US20080299022A1 - Process for producing liquid and, optionally, gaseous products from gaseous reactants - Google Patents
Process for producing liquid and, optionally, gaseous products from gaseous reactants Download PDFInfo
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- US20080299022A1 US20080299022A1 US12/192,337 US19233708A US2008299022A1 US 20080299022 A1 US20080299022 A1 US 20080299022A1 US 19233708 A US19233708 A US 19233708A US 2008299022 A1 US2008299022 A1 US 2008299022A1
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- slurry bed
- gas
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- bed zone
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- 239000000376 reactant Substances 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title description 55
- 239000002002 slurry Substances 0.000 claims abstract description 146
- 239000000047 product Substances 0.000 claims abstract description 25
- 238000009434 installation Methods 0.000 claims abstract description 17
- 239000012263 liquid product Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 description 142
- 239000003054 catalyst Substances 0.000 description 30
- 238000003786 synthesis reaction Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 239000012071 phase Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000007872 degassing Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Images
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1836—Heating and cooling the reactor
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
- B01J8/226—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement internally, i.e. the particles rotate within the vessel
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
- B01J8/28—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations the one above the other
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
- C10G2/343—Apparatus, reactors with moving solid catalysts according to the "moving-bed" method
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00141—Coils
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00539—Pressure
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/0061—Controlling the level
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Treating Waste Gases (AREA)
Abstract
An installation for producing liquid and, optionally, gaseous products from gaseous reactants. The installation has a reactor vessel having a vertically extending slurry bed zone; a first gas inlet in the vessel at a low level within the slurry bed zone for introducing gaseous reactants; a second gas inlet in the vessel at a level within the slurry bed zone which is above the first gas inlet for introducing recycled gas, the second gas inlet in the vessel being above the lower 20% of the vertical height of the slurry bed zone; a gas outlet in the vessel above the slurry bed zone, for withdrawing gas from a head space above the slurry bed zone and a liquid outlet in the vessel within the slurry bed zone, for withdrawing liquid product from the vessel.
Description
- THIS INVENTION relates to a process for producing liquid and, optionally, gaseous products from gaseous reactants. It relates also to an installation for producing liquid and, optionally, gaseous products from gaseous reactants.
- According to one aspect of the invention, there is provided a process for producing liquid and, optionally, gaseous products from gaseous reactants, which process includes
- feeding at a low level gaseous reactants and, optionally, a portion of a recycle gas stream into a vertically extending slurry bed of solid particles suspended in a suspension liquid inside a vessel;
- feeding, as an additional gas feed, at least a portion of the recycle gas stream into the slurry bed above the level at which the gaseous reactants are fed into the slurry bed and above the lower 20% of the vertical height of the slurry bed;
- allowing the gaseous reactants and recycled gas to react as they pass upwardly through the slurry bed, thereby to form liquid and, optionally, gaseous products, and with the liquid product forming together with the suspension liquid, a liquid phase of the slurry bed;
- allowing any gaseous product and unreacted gaseous reactants and unreacted recycled gas to disengage from the slurry bed into a head space above the slurry bed;
- withdrawing any gaseous product and unreacted gaseous reactants and unreacted recycled gas from the head space;
- withdrawing liquid phase from the slurry bed, to maintain the slurry bed at a desired level; and
- recycling at least some of the gaseous components from the head space to provide the recycle gas stream.
- The process preferably includes allowing slurry to pass downwardly from a high level in die slurry bed to a lower level thereof, using slurry redistribution means or slurry redistributors, thereby to redistribute solid particles within the slurry bed.
- Typically, the additional gas feed has very little impact on the vertical distribution of the solid particles in the slurry bed. When the vertical distribution of solid particles in the slurry bed of the present invention is compared to that of an identical process but in which all of the gaseous reactants and recycle gas are fed at a single or common low level into the slurry bed, it is found to be substantially the same;
- The additional gas feed may be fed at a level which is located between about 20% and about 80% of the vertical height of the slurry bed/Preferably, the additional gas feed is fed at a level which is located above 25%, more preferably above 30% of the vertical height of die slurry bed.
- While it is believed that the process can, at least in principle, have broader application, it is envisaged that the solid particles will normally be catalyst particles for catalyzing the reaction of the gaseous reactants into the liquid product, and, when applicable, the gaseous product; and the suspension liquid will normally, but not necessarily always, be the liquid product.
- Furthermore, while it is also believed that, in principle, the process can have broader application, it is envisaged that it will have particular application in hydrocarbon synthesis where the gaseous reactants are capable of reacting catalytically in the slurry bed to form liquid hydrocarbon product and, optionally, gaseous hydrocarbon product. In particular, the hydrocarbon synthesis may be Fischer-Tropsch synthesis, with the gaseous reactants being in the form of a synthesis gas stream comprising mainly carbon monoxide and hydrogen, and with both liquid and gaseous hydrocarbon products being produced.
- The process may include cooling the gas from the head space to condense liquid product, e.g. liquid hydrocarbons and reaction water, separating the liquid product from the gases to provide a tail gas, and recycling at least some of the tail gas to the slurry bed as the recycle gas stream.
- The slurry bed may thus be contained or provided in a reaction zone of a vessel in the form of a slurry reactor or bubble column. The slurry reactor or bubble column thus uses a three-phase system, i.e. solid catalyst particles, liquid product, and gaseous reactants (including any recycled gas) and, optionally, gaseous product and inert gases.
- The additional gas feed may be introduced into the slurry bed by means of a gas sparger.
- The additional gas feed may make up at least 10% of the total volumetric feed rate of gas entering the slurry bed. Typically, the additional gas feed does not make up more than 60% of the total volumetric feed rate of gas entering the slurry bed.
- The catalyst of the catalyst particles can be any desired Fischer-Tropsch catalyst, such as an iron-based catalyst, a cobalt-based catalyst, or any other Fischer-Tropsch catalyst. The catalyst particles may have a desired particle size range, e.g. no catalyst particles greater than 300 microns and less than 5% by mass of the catalyst particles being smaller than 22 microns.
- The slurry reactor or bubble column may thus be maintained at normal elevated pressure and temperature conditions associated with Fischer-Tropsch synthesis reactions, e.g. a predetermined operating pressure in the
range 10 to 50 bar, and a pre-determined temperature in the range 160° C. to 280° C., or even higher for the production of lower boiling point product. - The catalyst particles in the slurry bed are thus maintained in suspension by the turbulence created by the synthesis gas stream (fresh and recycled) passing through the slurry bed, i.e. bubbling through the slurry bed. The gas velocity through the slurry bed is thus sufficiently high to maintain the slurry bed in a state of turbulence or suspension.
- In one embodiment of the invention, the entire recycle gas stream being returned to the slurry bed forms part of the additional gas feed.
- The process may be characterised in that gas hold-up in the slurry bed is lower in a lower portion of the slurry bed than gas hold-up in a lower portion of a slurry bed of an identical process but in which all of the gaseous reactants and recycle gas are fed at a single low level into the slurry bed. Gas hold-up may be higher in an upper portion of the slurry bed than in an upper portion of the slurry bed of said identical process. However, overall gas hold-up in the slurry bed of the process of the invention will be lower than in the slurry bed of the conventional process.
- According to another aspect of the invention, there is provided an installation for producing liquid and, optionally, gaseous products from gaseous reactants, the installation comprising
- a reactor vessel having a vertically extending slurry bed zone which, in use, will contain a slurry bed of solid particles suspended in a suspension liquid;
- a first gas inlet in the vessel at a low level within the slurry bed zone, for introducing gaseous reactants into the vessel;
- a second gas inlet in the vessel at a level within the slurry bed zone which is above the first gas inlet, for introducing recycled gas into the vessel, with the second gas inlet in the vessel being above the lower 20% of the vertical height of the slurry bed zone;
- a gas outlet in the vessel above the slurry bed zone, for withdrawing gas from a head space above the slurry bed zone; and
- a liquid outlet in the vessel within the slurry bed zone, for withdrawing liquid product from the vessel.
- Preferably, the installation includes slurry redistribution means on one or more slurry redistributors through which, in use, slurry can be redistributed from a high level in the slurry bed to a lower level thereof, thereby to redistribute solid particles in the slurry bed.
- The second gas inlet may be at a level which is located between about 20% and about 80% of the vertical height of the slurry bed zone. Preferably, the second gas inlet is at a level above the lower 25%, more preferably above the lower 30% of the vertical height of the slurry bed zone.
- The second gas inlet may include a gas sparger.
- In this specification, the term ‘slurry redistribution means’ is intended to refer to physical apparatus used to redistribute slurry and catalyst particles vertically inside the reactor vessel, and does not refer to the slurry and catalyst particle redistribution action of the gas passing upwards through the slurry bed. The slurry redistribution means or slurry redistributors may thus include downcomers or draught tubes or mechanical redistribution apparatus such as pipes and pumps and filters.
- When the slurry redistribution means includes downcomers, the downcomers may be arranged in a first downcomer region and a second downcomer region, with the second downcomer region being vertically spaced with respect to the first downcomer region.
- The downcomers or draught tubes may thus be located at different levels or vertical elevations within the slurry bed or the slurry bed zone. The second downcomer region may be located at a higher level than the first downcomer region, and, if desired, further downcomer regions, each containing at least one downcomer or draught tube may be provided above the second downcomer region, with a third and any subsequent downcomer regions also being spaced vertically from one another.
- In one embodiment of the invention, the second downcomer region may overlap the first downcomer region. In other words, the lower end(s) of the downcomer(s) in the second downcomer region may overlap the upper end(s) of the downcomer(s) in the first downcomer region. In another embodiment of the invention, however, the second downcomer region may be located in non-overlapping relationship with respect to the first downcomer region. In other words, the lower end(s) of the downcomer(s) in the second downcomer region may be spaced with vertical clearance from the upper end(s) of the downcomer(s) in the first downcomer region.
- The downcomer(s) in the second downcomer region may be staggered with respect to that (those) in the first downcomer region, when the reactor or vessel is seen in plan view. In other words, the lower end(s) of the downcomer(s) in the second downcomer region preferably does(do) not discharge slurry directly above the upper end(s) of the downcomer(s) in the first downcomer region.
- Each downcomer may comprise a lower transport section and an upper disengagement or degassing section of greater cross-sectional area than the transport section. The sections are preferably circular in cross-section, is of cylindrical form, with an outwardly upwardly flaring connecting component connecting the disengagement section to the transport section. However, the disengagement section can, if desired, be in another suitable form, e.g. in the form of a rectangular or triangular section channel, as determined by the space available inside the reactor vessel.
- While each downcomer will normally be located entirely within the slurry bed i.e. inside the reactor, with the degassing section typically aligned axially with the transport section, the transport section and, optionally, part of the degassing section can, instead, be located outside the reactor, with the lower outlet end of the transport section and at least the upper inlet end of the degassing section then, however, being located inside the reactor in the slurry bed or the slurry bed zone.
- The process may include operating the slurry reactor such that the slurry bed is in a heterogeneous or chum-turbulent flow regime and comprises a dilute phase consisting of fast-rising large bubbles of gaseous reactants, and, possibly gaseous product, which traverse the reaction zone or slurry bed virtually in a plug flow manner, and a dense phase comprising liquid phase, i.e. liquid product, solid catalyst particles, and entrained smaller bubbles of gaseous reactants and, possibly, gaseous product.
- The invention will now be described in more detail with reference to the following Examples and the accompanying drawings, in which
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FIG. 1 shows schematically a longitudinal sectional view of an installation in accordance with the invention for producing liquid and gaseous products from gaseous reactants; -
FIG. 2 shows a graph of normalised gas hold-up versus normalised slurry bed height for a conventional Fischer-Tropsch process in which total gas feed is fed to a reactor bottom and for a Fischer-Tropsch process in accordance with the invention, both processes being modelled with the dilute phase and the dense phase in plug flow; -
FIG. 3 shows a graph of normalised partial pressure of CO, H2 and H2O versus normalised slurry bed height for the conventional process and the process of the invention for which the gas hold-up is shown inFIG. 2 ; and -
FIG. 4 shows a graph of normalised gas hold-up versus normalised slurry bed height for a conventional Fischer-Tropsch process in which total gas feed is fed to a reactor bottom and for a Fischer-Tropsch process in accordance with the invention, both processes being modelled with a plug flow dilute phase and a well-mixed dense phase. - In the drawings,
reference numeral 10 generally indicates an installation according to the invention for producing liquid and gaseous products from gaseous reactants. - The
installation 10 includes an upright cylindrical slurry reactor orbubble column 12, with abottom gas inlet 14 leading into a gas distributor (not shown) inside thereactor 12 and agas outlet 16 leading from the top of thereactor 12. Aliquid product outlet 18 leads from thereactor 12 at any convenient level. - The
reactor 12 includes a first downcomer region, generally indicated byreference numeral 20. Thedowncomer region 20 includes a downcomer, generally indicated byreference numeral 22. Thedowncomer 22 includes acylindrical transport section 24 of relatively small diameter, an outwardly flaring connectingcomponent 26 at an upper end of thetransport section 24, and a largerdiameter degassing section 28, a lower end of which is connected to the connectingcomponent 26. An upper end of thedegassing section 28 thus provides aninlet 40 for slurry, while a lower end of thetransport section 24 provides aslurry outlet 42. A coolingcoil 29 is also provided in thedowncomer region 20. - The
reactor 12 also includes a second downcomer region, generally indicated byreference numeral 30. Thedowncomer region 30 includes a downcomer, generally indicated byreference numeral 32. Thedowncomer 32 also includes atransport section 34 of relatively small diameter, an outwardly flaring connectingcomponent 36 at an upper end of thetransport section 34, and adegassing section 38 of relatively large diameter at an upper end of thetransport section 34. A lower end of thedegassing section 38 is thus connected to the connectingcomponent 36. An upper end of thedegassing section 38 provides a slurry inlet, while a lower end of thetransport section 34 provides a slurry outlet. A coolingcoil 39 is also provided in thedowncomer region 30. - The lower end of the
downcomer 32 is spaced with vertical clearance from the upper end of thedowncomer 22. Furthermore, thedowncomer 32 is not aligned axially with thedowncomer 22. In other words, thedowncomer 32 is staggered relative to thedowncomer 22 when thereactor 12 is seen in plan view. - The
gas inlet 14 is a first gas inlet. Asecond gas inlet 52 is provided at a level or an elevation above thefirst gas inlet 14. Thesecond gas inlet 52 also leads into a gas distributor which is not shown inside thereactor 12. - The
installation 10 further includes aseparation unit 54 in flow communication with thegas outlet 16 and acompressor 56 in flow communication with theseparation unit 54. A recyclegas stream line 58 leads from thecompressor 56 to thesecond gas inlet 52. Aliquid product line 60 leads from theseparation unit 54, with atail gas line 62 establishing flow communication between theseparation unit 54 and thecompressor 56. - In use, fresh synthesis gas comprising mainly carbon monoxide and hydrogen as gaseous reactants, is fed into the bottom of the
reactor 12 through thefirst gas inlet 14, the gas typically being uniformly distributed through a sparger system (not shown) inside thereactor 12. Simultaneously, a recycle gas stream (typically cooled) comprising typically hydrogen, carbon monoxide, methane and carbon dioxide is fed through thesecond gas inlet 52 into thereactor 12 at a level above thefirst gas inlet 14 through a sparger system (not shown) inside thereactor 12. Typically, thesecond gas inlet 52 is located at least about 20% of the vertical height of thereactor 12 above thefirst gas inlet 14. - The gaseous reactants, comprising the fresh synthesis gas and the recycled gas, pass upwardly through a
slurry bed 70 comprising Fischer-Tropsch catalyst particles, typically an iron or cobalt based catalyst, suspended in liquid product. The slurry bed is operated to have anormal level 72 above thesecond downcomer region 30, with ahead space 74 being provided above theslurry bed 70. As the synthesis gas bubbles through theslurry bed 70, the gaseous reactants therein react catalytically to form liquid product, which thus forms part of theslurry bed 70. From time to time, or continuously, liquid phase comprising liquid product is withdrawn through theoutlet 18, with catalyst particles being separated from the liquid product in a suitable internal or external separation system, e.g. using filters (not shown). If the separation system is located externally to the reactor, an additional system (not shown) to return the separated catalyst particles to the reactor is then provided. - The fresh synthesis feed gas and the recycled gas is introduced into the
reactor 12 at a rate sufficient to agitate and suspend all of the catalyst particles in the system without settling. The gas flow rates will be selected depending on the slurry concentration, catalyst density, suspending medium density and viscosity, and particular particle size used. Suitable gas flow rates include, for example, from about 5 cm/s to about 50 cm/s. However, gas velocities up to about 85 cm/s have been tested in bubble columns. The use of higher gas velocities has the disadvantage that it is accompanied by a higher gas hold-up in the reactor leaving relatively less space to accommodate the catalyst-containing slurry. Whatever gas flow rate is however selected, it should be sufficient to avoid particle settling and agglomeration. - Some slurry continuously passes downwardly through the
downcomers slurry bed 70, and also to ensure uniform heat redistribution throughout the slurry bed. - The
reactor 12 is operated so that theslurry bed 70 thereof is in a heterogeneous or chum-turbulent flow regime and comprises a dilute phase consisting of fast-rising larger bubbles of gaseous reactants and gaseous product which traverse the slurry bed virtually in plug flow fashion and a dense phase which comprises liquid product, solid catalyst particles and entrained smaller bubbles of gaseous reactants and gaseous product. - Boiler water as a heat exchange or transfer medium, is circulated through the coolant coils 29, 39. Heat is transferred from the
slurry bed 70 to the boiler water to form a mixture of steam and water. - Light hydrocarbon products, such as a C20 and below fraction is withdrawn from the reactor through the
gas outlet 16 and passed to theseparation unit 54. Typically, theseparation unit 54 comprises a series of coolers and a vapour-liquid separator and may optionally include further coolers and separators and possibly also a cryogenic unit for removal of hydrogen, carbon monoxide, methane and carbon dioxide from the C20 and below hydrocarbon fraction. Other separation technologies such as membrane units, pressure swing adsorption units and/or units for the selective removal of carbon dioxide may be employed. The separated gases comprising hydrogen, carbon monoxide and other gases are compressed and recycled by means of thecompressor 56 to provide the recycle gas stream. Condensed liquid hydrocarbons and reaction water is withdrawn from theseparation unit 54 by means of theflow line 60 for further working up. - It is to be appreciated that, although the
installation 10, as illustrated, indicates that all of the recycle gas stream is returned to thereactor 12, it is not necessarily so that the entire recycle gas stream has to be returned to thereactor 12. It is thus possible that only a portion of the recycle gas stream is returned to thereactor 12. It is also possible that a portion of the recycle gas stream is combined with the fresh synthesis gas to be fed into thereactor 12 through thefirst gas inlet 14. Typically, between about 10% and about 60% of the total volumetric feed rate of gas entering theslurry bed 70 is fed through thesecond gas inlet 52, with the volumetric ratio of recycled gas to fresh synthesis gas typically being between 0.1 and 1.5. - The Applicant has surprisingly found that higher reactor capacities can be achieved if at least a portion of the recycled gas is introduced at a higher level into the
reactor vessel 12 than the synthesis gas which is fed at the lower end of thereactor 12. As will be appreciated, this leads to cost savings for the construction of the reactor or, instead, to an increase in capacity for reactors modified to have a second, higher gas inlet. Although not wishing to be bound by theory, the Applicant believes that a possible explanation for the resulting higher reactor capacity is a lower gas hold-up when employing the invention. It is known that the volume of gases and vapours decreases as the Fischer-Tropsch reaction proceeds and gaseous reactants are converted to higher molecular weight hydrocarbon products. There is thus a vertical gradient in the volume of gases and vapours in thereactor 12. By feeding at least a portion of the recycled gas at a higher elevation into thereactor 12, there is a section of thereactor 12 below this higher elevation where the gas velocity is now lower and decreasing while the gas density is lower and increasing as the gas moves upward. Gas hold-up increases with gas density. Comparing this situation with the case where all of the gas is introduced at the lower end of thereactor 12, it will be noted that both a lower maximum velocity and a lower average velocity is achieved for the gas, as well as a lower average gas density in thereactor 12. The end result is thus a lower gas hold-up which allows more catalyst-containing slurry to be accommodated in a given reactor volume. Surprisingly, the extra catalyst more than compensates for the fact that some recycled gas bypasses a portion of the catalyst. Accordingly, for the same reactor volume, containing more catalyst, the flow of both fresh synthesis gas and recycled gas may be increased, relative to the case where all the gas is introduced at the lower end of the reactor, while still achieving the same level (or percentage) conversion of reactants in the synthesis gas. - It is a further advantage of the process of the invention, as illustrated, that the introduction of cooled gas above the bottom of the reactor, together with the use of slurry redistribution means can be employed to ensure a more uniform temperature in the slurry bed. This allows the cooling pipes in the slurry bed, which may be located in two or more banks, at different vertical locations, to be connected to a singe steam drum. This avoids the need for multiple steam drums operating at different temperatures and pressures.
- The following two examples illustrate some of the advantages set out hereinbefore.
- In these examples a conventional or base case Fischer-Tropsch process was mathematically modelled. For the conventional process, the model assumed that the total gas feed (fresh synthesis gas and recycled gas) is fed to the bottom of a slurry bubble column. A process in accordance with the invention was also modelled where the total recycle gas flow rate is fed at a level of 34% of the vertical height of a slurry bed in a slurry bubble column. In both cases, it was assumed that slurry redistribution means was present and was sufficient to ensure a uniform solid catalyst concentration in the slurry bed. For both cases, the solid catalyst concentration in the slurry bed was assumed to be constant. The models used a fresh feed synthesis gas H2/CO molar ratio of 1.925, a recycle gas to fresh gas feed ratio of 0.9 and a constant targeted overall H2 conversion of approximately 93%. In the models, this conversion was achieved by varying the flow rate of fresh synthesis gas feed to a slurry bed reactor of fixed size and which was the same size for both models. The choice of slightly sub-stoichiometric fresh gas feed was based on the well known effect that a sub-stoichiometric fresh gas feed enhances the selectivity to higher hydrocarbons and suppresses the methane selectivity.
- For Example 1, the models assumed that both a dilute and a slurry or dense phase of the slurry bed is in plug flow.
- The results of the mathematical simulations, using the models of Example 1, indicated that the process of the invention has an increased fresh synthesis gas feed rate of approximately 16% compared to the conventional process. It can thus be stated that the slurry bubble column conversion capacity is therefore approximately 16% more for the process of the invention than for the conventional process. The selectivity to C5 + products was almost unchanged, based on the expected catalyst selectivity behaviour for a known commercial catalyst.
- The process of the invention showed a total catalyst loading that is more than 5% larger for the same solids concentration in the slurry bed than the conventional case. This is as a result of a lower overall or total gas hold-up, despite the larger gas feed rate. The slurry bubble column productivity of the process of the invention is further aided by increased reagent concentration and H2/CO ratio in the portion of the slurry bed below the level where the recycled gas is introduced.
- The normalised gas hold-up and normalised partial pressure of selected gaseous components as a function of normalised slurry bed height are illustrated in
FIGS. 2 and 3 respectively, for both the conventional process and the process of the invention. It is to be noted that the level at which recycled gas is fed into the slurry bubble column of the process of the invention was selected so that the water partial pressure at this point matches the outlet water partial pressure. It is believed that high water partial pressure may be detrimental to catalyst performance. - In
FIG. 2 , graph A shows the gas hold-up for the conventional process and graph B shows the gas hold-up for the process of the invention. InFIG. 3 , graph A shows the partial pressure of H2 for the process of the invention and graph B shows the partial pressure of H2 for the conventional process, graph C shows the partial pressure of CO for the process of the invention and graph D shows the partial pressure of CO for the conventional process, and graph E shows the partial pressure of water for the process of the invention and graph F shows the partial pressure of water for the conventional process. - For Example 2, it was assumed that the dilute phase is in plug flow and the dense phase or slurry phase is well mixed. The results of the mathematical simulation using the models of Example 2 showed that the process of the invention can accommodate an increase in fresh synthesis gas feed of approximately 4% compared to the conventional process. The slurry bubble conversion capacity is therefore approximately 4% more for the process of the invention than for the conventional process. The selectivity for C5 + products remained almost unchanged.
- The process of the invention as modelled in Example 2 has a total catalyst loading that is approximately 4% larger for the same solids concentration in the slurry bed, compared to the solids concentration for the conventional process. This is due to the lower overall or total gas hold-up in the slurry bed of the conventional process, despite the larger gas feed rate.
-
FIG. 4 shows the normalised gas hold-up as a function of normalised slurry bed height for Example 2. Graph A shows the gas hold-up for the conventional process and graph B shows the gas hold-up for the process of the invention. - The true slurry bubble column behaviour of a conventional process and the process of the invention is expected to lie between the extremes illustrated in Examples 1 and 2 and will be influenced by the choice, capacity and arrangement of slurry redistribution means, if present.
Claims (6)
1-16. (canceled)
17. An installation for producing liquid and, optionally, gaseous products from gaseous reactants, the installation comprising
a reactor vessel having a vertically extending slurry bed zone which, in use, will contain a slurry bed of solid particles suspended in a suspension liquid;
a first gas inlet in the vessel at a low level within the slurry bed zone, for introducing gaseous reactants into the vessel;
a second gas inlet in the vessel at a level within the slurry bed zone which is above the first gas inlet, for introducing recycled gas into the vessel, with the second gas inlet in the vessel being above the lower 20% of the vertical height of the slurry bed zone;
a gas outlet in the vessel above the slurry bed zone, for withdrawing gas from a head space above the slurry bed zone; and
a liquid outlet in the vessel within the slurry bed zone, for withdrawing liquid product from the vessel.
18. The installation as claimed in claim 17 , which includes slurry redistribution means or slurry redistributors through which, in use, slurry can be redistributed from a high level in the slurry bed to a lower level thereof, thereby to redistribute solid particles within the slurry bed.
19. The installation as claimed in claim 17 , in which the second gas inlet is at a level which is located between 20% and 80% of the vertical height of the slurry bed zone.
20. The installation as claimed in claim 17 in which the second gas inlet is at a level above the lower 30% of the vertical height of the slurry bed zone.
21. The installation as claimed in claim 18 in which the slurry redistribution means or slurry redistributors include downcomers, the downcomers being arranged in at least a
Priority Applications (1)
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US12/192,337 US20080299022A1 (en) | 2003-05-16 | 2008-08-15 | Process for producing liquid and, optionally, gaseous products from gaseous reactants |
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US47132303P | 2003-05-16 | 2003-05-16 | |
PCT/IB2004/050656 WO2004101475A1 (en) | 2003-05-16 | 2004-05-12 | Process for producing liquid and, optionally, gaseous products from gaseous reactants |
US55595706A | 2006-07-27 | 2006-07-27 | |
US12/192,337 US20080299022A1 (en) | 2003-05-16 | 2008-08-15 | Process for producing liquid and, optionally, gaseous products from gaseous reactants |
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PCT/IB2004/050656 Division WO2004101475A1 (en) | 2003-05-16 | 2004-05-12 | Process for producing liquid and, optionally, gaseous products from gaseous reactants |
US55595706A Division | 2003-05-16 | 2006-07-27 |
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US12/192,337 Abandoned US20080299022A1 (en) | 2003-05-16 | 2008-08-15 | Process for producing liquid and, optionally, gaseous products from gaseous reactants |
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US (2) | US7439274B2 (en) |
EP (1) | EP1636151B1 (en) |
JP (1) | JP4966654B2 (en) |
CN (1) | CN100378043C (en) |
AT (1) | ATE405534T1 (en) |
AU (1) | AU2004238648B2 (en) |
BR (1) | BRPI0410365B1 (en) |
CA (1) | CA2525007C (en) |
DE (1) | DE602004015984D1 (en) |
NO (1) | NO20055938L (en) |
RU (1) | RU2342355C2 (en) |
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Cited By (2)
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US9604892B2 (en) | 2011-08-04 | 2017-03-28 | Stephen L. Cunningham | Plasma ARC furnace with supercritical CO2 heat recovery |
US10066275B2 (en) | 2014-05-09 | 2018-09-04 | Stephen L. Cunningham | Arc furnace smeltering system and method |
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GB2429714B (en) * | 2004-05-10 | 2008-12-17 | Sasol Technology | The production of liquid and,optionally,gaseous hydrocarbons from gaseous reactants into an expanded slurry bed |
US8013025B2 (en) | 2005-03-17 | 2011-09-06 | Sasol Technology (Proprietary) Limited | Method of operating a three-phase slurry reactor |
KR20080009267A (en) | 2005-03-17 | 2008-01-28 | 사솔 테크놀로지(프로프라이어터리) 리미티드 | Plate-type fluid bed reactor |
FR2900066B1 (en) * | 2006-04-21 | 2008-05-30 | Inst Francais Du Petrole | NOVEL INTERNAL EXCHANGER FOR SOLID FLUIDIZED GAS REACTOR SOLID LIQUID GAS, IMPLEMENTING A HIGHLY EXOTHERMIC REACTION. |
FR2900065B1 (en) | 2006-04-21 | 2008-05-30 | Inst Francais Du Petrole | NEW INTERNAL EXCHANGER FOR SOLID LIQUID GAS REACTOR FOR FISCHER TROPSCH SYNTHESIS. |
JP5143901B2 (en) * | 2007-08-24 | 2013-02-13 | サソール テクノロジー(プロプライエタリー)リミテッド | Process for producing liquid and gaseous products from gaseous reactants |
CN102165038B (en) * | 2008-09-30 | 2013-10-16 | 日本石油天然气·金属矿物资源机构 | Hydrocarbon synthesis reaction apparatus, hydrocarbon synthesis reaction system, and hydrocarbon synthesis method |
BR112013014824B1 (en) * | 2010-12-13 | 2019-12-17 | Sasol Tech Pty Ltd | slurry phase apparatus |
CN103596674B (en) * | 2011-06-07 | 2015-12-02 | 沙索技术有限公司 | For being produced the method for at least one product in slurry bed system by least one gaseous reactant |
CN102703107B (en) * | 2012-06-26 | 2015-04-01 | 武汉凯迪工程技术研究总院有限公司 | Method for manufacturing liquid hydrocarbon product with synthetic gas produced by biomass |
WO2023118974A1 (en) * | 2021-12-24 | 2023-06-29 | Vinati Organics Limited | An agitator reactor for synthesis of acrylamido tertiary butyl sulfonic acid and process implemented thereon |
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BRPI0410365B1 (en) | 2014-09-09 |
JP2007501121A (en) | 2007-01-25 |
ZA200508993B (en) | 2006-12-27 |
ATE405534T1 (en) | 2008-09-15 |
CN100378043C (en) | 2008-04-02 |
US7439274B2 (en) | 2008-10-21 |
US20070043125A1 (en) | 2007-02-22 |
CA2525007C (en) | 2012-02-14 |
AU2004238648B2 (en) | 2009-05-14 |
EP1636151B1 (en) | 2008-08-20 |
CN1787982A (en) | 2006-06-14 |
BRPI0410365A (en) | 2006-05-30 |
DE602004015984D1 (en) | 2008-10-02 |
WO2004101475A1 (en) | 2004-11-25 |
JP4966654B2 (en) | 2012-07-04 |
AU2004238648A1 (en) | 2004-11-25 |
EP1636151A1 (en) | 2006-03-22 |
NO20055938L (en) | 2005-12-14 |
RU2005138918A (en) | 2006-05-10 |
CA2525007A1 (en) | 2004-11-25 |
RU2342355C2 (en) | 2008-12-27 |
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