EP2115097A1 - Improved process for converting carbon-based energy carrier material - Google Patents
Improved process for converting carbon-based energy carrier materialInfo
- Publication number
- EP2115097A1 EP2115097A1 EP08709128A EP08709128A EP2115097A1 EP 2115097 A1 EP2115097 A1 EP 2115097A1 EP 08709128 A EP08709128 A EP 08709128A EP 08709128 A EP08709128 A EP 08709128A EP 2115097 A1 EP2115097 A1 EP 2115097A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon
- based energy
- energy carrier
- reaction products
- carrier material
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000012876 carrier material Substances 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002028 Biomass Substances 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- -1 heavy crudes Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012808 vapor phase Substances 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 235000013847 iso-butane Nutrition 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 229920001059 synthetic polymer Polymers 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 241000949477 Toona ciliata Species 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
- C10B49/20—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
-
- 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
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- the present invention relates to a catalytic process of converting a carbon- based energy carrier material to a liquid or gaseous fuel.
- Alternate materials further include waste supplies of synthetic resins.
- These synthetic resins may be virgin materials, for example rejects from molding and drawing operations, and used materials, such as recycled packaging materials.
- biomass in particular biomass containing cellulose, lignin, and lignocellulose.
- the present invention provides an improved process for converting a carbon-based energy carrier material to a liquid or gaseous fuel.
- the process is characterized in that the conversion temperature is less than 450 0 C, preferably less than 400 0 C, and in that the exposure time of reaction products to elevated temperatures and to contact with catalytic material is kept short.
- the present invention relates to a process for converting a solid or highly viscous carbon-based energy carrier material to liquid and gaseous reaction products, said process comprising the steps of: a) contacting the carbon-based energy carrier material with a particulate catalyst material b) converting the carbon-based energy carrier material at a reaction temperature between 200 0 C and 450 0 C, preferably between 250 0 C and 350 0C, thereby forming reaction products in the vapor phase; c) separating the vapor phase reaction products from the particulate catalyst material within 10 seconds after said reaction products are formed; d) quenching the reaction products to a temperature below 200 0 C.
- reaction temperature in step b) of less than 450 0 C, preferably less than 400 0 C. More preferably the reaction temperature is less than 350 0 C, still more preferably less than 300 0 C, and most preferably less than 250 0 C.
- This reaction temperature is made possible by using a catalytic material selected from the group of cationic clays, anionic clays, natural clays, hydrotalcite-like materials, layered materials, ores, minerals, metal oxides, hydroxides and carbonates of the alkaline and alkaline earth metals, and mixtures thereof.
- the catalyst particles are of a size suitable for heterogeneous catalysis.
- small catalyst particle sizes are preferred in heterogeneous catalysis, because the smaller a particle the greater the fraction of the available atoms that are present at the surface of the particle. Therefore, particle sizes of less than 100 microns are suitable, particles of less than 1 ,000 nanometers being preferred, particle sizes of less than 100 nm being more preferred. It has, however, been discovered that below a particle size of about 10 nm (the "Iglesia limit") many heterogeneous catalytic compounds lose their catalytic properties. For this reason catalytic particles having a particle size of less than 10 nm are not desirable. Another reason to avoid these very small particles is the potential health hazards related to the use of very fine nano particles.
- the carbon-based energy carrier material may be from mineral, synthetic or biological origin.
- Materials from mineral origin include heavy crudes, shale oils, tars (e.g., from tar sands) and bitumen.
- Materials from synthetic origin include waste supplies of synthetic resins. These synthetic resins may be virgin materials, for example rejects from molding and drawing operations, and used materials, such as recycled packaging materials.
- Materials from biological origin include biomass, in particular solid biomass containing cellulose, lignin, and lignocellulose.
- a preferred biomass is biomass of aquatic origin, such as algae.
- the carbon-based energy carrier material is either a viscous liquid or a solid, making it difficult to establish an intimate contact between the carbon-based energy carrier material and the particulate catalyst material. It may be necessary to mill the carbon-based energy carrier material together with the particulate catalyst material. In a preferred embodiment of the process, the particulate catalyst material may be "sand blasted" onto the carbon-based energy carrier material. For this purpose the particulate catalyst material is taken up in a stream of inert gas, and the inert gas is caused to flow, e.g., by means of a compressor. In his manner the catalyst particles are given a velocity of at least 1 m/s, preferably at least 10 m/s.
- the stream of gas is then impinged upon the carbon-based energy carrier material. Due to their kinetic energy the catalyst particles penetrate the carbon- based energy carrier material, thereby providing the necessary intimate contact. [0014] The sand blasting of particles onto the carbon-based energy carrier material causes mechanical breakup of the latter, which is of particular advantage if this material is a solid.
- the effect can be reinforced by mixing the catalyst particles with particulate inert material.
- the inert material has a particle size similar to that of the catalyst material.
- step a) is carried out in a chemical reactor, such as a fluidized bed reactor, a riser reactor, or a downer reactor.
- step b) may be carried out in the same reactor as step a).
- reaction products are formed having molecular weights such that these products are in gas or liquid form when at room temperature. At the reaction temperature these reaction products are all in the gas form, which is referred to herein as "reaction products in the vapor phase". It is an important aspect of the present invention that the reaction products in the vapor phase are quickly separated from the particulate catalyst material. Specifically, the reaction products in the vapor phase are separated from the catalyst particles within 10 seconds after they are formed, preferably within 5 seconds, more preferably within 3 seconds.
- the reaction products generally comprise hydrocarbons and steam. toon] This separation may be accomplished by applying reduced pressure to the zone of the reactor where this separation takes place. Preferably the reduced pressure is a "vacuum" of less than 500 mBar.
- This rapid separation of the reaction products from the catalyst material is an important factor in limiting the degradation of the reaction products. Degradation can be diminished further by rapidly cooling the reaction products after they are separated from the catalyst material. If the separation step involves applying reduced pressure, some cooling of the reaction products will occur as a result of their adiabatic expansion. Further cooling may be accomplished by any means known in the art, for example by pumping the reaction products through a heat exchanger in counter-flow with a cooling medium, such as chilled water. [0019] Preferably, the reaction products are cooled to a temperature below 200 0 C, preferably below 150 0 C, within 10 seconds, preferably within 3 seconds, after being separated from the catalytic material.
- reaction products remain adsorbed to the catalyst particles after separating step c). These materials may be removed by stripping, using methods well known in the art. For example, stripping conditions as used in FCC units are suitable. Although the reaction products removed by stripping may have been in contact with the catalyst material longer than the desired 10 seconds, these materials are not necessarily fully deteriorated.
- coke may form on the catalyst surface.
- This coke can be burned off by exposing the catalyst to an oxidative environment, such as air, at elevated temperature.
- This optional step may be carried out in a regenerator of the type known from FCC processes.
- This burning-off step results in the production of CO 2 .
- this CO 2 is used in the production of biomass, for example by spraying it onto crops or trees under conditions that are favorable for photosynthesis.
- the CO 2 is used in the production of aquatic biomass, for example by bubbling it through a pond in which algae are grown.
- the heat generated during the optional regeneration step may be used to supply the heat for the endothermic reaction of step b).
- hot catalyst particles from the regenerator are recycled to step a) or b) of the process.
- the amount of coke deposit may be such that the amount of heat generated during the regeneration step may be greater than what is need for fueling the conversion reaction. If this is the case, excess heat may be removed from the process by cooling the catalyst particles to a desired temperature prior to recycling them into the reactor.
- the desired temperature is determined by the heat balance for the process, and the desired reaction temperature for step b). Accordingly, the desired temperature of the catalyst particles just prior to recycle may be determined in a manner similar to that used in FCC processes.
- heat is removed from the regenerated catalyst particles, this heat may be used for generating steam, hot water, or electricity.
- the process is carried out in an FCC unit. It may be desirable to carry out step a) in a pretreatment reactor, prior to introduction of the carbon-based energy carrier material into the riser of the FCC unit.
- a reactive gas is present during at least part of step b).
- This reactive gas may have oxidative or reductive properties, or the reactive gas may be reactive in isomerisation or alkylation properties.
- reactive gases having oxidative properties include air and oxygen, as well as mixtures of oxygen and an inert gas such as nitrogen.
- gases having reductive properties include carbon monoxide, hydrogen sulfide, and hydrogen. Hydrogen may be less preferred, as it may require a high pressure.
- Gases having alkylation or isomerisation properties include iso-butane, naphtene, volatile organic acids, and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalytic process is disclosed for converting solid or high viscosity carbon-based energy carrier materials, such as heavy crudes, oil sands, synthetic polymeric wastes and cellulosic or aquatic biomass. The conversion temperature is less than 450°C. The reaction products are separated from the catalyst within 10 seconds after being formed. The temperature of the reaction products is lowered to less than 200°C within 10 seconds after being formed. The process results in less deterioration of the reaction products.
Description
IMPROVED PROCESS FOR CONVERTING CARBON-BASED ENERGY
CARRIER MATERIAL
BACKGROUND OF THE INVENTION
1. Field of the Invention
[oooi] The present invention relates to a catalytic process of converting a carbon- based energy carrier material to a liquid or gaseous fuel.
2. Description of the Related Art
[0002] As the supply of light crude diminishes, alternate materials are being developed as a source of liquid and gaseous fuels. Alternate materials being considered include mineral energy carriers, such as heavy crudes, shale oils, tars (e.g., from tar sands) and bitumen.
[0003] Alternate materials further include waste supplies of synthetic resins. These synthetic resins may be virgin materials, for example rejects from molding and drawing operations, and used materials, such as recycled packaging materials.
[0004] Yet another, and potentially the most important, source of alternate carbon- based energy carrier material includes biomass, in particular biomass containing cellulose, lignin, and lignocellulose.
[0005] Processes have been developed for converting these materials to liquid and gaseous fuels. Catalysts have been proposed for use in such processes. Even when catalysts are used, however, the conversion reaction requires relatively high reaction temperatures, often in excess of 450 0C. Exposure of the reaction products to these reaction conditions results in a significant deterioration of the reaction products. As a result, valuable materials are converted to undesirable materials such as gas, char and coke, which foul and deactivate the catalyst particles and reduce the yield of the reaction process.
[0006] The present invention provides an improved process for converting a carbon-based energy carrier material to a liquid or gaseous fuel. The process is characterized in that the conversion temperature is less than 450 0C, preferably less
than 400 0C, and in that the exposure time of reaction products to elevated temperatures and to contact with catalytic material is kept short.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a process for converting a solid or highly viscous carbon-based energy carrier material to liquid and gaseous reaction products, said process comprising the steps of: a) contacting the carbon-based energy carrier material with a particulate catalyst material b) converting the carbon-based energy carrier material at a reaction temperature between 200 0C and 450 0C, preferably between 250 0C and 350 0C, thereby forming reaction products in the vapor phase; c) separating the vapor phase reaction products from the particulate catalyst material within 10 seconds after said reaction products are formed; d) quenching the reaction products to a temperature below 200 0C.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0008] The following is a description of certain embodiments of the invention, given by way of example only.
[0009] An important aspect of the present invention is the reaction temperature in step b) of less than 450 0C, preferably less than 400 0C. More preferably the reaction temperature is less than 350 0C, still more preferably less than 300 0C, and most preferably less than 250 0C. This reaction temperature is made possible by using a catalytic material selected from the group of cationic clays, anionic clays, natural clays, hydrotalcite-like materials, layered materials, ores, minerals, metal oxides, hydroxides and carbonates of the alkaline and alkaline earth metals, and mixtures thereof.
[ooio] The catalyst particles are of a size suitable for heterogeneous catalysis. As a general rule, small catalyst particle sizes are preferred in heterogeneous catalysis, because the smaller a particle the greater the fraction of the available atoms that are present at the surface of the particle. Therefore, particle sizes of less than 100 microns are suitable, particles of less than 1 ,000 nanometers being preferred, particle sizes of less than 100 nm being more preferred. It has, however, been discovered that below a particle size of about 10 nm (the "Iglesia limit") many heterogeneous catalytic compounds lose their catalytic properties. For this reason catalytic particles having a particle size of less than 10 nm are not desirable. Another reason to avoid these very small particles is the potential health hazards related to the use of very fine nano particles.
[ooii] The carbon-based energy carrier material may be from mineral, synthetic or biological origin. Materials from mineral origin include heavy crudes, shale oils, tars (e.g., from tar sands) and bitumen. Materials from synthetic origin include waste supplies of synthetic resins. These synthetic resins may be virgin materials, for example rejects from molding and drawing operations, and used materials, such as recycled packaging materials. Materials from biological origin include biomass, in particular solid biomass containing cellulose, lignin, and lignocellulose. A preferred biomass is biomass of aquatic origin, such as algae.
[0012] The carbon-based energy carrier material is either a viscous liquid or a solid, making it difficult to establish an intimate contact between the carbon-based energy carrier material and the particulate catalyst material. It may be necessary to mill the carbon-based energy carrier material together with the particulate catalyst material. In a preferred embodiment of the process, the particulate catalyst material may be "sand blasted" onto the carbon-based energy carrier material. For this purpose the particulate catalyst material is taken up in a stream of inert gas, and the inert gas is caused to flow, e.g., by means of a compressor. In his manner the catalyst particles are given a velocity of at least 1 m/s, preferably at least 10 m/s.
[0013] The stream of gas is then impinged upon the carbon-based energy carrier material. Due to their kinetic energy the catalyst particles penetrate the carbon- based energy carrier material, thereby providing the necessary intimate contact.
[0014] The sand blasting of particles onto the carbon-based energy carrier material causes mechanical breakup of the latter, which is of particular advantage if this material is a solid. The effect can be reinforced by mixing the catalyst particles with particulate inert material. Preferably the inert material has a particle size similar to that of the catalyst material.
[0015] In a particularly preferred embodiment of the process, step a) is carried out in a chemical reactor, such as a fluidized bed reactor, a riser reactor, or a downer reactor. Conveniently, step b) may be carried out in the same reactor as step a).
[0016] In step b) reaction products are formed having molecular weights such that these products are in gas or liquid form when at room temperature. At the reaction temperature these reaction products are all in the gas form, which is referred to herein as "reaction products in the vapor phase". It is an important aspect of the present invention that the reaction products in the vapor phase are quickly separated from the particulate catalyst material. Specifically, the reaction products in the vapor phase are separated from the catalyst particles within 10 seconds after they are formed, preferably within 5 seconds, more preferably within 3 seconds. The reaction products generally comprise hydrocarbons and steam. toon] This separation may be accomplished by applying reduced pressure to the zone of the reactor where this separation takes place. Preferably the reduced pressure is a "vacuum" of less than 500 mBar.
[0018] This rapid separation of the reaction products from the catalyst material is an important factor in limiting the degradation of the reaction products. Degradation can be diminished further by rapidly cooling the reaction products after they are separated from the catalyst material. If the separation step involves applying reduced pressure, some cooling of the reaction products will occur as a result of their adiabatic expansion. Further cooling may be accomplished by any means known in the art, for example by pumping the reaction products through a heat exchanger in counter-flow with a cooling medium, such as chilled water.
[0019] Preferably, the reaction products are cooled to a temperature below 200 0C, preferably below 150 0C, within 10 seconds, preferably within 3 seconds, after being separated from the catalytic material.
[0020] Some reaction products remain adsorbed to the catalyst particles after separating step c). These materials may be removed by stripping, using methods well known in the art. For example, stripping conditions as used in FCC units are suitable. Although the reaction products removed by stripping may have been in contact with the catalyst material longer than the desired 10 seconds, these materials are not necessarily fully deteriorated.
[0021] During the reaction coke may form on the catalyst surface. This coke can be burned off by exposing the catalyst to an oxidative environment, such as air, at elevated temperature. This optional step may be carried out in a regenerator of the type known from FCC processes.
[0022] This burning-off step results in the production of CO2. In a preferred embodiment this CO2 is used in the production of biomass, for example by spraying it onto crops or trees under conditions that are favorable for photosynthesis. In a particularly preferred embodiment the CO2 is used in the production of aquatic biomass, for example by bubbling it through a pond in which algae are grown.
[0023] The heat generated during the optional regeneration step may be used to supply the heat for the endothermic reaction of step b). To this end, hot catalyst particles from the regenerator are recycled to step a) or b) of the process. The amount of coke deposit may be such that the amount of heat generated during the regeneration step may be greater than what is need for fueling the conversion reaction. If this is the case, excess heat may be removed from the process by cooling the catalyst particles to a desired temperature prior to recycling them into the reactor. The desired temperature is determined by the heat balance for the process, and the desired reaction temperature for step b). Accordingly, the desired temperature of the catalyst particles just prior to recycle may be determined in a manner similar to that used in FCC processes.
[0024] If heat is removed from the regenerated catalyst particles, this heat may be used for generating steam, hot water, or electricity.
[0025] In a preferred embodiment the process is carried out in an FCC unit. It may be desirable to carry out step a) in a pretreatment reactor, prior to introduction of the carbon-based energy carrier material into the riser of the FCC unit.
[0026] In a preferred embodiment of the invention a reactive gas is present during at least part of step b). This reactive gas may have oxidative or reductive properties, or the reactive gas may be reactive in isomerisation or alkylation properties. Examples of reactive gases having oxidative properties include air and oxygen, as well as mixtures of oxygen and an inert gas such as nitrogen.
[0027] Examples of gases having reductive properties include carbon monoxide, hydrogen sulfide, and hydrogen. Hydrogen may be less preferred, as it may require a high pressure.
[0028] Gases having alkylation or isomerisation properties include iso-butane, naphtene, volatile organic acids, and the like.
[0029] Thus, the invention has been described by reference to certain embodiments discussed above. It will be recognized that these embodiments are susceptible to various modifications and alternative forms well known to those of skill in the art.
Claims
1. A process for converting a solid or highly viscous carbon-based energy carrier material to liquid and gaseous reaction products, said process comprising the steps of: a) contacting the carbon-based energy carrier material with a particulate catalyst material b) converting the carbon-based energy carrier material at a reaction temperature between 200 0C and 450 0C, thereby forming reaction products in the vapor phase; c) separating the vapor phase reaction products from the particulate catalyst material within 10 seconds after said reaction products are formed; d) optionally quenching the reaction products to a temperature below 200 0C.
2. The process of claim 1 comprising the additional step of stripping reaction products from the particulate catalyst material.
3. The process of claim 1 or 2 comprising the additional step of burning off any coke formed on the particulate catalyst material.
4. The process of claim 2 or 3 comprising the further step of recycling the particulate catalyst material to step a) or b).
5. The process of any one of the preceding claims whereby a reactive gas is present during step b).
6. The process of claim 5 wherein the reactive gas has oxidative or reductive properties.
7. The process of claim 5 wherein the reactive gas is reactive in isomerisation or alkylation reactions.
8. The process of claim 6 wherein the reactive gas comprises oxygen, hydrogen, hydrogen sulfide, or carbon monoxide.
9. The process of claim 7 wherein the reactive gas comprises iso-butane, naphtene, or a volatile organic acid.
10. The process of any one of the preceding claims wherein the catalytic material comprises cationic clays, anionic clays, natural clays, hydrotalcite-like materials, layered materials, ores, minerals, metal oxides, hydroxides and carbonates of the alkaline and alkaline earth metals, or mixtures thereof.
11.The process of any one of the preceding claims wherein the carbon-based energy carrier material is of mineral origin.
12. The process of claim 11 wherein the carbon-based energy carrier material is a tar, a heavy crude, or a bitumen.
13. The process of any one of claims 1 through 10 wherein the carbon-based energy carrier material is a synthetic polymer.
14. The process of any one of claims 1 through 10 wherein the carbon-based energy carrier material is a solid biomass.
15. The process of claim 14 wherein the solid biomass comprises cellulose, lignin, or lignocellulose.
16. The process of claim 14 wherein the solid biomass is of aquatic origin.
17. The process of any one of claims 3 - 16 whereby the CO2 is utilized in the production of biomass.
18. The process of claim 17 whereby the CO2 is utilized in the production of aquatic biomass.
19. The process of any one of the preceding claims wherein step a) comprises milling of the carbon-based energy carrier material in the presence of the particulate catalyst material.
20. The process of any one of the preceding claims wherein step a) comprises the steps of:
(i) taking up the particulate catalyst material in a stream of a carrier gas; (ii) causing the gas stream to flow such that the particulate catalyst material reaches a velocity of at least 1 m/s, preferably at least 10 m/s (iii) impinging the catalyst particles onto the carbon-based energy carrier material.
21.The process of claim 17 wherein the carrier gas further comprises a particulate inert material.
22. The process of claim 17 or 18 wherein step a) is carried out in a fluidized bed, a riser reactor, or a downer reactor.
23. The process of any one of the preceding claims wherein the reaction temperature in step b) is less than 350 0C, preferably less than 300 0C, more preferably less than 250 0C.
24. The process of any one of the preceding claims wherein the vapor phase reaction products comprise steam, hydrocarbons, or a mixture thereof.
25. The process of claim 3 wherein the coke is burned off with air.
26. The process of claim 3 or 22 comprising the further step of cooling the particulate catalyst material after the coke has been burned off.
27. The process of claim 23 whereby heat recovered from the particulate catalyst material is used for generating steam, hot water, or electricity.
28. The process of any one of the preceding claims whereby at least step b) is carried out in an FCC unit.
29. The process of any one of the preceding claims whereby at least step b) is carried out in a downer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08709128A EP2115097A1 (en) | 2007-02-20 | 2008-02-20 | Improved process for converting carbon-based energy carrier material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07102737A EP1970425A1 (en) | 2007-02-20 | 2007-02-20 | Improved process for converting carbon-based energy carrier material |
| EP08709128A EP2115097A1 (en) | 2007-02-20 | 2008-02-20 | Improved process for converting carbon-based energy carrier material |
| PCT/EP2008/052050 WO2008101949A1 (en) | 2007-02-20 | 2008-02-20 | Improved process for converting carbon-based energy carrier material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2115097A1 true EP2115097A1 (en) | 2009-11-11 |
Family
ID=38120658
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07102737A Withdrawn EP1970425A1 (en) | 2006-05-05 | 2007-02-20 | Improved process for converting carbon-based energy carrier material |
| EP08709128A Withdrawn EP2115097A1 (en) | 2007-02-20 | 2008-02-20 | Improved process for converting carbon-based energy carrier material |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07102737A Withdrawn EP1970425A1 (en) | 2006-05-05 | 2007-02-20 | Improved process for converting carbon-based energy carrier material |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20100187162A1 (en) |
| EP (2) | EP1970425A1 (en) |
| BR (1) | BRPI0807539A2 (en) |
| CA (1) | CA2679348A1 (en) |
| WO (1) | WO2008101949A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007128798A1 (en) | 2006-05-05 | 2007-11-15 | Bioecon International Holding N.V. | Improved process for converting carbon-based energy carrier material |
| US8617261B2 (en) | 2007-06-25 | 2013-12-31 | Kior, Inc. | Liquid fuel from aquatic biomass |
| JP5662168B2 (en) | 2008-03-04 | 2015-01-28 | ユニバーシティ オブ マサチューセッツ | Catalytic pyrolysis of solid biomass and related biofuels, aromatics, and olefinic compounds |
| WO2010002792A2 (en) | 2008-06-30 | 2010-01-07 | Kior, Inc. | Co-processing solid biomass in a conventional petroleum refining process unit |
| EP2199366A1 (en) * | 2008-12-10 | 2010-06-23 | KiOR, Inc. | Conversion of biomass to bio-oil using inorganic carbonates and decomposition and regeneration of inorganic carbonates |
| US8524959B1 (en) | 2009-02-18 | 2013-09-03 | Kior, Inc. | Biomass catalytic conversion process and apparatus for use therein |
| US8558043B2 (en) | 2009-03-04 | 2013-10-15 | Kior, Inc. | Modular biomass treatment unit |
| US8063258B2 (en) | 2009-05-22 | 2011-11-22 | Kior Inc. | Catalytic hydropyrolysis of organophillic biomass |
| WO2010135734A1 (en) | 2009-05-22 | 2010-11-25 | Kior Inc. | Processing biomass with a hydrogen source |
| US8623634B2 (en) | 2009-06-23 | 2014-01-07 | Kior, Inc. | Growing aquatic biomass, and producing biomass feedstock and biocrude therefrom |
| CN102666796B (en) | 2009-09-09 | 2016-06-29 | 马萨诸塞大学 | Optionally employ olefin recycle catalysis pyrolysis biomass and hydrocarbon material for preparing the system and method for aromatic compounds and there is the catalyst for being catalyzed pyrolysis of selection granularity |
| US8057641B2 (en) | 2010-07-19 | 2011-11-15 | Kior Inc. | Method and apparatus for pyrolysis of a biomass |
| US8772556B2 (en) | 2010-09-22 | 2014-07-08 | Kior, Inc. | Bio-oil production with optimal byproduct processing |
| US8647398B2 (en) * | 2010-10-22 | 2014-02-11 | Kior, Inc. | Production of renewable biofuels |
| US9017428B2 (en) | 2010-11-16 | 2015-04-28 | Kior, Inc. | Two-stage reactor and process for conversion of solid biomass material |
| WO2012083998A1 (en) | 2010-12-20 | 2012-06-28 | Shell Internationale Research Maatschappij B.V. | Process for catalytic cracking of a lipid-containing feedstock derived from microalgae to produce hydrocarbons |
| WO2012083999A1 (en) | 2010-12-20 | 2012-06-28 | Shell Internationale Research Maatschappij B.V. | Process for catalytic cracking of a lipid - containing feedstock derived from microalgae to produce hydrocarbons |
| WO2012084000A1 (en) | 2010-12-20 | 2012-06-28 | Shell Internationale Research Maatschappij B.V. | Process for catalytic cracking of aquatic microbial biomass |
| US8236173B2 (en) | 2011-03-10 | 2012-08-07 | Kior, Inc. | Biomass pretreatment for fast pyrolysis to liquids |
| US8927793B2 (en) * | 2011-07-29 | 2015-01-06 | Uop Llc | Processes for converting lignocellulosics to reduced acid pyrolysis oil |
| AU2013207454A1 (en) | 2012-01-06 | 2014-08-07 | Kior, Inc. | Two-stage reactor and process for conversion of solid biomass material |
| US9035116B2 (en) | 2012-08-07 | 2015-05-19 | Kior, Inc. | Biomass feed system including gas assist |
| JP7289879B2 (en) * | 2020-08-05 | 2023-06-12 | インディアン オイル コーポレイション リミテッド | Co-conversion process of waste plastics and hydrocarbon raw materials |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1123774A (en) * | 1980-02-25 | 1982-05-18 | Marten Ternan | Catalytic conversion of heavy hydrocarbon materials |
| CA1163595A (en) * | 1980-12-18 | 1984-03-13 | Christian Roy | Organic products and liquid fuels from lignocellulosic materials by vacuum pyrolysis |
| US5792340A (en) * | 1990-01-31 | 1998-08-11 | Ensyn Technologies, Inc. | Method and apparatus for a circulating bed transport fast pyrolysis reactor system |
| US7202389B1 (en) * | 1999-11-11 | 2007-04-10 | Nederlandse Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek Tno | Flash-pyrolysis in a cyclone |
| WO2002014742A1 (en) * | 2000-08-10 | 2002-02-21 | Rj Leegroup, Inc. | Low energy method of pyrolysis of hydrocarbon materials such as rubber |
| US6893492B2 (en) * | 2003-09-08 | 2005-05-17 | The United States Of America As Represented By The Secretary Of Agriculture | Nanocomposites of cellulose and clay |
| WO2007128798A1 (en) * | 2006-05-05 | 2007-11-15 | Bioecon International Holding N.V. | Improved process for converting carbon-based energy carrier material |
-
2007
- 2007-02-20 EP EP07102737A patent/EP1970425A1/en not_active Withdrawn
-
2008
- 2008-02-20 BR BRPI0807539-5A2A patent/BRPI0807539A2/en not_active IP Right Cessation
- 2008-02-20 US US12/527,894 patent/US20100187162A1/en not_active Abandoned
- 2008-02-20 WO PCT/EP2008/052050 patent/WO2008101949A1/en not_active Ceased
- 2008-02-20 CA CA002679348A patent/CA2679348A1/en not_active Abandoned
- 2008-02-20 EP EP08709128A patent/EP2115097A1/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2008101949A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1970425A1 (en) | 2008-09-17 |
| CA2679348A1 (en) | 2008-08-28 |
| BRPI0807539A2 (en) | 2014-06-10 |
| US20100187162A1 (en) | 2010-07-29 |
| WO2008101949A1 (en) | 2008-08-28 |
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