a system for generating a hydrogen rich gas from pyrolysis of carbonaceous material
  • FIG 2 is a schematic drawing of a system for upgrading tar oil from pyrolysis of carbonaceous material.
  • the figures show non-limiting embodiments which are examples on the invention only; these embodiments are thus not intended to be limiting to the invention. Similar units and streams are denoted with similar reference numbers in the drawings.
  • FIG 1 there is shown a schematic drawing of a system 100 for generating a hydrogen rich gas from pyrolysis of carbonaceous material.
  • Carbonaceous material 105 such as coal or biomass, is fed to a pyrolysis reactor 10.
  • Pyrolysis carried out in the pyrolysis reactor 10 at a pressure close to atmospheric and at a temperature of about 550° will produce a gas 1 10 high in tars and water.
  • the pyrolysis may be operated at pressures in the range from 0.1 to 5 bar atm.
  • the pyrolysis also results in liquid and/or solid residue 1 18, which is outlet from a first output of the pyrolysis reactor.
  • the gas 1 10 is outlet from a second outlet from the pyrolysis reactor 10.
  • a cyclone unit 20 filters off a fraction of the gas 1 10, typically particles and/or solid matter within the gas 1 10, and returns the filtered off fraction 1 15 to the pyrolysis reactor 10 for further pyrolysis whilst the gas 1 10 high in tars excluding the filtered off fraction 1 15, viz. a pyrolysis gas 120, is led to a quenching unit 30.
  • the quenching unit 30 comprises a cooling unit 32 and a separation unit 34.
  • the cooling unit 32 is arranged for cooling the pyrolysis gas 120 sufficiently for condensing it, so that the output stream 124 from the cooling unit 32 is a mixture of liquid and gas.
  • a cooling medium is used for cooling down the pyrolysis gas 120 in or- der to provide cooling.
  • the cooling medium is any appropriate gas or liquid, e.g. water or salt water, of an appropriate temperature.
  • a heat exchanger may also be used for further cooling down of the pyrolysis gas.
  • the stream 124 from the cooling unit is led into the separation unit 34 which is arranged to separate water from tar oil and gas.
  • Three streams 126, 128 and 130 are output from the separation unit 34 and thus from quenching unit 30.
  • the separation unit 34 may be a tank with a lower outlet for the tar oil stream 128, an outlet for the water stream 126 placed above the outlet for tar oil stream, whilst the outlet for the off gas stream is typically placed at the upper side of the separation unit 34 Typically, if 1 ton of coal is fed into the pyrolysis reactor, 0.1 ton of tar oil is output from the quenching device 30 in the tar oil stream 128.
  • the composition of the off gas 130 depends upon the conditions, in particular the temperature, of the pyrolysis reactor 10. Exemplary compositions are given below, in a case where the carbonaceous material is coal:
  • Table 1 Composition of the off gas 130 as a function of the temperature of the pyroly- sis reactor 10.
  • composition of off gasses from pyrolysis of coal may e.g. be found in Dual et al., Characterization of gases and solid residues from closed system pyrolysis of peat and coal at two heating rates, Fuel, 90, 2011 ; or in Kawamura et al., Study on coal flash py- rolysis, Nippon Steel Technical report n°57, April 1993.
  • the amount of C0 2, C 2 H 4 , C 2 H 6 and C 3 H 8 are highest at the lower temperatures and falls for increasing temperatures of the pyrolysis reactor 10.
  • the amounts of H 2 and CH4 in the pyrolysis off gas for a pyrolysis reactor 10 operating between about 450°C and about 650°C increase with an increasing temperature.
  • the amount of CO in the pyrolysis off gas does not vary very much with varying temperatures of the pyrolysis reactor operating between about 450°C and about 650°C.
  • Heating value of the off gas is at its highest at about an operating temperature of about 500°C, and varies between about 5500 and 6300 kcal/m 3 , when the temperature of the pyrolysis reactor 10 varies between about 450°C to about 650°C.
  • the off gas 130 is fed to the hydrogen generation unit 40.
  • the hydrogen generation unit 40 may be any appropriate unit arranged for reforming hydrocarbons in the off gas 130 into a hydrogen and carbon monoxide.
  • the hydrogen generation unit 40 may be a catalytic partial oxidation (CPO) unit, a partial oxidation (POX) unit or a plasma unit.
  • the system 100 may further comprise a preheating section downstream the quenching device 30 and upstream the hydrogen generation unit 40.
  • the preheating section is not shown in figure 1 or 2.
  • the preheating unit is arranged to preheat the off gas 130 to a temperature in the range between about 500°C and about 800°C.
  • the system 100 comprises a heat recovery section (not shown in figures 1
  • the system 100 further comprises a water gas shift section 50 downstream the hydrogen generation unit 40 and upstream a gas separation unit 60.
  • the stream 140 from the hydrogen generation unit 40 is a reformed off gas stream, which is led to a water gas shift unit 50 for conversion of monoxide and water/steam in the reformed off gas 140 to carbon dioxide and hydrogen (H 2 ).
  • the output stream 150 from the water gas shift unit 50 is led to a gas separation unit 60 which is arranged for separating the reformed shifted off gas 150 into a hydrogen rich gas 160 and a hydrogen lean gas 162.
  • reformed off gas 140' is led directly to the gas separation unit 60.
  • the gas separation unit 60 is arranged for separating the hydrogen rich gas from other components (Carbon oxides, methane, nitrogen) of the reformed off gas 140 or 140'.
  • the gas separation unit 60 is e.g. a pres- sure swing absorption unit.
  • a hydrogen rich gas stream 160 and a hydrogen lean gas stream 162 are output from the gas separation unit 60.
  • the hydrogen rich gas stream 160 may be pure or almost pure hydrogen.
  • the hydrogen lean gas stream 162 may be recycled to the pyrolysis unit, be routed to another chemical plant, be used directly or be burned off or otherwise disposed of.
  • the hydrogen generation unit 40 may thus be a catalytic partial oxidation (CPO) unit, a partial oxidation (POX) unit or a plasma unit. These units are now described in more detail.
  • the hydrogen generation unit 40 is a plasma unit.
  • the plasma unit comprises a plasma chamber, a plasma torch arranged to generate a plasma jet, a first input for inletting a torch feeding gas, a second input for inletting the off gas.
  • the plas- ma unit comprises a first output for outletting plasma treated gas and a second output for outletting solid and/or liquid residue.
  • the plasma chamber may have a further air or steam injection input.
  • the plasma chamber is typically an empty refractory lined reactor; that is, no catalyst material is typically present within the refractory lined plasma chamber.
  • the plasma torch is arranged to provide a plasma torch having a temperature of between about 3500°C and about 5000°C.
  • the pyrolysis off gas 130 within the plasma chamber obtains a temperature of up to 1500°C.
  • the combination of a high temperature and the formation of very reactive radicals in the plasma region favours reforming reactions with C0 2 and/or H 2 0 if are present.
  • the plasma unit may e.g. be a plasma unit as described in US2009077887AA.
  • the hydrogen generation unit is a catalytic partial oxidation
  • CPO unit comprising a reactor with a precious metal catalyst and optionally also a nickel based catalyst.
  • the reactor is typically refractory lined and loaded with a precious metal catalyst such as Rh or Pt supported on alumina.
  • the refractory lined reactor may additionally contain a nickel based catalyst.
  • the catalytic partial oxidation unit has a first input for inletting the off gas, and a second input for inletting an oxidation gas and an output for outletting partially oxidized gas.
  • the CPO unit typically also includes a gas mixing device for mixing the off gas and the oxidation gas. During operating of the system, the amount of oxidation gas is adjusted so as to ensure that the temperature of the partially oxidized gas is in the range from about 700°C to about 1050°C.
  • the oxidation gas is air, oxygen enriched air or pure oxygen.
  • the CPO unit typically comprises a gas cleaning unit upstream of the CPO reactor.
  • the gas cleaning unit is arranged to remove poisons such as chlorine containing molecules, sulphur containing molecules, heavy metals, tars from the off gas stream entering the CPO reactor with catalyst for catalysing the CPO reaction.
  • CPO can be used to partially oxidize a hydrocarbon into CO and H 2 .
  • the amount of air (or enriched air or pure 0 2 ) is adjusted so that oxidation reaction do not go all the way to combustion (therefore producing C0 2 and H 2 0) but are limited to CO and H 2 .
  • the generation unit is a partial oxidation (POX) unit comprising a reactor with a reaction chamber.
  • the reactor chamber is typically an empty refractory lined reactor.
  • the partial oxidation unit comprises a first input for inletting the off gas, a second input for inletting an oxidation gas, and an output for outletting partially oxidized gas.
  • the POX unit moreover comprises a gas mixing device for mixing the off gas and the oxidation gas. During operating of the system, the amount of oxidation gas is adjusted so as to ensure that the temperature of the partially oxidized gas is in the range from about 1200°C to about 1300°C.
  • POX may be seen as the thermal version of CPO. A high temperature is reached with the injection of significant amount of air. Similar to the CPO reaction, the POX reaction conditions must favour partial oxidation conditions. Temperatures in the vicinity of 1200-1300°C are often required to get enough hydrocarbon conversion. Since no cata- lyst is present, POX is not sensitive to poisons.
  • FIG 2 there is shown a schematic drawing of a system 200 for upgrading tar oil from pyrolysis of carbonaceous material.
  • the units 10, 20, 30, 32, 34, 40, 50 and 60 as well as the streams 105, 110, 115, 118, 120, 124, 126, 128, 130, 140, 140', 150, 160 and 162 of the system 100 shown in figure 1 are also part of the system 200 for upgrading tar oil from pyrolysis of carbonaceous material.
  • the system 200 shown in figure 2 differs from the system 100 shown in figure 1 by the unit 70.
  • the unit 70 is a tar hydro processing section.
  • the system 200 comprises comprises a conduit from leading hydrogen rich gas 160 from the system 100 for generating a hydrogen rich gas to the tar hydro processing section 70.
  • the tar oil stream 128 from the quench unit 30 is also led into the tar hydro processing section 70.
  • the tar hydro processing section 70 may be a single hydro pro- cessing reactor having one or more reactor beds; alternative the tar hydro processing section may comprise more than one hydro processing reactor, each having one or more reactor beds. In both these cases, hydrogen rich gas may be added between reactor beds, mainly for temperature control.
  • the hydrogen rich gas stream 160 is used in the tar oil upgrading unit 70 for hydrogenating aromatic and poly-aromatic molecules. From the hydro processing section 70 a hydro treated product 170 is obtained, which has low nitrogen content and a low content of aromatics.
  • a product stream 170 in the form of an upgraded or improved tar oil stream is outlet from the unit 70.
  • 1 ton of coal typically provides 0.1 ton of tar oil, water and 150 Nm 3 of off gas.
  • the composition of the off gas typically depends on the pyrolysis temperature as indicate in Table 1 above. Usually, a temperature of between about 500°C and about 550°C is the preferred pyrolysis temperature. Impurities are mainly tars, H 2 S (between 0.1 to 0.5 mol%), metals, chlorine.
  • the hydrogen generation unit is a plasma unit.
  • the plasma unit will carry out the following mail reactions:
  • Reactions with C0 2 are the main target since C0 2 is already present in the gas, but air can be injected too to lift up the gas temperature. It is also possible to inject water or extra C0 2 into the plasma unit.
  • Table 2 Compositions of off gas 130 into plasma unit, air injected into plasma unit and reformed off gas 140 from plasma unit. From Table 2 it is seen that the reformed off gas 140 has 32.45 mol% H 2 in a total output flow from the plasma unit of 61668 Nm 3 /h. This corresponds to 61668 Nm 3 /h for flow of the off gas 130 of 37500 Nm 3 /h into the plasma unit.
  • the plasma unit according to the invention for converting or reforming hydrocarbons in the off gas 130 into hydrogen, it is not even necessary to shift the gas in a water gas shift unit 50. However, if more hydrogen is needed, such a water gas shift unit may be used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Industrial Gases (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention concerne un système pour produire un gaz riche en hydrogène à partir de la pyrolyse d'une matière carbonée. Le système comprend a) un réacteur de pyrolyse agencé de manière à effectuer une pyrolyse sur une matière carbonée, le réacteur de pyrolyse comprenant une sortie permettant de faire sortir un gaz de pyrolyse ; b) un dispositif d'extinction conçu pour séparer ledit gaz de pyrolyse en effluents liquides et en gaz dégagé ; c) une unité de génération d'hydrogène conçue pour produire de l'hydrogène à partir dudit gaz dégagé en facilitant le reformage à sec et/ou des réactions d'oxydation d'hydrocarbures dans ledit gaz dégagé en un gaz dégagé reformé comprenant du monoxyde de carbone et d'hydrogène ; et d) une unité de séparation de gaz conçue pour séparer ledit gaz dégagé reformé en un gaz riche en hydrogène et en un gaz pauvre en hydrogène. L'invention concerne également un procédé permettant de produire un gaz riche en hydrogène à partir de la pyrolyse d'une matière carbonée, un système de valorisation d'huile d'anthracène à partir d'une pyrolyse de matière carbonée et un procédé de valorisation d'huile d'anthracène.
PCT/EP2016/071135 2015-09-23 2016-09-08 Système et procédé pour le traitement de gaz dégagé par pyrolyse Ceased WO2017050580A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA201500556 2015-09-23
DKPA201500556 2015-09-23

Publications (1)

Publication Number Publication Date
WO2017050580A1 true WO2017050580A1 (fr) 2017-03-30

Family

ID=56883803

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/071135 Ceased WO2017050580A1 (fr) 2015-09-23 2016-09-08 Système et procédé pour le traitement de gaz dégagé par pyrolyse

Country Status (1)

Country Link
WO (1) WO2017050580A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110540857A (zh) * 2019-08-05 2019-12-06 北京联谊华海能源科技有限公司 生物质制取化工原料和液体燃料的方法
CN110540856A (zh) * 2019-08-05 2019-12-06 北京联谊华海能源科技有限公司 生物质制取化工原料和液体燃料的方法
WO2021163110A1 (fr) * 2020-02-10 2021-08-19 Eastman Chemical Company Traitement de produits lourds de pyrolyse par gazéification par oxydation partielle
CN117819477A (zh) * 2023-12-29 2024-04-05 新疆乾海环保科技有限公司 风电光电等离子体裂解水蒸汽重整煤炭热解气制氢系统
FI20236249A1 (en) * 2023-11-08 2025-05-09 Neste Oyj Hydrogen liquefaction of carbonaceous feedstock
WO2025132467A1 (fr) * 2023-12-22 2025-06-26 Topsoe A/S Procédé pour la stabilisation d'un produit brut hydrocarboné instable

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100018116A1 (en) * 2008-07-23 2010-01-28 Latif Mahjoob System and method for converting solids into fuel
US20100064573A1 (en) * 2008-09-15 2010-03-18 Mario Araya Brenes Method for producing a liquid biofuel or at least one of its primary components
US20100237290A1 (en) * 2006-12-22 2010-09-23 Institut Francais Du Petrole Method for Producing a Purified Synthesis Gas from a Biomass Including a Purification Step Upstream from the Partial Oxidation
WO2014145223A1 (fr) * 2013-03-15 2014-09-18 Battelle Memorial Institute Réacteur catalytique en phase vapeur pour l'amélioration de combustibles produits par pyrolyse éclair de biomasse

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100237290A1 (en) * 2006-12-22 2010-09-23 Institut Francais Du Petrole Method for Producing a Purified Synthesis Gas from a Biomass Including a Purification Step Upstream from the Partial Oxidation
US20100018116A1 (en) * 2008-07-23 2010-01-28 Latif Mahjoob System and method for converting solids into fuel
US20100064573A1 (en) * 2008-09-15 2010-03-18 Mario Araya Brenes Method for producing a liquid biofuel or at least one of its primary components
WO2014145223A1 (fr) * 2013-03-15 2014-09-18 Battelle Memorial Institute Réacteur catalytique en phase vapeur pour l'amélioration de combustibles produits par pyrolyse éclair de biomasse

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110540857A (zh) * 2019-08-05 2019-12-06 北京联谊华海能源科技有限公司 生物质制取化工原料和液体燃料的方法
CN110540856A (zh) * 2019-08-05 2019-12-06 北京联谊华海能源科技有限公司 生物质制取化工原料和液体燃料的方法
CN110540856B (zh) * 2019-08-05 2020-05-26 北京海国龙油能源科技有限公司 生物质制取化工原料和液体燃料的方法
CN110540857B (zh) * 2019-08-05 2020-05-26 北京海国龙油能源科技有限公司 生物质制取化工原料和液体燃料的方法
WO2021163110A1 (fr) * 2020-02-10 2021-08-19 Eastman Chemical Company Traitement de produits lourds de pyrolyse par gazéification par oxydation partielle
FI20236249A1 (en) * 2023-11-08 2025-05-09 Neste Oyj Hydrogen liquefaction of carbonaceous feedstock
FI131475B1 (en) * 2023-11-08 2025-05-09 Neste Oyj Hydrogen liquefaction of carbonaceous feedstock
WO2025099363A1 (fr) 2023-11-08 2025-05-15 Neste Oyj Hydroliquéfaction d'une charge d'alimentation carbonée
WO2025132467A1 (fr) * 2023-12-22 2025-06-26 Topsoe A/S Procédé pour la stabilisation d'un produit brut hydrocarboné instable
CN117819477A (zh) * 2023-12-29 2024-04-05 新疆乾海环保科技有限公司 风电光电等离子体裂解水蒸汽重整煤炭热解气制氢系统

Similar Documents

Publication Publication Date Title
WO2017050580A1 (fr) Système et procédé pour le traitement de gaz dégagé par pyrolyse
EP2403926B1 (fr) Processus de transformation thermochimique de la biomasse
RU2600733C2 (ru) Способ переработки тяжелой нефти и битума
JP5851043B2 (ja) スラリー水添分解工程から固体触媒により重質残油をガス化する方法
CN116018317A (zh) 用于合成烃的方法
RU2011144858A (ru) Гидропиролиз биомассы для получения высококачественного жидкого горючего
WO2021185869A1 (fr) Production d'hydrocarbures
WO2011112484A1 (fr) Utilisation de carburants fossiles pour augmenter les avantages d'un carburant à base de biomasse
TW201438987A (zh) 平行製造氫、一氧化碳及含碳產物的方法
Speight Gasification processes for syngas and hydrogen production
JP2014521581A5 (fr)
EA033831B1 (ru) Способ конверсии природного газа в углеводородные продукты и установка для осуществления способа
US20070289898A1 (en) Supercritical Water Processing of Extra Heavy Crude in a Slurry-Phase Up-Flow Reactor System
CN115151625B (zh) 将原油直接提质为氢和化学品的系统和工艺
US9074148B2 (en) Hydrogen and carbon utilization in synthetic fuels production plants
GB2056479A (en) Producing liquid hydrocarbon streams by hydrogenation of fossil-based feedstock
EP0018998A1 (fr) Procede integre de liquefaction du charbon-gazeification-reformage de naphta.
US10266775B2 (en) Process for producing a hydrocarbon product flow from a gaseous hydrocarbonaceous feed flow and related installation
CN113226980B (zh) 用于制备氢气、一氧化碳和含碳产物的方法和设备
JP7482164B2 (ja) 炭化水素の直接分解方法
JP2025541768A (ja) 炭化水素の合成プロセス
EP0018996A4 (fr) Procede de liquefaction-gazeification du charbon comprenant le reformage du naphta produit.
WO2014123454A1 (fr) Procédé de transformation de gaz d'hydrocarbure en produits pétroliers synthétiques liquides stables et installation énergétique pour sa mise en oeuvre
EP2830992B1 (fr) Procédé intégré pour la gazéification de pétrole brut total dans un gazéifieur à membrane et génération d'électricité
US20140296595A1 (en) Methods And Apparatus For Producing Aromatics From Coal

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16762811

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16762811

Country of ref document: EP

Kind code of ref document: A1