WO2013087480A2 - Catalytic cracking of pyrolysis derived organic molecules - Google Patents

Catalytic cracking of pyrolysis derived organic molecules Download PDF

Info

Publication number
WO2013087480A2
WO2013087480A2 PCT/EP2012/074506 EP2012074506W WO2013087480A2 WO 2013087480 A2 WO2013087480 A2 WO 2013087480A2 EP 2012074506 W EP2012074506 W EP 2012074506W WO 2013087480 A2 WO2013087480 A2 WO 2013087480A2
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
inorganic
catalytic material
reaction chamber
pyrolysis
Prior art date
Application number
PCT/EP2012/074506
Other languages
French (fr)
Other versions
WO2013087480A4 (en
WO2013087480A3 (en
WO2013087480A9 (en
Inventor
Andrew Holt
Kirsty BONNER
Ioulia ZIMOZDRA
Original Assignee
Catal International Limited
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 Catal International Limited filed Critical Catal International Limited
Publication of WO2013087480A2 publication Critical patent/WO2013087480A2/en
Publication of WO2013087480A3 publication Critical patent/WO2013087480A3/en
Publication of WO2013087480A4 publication Critical patent/WO2013087480A4/en
Publication of WO2013087480A9 publication Critical patent/WO2013087480A9/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10G3/62—Catalyst regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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 the catalytic cracking of pyrolysis derived organic molecules.
  • Pyrolysis reactions are well known in the art. Pyrolysis involves the thermo chemical decomposition of organic molecules at high temperatures in a deoxygenated environment. Pyrolysis is a specific type of thermolysis. The Pyrolysis of organic compounds involves the cleavage of chemical bonds and the chemical rearrangement of the organic compounds undergoing pyrolysis. The resultant products are commonly in the form of viscous oil having high carbon content and containing entrained water.
  • Pyrolysis reactions differ from combustion in that the reactions take place in the absence of oxygen. Although pyrolysis reactions generally take place in an oxygen deficient atmosphere a certain amount of oxidation of the carbon molecules may occur as a consequence of reactions with liberated water at high temperature.
  • the resultant carbonaceous oil products derived from pyrolysis reactions contain a wide range of varying molecular weight organic components.
  • the catalytic process as outlined herein relates to a catalytic process and catalysts used therein, to convert high molecular weight complex organic molecules, derived from the thermal pyrolysis of carbonaceous materials, to lower molecular weight organic components suitable for processing and/or conversion into liquid fuels.
  • the process is particularly, but not exclusively, concerned with a process and catalysts thereof, for the conversion and reforming of oils derived from the fluid bed pyrolysis of solid carbonaceous materials, to hydrocarbons and oxygenated molecules. Such molecules are suitable for purification and inclusion in fuel blends or are used as feed components for hydrogenation and/or hydrocracking processing to produce transportation or stationary power source fuels.
  • the process and corresponding catalysts referred to herein may be used to convert and reform high molecular weight components of pyrolysis derived organic oils, such as lignins and cellulosic materials to products including a wide range of lower molecular weight hydrocarbons and oxygenated compounds. Additionally the process may be used to convert pyrolysis derived organic oils containing high levels of contaminants which commonly deactivate traditional Petroleum Refinery upgrading catalysts by pore blockage.
  • Pyrolysis oils range from heavy, high viscosity oils to lighter oils dependant on the pyrolysis feedstock origin, the ageing time in contact with oxygen, the pH of the oil and level of contaminants.
  • the oils may also contain dispersed water in which are dissolved inorganic ionic species, such as sodium, potassium, sulphate, chlorides and trace heavy metals.
  • the oils contain free organic acids which produce low pH values and may also be dissolved in the water phase.
  • the fresh oils are readily handled and manipulated, however the oils undergo self-polymerisation with age and in contact with air and become increasingly difficult to manipulate as a consequence of the viscosity increase.
  • Heating pyrolysis derived oils causes the viscosity of the oils to increase due to internal polymerisation of the complex molecules. Therefore due to this problem pyrolysis derived oils cannot be readily and easily preheated in bulk for catalytic processing.
  • the oil containing dispersed water has a typical elemental analysis by weight as:
  • Thermal catalytic cracking methods exemplified by the Fluid Catalytic Cracking (FCC) process used in the petroleum industry cannot be used directly to process pyrolysis oils due to problems of self-polymerisation of the oil in the feed pre-heater sections, the inability of the FCC catalyst to adsorb the oil into the internal zeolitic porosity resulting in the substantial formation of very high molecular weight carbonaceous polymers ('coke') on the external surface blocking access to the internal active zeolite sites.
  • the FCC unit is a heat balanced process and the amount of 'coke' determines the throughput conversion. High coke deposition significantly reduces the conversion rates and efficiency of the process.
  • Biomass pyrolysis oils are produced from the rapid thermal degradation of organic materials, typically, waste wood, grass, straw and other organic materials.
  • These pyrolysis derived oils are dark, viscous, high molecular weight blends of a wide range of complex organic species and also contain entrained/suspended water and other ionic inorganic contaminants.
  • Such oils commonly contain lignins, sugars, aldehydes and organic acids, amongst many other functional groups, and are unstable with respect to polymerisation i.e. they will oxidise and polymerise on standing and will continue to polymerise and become more viscous upon heating.
  • Such pyrolysis derived oils have high Carbon and Oxygen content and a low Hydrogen :Carbon ratio.
  • Fluid cracking catalysts are in microsphere powder form.
  • HDS hydrodesulphurisation
  • Typical catalytic reforming and hydrodesulphurisation (HDS) catalysts used in petroleum oil refining processes have pores with diameters in the region of 20-250 A diameter and further may have a zeolite component having pores in the diameter region of 3-10 A.
  • Esterification of pyrolysis oils has been proposed by several researchers, and specifically reactive distillation esterification, where claims have been made for esterification using low molecular weight alcohols, typically ethanol and methanol, to react with acidic components in the oils.
  • oils contain sufficient acid for reaction, however in practise the oils contain limited amounts of low molecular weight organic acids, typically low molecular weight, C2 - C4, meaning that the product of esterification, a low molecular weight ester, has limited commercial use as a fuel.
  • low molecular weight organic acids typically low molecular weight, C2 - C4
  • Pyrolysis oils also contain substantial levels of entrained water which reduces the activity of acidic esterification catalysts and, due to the production of water in the esterification reaction, shifts the chemical equilibrium away from the required products. Esterification, whilst chemically of interest, cannot readily be considered a viable and effective route to upgrading raw pyrolysis oil for transportation fuels
  • a catalyst system for cracking pyrolysis derived organic molecules comprising;
  • the first inorganic catalytic material has a pyrolysis organic molecule pore absorption volume of at least two times that of the second inorganic catalytic material
  • the mass ratio of the first inorganic catalytic material and the second inorganic catalytic material is in the range of 10:1 to 1 :10.
  • the at least first inorganic catalytic material and the second inorganic catalytic material are thermally stable.
  • the at least first inorganic material and the second inorganic catalytic material may be spherical.
  • the at least first inorganic catalytic material preferably comprises pores with diameters in the range 100 - 1 .000.000 A.
  • the first inorganic component may further contain catalytically active metal compounds.
  • the second inorganic catalytic material preferably comprises a crystalline zeolite component.
  • the crystalline zeolite may further comprise pore diameters in the range 3 - 25 A.
  • the crystalline zeolite may further comprise catalytically active compounds contained within an amorphous or crystalline porous binder.
  • the crystalline zeolite may further comprise catalytically active metals contained with an amorphous or crystalline porous binder.
  • the second inorganic catalytic material may comprise at least one amorphous inorganic oxide.
  • the second inorganic catalytic material may comprise at least one amorphous catalytic material configured to promote the reformation of gas phase molecules to low molecular weight organic material.
  • a process for cracking pyrolysis derived organic molecules using a catalyst comprising: at least a first inorganic catalytic material and a second inorganic catalytic material; wherein the first inorganic catalytic material has a pyrolysis organic molecule pore absorption volume of at least two times that of the second inorganic catalytic material; and the mass ratio of the first inorganic catalytic material and the second inorganic catalytic material is in the range of 10:0.1 ;
  • the process comprising the steps of: mixing the pyrolysis derived organic molecules with the catalyst system at a temperature less than 100 Q C to form a dry mixture; heating the dry mixture to a temperature between 200-1000 Q C in a reaction chamber; separating a gaseous phase crude product out of the reaction chamber from a coke (solid carbonaceous material) deactivated solid phase catalyst mixture; condensing the gaseous phase crude product to separate out a lower molecular weight organic product from a produced aqueous phase; separating and oxidatively regenerating the catalyst from the solid phase catalyst mixture; and cooling the regenerated catalyst to below 100 degrees Celsius.
  • the at least first inorganic catalyst material and the second inorganic catalytic material are thermally stable.
  • the at least first inorganic catalyst material and the second inorganic catalyst material may be spherical.
  • the first inorganic catalyst material may further comprise pores with diameters in the range 100 - 1 .000.000 A.
  • the first inorganic material preferably contains catalytically active metal components
  • the second inorganic catalytic material preferably comprises crystalline zeolite.
  • the crystalline zeolite preferably comprises pore diameters in the range 3 - 25 A.
  • the crystalline zeolite may further comprise catalytically activating compounds contained within an amorphous or crystalline porous binder.
  • the crystalline zeolite may further comprise catalytically active metals contained with an amorphous or crystalline porous binder.
  • the second inorganic catalytic material preferably comprises at least one amorphous inorganic oxide.
  • the second comprises at least one amorphous catalytic component configured to promote the reformation of gas phase molecules to low molecular weight organic material.
  • Inorganic ionic contaminants are preferably adsorbed in the internal pore surface of the first inorganic catalytic material, upon mixing the catalysts with the pyrolysis derived organic molecules.
  • the first inorganic catalytic material may be physically separated from the crystalline zeolite material. The physical separation may be carried out by physical sieving.
  • a flow of non-oxygen containing gas is preferably passed over the catalyst.
  • the reaction chamber comprises a rotating reactor.
  • the rotating reactor is preferably tubular in shape, and may advantageously be inclined.
  • a separator vessel preferably separates the gaseous crude product from the solid phase catalyst mixture out of the reaction chamber.
  • a condenser is preferably connected to an outlet of the separator vessel to condense a gaseous crude product outlet stream.
  • Regeneration of the catalyst mixture is preferably undertaken in a catalyst regeneration vessel to remove carbonaceous material by oxidative combustion.
  • the dry mixture preferably moves through the reaction chamber under gravity.
  • the reaction chamber preferably comprises an inlet and an outlet.
  • the reaction chamber may further comprise a central rotating screw feeder to transport the dry mixture from the inlet to the outlet.
  • Non-condensed gases flowing from outlet of the reaction chamber are preferably recycled back to the inlet of the reaction chamber.
  • the non-oxygen containing gas may comprise hydrogen, nitrogen, carbon dioxide, carbon monoxide, low molecular weight hydrocarbon gases or mixtures thereof.
  • Other aspects are as set out in the claims herein.
  • Figure 1 illustrates schematically a catalytic process for cracking pyrolysis derived organic molecules according to a preferred embodiment.
  • catalytic process for cracking of pyrolysis derived organic molecules 17 comprises dry mixture of reagents and catalysts 1 , mixed components 2, reaction chamber 3, furnace/heat source 4, gaseous phase crude product 5, condenser vessel 6, condensed crude product 7, separation chamber 8, reaction product 9, by-product 10, incondensable gasses 1 1 , solid phase catalyst mixture 12, regeneration/combustion chamber
  • the first stage involves combining a dry mixture of reagents and catalysts 1 .
  • the dry mixture of reagents and catalysts 1 comprises a first catalytic material shown in Figure 1 as (A) and a second catalytic material shown in Figure 1 as (B).
  • the first catalytic material is preferably inorganic, thermally stable to temperatures of up to 1500 Q C, and furthermore has pores having diameters of between 100 - 1 .000.000 A.
  • the first catalytic material (A) and the second catalytic material (B) make up the catalyst for process 17.
  • the first inorganic catalytic material (A) in the dry mixture of reagents and catalyst 1 is a high pore volume catalytic material and may comprise a low surface area aluminous sphere
  • the high porosity catalytic material (A) preferably comprises an inorganic material with low cracking activity and having a majority of pores with diameters between 100 - 1 .000.000 A, i.e. a high pore volume and low surface area.
  • the second inorganic catalytic material (B) of dry mixture 1 has a low pore volume for absorption of pyrolysis oils and the mass ratio of the high pore volume material (A) relative to the lower pore volume material (B) is in the range of 10:1 - 1 :10. Furthermore, the high pore volume material (A) has a pyrolysis oil absorption pore volume which is at least twice that of additional materials in the dry mixture 1 .
  • the low pore volume catalytic material (B) may comprise any one of the following:
  • Crystalline zeolite materials with a defined porous structure and pores with diameters between 3 and 25 A.
  • Amorphous and/or crystalline zeolite catalytic materials which promote the reformation of the gas phase components to required products.
  • the pyrolysis derived oils and other organic materials are also added to the dry mixture 1 .
  • a majority of inorganic ionic contaminants or impurities which are dissolved or contained within the aqueous component of the pyrolysis derived oils and organic molecules, are adsorbed on the internal pore surface of the first inorganic catalytic material (A).
  • the amount of pyrolysis oil that can be absorbed by the catalyst is significantly increased and the catalyst/oil ratio is reduced. This allows for a substantial increased rate of oil/per catalyst volume to be introduced into the thermal cracking reaction chamber 3, therefore increasing the conversion rate of pyrolysis derived organic molecules into lower molecular weight components within a reduced timeframe.
  • the contaminant laden high pore volume material (A) has adsorbed the inorganic ironic contaminants and may be physically separated from the second inorganic catalytic material (B) by physical size sieving.
  • Physical size sieving or particle sieving is a method of separating particles of different sizes.
  • a sieve commonly comprises a mesh structure having openings of predetermined widths used to separate large particles from smaller particles
  • any surface debris adsorbing or adhering to the outside of the high pore volume catalytic material (A) may also be removed.
  • the free flowing oil laden spheres comprises the organic pyrolysis derived molecules/oils which have been absorbed into the pores of catalytic material A and oil coated catalytic material B.
  • the reaction chamber 3 is tubular and rotatable such that the furnace/heat source 4 can evenly heat the reaction chamber 3 such as to provide a controlled temperature profile and preferably an even internal temperature distribution in the reaction chamber 3.
  • the furnace or heat source can be varied in temperature and/or heat output such that the reaction conditions can be altered such as to speed up or slow down the reaction or for example if the temperature was set too high, the temperature could be altered accordingly.
  • the chamber 3 Before the mixed components 2 are transported into reaction chamber 3, the chamber 3 is pre-heated by furnace/heat source 4 at a desired temperature of between 200 - 1 .000 Q C. The introduction of heat initiates the catalytic reaction such that the high molecular weight pyrolysis oil organic compounds are broken down into smaller compounds.
  • the reaction chamber 3 is pre-heated before the mixed components 2 are introduced such that the mixed components 2 are immediately subjected to the optimum reaction conditions therefore allowing for efficient maximum production.
  • reaction chamber 3 is inclined such that reactants and reagents can flow under gravity through the reaction chamber 3 to an outlet (not shown) of the reaction chamber 3.
  • reaction chamber 3 further comprises a screw thread running through the centre of reaction chamber 3 such as to facilitate transport of mixed components 2 from the inlet to the outlet of the reaction chamber 3.
  • reaction chamber 3 and furnace/heat source 4 may be configured as a stacked furnace or a fluid bed furnace.
  • reaction chamber 3 the components are heated and left to react typically for between 0.1 minute to one hour.
  • the oils in the oil laden catalytic sphere undergo thermal catalytic cracking.
  • a flow of non-oxygen containing gas is passed over the catalyst.
  • the gas is comprised of hydrocarbons, nitrogen, carbon dioxide or hydrogen, or recycled thermally cracked gas produced during the thermal reaction.
  • the catalytic cracking reaction in reaction chamber 3 can take place in an oxygen deficient atmosphere.
  • the condenser vessel condenses a mixture of low molecular weight organic molecules and water to form an oil-water layer (condensed crude product) 7.
  • the condensed crude product 7 is then transported to a separation chamber 8, whereby the water by-product 10 is separated from the organic layer reaction product 9 to result in the desired low molecular weight organic oils 9 being separated out as a product.
  • Any incondensable gas phase products 1 1 that could not be condensed in condenser vessel 6, are re-directed back to the inlet (not shown) of reaction chamber 3 such as to be re-cycled and passed over the mixed components 2 which react in reaction chamber 3 to form part of the oxygen deficient atmospheric conditions of chamber 3.
  • the solid phase catalyst mixture 12 Concurrently with the gaseous phase crude products 5 being transported to condenser 6, the solid phase catalyst mixture 12 is transported out of the reaction chamber 3. [00082]
  • the solid phase catalyst mixture 12 comprises first inorganic catalytic material A and second inorganic catalytic material B as well as carbonaceous solid impurities. [00083]
  • the solid phase catalyst mixture 12 is transported to a regeneration/combustion chamber 13.
  • the solid phase catalyst mixture 12 is exposed to an oxygen containing gas 14 and heat, such as to undergo combustion of the carbon of the solid phase catalyst mixture 12 to separate the carbon from the catalytic materials A and B as oxides of carbon 15 (combustion by-product).
  • the combustion by-product 15 is predominantly carbon dioxide, CO , with inclusions of water and carbon monoxide, CO.
  • the combustion stage of process 17 allows catalytic materials A and B (regenerated catalyst) 16 to be re-cycled and regenerated. Therefore the recycled catalyst 16 can be re-used in the process through introduction of the recycled catalyst 16 into the stage of forming a dry mixture of oil and catalyst 1 of catalytic process 17.
  • the catalyst regeneration vessel 13 is isolated from the reaction chamber 3 and allows for carbonaceous material to be removed from the catalytic materials A and B by controlled oxidative combustion.
  • the primary objective of the catalytic process or cracking of pyrolysis derived organic molecules 17 is to reduce the molecular weight of the organic components of raw pyrolysis derived oils by thermal cracking of the high molecular weight components and to partially remove chemically bound oxygen as water.
  • the low molecular weight reaction products 9 resultant from process 17 can be subsequently used for the refining of the low molecular reaction products 9 to fuels or chemicals for commercial/industrial use.
  • the invention relates to a catalytic process and catalysts used therein to convert high molecular weight complex organic molecules, derived from the thermal pyrolysis of carbonaceous materials, to lower molecular weight molecules suitable for processing into liquid fuels.
  • the invention is particularly, but not exclusively, concerned with a process and catalysts for the conversion and reforming of oils derived from the fluid bed pyrolysis of carbonaceous materials to hydrocarbons and oxygenated molecules.
  • Such molecules are suitable for purification and inclusion in fuel blends or are used as feed components for hydrogenation and/or hydrocracking processing to produce transportation or stationary power source fuels.
  • the process and catalysts referred to may be used to convert and reform high molecular weight components of pyrolysis oils, such as lignins and cellulosic materials to a product containing a wide range of lower molecular weight hydrocarbons and oxygenated compounds. Additionally the process may be used to convert pyrolysis oils containing high levels of contaminants which would typically deactivate traditional Petroleum Refinery upgrading catalysts.
  • novel process and catalysts developed for the upgrading of pyrolysis oil and described herein remove the constraints on thermally and catalytically processing pyrolysis oil previously indicated by making use of a blend of a high porosity oil carrier, which has a relatively low thermal catalytic cracking activity, and a higher cracking activity catalyst which further catalyses and reforms the gas phase components from the high porosity carrier into lower molecular weight hydrocarbons and oxygenates.
  • Example 1 [00094] 50 ml of high pore volume catalyst comprising a low surface area alumina, 3.5 mm diameter, sphere which had been previously calcinated at 1200°C for 4 hours, was heated to 40°C in a beaker and raw pyrolysis oil, containing 20% volume aqueous components, added to the warm spheres until 12.0 g of oil had been absorbed into the spheres to produce a free flowing brown spherical material 1 which did not self-adhere or stick to the walls of the glass beaker.
  • the oil loaded (laden) spheres 2 were loaded into a lock hopper 3 sitting on top of a 1 " diameter vertical reactor tube heated 4 to 632° C.
  • the reactor 3 was equipped with an internal poppet valve with gas passage holes located in the centre of the furnace and a lock hopper system at the exit of the reactor.
  • Evolved gases 5 from the cracking reaction were removed via a central 1 ⁇ 4" gas discharge tube connected to the poppet valve and condensed externally.
  • a flow of LPG gas was continuously passed through the reactor at a rate of 250 ml/minute.
  • the catalyst/oil blend was dropped from the upper lock hopper into the furnace and kept in the furnace for 30 minutes after which time the internal valve was opened and the catalyst dropped out into the lower lock hopper system.
  • Evolved gases 5 were condensed out in liquid nitrogen cooled tubes 6, collected, weighed and analysed.
  • the liquid product 7 consisted of two phases with an upper aqueous phase and mobile lower organic phase.
  • GC-MS analysis of the aqueous product 10 indicates that the primary component is Acetic acid with lower levels of Alcohols, Ketones, Aldehydes and Phenols.
  • Analysis of the oil layer 9 indicated a complex mixture of ketones, phenolics, sugars and unconverted lignins.
  • Example 2 50 ml of high porosity catalyst comprising a low surface area, alumina 3.5 mm diameter, sphere was mixed with 26 ml of a zeolite catalyst sphere, diameter 2mm, composed of 50 % weight ZSM-5 zeolite and 50 % alumina -clay binder. The blend was heated to 48°C and raw pyrolysis oil , containing 20% volume aqueous components, added to the warm spheres until 13.05 g of oil had been absorbed to produce a free flowing dark brown spherical blended material 1 which did not stick to the glass beaker or self-adhere.
  • Evolved gases 5 were condensed out in liquid nitrogen cooled tubes 6, collected, weighed and analysed.
  • the liquid product 7 was a two phase liquid with an upper organic phase 9 and a lower aqueous phase 10. There was an indication of a lower heavier oil phase which appeared as dispersed droplets in the aqueous phase.
  • GC-MS analysis of the non-aqueous upper phase 9 indicates that the components are a blend of hydrocarbons - toluene, xylenes, naphthalenes, ketones, aldehydes and phenols with minor levels of sugars and lignin species.
  • Analysis of the aqueous product 10 indicates that the primary components are Acetic acid and Hydroxypropanone with lower levels of Alcohols, Ketones, Aldehydes and Phenols.
  • the example demonstrates the use of a continuous rotary furnace 3 for the reaction.
  • 500 ml of high porosity catalyst comprising an alumina 3.5 mm diameter sphere were heated to 40°C and raw pyrolysis oil, containing 20% wt. aqueous phase, added to the warm spheres until 170g of oil had been absorbed to produce a free flowing dark brown spherical material 1 .
  • the oil loaded (laden) spheres 2 were loaded into a sealed hopper 3 equipped with a rotary screw feeder connected via a sealed rotary joint to the inclined furnace.
  • the spheres 2 were continuously fed into the rotating, inclined, 2" diameter reactor 3 of 1 .3 m length which was heated in the centre by an external furnace 4 with a set point control of 600 Q C.
  • the spheres 2 moved down the inclined reactor through the heated reaction zone and into the catalyst-gas separation vessel where the spheres are continuously removed to be regenerated by oxidative methods.
  • the gas phase products 5 are separated from the carbon laden spheres 12 and condensed 6.
  • the liquid product 7 from this process separates into a 2 phase mixture with an upper aqueous phase and a lower heavy organic phase in the approximate volume ratios of 9:1 , Aq:oil.
  • GC-MS analysis of the aqueous layer 10 indicates the predominance of Acetic acid and Hydroxypropanone with a range of Phenolic compounds and minor amounts of ketones, Aldehydes, furans and sugars. The lower phase was not analysed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A process and catalyst system for thermal catalytic cracking of pyrolysis derived organic molecules comprising at least a first inorganic catalytic material and a second inorganic catalytic material. The first inorganic catalytic material has a pyrolysis organic molecule pore absorption volume of at least two times that of the second inorganic catalytic material and the mass ratio of the first inorganic catalytic material and the second inorganic catalytic material is in the range of 10:0.1.

Description

CATALYTIC CRACKING OF PYROLYSIS DERIVED ORGANIC
MOLECULES Field of the Invention
[0001] The present invention relates to the catalytic cracking of pyrolysis derived organic molecules.
Background of the Invention
[0002] Pyrolysis reactions are well known in the art. Pyrolysis involves the thermo chemical decomposition of organic molecules at high temperatures in a deoxygenated environment. Pyrolysis is a specific type of thermolysis. The Pyrolysis of organic compounds involves the cleavage of chemical bonds and the chemical rearrangement of the organic compounds undergoing pyrolysis. The resultant products are commonly in the form of viscous oil having high carbon content and containing entrained water.
[0003] Pyrolysis reactions differ from combustion in that the reactions take place in the absence of oxygen. Although pyrolysis reactions generally take place in an oxygen deficient atmosphere a certain amount of oxidation of the carbon molecules may occur as a consequence of reactions with liberated water at high temperature. The resultant carbonaceous oil products derived from pyrolysis reactions contain a wide range of varying molecular weight organic components. [0004] The catalytic process as outlined herein relates to a catalytic process and catalysts used therein, to convert high molecular weight complex organic molecules, derived from the thermal pyrolysis of carbonaceous materials, to lower molecular weight organic components suitable for processing and/or conversion into liquid fuels.
[0005] The process is particularly, but not exclusively, concerned with a process and catalysts thereof, for the conversion and reforming of oils derived from the fluid bed pyrolysis of solid carbonaceous materials, to hydrocarbons and oxygenated molecules. Such molecules are suitable for purification and inclusion in fuel blends or are used as feed components for hydrogenation and/or hydrocracking processing to produce transportation or stationary power source fuels. [0006] The process and corresponding catalysts referred to herein may be used to convert and reform high molecular weight components of pyrolysis derived organic oils, such as lignins and cellulosic materials to products including a wide range of lower molecular weight hydrocarbons and oxygenated compounds. Additionally the process may be used to convert pyrolysis derived organic oils containing high levels of contaminants which commonly deactivate traditional Petroleum Refinery upgrading catalysts by pore blockage.
[0007] Pyrolysis oils range from heavy, high viscosity oils to lighter oils dependant on the pyrolysis feedstock origin, the ageing time in contact with oxygen, the pH of the oil and level of contaminants. The oils may also contain dispersed water in which are dissolved inorganic ionic species, such as sodium, potassium, sulphate, chlorides and trace heavy metals. The oils contain free organic acids which produce low pH values and may also be dissolved in the water phase. The fresh oils are readily handled and manipulated, however the oils undergo self-polymerisation with age and in contact with air and become increasingly difficult to manipulate as a consequence of the viscosity increase. Heating pyrolysis derived oils causes the viscosity of the oils to increase due to internal polymerisation of the complex molecules. Therefore due to this problem pyrolysis derived oils cannot be readily and easily preheated in bulk for catalytic processing.
[0008] A typical analysis of pyrolysis oil is;
Water 20 - 25 % wt.
Oil 75 - 80 % wt.
[0009] The oil containing dispersed water has a typical elemental analysis by weight as:
Carbon 43% Hydrogen 8%
Oxygen 49%
[00010] Proposals for processing the high viscosity, thermally unstable molecules have addressed several types of reaction schemes, for example; combination hydrogenation and hydrocracking process; thermal catalytic cracking using a zeolite catalyst; esterification using alcohols and fixed bed acidic catalysts; gasification under low oxygen conditions to produce a synthesis gas
(CO + H2) and a range of high pressure catalysed hydrothermal conversion reactions.
[00011] Combination hydrogenation and hydrocracking reactions on the raw pyrolysis oils typically require a pre-treatment stage to remove contaminants prior to the hydrogenation catalyst, very high hydrogen partial pressures and a supply of large volumes of hydrogen to remove oxygen from the oxygenated molecules as water and to saturate cracked unstable species. Direct commercial scale hydrogenation and hydrocracking requires substantial capital investment and is an expensive operation but does produce a product suitable for consideration in fuels.
[00012] Thermal catalytic cracking methods exemplified by the Fluid Catalytic Cracking (FCC) process used in the petroleum industry cannot be used directly to process pyrolysis oils due to problems of self-polymerisation of the oil in the feed pre-heater sections, the inability of the FCC catalyst to adsorb the oil into the internal zeolitic porosity resulting in the substantial formation of very high molecular weight carbonaceous polymers ('coke') on the external surface blocking access to the internal active zeolite sites. The FCC unit is a heat balanced process and the amount of 'coke' determines the throughput conversion. High coke deposition significantly reduces the conversion rates and efficiency of the process. Use of a classical FCC process and catalyst for pyrolysis oil feed processing therefore has significant drawbacks which modify the technical and commercial viability of the system. [00013] Biomass pyrolysis oils are produced from the rapid thermal degradation of organic materials, typically, waste wood, grass, straw and other organic materials.
[00014] These pyrolysis derived oils are dark, viscous, high molecular weight blends of a wide range of complex organic species and also contain entrained/suspended water and other ionic inorganic contaminants. [00015] Such oils commonly contain lignins, sugars, aldehydes and organic acids, amongst many other functional groups, and are unstable with respect to polymerisation i.e. they will oxidise and polymerise on standing and will continue to polymerise and become more viscous upon heating. [00016] Such pyrolysis derived oils have high Carbon and Oxygen content and a low Hydrogen :Carbon ratio.
[00017] The majority of metal oxide catalysts used in the oil refining and petrochemical industries for catalytic thermal cracking of high molecular weight oils have high BET surfaces areas (50-700 square metres per gram) and have pores with diameters in the ranges of 3-500 A and are of spherical or cylindrical configuration.
[00018] Fluid cracking catalysts (FCC) are in microsphere powder form.
[00019] Typically catalytic reforming and hydrodesulphurisation (HDS) catalysts used in petroleum oil refining processes have pores with diameters in the region of 20-250 A diameter and further may have a zeolite component having pores in the diameter region of 3-10 A. [00020] Esterification of pyrolysis oils has been proposed by several researchers, and specifically reactive distillation esterification, where claims have been made for esterification using low molecular weight alcohols, typically ethanol and methanol, to react with acidic components in the oils. Production of ethyl/methyl esters of organic acids present in pyrolysis oil is chemically viable when the oils contain sufficient acid for reaction, however in practise the oils contain limited amounts of low molecular weight organic acids, typically low molecular weight, C2 - C4, meaning that the product of esterification, a low molecular weight ester, has limited commercial use as a fuel.
[00021] Pyrolysis oils also contain substantial levels of entrained water which reduces the activity of acidic esterification catalysts and, due to the production of water in the esterification reaction, shifts the chemical equilibrium away from the required products. Esterification, whilst chemically of interest, cannot readily be considered a viable and effective route to upgrading raw pyrolysis oil for transportation fuels
Summary of the Invention
[00022] According to a first aspect of the present invention, there is provided a catalyst system for cracking pyrolysis derived organic molecules comprising;
at least a first inorganic catalytic material and a second inorganic catalytic material;
wherein the first inorganic catalytic material has a pyrolysis organic molecule pore absorption volume of at least two times that of the second inorganic catalytic material; and
the mass ratio of the first inorganic catalytic material and the second inorganic catalytic material is in the range of 10:1 to 1 :10. [00023] Preferably, the at least first inorganic catalytic material and the second inorganic catalytic material are thermally stable. [00024] The at least first inorganic material and the second inorganic catalytic material may be spherical.
[00025] The at least first inorganic catalytic material preferably comprises pores with diameters in the range 100 - 1 .000.000 A.
[00026] The first inorganic component may further contain catalytically active metal compounds. [00027] The second inorganic catalytic material preferably comprises a crystalline zeolite component.
[00028] The crystalline zeolite may further comprise pore diameters in the range 3 - 25 A.
[00029] The crystalline zeolite may further comprise catalytically active compounds contained within an amorphous or crystalline porous binder.
[00030] Alternatively, the crystalline zeolite may further comprise catalytically active metals contained with an amorphous or crystalline porous binder.
[00031] The second inorganic catalytic material may comprise at least one amorphous inorganic oxide.
[00032] Alternatively, the second inorganic catalytic material may comprise at least one amorphous catalytic material configured to promote the reformation of gas phase molecules to low molecular weight organic material. [00033] According to a second embodiment of the present invention, there is provided a process for cracking pyrolysis derived organic molecules using a catalyst comprising: at least a first inorganic catalytic material and a second inorganic catalytic material; wherein the first inorganic catalytic material has a pyrolysis organic molecule pore absorption volume of at least two times that of the second inorganic catalytic material; and the mass ratio of the first inorganic catalytic material and the second inorganic catalytic material is in the range of 10:0.1 ;
the process comprising the steps of: mixing the pyrolysis derived organic molecules with the catalyst system at a temperature less than 100Q C to form a dry mixture; heating the dry mixture to a temperature between 200-1000Q C in a reaction chamber; separating a gaseous phase crude product out of the reaction chamber from a coke (solid carbonaceous material) deactivated solid phase catalyst mixture; condensing the gaseous phase crude product to separate out a lower molecular weight organic product from a produced aqueous phase; separating and oxidatively regenerating the catalyst from the solid phase catalyst mixture; and cooling the regenerated catalyst to below 100 degrees Celsius. [00034] Preferably, the at least first inorganic catalyst material and the second inorganic catalytic material are thermally stable. [00035] The at least first inorganic catalyst material and the second inorganic catalyst material may be spherical.
[00036] The first inorganic catalyst material may further comprise pores with diameters in the range 100 - 1 .000.000 A.
[00037] The first inorganic material preferably contains catalytically active metal components [00038] The second inorganic catalytic material preferably comprises crystalline zeolite.
[00039] The crystalline zeolite preferably comprises pore diameters in the range 3 - 25 A.
[00040] The crystalline zeolite may further comprise catalytically activating compounds contained within an amorphous or crystalline porous binder. [00041] Alternatively, the crystalline zeolite may further comprise catalytically active metals contained with an amorphous or crystalline porous binder.
[00042] The second inorganic catalytic material preferably comprises at least one amorphous inorganic oxide.
[00043] Alternatively, the second comprises at least one amorphous catalytic component configured to promote the reformation of gas phase molecules to low molecular weight organic material. [00044] Inorganic ionic contaminants are preferably adsorbed in the internal pore surface of the first inorganic catalytic material, upon mixing the catalysts with the pyrolysis derived organic molecules. [00045] The first inorganic catalytic material may be physically separated from the crystalline zeolite material. The physical separation may be carried out by physical sieving.
[00046] Upon keeping the dry mixture at a temperature between 200-1000QC in the reaction chamber, a flow of non-oxygen containing gas is preferably passed over the catalyst.
[00047] Preferably, the reaction chamber comprises a rotating reactor. The rotating reactor is preferably tubular in shape, and may advantageously be inclined.
[00048] A separator vessel preferably separates the gaseous crude product from the solid phase catalyst mixture out of the reaction chamber. A condenser is preferably connected to an outlet of the separator vessel to condense a gaseous crude product outlet stream.
[00049] Regeneration of the catalyst mixture is preferably undertaken in a catalyst regeneration vessel to remove carbonaceous material by oxidative combustion.
[00050] The dry mixture preferably moves through the reaction chamber under gravity.
[00051] The reaction chamber preferably comprises an inlet and an outlet. The reaction chamber may further comprise a central rotating screw feeder to transport the dry mixture from the inlet to the outlet.
[00052] Non-condensed gases flowing from outlet of the reaction chamber are preferably recycled back to the inlet of the reaction chamber. [00053] The non-oxygen containing gas may comprise hydrogen, nitrogen, carbon dioxide, carbon monoxide, low molecular weight hydrocarbon gases or mixtures thereof. [00054] Other aspects are as set out in the claims herein.
Brief Description of the Drawings
[00055] For a better understanding of the invention and to show how the same may be carried into effect, there will now be described by way of example only, specific embodiments, methods and processes according to the present invention with reference to the accompanying drawings in which:
Figure 1 illustrates schematically a catalytic process for cracking pyrolysis derived organic molecules according to a preferred embodiment.
Detailed Description of the Embodiments
[00056] There will now be described by way of example a specific mode contemplated by the inventors. In the following description numerous specific details are set forth in order to provide a thorough understanding. It will be apparent however, to one skilled in the art, that the present invention may be practiced without limitation to these specific details. In other instances, well known methods and structures have not been described in detail so as not to unnecessarily obscure the description. [00057] Referring to Figure 1 herein catalytic process for cracking of pyrolysis derived organic molecules 17 comprises dry mixture of reagents and catalysts 1 , mixed components 2, reaction chamber 3, furnace/heat source 4, gaseous phase crude product 5, condenser vessel 6, condensed crude product 7, separation chamber 8, reaction product 9, by-product 10, incondensable gasses 1 1 , solid phase catalyst mixture 12, regeneration/combustion chamber
13, air source 14, combustion by-product 15 and regenerated catalyst 16. [00058] Referring to the catalytic process for cracking of pyrolysis derived organic molecules 17, the first stage involves combining a dry mixture of reagents and catalysts 1 . The dry mixture of reagents and catalysts 1 comprises a first catalytic material shown in Figure 1 as (A) and a second catalytic material shown in Figure 1 as (B). The first catalytic material is preferably inorganic, thermally stable to temperatures of up to 1500Q C, and furthermore has pores having diameters of between 100 - 1 .000.000 A. The first catalytic material (A) and the second catalytic material (B) make up the catalyst for process 17. However, additional catalytic material or reagents may be added to the dry mixture at the start of process 17 in order to facilitate the catalytic process. The first inorganic catalytic material (A) in the dry mixture of reagents and catalyst 1 , is a high pore volume catalytic material and may comprise a low surface area aluminous sphere The high porosity catalytic material (A) preferably comprises an inorganic material with low cracking activity and having a majority of pores with diameters between 100 - 1 .000.000 A, i.e. a high pore volume and low surface area.
[00059] The second inorganic catalytic material (B) of dry mixture 1 , has a low pore volume for absorption of pyrolysis oils and the mass ratio of the high pore volume material (A) relative to the lower pore volume material (B) is in the range of 10:1 - 1 :10. Furthermore, the high pore volume material (A) has a pyrolysis oil absorption pore volume which is at least twice that of additional materials in the dry mixture 1 . [00060] Preferably, the low pore volume catalytic material (B) may comprise any one of the following:
• Crystalline zeolite materials with a defined porous structure and pores with diameters between 3 and 25 A.
• Crystalline zeolite materials with defined porous structures and pore diameters, and additionally catalytically activating compounds or metals, contained within an amorphous or crystalline porous binder. • Amorphous inorganic oxide catalysts and materials which undergo a chemical reduction during the reaction by virtue of their donation of chemically contained oxide species.
• Amorphous and/or crystalline zeolite catalytic materials which promote the reformation of the gas phase components to required products.
[00061] The pyrolysis derived oils and other organic materials are also added to the dry mixture 1 . By virtue of the higher absorbent pore capacity (volume) of the first inorganic material (A) a majority of inorganic ionic contaminants or impurities which are dissolved or contained within the aqueous component of the pyrolysis derived oils and organic molecules, are adsorbed on the internal pore surface of the first inorganic catalytic material (A).
[00062] Typically, the addition of raw pyrolysis oils to a traditional high surface area first inorganic catalytic material based upon an alumina or zeolite component produces a sticky mass with minimal adsorption of the pyrolysis oils into the catalyst body. The viscosity of the oil is such that penetration of oil into the interior of the catalyst does not penetrate further than the external surface and "eggshell" coatings are formed. Hence the ratio of catalyst oil (cat/oil) is very high.
[00063] Heating pyrolysis derived oils prior to contact with the catalyst, to a temperature considered sufficient to reduce the viscosity of the pyrolysis oils, as is typically undertaken in many heavy hydrocarbon conversion reactions, induces self - polymerisation reactions within the oil and the viscosity may further increase, therefore decreasing catalytic activity. [00064] By reducing the surface area and increasing the diameter of the pores of the catalyst (catalytic material A) which, preferably comprise alumina and/or metal oxide based materials, the adsorption of the oil into the catalyst is significantly enhanced at relatively low temperatures and the problem of surface "eggshell" formation on the catalyst is significantly reduced.
[00065] Therefore, the amount of pyrolysis oil that can be absorbed by the catalyst is significantly increased and the catalyst/oil ratio is reduced. This allows for a substantial increased rate of oil/per catalyst volume to be introduced into the thermal cracking reaction chamber 3, therefore increasing the conversion rate of pyrolysis derived organic molecules into lower molecular weight components within a reduced timeframe.
[00066] At either the dry mixture of reagents and catalyst 1 stage, or mixed components 2 stage, the contaminant laden high pore volume material (A) has adsorbed the inorganic ironic contaminants and may be physically separated from the second inorganic catalytic material (B) by physical size sieving. Physical size sieving or particle sieving is a method of separating particles of different sizes. A sieve commonly comprises a mesh structure having openings of predetermined widths used to separate large particles from smaller particles
[00067] In addition, any surface debris adsorbing or adhering to the outside of the high pore volume catalytic material (A) may also be removed.
[00068] Once the pyrolysis derived oils and catalytic material (A) and (B) mixture 1 , have been introduced to the process 17 the resultant free flowing oil laden spheres (mixed components) 2, is transported to an inlet (not shown) of a reaction chamber 3.
[00069] The free flowing oil laden spheres comprises the organic pyrolysis derived molecules/oils which have been absorbed into the pores of catalytic material A and oil coated catalytic material B.
[00070] Preferably, the reaction chamber 3 is tubular and rotatable such that the furnace/heat source 4 can evenly heat the reaction chamber 3 such as to provide a controlled temperature profile and preferably an even internal temperature distribution in the reaction chamber 3. [00071] Preferably the furnace or heat source can be varied in temperature and/or heat output such that the reaction conditions can be altered such as to speed up or slow down the reaction or for example if the temperature was set too high, the temperature could be altered accordingly.
[00072] Before the mixed components 2 are transported into reaction chamber 3, the chamber 3 is pre-heated by furnace/heat source 4 at a desired temperature of between 200 - 1 .000Q C. The introduction of heat initiates the catalytic reaction such that the high molecular weight pyrolysis oil organic compounds are broken down into smaller compounds. The reaction chamber 3 is pre-heated before the mixed components 2 are introduced such that the mixed components 2 are immediately subjected to the optimum reaction conditions therefore allowing for efficient maximum production.
[00073] Preferably, reaction chamber 3 is inclined such that reactants and reagents can flow under gravity through the reaction chamber 3 to an outlet (not shown) of the reaction chamber 3. Furthermore, preferably reaction chamber 3 further comprises a screw thread running through the centre of reaction chamber 3 such as to facilitate transport of mixed components 2 from the inlet to the outlet of the reaction chamber 3.
[00074] Alternatively, the reaction chamber 3 and furnace/heat source 4 may be configured as a stacked furnace or a fluid bed furnace.
[00075] Once the free flowing oil laden sphere (mixed components
2) have been introduced into reaction chamber 3, the components are heated and left to react typically for between 0.1 minute to one hour. During this phase of the process the oils in the oil laden catalytic sphere undergo thermal catalytic cracking.
[00076] During the thermal cracking of the mixed components 2 in the reaction chamber 3, a flow of non-oxygen containing gas is passed over the catalyst. Preferably, the gas is comprised of hydrocarbons, nitrogen, carbon dioxide or hydrogen, or recycled thermally cracked gas produced during the thermal reaction. By introducing such gases, the catalytic cracking reaction in reaction chamber 3 can take place in an oxygen deficient atmosphere.
[00077] Following thermal cracking of the pyrolysis derived oils in reaction chamber 3, gas phase lower molecular weight organic products 5 which are produced, flow out of the outlet (not shown) of reaction chamber 3 and into a condenser vessel 6.
[00078] The condenser vessel condenses a mixture of low molecular weight organic molecules and water to form an oil-water layer (condensed crude product) 7. [00079] The condensed crude product 7 is then transported to a separation chamber 8, whereby the water by-product 10 is separated from the organic layer reaction product 9 to result in the desired low molecular weight organic oils 9 being separated out as a product. [00080] Any incondensable gas phase products 1 1 that could not be condensed in condenser vessel 6, are re-directed back to the inlet (not shown) of reaction chamber 3 such as to be re-cycled and passed over the mixed components 2 which react in reaction chamber 3 to form part of the oxygen deficient atmospheric conditions of chamber 3.
[00081] Concurrently with the gaseous phase crude products 5 being transported to condenser 6, the solid phase catalyst mixture 12 is transported out of the reaction chamber 3. [00082] The solid phase catalyst mixture 12 comprises first inorganic catalytic material A and second inorganic catalytic material B as well as carbonaceous solid impurities. [00083] The solid phase catalyst mixture 12 is transported to a regeneration/combustion chamber 13.
[00084] Once in the regeneration/combustion chamber 13, the solid phase catalyst mixture 12 is exposed to an oxygen containing gas 14 and heat, such as to undergo combustion of the carbon of the solid phase catalyst mixture 12 to separate the carbon from the catalytic materials A and B as oxides of carbon 15 (combustion by-product). The combustion by-product 15 is predominantly carbon dioxide, CO , with inclusions of water and carbon monoxide, CO.
[00085] The combustion stage of process 17 allows catalytic materials A and B (regenerated catalyst) 16 to be re-cycled and regenerated. Therefore the recycled catalyst 16 can be re-used in the process through introduction of the recycled catalyst 16 into the stage of forming a dry mixture of oil and catalyst 1 of catalytic process 17.
[00086] The catalyst regeneration vessel 13 is isolated from the reaction chamber 3 and allows for carbonaceous material to be removed from the catalytic materials A and B by controlled oxidative combustion.
[00087] The primary objective of the catalytic process or cracking of pyrolysis derived organic molecules 17 is to reduce the molecular weight of the organic components of raw pyrolysis derived oils by thermal cracking of the high molecular weight components and to partially remove chemically bound oxygen as water.
[00088] The low molecular weight reaction products 9 resultant from process 17, can be subsequently used for the refining of the low molecular reaction products 9 to fuels or chemicals for commercial/industrial use.
[00089] The invention relates to a catalytic process and catalysts used therein to convert high molecular weight complex organic molecules, derived from the thermal pyrolysis of carbonaceous materials, to lower molecular weight molecules suitable for processing into liquid fuels.
[00090] The invention is particularly, but not exclusively, concerned with a process and catalysts for the conversion and reforming of oils derived from the fluid bed pyrolysis of carbonaceous materials to hydrocarbons and oxygenated molecules. Such molecules are suitable for purification and inclusion in fuel blends or are used as feed components for hydrogenation and/or hydrocracking processing to produce transportation or stationary power source fuels.
[00091] The process and catalysts referred to may be used to convert and reform high molecular weight components of pyrolysis oils, such as lignins and cellulosic materials to a product containing a wide range of lower molecular weight hydrocarbons and oxygenated compounds. Additionally the process may be used to convert pyrolysis oils containing high levels of contaminants which would typically deactivate traditional Petroleum Refinery upgrading catalysts. [00092] The novel process and catalysts developed for the upgrading of pyrolysis oil and described herein remove the constraints on thermally and catalytically processing pyrolysis oil previously indicated by making use of a blend of a high porosity oil carrier, which has a relatively low thermal catalytic cracking activity, and a higher cracking activity catalyst which further catalyses and reforms the gas phase components from the high porosity carrier into lower molecular weight hydrocarbons and oxygenates.
[00093] Specific reaction conditions and sub-processes of catalytic process 1 7 have been described below according to preferred reaction conditions.
Example 1 [00094] 50 ml of high pore volume catalyst comprising a low surface area alumina, 3.5 mm diameter, sphere which had been previously calcinated at 1200°C for 4 hours, was heated to 40°C in a beaker and raw pyrolysis oil, containing 20% volume aqueous components, added to the warm spheres until 12.0 g of oil had been absorbed into the spheres to produce a free flowing brown spherical material 1 which did not self-adhere or stick to the walls of the glass beaker.
[0095] The oil loaded (laden) spheres 2 were loaded into a lock hopper 3 sitting on top of a 1 " diameter vertical reactor tube heated 4 to 632° C. The reactor 3 was equipped with an internal poppet valve with gas passage holes located in the centre of the furnace and a lock hopper system at the exit of the reactor. Evolved gases 5 from the cracking reaction were removed via a central ¼" gas discharge tube connected to the poppet valve and condensed externally. A flow of LPG gas was continuously passed through the reactor at a rate of 250 ml/minute. The catalyst/oil blend was dropped from the upper lock hopper into the furnace and kept in the furnace for 30 minutes after which time the internal valve was opened and the catalyst dropped out into the lower lock hopper system. Evolved gases 5 were condensed out in liquid nitrogen cooled tubes 6, collected, weighed and analysed. The liquid product 7 consisted of two phases with an upper aqueous phase and mobile lower organic phase.
[0096] A total of 6g of liquid products were collected after the frozen product had warmed to room temperature. 3g of carbonaceous deposits formed on the alumina spheres.
[0097] GC-MS analysis of the aqueous product 10 indicates that the primary component is Acetic acid with lower levels of Alcohols, Ketones, Aldehydes and Phenols. Analysis of the oil layer 9 indicated a complex mixture of ketones, phenolics, sugars and unconverted lignins.
Example 2 [0098] 50 ml of high porosity catalyst comprising a low surface area, alumina 3.5 mm diameter, sphere was mixed with 26 ml of a zeolite catalyst sphere, diameter 2mm, composed of 50 % weight ZSM-5 zeolite and 50 % alumina -clay binder. The blend was heated to 48°C and raw pyrolysis oil , containing 20% volume aqueous components, added to the warm spheres until 13.05 g of oil had been absorbed to produce a free flowing dark brown spherical blended material 1 which did not stick to the glass beaker or self-adhere.
[0099] The oil loaded (laden) spheres 2 were loaded into a lock hopper 3 sitting on top of a 1 " diameter vertical reactor tube heated 4 to 613°C which was equipped with an internal poppet valve with gas passage holes. The poppet valve was located in the centre of the furnace and a lock hopper system at the exit of the reactor. Evolved gases 5 from the cracking reaction were removed via a central ¼" gas tube connected to the poppet valve and condensed 6 externally. A flow of LPG gas of 200 ml/minute was continuously passed through the reactor. The catalyst/oil blend was dropped from the upper lock hopper into the furnace and kept in the furnace for 30 minutes after which time the internal valve was opened and the catalyst dropped out into the lower lock hopper system. Evolved gases 5 were condensed out in liquid nitrogen cooled tubes 6, collected, weighed and analysed. The liquid product 7 was a two phase liquid with an upper organic phase 9 and a lower aqueous phase 10. There was an indication of a lower heavier oil phase which appeared as dispersed droplets in the aqueous phase.
[0100] A total of 10.65 g of liquids were collected after the frozen product had warmed to room temperature. 3.2g of carbonaceous deposits formed on the catalyst spheres.
[0101] GC-MS analysis of the non-aqueous upper phase 9 indicates that the components are a blend of hydrocarbons - toluene, xylenes, naphthalenes, ketones, aldehydes and phenols with minor levels of sugars and lignin species. Analysis of the aqueous product 10 indicates that the primary components are Acetic acid and Hydroxypropanone with lower levels of Alcohols, Ketones, Aldehydes and Phenols.
Example3
[0102] The example demonstrates the use of a continuous rotary furnace 3 for the reaction. 500 ml of high porosity catalyst comprising an alumina 3.5 mm diameter sphere were heated to 40°C and raw pyrolysis oil, containing 20% wt. aqueous phase, added to the warm spheres until 170g of oil had been absorbed to produce a free flowing dark brown spherical material 1 .
[0103] The oil loaded (laden) spheres 2 were loaded into a sealed hopper 3 equipped with a rotary screw feeder connected via a sealed rotary joint to the inclined furnace. The spheres 2 were continuously fed into the rotating, inclined, 2" diameter reactor 3 of 1 .3 m length which was heated in the centre by an external furnace 4 with a set point control of 600Q C. The spheres 2 moved down the inclined reactor through the heated reaction zone and into the catalyst-gas separation vessel where the spheres are continuously removed to be regenerated by oxidative methods. The gas phase products 5 are separated from the carbon laden spheres 12 and condensed 6. The liquid product 7 from this process separates into a 2 phase mixture with an upper aqueous phase and a lower heavy organic phase in the approximate volume ratios of 9:1 , Aq:oil.
[0104] GC-MS analysis of the aqueous layer 10 indicates the predominance of Acetic acid and Hydroxypropanone with a range of Phenolic compounds and minor amounts of ketones, Aldehydes, furans and sugars. The lower phase was not analysed.
Example 4
[0105] 500 ml of high porosity, low surface area, catalyst comprising an alumina 3.5 mm diameter sphere were mixed with 500 ml of a zeolite catalyst sphere, diameter 2mm, composed of 50 % weight ZSM-5 zeolite and 50 % alumina binder. The blend was heated to 40°C and raw pyrolysis oil, containing 20% wt. aqueous phase, added to the warm spheres until 190g of oil had been absorbed to produce a free flowing dark brown spherical material 1 . [0106] The oil laden spheres 2 were loaded into a sealed hopper 3 equipped with a rotary screw feeder connected via a sealed rotary joint to the inclined furnace and processed as per the example No 3. The liquid product from this process separates into a 3 phase mixture with an upper organic phase, a middle/intermediate aqueous phase and a lower organic phase in the relative volume ratios of 0.5:8:1 - uppermiddle lower phases.

Claims

Claims
1 . A catalyst system for cracking pyrolysis derived organic molecules comprising: at least a first inorganic catalytic material and a second inorganic catalytic material; wherein the first inorganic catalytic material has a pyrolysis organic molecule pore absorption volume of at least two times that of the second inorganic catalytic material; and the mass ratio of the first inorganic catalytic material and the second inorganic catalytic material is in the range of 10:1 to 1 :10.
2. A catalyst as claimed in claim 1 wherein the at least first inorganic catalyst material and the second inorganic catalyst material are thermally stable.
3. A catalyst as claimed in either claim 1 or claim 2 wherein the at least first inorganic catalyst material and the second inorganic catalyst material are spherical.
4. A catalyst as claimed in anyone of the preceding claims wherein the at least first inorganic catalyst material comprises pores with diameters in the range 100 - 1 .000.000 A.
5. A catalyst as claimed in anyone of the preceding claims wherein the at least first inorganic catalyst material contains catalytically active metal compounds
6. A catalyst as claimed in anyone of the preceding claims wherein the second inorganic catalytic material comprises a crystalline zeolite component.
7. A catalyst as claimed in claim 6 wherein the crystalline zeolite comprises pore diameters in the range 3 - 25 A.
8. A catalyst as claimed in claims 6 or 7 wherein the crystalline zeolite component further comprises catalytically activating compounds contained within an amorphous or crystalline porous binder.
9. A catalyst as claimed in claims 6 or 7 wherein the crystalline zeolite further comprises catalytically active metal compounds contained with an amorphous or crystalline porous binder.
10. A catalyst as claimed in anyone of claims 1 -4 wherein the second inorganic catalytic material comprises at least one amorphous inorganic oxide.
1 1 . A catalyst as claimed in anyone of claims 1 -4 wherein the second inorganic catalyst material comprises at least one amorphous catalytic material configured to promote the reformation of gas phase molecules to low weight organic material.
12. A process for cracking pyrolysis derived organic molecules using a catalyst comprising: at least a first inorganic catalytic material and a second inorganic catalytic material; wherein the first inorganic catalytic material has a pyrolysis organic molecule pore absorption volume of at least two times that of the second inorganic catalytic material; and the mass ratio of the first inorganic catalytic material and the second inorganic catalytic material is in the range of 10;1 to
1 :10; the process comprising the steps of: mixing the pyrolysis derived organic molecules with the catalyst at a temperature less than 100Q Celsius to form a dry mixture; keeping the dry mixture at a temperature between 200Q centigrade to 1 ,000Q centigrade in a reaction chamber; separating a gaseous phase crude product out of the reaction chamber from a solid phase catalyst mixture; condensing the gaseous phase crude product to separate out a low molecular weight product; regenerating the catalyst from the solid phase catalyst mixture; and cooling the regenerated catalyst.
13. A process as claimed in claim 12 wherein the at least first inorganic catalyst material and the second inorganic catalyst material are thermally stable.
14. A process as claimed in either claim 12 or 13 wherein the at least first inorganic catalyst material and the second inorganic catalyst material are spherical.
15. A process as claimed in anyone of claims 12-14 wherein the at least first inorganic catalyst material comprises pores with diameters in the range 100 - 1 .000.000 A.
16. A process as claimed in anyone of claims 12-14 wherein the second inorganic catalytic material comprises a crystalline zeolite component.
17. A process as claimed in claim 16 wherein the crystalline zeolite comprises pore diameters in the range 3 - 25 A.
18. A process as claimed in claims 16 or 17 wherein the crystalline zeolite further comprises catalytically activating compounds contained within an amorphous or crystalline porous binder.
19. A process as claimed in claims 16 or 17 wherein the crystalline zeolite further comprises metals contained with an amorphous or crystalline porous binder.
20. A process as claimed in anyone of claims 12-14 wherein the second inorganic catalytic material comprises at least one amorphous inorganic oxide.
21 . A process as claimed in anyone of claims 12-14 wherein the second inorganic catalyst material comprises at least one amorphous catalytic component configured to promote the reformation of gas phase molecules to low molecular weight organic material.
22. A process as claimed is only one of claims 12-20 wherein upon the mixing of the catalysts with the pyrolysis derived organic molecules, inorganic ionic contaminants are adsorbed in the internal pore surface of the first inorganic catalytic material.
23. A process as claimed in claim 12 wherein the first inorganic catalytic material may be physically separated from the crystalline zeolite material.
24. A process as claimed in claim 23 wherein the physical separation is carried out by physical sieving.
25. A process as claimed in claim 12 wherein upon keeping the dry mixture at a temperature between 200-1000QC in the reaction chamber, a flow of non-oxygen containing gas is passed over the catalyst.
26. A process as claimed in claim 12 wherein the reaction chamber comprises a rotating reactor.
27. A process as claimed in claims 12 and 26 wherein the rotating reactor is tubular in shape.
28. A process as claimed in either claim 26 or 27 wherein the rotating reactor is inclined.
29. A process as claimed in claim 12 wherein a separator vessel separates the gaseous crude product from the solid phase catalyst mixture out of the reaction chamber.
30. A process as claimed in claim 29 wherein a condenser is connected to an outlet of the separator vessel to condense a gaseous crude product outlet stream.
31 . A process as claimed in any one of claims 12-30 wherein the regenerating of the catalyst mixture is undertaken in a catalyst regeneration vessel to remove carbonaceous material by oxidative combustion.
32. A process as claimed in any one of claims 12-31 wherein the dry mixture moves through the reaction chamber under gravity.
33. A process as claimed in any one of claims 12-32 wherein the reaction chamber comprises an inlet and an outlet.
34. A process as claimed in claim 33 wherein the reaction chamber comprises a central rotating screw feeder to transport the dry mixture from the inlet to the outlet.
35. A process as claimed in claim 12 wherein non-condensed gases flowing from outlet of the reaction chamber are recycled back to the inlet of the reaction chamber.
36. A process as claimed in claims 12 and 35 wherein the non-oxygen containing gas may comprise hydrogen, nitrogen, carbon dioxide, carbon monoxide, low molecular weight hydrocarbon gases or mixtures thereof.
PCT/EP2012/074506 2011-12-13 2012-12-05 Catalytic cracking of pyrolysis derived organic molecules WO2013087480A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1121365.9 2011-12-13
GB1121365.9A GB2497543B (en) 2011-12-13 2011-12-13 Catalytic cracking of pyrolysis derived organic molecules

Publications (4)

Publication Number Publication Date
WO2013087480A2 true WO2013087480A2 (en) 2013-06-20
WO2013087480A3 WO2013087480A3 (en) 2013-08-15
WO2013087480A4 WO2013087480A4 (en) 2013-10-24
WO2013087480A9 WO2013087480A9 (en) 2013-12-19

Family

ID=45560348

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/074506 WO2013087480A2 (en) 2011-12-13 2012-12-05 Catalytic cracking of pyrolysis derived organic molecules

Country Status (2)

Country Link
GB (1) GB2497543B (en)
WO (1) WO2013087480A2 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2694673A (en) * 1950-10-21 1954-11-16 Standard Oil Dev Co Catalytic cracking of hydrocarbon oils with specific pore size silica-alumina catalysts
US4320241A (en) * 1980-08-28 1982-03-16 Occidental Research Corporation Process for converting oxygenated hydrocarbons into hydrocarbons
US6613710B2 (en) * 2001-09-25 2003-09-02 Indian Oil Corporation Limited Process for preparation of bi-functional fluid catalytic cracking catalyst composition
EP1892280A1 (en) * 2006-08-16 2008-02-27 BIOeCON International Holding N.V. Fluid catalytic cracking of oxygenated compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Also Published As

Publication number Publication date
GB2497543A (en) 2013-06-19
GB2497543B (en) 2015-09-02
WO2013087480A4 (en) 2013-10-24
GB201121365D0 (en) 2012-01-25
WO2013087480A3 (en) 2013-08-15
WO2013087480A9 (en) 2013-12-19

Similar Documents

Publication Publication Date Title
CA2959802C (en) Use of carbon dioxide generated by hydropyrolysis for process inertization
AU2018203928B2 (en) Hydropyrolysis of biomass-containing feedstocks
EP1725633B1 (en) Process and plant for conversion of waste material to liquid fuel
ES2864545T3 (en) Olefin recycling process for the catalytic pyrolysis of biomass and hydrocarbon materials in a fluidized bed for the production of aromatic compounds
CN103124712B (en) Multi-stage biological matter transforms
CA2901767A1 (en) Method of hydrogasification of biomass to methane with low depositable tars
JPH022917B2 (en)
WO2013087480A2 (en) Catalytic cracking of pyrolysis derived organic molecules
ES2706283T3 (en) Process and plant for the conversion of residual material into liquid fuel
RU2160698C1 (en) Method of production of hydrogen and carbon material
CN116083119B (en) Catalytic conversion method for producing propylene and high aromatic hydrocarbon gasoline by co-refining waste plastic oil and heavy oil
Susa et al. Pyrolysis of biomass in a laboratory pyrolysis unit with a screw type reactor and a secondary decomposition reactor

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12795818

Country of ref document: EP

Kind code of ref document: A2