CA2326440C - Heat treated fischer-tropsch catalyst particles - Google Patents
Heat treated fischer-tropsch catalyst particles Download PDFInfo
- Publication number
- CA2326440C CA2326440C CA002326440A CA2326440A CA2326440C CA 2326440 C CA2326440 C CA 2326440C CA 002326440 A CA002326440 A CA 002326440A CA 2326440 A CA2326440 A CA 2326440A CA 2326440 C CA2326440 C CA 2326440C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst particles
- fischer
- catalyst
- tropsch
- particles
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000002245 particle Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052742 iron Inorganic materials 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 description 21
- 239000002002 slurry Substances 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 5
- 238000011027 product recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000004813 Moessbauer spectroscopy Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/30—
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- 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
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- B01J35/393—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
Abstract
The invention provides heat treated self-supported precipitated iron-based Fischer-Tropsch catalyst particles. The particles of the present invention are breakage resistant and exhibit superior synthesis performance. The invention also provides a method for producing said particles and a process using said particles.
Description
HEAT TREATED FISCHER-TROPSCH CATALYST PARTICLES
This invention relates to catalysts. More particularly the invention relates to a method of making breakage resistant self-supported precipitated iron-based Fischer-Tropsch catalyst particles, to a method of making self-supported precipitated iron-based Fischer-Tropsch catalyst particles having superior synthesis performance or activity, to catalyst particles made according to the methods. and to the use of said catalyst particles in a slurry bed Fischer-Tropsch reactor.
BACKGROUND OF THE INVENTION
US Patent Nos. 5324335 and 5504118 disclose the production of roughly spherical iron-based Fischer-Tropsch catalyst particles having diameters in the range of between 1 and 50 microns which are annealed by heating in air at about 316°C (600°F) to drive off residual moisture and to stabilise the catalyst.
The annealing step i.e. the heating and gradual controlled cooling, converts the Goethite to Hematite whereafter the catalyst may be activated and used.
According to these patents, the annealing does not lead to a breakage resistant or a superior performance catalyst particle.
t South African Patent No. 9017530 discloses the production of an iron-based Fischer-Tropsch catalyst including from 1 to 80% by mass of activated carbon.
This catalyst shows improved breakage resistance over conventional catalyst, particularly where the particle diameters are below about 45 micron. The catalyst particle of this patent does not have superior synthesis performance and is expected to' hydrothermally sinter at about 300°C.
A need thus exists for breakage resistant iron-based Fischer-Tropsch catalyst particles, in particular for use in a low temperature Fischer-Tropsch process, such as that carried out in a slurry bed reactor, for the production of, amongst others, wax and other syncrudes, as well as chemicals. The breakage resistant self-supported precipitated iron-based Fischer-Tropsch catalyst particles will ideally inhibit the formation of catalyst fines in the reactor thereby maintaining the performance of the reactor and reduce the contamination of down stream processes and catalysts by the catalyst fines.
In this specification, unless the context clearly indicates to the contrary, the term "fines" when used in relation to catalysts and catalyst particles is to be understood to mean particles which due to their dimensions, when present at a concentration of about 30% of the total catalyst, tend to reduce the pertormance of the solid separation system of a Fischer-Tropsch slurry bed reactor.
Typically fines have a diameter of less than about 45 microns, usually about 22 microns.
This invention relates to catalysts. More particularly the invention relates to a method of making breakage resistant self-supported precipitated iron-based Fischer-Tropsch catalyst particles, to a method of making self-supported precipitated iron-based Fischer-Tropsch catalyst particles having superior synthesis performance or activity, to catalyst particles made according to the methods. and to the use of said catalyst particles in a slurry bed Fischer-Tropsch reactor.
BACKGROUND OF THE INVENTION
US Patent Nos. 5324335 and 5504118 disclose the production of roughly spherical iron-based Fischer-Tropsch catalyst particles having diameters in the range of between 1 and 50 microns which are annealed by heating in air at about 316°C (600°F) to drive off residual moisture and to stabilise the catalyst.
The annealing step i.e. the heating and gradual controlled cooling, converts the Goethite to Hematite whereafter the catalyst may be activated and used.
According to these patents, the annealing does not lead to a breakage resistant or a superior performance catalyst particle.
t South African Patent No. 9017530 discloses the production of an iron-based Fischer-Tropsch catalyst including from 1 to 80% by mass of activated carbon.
This catalyst shows improved breakage resistance over conventional catalyst, particularly where the particle diameters are below about 45 micron. The catalyst particle of this patent does not have superior synthesis performance and is expected to' hydrothermally sinter at about 300°C.
A need thus exists for breakage resistant iron-based Fischer-Tropsch catalyst particles, in particular for use in a low temperature Fischer-Tropsch process, such as that carried out in a slurry bed reactor, for the production of, amongst others, wax and other syncrudes, as well as chemicals. The breakage resistant self-supported precipitated iron-based Fischer-Tropsch catalyst particles will ideally inhibit the formation of catalyst fines in the reactor thereby maintaining the performance of the reactor and reduce the contamination of down stream processes and catalysts by the catalyst fines.
In this specification, unless the context clearly indicates to the contrary, the term "fines" when used in relation to catalysts and catalyst particles is to be understood to mean particles which due to their dimensions, when present at a concentration of about 30% of the total catalyst, tend to reduce the pertormance of the solid separation system of a Fischer-Tropsch slurry bed reactor.
Typically fines have a diameter of less than about 45 microns, usually about 22 microns.
A further long felt need which exists is that for self-supported precipitated iron-based Fischer-Tropsch catalyst particles having superior synthesis performance or activity, in particular for use in a low temperature Fischer-Tropsch process, such as that carried out in a slurry bed reactor, for the production of wax and other syncrudes, as well as chemicals.
BRIEF SUMMARY OF THE INVENTION
It is well expected that heat treatment of self-supported precipitated catalyst particles has a negative effect on the activity thereof. In particular, the catalyst particle surface area and pore volume are likely to be reduced at temperatures above 250°C. Those skilled in the art therefore generally tend to avoid such heat treatment of such Fischer-Tropsch catalyst material.
Surprisingly it has now been found that the breakage resistance and the synthesis performance or activity of self-supported precipitated iron-based Fischer-Tropsch catalyst particles can be increased by the heat treatment thereof at temperatures of at least 250°C.
BRIEF SUMMARY OF THE INVENTION
It is well expected that heat treatment of self-supported precipitated catalyst particles has a negative effect on the activity thereof. In particular, the catalyst particle surface area and pore volume are likely to be reduced at temperatures above 250°C. Those skilled in the art therefore generally tend to avoid such heat treatment of such Fischer-Tropsch catalyst material.
Surprisingly it has now been found that the breakage resistance and the synthesis performance or activity of self-supported precipitated iron-based Fischer-Tropsch catalyst particles can be increased by the heat treatment thereof at temperatures of at least 250°C.
Accordingly, the invention provides a method of producing self-supported precipitated iron-based catalyst particles for use in a Fischer-Tropsch slurry-bed process, the said particles being breakage resistant and thus inhibiting the formation of catalyst fines, the method including the heat treatment of the said particles at a temperature of at least 250°C.
The heat treatment may be calcination of the said particles at a temperature of at least 250°C.
The heat treatment of the said catalyst particles may be carried out at a temperature of between 250 °C and 500 °C, preferably between 320 °C and 500 °C, more preferably between 360 °C and 390 °C, most preferably at 380°C.
According to a second aspect of the invention, there is provided a method of producing self-supported precipitated iron-based catalyst particles for use in a Fischer-Tropsch slurry-bed process, the catalyst particles having a superior synthesis performance or activity under low temperature Fischer-Tropsch slurry-bed operating conditions, the method including the heat treatment of the said catalyst particles at a temperature of at least 250 °C.
The heat treatment temperature of the method may be between 250 °C
and 500°C, preferably between 320°C and 500°C, more preferably between 360°C
and 390°C, most preferably 380°C.
The heat treatment may be calcination of the said particles at a temperature of at least 250°C.
The heat treatment of the said catalyst particles may be carried out at a temperature of between 250 °C and 500 °C, preferably between 320 °C and 500 °C, more preferably between 360 °C and 390 °C, most preferably at 380°C.
According to a second aspect of the invention, there is provided a method of producing self-supported precipitated iron-based catalyst particles for use in a Fischer-Tropsch slurry-bed process, the catalyst particles having a superior synthesis performance or activity under low temperature Fischer-Tropsch slurry-bed operating conditions, the method including the heat treatment of the said catalyst particles at a temperature of at least 250 °C.
The heat treatment temperature of the method may be between 250 °C
and 500°C, preferably between 320°C and 500°C, more preferably between 360°C
and 390°C, most preferably 380°C.
5 PCTlGB98/03004 Typically the said catalyst particles are maintained at the heat treatment temperature for at least 0.1 hours, preferably between 0.2 and 12 hours, more preferably between 0.5 and 4 hours.
According to a further aspect of the invention there are provided self-supported precipitated iron-based catalyst particles for use in a Fischer-Tropsch slurry-bed process, the said catalyst particles being produced according to a method of heat treatment of the said catalyst particles as described above.
According to yet a further aspect of the invention, there is provided a method of maintaining the performance of a solid separation system of a Fischer-Tropsch process slurry bed reactor where a reduction in performance is caused by an increase in catalyst particle fines in the slurry bed reactor, the method including the use of the catalyst particles as described above.
According to yet a further aspect of the invention, there is provided a process for synthesis of syncrudes and/or chemicals, for example, waxes, the process comprising the step of contacting a suitable synthesis gas, at suitable temperatures and pressures in a Fischer-Tropsch slurry-bed reactor, with self-supported precipitated iron-based Fischer-Tropsch catalyst particles as described above.
The process may be carried out in a suitable vessel, with unreacted reactants and gaseous product being withdrawn above the slurry bed, and separated liquid product also being withdrawn from the vessel.
Typical suitable operating temperatures for the process are temperatures in the range "160°C to ' 280°C, or even higher for production of lower boiling point product.
Typical suitable operating pressures are pressures in the range 18 Bar to 50 Bar.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure. 1. is a graph of the liquid product recovery rate as a function of cycle number for a synthesis run with untreated catalyst particles.
Figure. 2. is a graph of the liquid product recovery rate as a function of cycle number for a synthesis run with heat treated catalyst particles.
Figure. 3. is a graph illustrating the increase in catalyst activity after addition of calcined catalyst.
Figure. 4. are micrographs of on line uncalcined catalyst particles at magnifications of x100, x150, x200, x250, x300, and x500.
Figure. 5. are micrographs of on line heat treated catalyst particles at magnifications of x100, x150, x200, x250, x300, and x500.
According to a further aspect of the invention there are provided self-supported precipitated iron-based catalyst particles for use in a Fischer-Tropsch slurry-bed process, the said catalyst particles being produced according to a method of heat treatment of the said catalyst particles as described above.
According to yet a further aspect of the invention, there is provided a method of maintaining the performance of a solid separation system of a Fischer-Tropsch process slurry bed reactor where a reduction in performance is caused by an increase in catalyst particle fines in the slurry bed reactor, the method including the use of the catalyst particles as described above.
According to yet a further aspect of the invention, there is provided a process for synthesis of syncrudes and/or chemicals, for example, waxes, the process comprising the step of contacting a suitable synthesis gas, at suitable temperatures and pressures in a Fischer-Tropsch slurry-bed reactor, with self-supported precipitated iron-based Fischer-Tropsch catalyst particles as described above.
The process may be carried out in a suitable vessel, with unreacted reactants and gaseous product being withdrawn above the slurry bed, and separated liquid product also being withdrawn from the vessel.
Typical suitable operating temperatures for the process are temperatures in the range "160°C to ' 280°C, or even higher for production of lower boiling point product.
Typical suitable operating pressures are pressures in the range 18 Bar to 50 Bar.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure. 1. is a graph of the liquid product recovery rate as a function of cycle number for a synthesis run with untreated catalyst particles.
Figure. 2. is a graph of the liquid product recovery rate as a function of cycle number for a synthesis run with heat treated catalyst particles.
Figure. 3. is a graph illustrating the increase in catalyst activity after addition of calcined catalyst.
Figure. 4. are micrographs of on line uncalcined catalyst particles at magnifications of x100, x150, x200, x250, x300, and x500.
Figure. 5. are micrographs of on line heat treated catalyst particles at magnifications of x100, x150, x200, x250, x300, and x500.
DETAILED DESCRIPTION OF THE INVENTION
The invention will now be illustrated by means of the following non-limiting examples:
EXAMPLE i This example illustrates that the heat treatment of self-supported precipitated iron-based Low Temperature Fischer Tropsch catalyst particles for slurry bed application results in an increase in the mechanical strength of the said catalyst.
For a laboratory microscale operation, 250 grams of pilot plant and commercially prepared catalyst was placed in a porcelain dish in a muffle furnace. The furnace was subsequently heated to the desired heat treatment temperature at a heating rate of 1°C/min. The heat treatment or calcination temperature (as indicated in Table 1 below) was maintained for 4 hours after which the furnace was allowed to cool down to below 100°C.
Table 1: Catalyst physical properties as a function of ealcination temperatlrre Sample Calc.tempArea Pare % fines "C ~Ig vol <~~um ~g after JI
Pilot Planttmralc 288 0.03 1 l.6 l care yst 300 286 0.64 2.8 400 363 0.63 3.7 SUO 243 0.60 2.1 Comma~cial uncalc X93 O.b2 11.4 catalyst 300 ~T 0.61 t.1 400 24? 0.67 1.6 500 '?5 0.60 1.9 Pilot Plant Rotary Kittt Commercial turalc 289 0.60 l 12'.2 cata yst 385 241 0.54 s,g _ '7 _ ~
. ' ~ CA 02326440 2004-10-27 For, larger. scale operation the catalyst was fed from a hopper at room temperature to a portable pilot plant scale rotary kiln. This kiln had a refractory lining and was electrically heated. The dimensions of this equipment were as follows: length=2.im, diameter=0.47m, inclination=2°, rotational speed=1 rpm.
The average temperature inside the kiln was controlled at 385°C. The feed rate was varied around 30 kg/h which resulted in a residence time of close to 1 hour.
1500 kg of catalyst was heat treated in this manner.
A sample of catalyst particles that were heat treated according to the manner described above was subjected to a Jet Impingement test. In this test a jet of air is used to impinge fresh catalyst particles against a plate. The smaller than 22 micron fraction of jet impinged sample is normally taken as a measure of the catalyst particle mechanical strength. Table 1 shows the results that were achieved from this test. Standard pilot plant prepared catalyst particles, and standard commercially prepared catalyst particles were used as reference materials.
Table 2: Behaviour after repeated iet impingement increase in % fines <
22frrn.
Uncatcined CalCirted at 300'C
Before Jei Impin 0 0 ernent After Jet Impingement11.6 2.8 After Jet 1m ingement29.4 18'.5 After Jet Imaingement22.4 t 9.5 3: , Table 2 also reflects the results obtained from a repeated jet impingement test conducted on a sample that was heat treated at 300°C. Repeated jet impingement results indicated that the heat treated catalyst particles are stronger even after the initial break-up. It can be concluded that heat treatment induces strength to the whole particle, and not only to the outer shell of the particle.
This example illustrates that heat treatment of standard self-supported precipitated iron based Low Temperature Fischer Tropsch slurry bed catalyst _g_ ' ~ CA 02326440 2004-10-27 particles does not alter the iron phase composition nor the crystallinity of the said catalyst particles; but rather promotes the enhancement of the catalyst particles' mechanical strength.
The phase composition and relative crystallite size of both the untreated standard catalyst particles and the heat treated samples were determined by Mossbauer spectroscopy at 4.2 K. The parameters are presented in Table 3.
Table 3 : ~lossbauer spectroscopic parameters Uncalcined Caldned sample sample Hyperfine field (H) 517.6 515.3 (1') 496.9 495.3 473.8 472.6 444.4 442.5 Isomer shiFt (ba 0.757 0.761 (mm.s~') 0.744 0.74?
0.717 O.T11-0.678 0:669 Quadropole spucc~ o.olo o.oog (e~ (~.sv) o.ola o.013 0.024 0.026 0.021 0.024 Both samples can be described as highly dispersed Fe(III)oxide. The Fe-phase has been identified as a-Fe203. The particles display superparamagnetic behavior and from the quadropole splitting parameter the size of the primary particles was estimated as between 2 and 4 nm.
At 77K the heat treated sample shows a slight increase in the D value, indicating a corresponding decrease in the primary particle size. Based on these results it would seem as if the heat treatment causes a restructuring or reordering of the ions making up the primary particle, thus leading to a state of lower energy i.e.
a stronger particle.
This example illustrates that heat treatment of the catalyst particles results in a major improvement of the solid separation system pertormance of said catalyst particles as experienced in a semi-works pilot plant reactor.
The liquid product recovery rate as a function of cycle number for a synthesis run with untreated catalyst particles is depicted in Figure 1. The separation rate levels obtained from a synthesis run operating with these standard catalyst particles only reached, a maximum of 350 relative units per hour.
Data for a similar synthesis run with heat treated catalyst is presented in Figure 2. The average liquid product recovery rate is clearly above 1000 relative units per hour.
This specific example illustrates that calcining or heat treating standard self supported precipitated iron-based Low Temperature Fischer-Tropsch catalyst particles for slurry bed application results in a significant reduction of the amount of fines that the catalyst particles generate under normal Fischer-Tropsch synthesis conditions.
Particle size distributions of representative an line catalyst particle samples were obtained for periods when untreated and heat treated catalyst particles were run respectively as outlined in example 3 above. A comparison of the catalyst fines content is presented in Table 4. The heat treated catalyst clearly shows a dramatic decrease in the amount of fines present in the reactor.
Table 4': On line quantificatt~ of tataiy~ fines Volume(% <) Particle diame~er Uncalcined Caldned catalyst (um) catalyst 22 10.1 0.
11 5.6 0.16 1.9 0.02 _ 1 p-_ Scanning electron micrographs of the above mentioned untreated and heat treated on-tine catalyst particle samples are presented in Figures 4 and 5 respectively, The absence of fine catalyst particles in the heat treated sample is once again obvious for the heat treated version.
This example shows that there is a marked. increase in activity of standard self-supported precipitated iron-based Fischer-Tropsch catalyst particles upon heat treatment. This is elegantly illustrated in Figure 3. The catalyst activity shows a continuous increase after the change to heat treated catalyst particles which is indicated by a vertical bar in Figure 3.
This example illustrates that removal of residual moisture from freshly prepared catalyst particles does not lead to mechanically stronger catalyst particles.
A sample of untreated standard catalyst particles was treated in a vacuum oven at 100°C until the moisture content was half the original value. Both.
the untreated and the vacuum.dried samples were subsequently subjected to a Jet Impingement (JI) test in order to measure their mechanical strength. The results are compared with a heat treated example in Table 5.
Table 5: ; MEChanicat str~gtn or dries samples Sample - . 95 Moisture 96 fires <2Z~m after 31 Stat~datd ? 7 9.7 l7cied 3.0 7.p Caleined 1.3 1.5
The invention will now be illustrated by means of the following non-limiting examples:
EXAMPLE i This example illustrates that the heat treatment of self-supported precipitated iron-based Low Temperature Fischer Tropsch catalyst particles for slurry bed application results in an increase in the mechanical strength of the said catalyst.
For a laboratory microscale operation, 250 grams of pilot plant and commercially prepared catalyst was placed in a porcelain dish in a muffle furnace. The furnace was subsequently heated to the desired heat treatment temperature at a heating rate of 1°C/min. The heat treatment or calcination temperature (as indicated in Table 1 below) was maintained for 4 hours after which the furnace was allowed to cool down to below 100°C.
Table 1: Catalyst physical properties as a function of ealcination temperatlrre Sample Calc.tempArea Pare % fines "C ~Ig vol <~~um ~g after JI
Pilot Planttmralc 288 0.03 1 l.6 l care yst 300 286 0.64 2.8 400 363 0.63 3.7 SUO 243 0.60 2.1 Comma~cial uncalc X93 O.b2 11.4 catalyst 300 ~T 0.61 t.1 400 24? 0.67 1.6 500 '?5 0.60 1.9 Pilot Plant Rotary Kittt Commercial turalc 289 0.60 l 12'.2 cata yst 385 241 0.54 s,g _ '7 _ ~
. ' ~ CA 02326440 2004-10-27 For, larger. scale operation the catalyst was fed from a hopper at room temperature to a portable pilot plant scale rotary kiln. This kiln had a refractory lining and was electrically heated. The dimensions of this equipment were as follows: length=2.im, diameter=0.47m, inclination=2°, rotational speed=1 rpm.
The average temperature inside the kiln was controlled at 385°C. The feed rate was varied around 30 kg/h which resulted in a residence time of close to 1 hour.
1500 kg of catalyst was heat treated in this manner.
A sample of catalyst particles that were heat treated according to the manner described above was subjected to a Jet Impingement test. In this test a jet of air is used to impinge fresh catalyst particles against a plate. The smaller than 22 micron fraction of jet impinged sample is normally taken as a measure of the catalyst particle mechanical strength. Table 1 shows the results that were achieved from this test. Standard pilot plant prepared catalyst particles, and standard commercially prepared catalyst particles were used as reference materials.
Table 2: Behaviour after repeated iet impingement increase in % fines <
22frrn.
Uncatcined CalCirted at 300'C
Before Jei Impin 0 0 ernent After Jet Impingement11.6 2.8 After Jet 1m ingement29.4 18'.5 After Jet Imaingement22.4 t 9.5 3: , Table 2 also reflects the results obtained from a repeated jet impingement test conducted on a sample that was heat treated at 300°C. Repeated jet impingement results indicated that the heat treated catalyst particles are stronger even after the initial break-up. It can be concluded that heat treatment induces strength to the whole particle, and not only to the outer shell of the particle.
This example illustrates that heat treatment of standard self-supported precipitated iron based Low Temperature Fischer Tropsch slurry bed catalyst _g_ ' ~ CA 02326440 2004-10-27 particles does not alter the iron phase composition nor the crystallinity of the said catalyst particles; but rather promotes the enhancement of the catalyst particles' mechanical strength.
The phase composition and relative crystallite size of both the untreated standard catalyst particles and the heat treated samples were determined by Mossbauer spectroscopy at 4.2 K. The parameters are presented in Table 3.
Table 3 : ~lossbauer spectroscopic parameters Uncalcined Caldned sample sample Hyperfine field (H) 517.6 515.3 (1') 496.9 495.3 473.8 472.6 444.4 442.5 Isomer shiFt (ba 0.757 0.761 (mm.s~') 0.744 0.74?
0.717 O.T11-0.678 0:669 Quadropole spucc~ o.olo o.oog (e~ (~.sv) o.ola o.013 0.024 0.026 0.021 0.024 Both samples can be described as highly dispersed Fe(III)oxide. The Fe-phase has been identified as a-Fe203. The particles display superparamagnetic behavior and from the quadropole splitting parameter the size of the primary particles was estimated as between 2 and 4 nm.
At 77K the heat treated sample shows a slight increase in the D value, indicating a corresponding decrease in the primary particle size. Based on these results it would seem as if the heat treatment causes a restructuring or reordering of the ions making up the primary particle, thus leading to a state of lower energy i.e.
a stronger particle.
This example illustrates that heat treatment of the catalyst particles results in a major improvement of the solid separation system pertormance of said catalyst particles as experienced in a semi-works pilot plant reactor.
The liquid product recovery rate as a function of cycle number for a synthesis run with untreated catalyst particles is depicted in Figure 1. The separation rate levels obtained from a synthesis run operating with these standard catalyst particles only reached, a maximum of 350 relative units per hour.
Data for a similar synthesis run with heat treated catalyst is presented in Figure 2. The average liquid product recovery rate is clearly above 1000 relative units per hour.
This specific example illustrates that calcining or heat treating standard self supported precipitated iron-based Low Temperature Fischer-Tropsch catalyst particles for slurry bed application results in a significant reduction of the amount of fines that the catalyst particles generate under normal Fischer-Tropsch synthesis conditions.
Particle size distributions of representative an line catalyst particle samples were obtained for periods when untreated and heat treated catalyst particles were run respectively as outlined in example 3 above. A comparison of the catalyst fines content is presented in Table 4. The heat treated catalyst clearly shows a dramatic decrease in the amount of fines present in the reactor.
Table 4': On line quantificatt~ of tataiy~ fines Volume(% <) Particle diame~er Uncalcined Caldned catalyst (um) catalyst 22 10.1 0.
11 5.6 0.16 1.9 0.02 _ 1 p-_ Scanning electron micrographs of the above mentioned untreated and heat treated on-tine catalyst particle samples are presented in Figures 4 and 5 respectively, The absence of fine catalyst particles in the heat treated sample is once again obvious for the heat treated version.
This example shows that there is a marked. increase in activity of standard self-supported precipitated iron-based Fischer-Tropsch catalyst particles upon heat treatment. This is elegantly illustrated in Figure 3. The catalyst activity shows a continuous increase after the change to heat treated catalyst particles which is indicated by a vertical bar in Figure 3.
This example illustrates that removal of residual moisture from freshly prepared catalyst particles does not lead to mechanically stronger catalyst particles.
A sample of untreated standard catalyst particles was treated in a vacuum oven at 100°C until the moisture content was half the original value. Both.
the untreated and the vacuum.dried samples were subsequently subjected to a Jet Impingement (JI) test in order to measure their mechanical strength. The results are compared with a heat treated example in Table 5.
Table 5: ; MEChanicat str~gtn or dries samples Sample - . 95 Moisture 96 fires <2Z~m after 31 Stat~datd ? 7 9.7 l7cied 3.0 7.p Caleined 1.3 1.5
Claims (14)
1. A method of producing catalyst particles suitable for use in a Fischer-Tropsch slurry-bed process, said method comprising the step of:
heat treating precipitated a-Fe2O3-based particles at a temperature of from 320° C. to 500° C., whereby self-supported precipitated a-Fe2O3-based catalyst particles are obtained.
heat treating precipitated a-Fe2O3-based particles at a temperature of from 320° C. to 500° C., whereby self-supported precipitated a-Fe2O3-based catalyst particles are obtained.
2. A method as claimed in claim 1, wherein the heat treating is carried out at a temperature of from 360° C. to 500° C.
3. A method as claimed in claim 1, wherein the heat treating is carried out at a temperature of from 360° C. to 390° C.
4. A method as claimed in claim 1, wherein the heat treating is carried out at a temperature of 380° C.
5. A method as claimed in claim 1, wherein said catalyst particles have an average observed Fischer-Tropsch activity in excess of 1.2 under low temperature Fischer-Tropsch operating conditions.
6. A method as claimed in claim 1, wherein the heat treating is carried out at a temperature of from 380° C. to 500° C.
7. A method as claimed in claim 1, wherein the heat treating is carried out at a temperature of from 380° C. to 390° C.
8. A method as claimed in claim 1, wherein the heat treating is carried out at a temperature of from 390° C. to 500° C.
9. A method as claimed in claim 1, wherein said heat treating is conducted for at least 0.1 hours.
10. A method as claimed in claim 1, wherein said heat treating is conducted for between 0.5 and 4 hours.
11. A method as claimed in claim 1, wherein said catalyst particles exhibit superior synthesis performance under low temperature Fischer-Tropsch operating conditions and being breakage resistant and thus inhibiting the formation of catalyst fines.
12. A method as claimed in claim 1, wherein said particles exhibit superior activity under low temperature Fischer-Tropsch operating conditions.
13. A method as claimed in claim 1, wherein said particles exhibit superior breakage resistance under low temperature Fischer-Tropsch operating conditions.
14. A method as claimed in claim 1, wherein said particles exhibit reduced catalyst fines formation under low temperature Fischer-Tropsch operating conditions.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA98/2737 | 1998-04-01 | ||
| ZA9802737A ZA982737B (en) | 1998-04-01 | 1998-04-01 | Heat treated fischer-tropsch catalyst particles. |
| PCT/GB1998/003004 WO1999049965A1 (en) | 1998-04-01 | 1998-10-07 | Heat treated fischer-tropsch catalyst particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2326440A1 CA2326440A1 (en) | 1999-10-07 |
| CA2326440C true CA2326440C (en) | 2006-01-10 |
Family
ID=25586926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002326440A Expired - Fee Related CA2326440C (en) | 1998-04-01 | 1998-10-07 | Heat treated fischer-tropsch catalyst particles |
Country Status (18)
| Country | Link |
|---|---|
| US (3) | US6716790B1 (en) |
| EP (2) | EP1068008A1 (en) |
| JP (1) | JP3839666B2 (en) |
| KR (1) | KR100396325B1 (en) |
| CN (2) | CN1108188C (en) |
| AP (1) | AP2000001954A0 (en) |
| AR (1) | AR018034A1 (en) |
| AU (1) | AU743613B2 (en) |
| BR (1) | BR9815753A (en) |
| CA (1) | CA2326440C (en) |
| EA (1) | EA003416B1 (en) |
| ID (1) | ID22355A (en) |
| MY (1) | MY118560A (en) |
| NO (2) | NO323981B1 (en) |
| NZ (1) | NZ507418A (en) |
| PL (1) | PL343169A1 (en) |
| WO (1) | WO1999049965A1 (en) |
| ZA (1) | ZA982737B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2002132843A (en) * | 2000-06-20 | 2004-06-27 | САСОЛ ТЕКНОЛОДЖИ (ПиТиУай) ЛТД. (ZA) | HYDROCARBON SYNTHESIS CATALYST AND METHOD FOR ITS PRODUCTION |
| US7259286B2 (en) * | 2000-08-28 | 2007-08-21 | Research Triangle Institute | Attrition resistant bulk iron catalysts and processes for preparing and using same |
| US20070217338A1 (en) * | 2006-03-14 | 2007-09-20 | Sbc Knowledge Ventures L.P. | Method and apparatus for out-of-band XDSL troubleshooting and testing |
| US9018128B2 (en) * | 2007-09-14 | 2015-04-28 | Res Usa Llc | Promoted, attrition resistant, silica supported precipitated iron catalyst |
| KR20110057218A (en) * | 2008-09-10 | 2011-05-31 | 바스프 에스이 | Integrated method for producing carbonyl iron powder and hydrocarbons |
| KR101087165B1 (en) | 2009-07-20 | 2011-11-25 | (주)시너지 | The method for preparing of Fe based catalyst used in Fischer-Tropsch systhesis reaction and that of liquid hydrocarbon using Fe based catalyst |
| JP2013146652A (en) * | 2012-01-17 | 2013-08-01 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | Fischer-tropsch synthesis catalyst and method for producing the same |
| EP2956238A4 (en) * | 2013-02-13 | 2016-10-26 | Res Usa Llc | Catalyst for low temperature slurry bed fischer-tropsch synthesis |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3131255C2 (en) * | 1981-08-07 | 1986-02-13 | VEG-Gasinstituut N.V., Apeldoorn | Process for the preparation of a ferric oxide catalyst or absorbent |
| US4552855A (en) * | 1982-12-30 | 1985-11-12 | Ozin Geoffrey A | Metal zeolite catalyst preparation |
| DE3368020D1 (en) | 1982-12-30 | 1987-01-15 | Ozin Geoffrey A | Metal zeolite catalyst preparation |
| US4618597A (en) * | 1983-12-20 | 1986-10-21 | Exxon Research And Engineering Company | High surface area dual promoted iron/managanese spinel compositions |
| US4621102A (en) * | 1983-12-20 | 1986-11-04 | Exxon Research And Engineering Co. | Fischer-Tropsch hydrocarbon synthesis with high surface area Cu and K promoted reduced-carbided iron/manganese spinels |
| US5118715A (en) * | 1983-12-20 | 1992-06-02 | Exxon Research And Engineering Company | Selective fixed-bed fischer-tropsch synthesis with high surface area Cu and K promoted, iron/manganese spinels |
| US5621155A (en) * | 1986-05-08 | 1997-04-15 | Rentech, Inc. | Process for the production of hydrocarbons |
| US5645613A (en) * | 1992-04-13 | 1997-07-08 | Rentech, Inc. | Process for the production of hydrocarbons |
| US5324335A (en) * | 1986-05-08 | 1994-06-28 | Rentech, Inc. | Process for the production of hydrocarbons |
| US5504118A (en) * | 1986-05-08 | 1996-04-02 | Rentech, Inc. | Process for the production of hydrocarbons |
| US5545674A (en) * | 1987-05-07 | 1996-08-13 | Exxon Research And Engineering Company | Surface supported cobalt catalysts, process utilizing these catalysts for the preparation of hydrocarbons from synthesis gas and process for the preparation of said catalysts |
| US4874382A (en) * | 1987-10-15 | 1989-10-17 | Servetus Partnership | Safety syringe |
| US4955870A (en) * | 1988-08-23 | 1990-09-11 | Ridderheim Kristen A | Hypodermic syringe with retractable needle |
| IT1225440B (en) * | 1988-12-07 | 1990-11-13 | Nacci Gaetano | PISTON FOR SYRINGES THAT AUTOMATICALLY MAKES THE HYPODERMIC NEEDLE, MODIFIED PURPOSE, AFTER USE |
| US5129884A (en) * | 1990-01-16 | 1992-07-14 | Dysarz Edward D | Trap in barrel one handed retracted intervenous catheter device |
| US5389076A (en) * | 1994-04-05 | 1995-02-14 | Shaw; Thomas J. | Single use medical device with retraction mechanism |
-
1998
- 1998-04-01 ZA ZA9802737A patent/ZA982737B/en unknown
- 1998-10-07 KR KR10-2000-7010761A patent/KR100396325B1/en not_active IP Right Cessation
- 1998-10-07 CA CA002326440A patent/CA2326440C/en not_active Expired - Fee Related
- 1998-10-07 US US09/601,076 patent/US6716790B1/en not_active Expired - Fee Related
- 1998-10-07 AP APAP/P/2000/001954A patent/AP2000001954A0/en unknown
- 1998-10-07 CN CN98813709A patent/CN1108188C/en not_active Expired - Lifetime
- 1998-10-07 EA EA200001011A patent/EA003416B1/en not_active IP Right Cessation
- 1998-10-07 PL PL98343169A patent/PL343169A1/en unknown
- 1998-10-07 EP EP98946574A patent/EP1068008A1/en not_active Withdrawn
- 1998-10-07 EP EP04027800A patent/EP1506811A3/en not_active Withdrawn
- 1998-10-07 AU AU93577/98A patent/AU743613B2/en not_active Expired
- 1998-10-07 CN CNB031206425A patent/CN1235683C/en not_active Expired - Lifetime
- 1998-10-07 JP JP2000540924A patent/JP3839666B2/en not_active Expired - Fee Related
- 1998-10-07 WO PCT/GB1998/003004 patent/WO1999049965A1/en not_active Application Discontinuation
- 1998-10-07 BR BR9815753-1A patent/BR9815753A/en not_active IP Right Cessation
- 1998-10-07 NZ NZ507418A patent/NZ507418A/en unknown
- 1998-10-08 MY MYPI98004603A patent/MY118560A/en unknown
- 1998-12-01 ID IDP981563A patent/ID22355A/en unknown
- 1998-12-22 AR ARP980106615A patent/AR018034A1/en not_active Application Discontinuation
-
2000
- 2000-09-20 NO NO20004710A patent/NO323981B1/en not_active IP Right Cessation
-
2003
- 2003-10-02 US US10/677,588 patent/US6951893B2/en not_active Expired - Lifetime
- 2003-10-02 US US10/677,878 patent/US7547657B2/en not_active Expired - Fee Related
-
2005
- 2005-10-10 NO NO20054635A patent/NO326275B1/en not_active IP Right Cessation
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1444040B1 (en) | Process for activating cobalt catalysts | |
| AU666265B2 (en) | Structurally modified alumina supports, and heat transfer solids for high temperature fluidized bed reactions | |
| AU2008247041B2 (en) | Catalysts | |
| US9327273B2 (en) | Catalysts | |
| EP3496856B1 (en) | A cobalt-containing catalyst composition | |
| AU2005324772B2 (en) | Producing supported cobalt catalysts for the Fisher-Tropsch synthesis | |
| NO326275B1 (en) | Process for synthesizing a Fischer-Tropsch product | |
| EP2704827B1 (en) | A process for preparing a cobalt-containing hydrocarbon synthesis catalyst precursor | |
| CN107429167A (en) | Hydrocarbon synthesis catalyst, Its Preparation Method And Use | |
| CA2122159C (en) | High surface purity heat transfer solids for high temperature fluidized bed reactions | |
| US4975267A (en) | Stable K2 FE22 O34 potassium ferrite phase and method of manufacture | |
| MXPA00009681A (en) | Heat treated fischer-tropsch catalyst particles | |
| Brumberger et al. | In situ small-angle X-ray scattering observations of Pt/NaY catalysts during processing: sintering of Pt | |
| CZ20003444A3 (en) | Heat treatment process of Fischer-Tropsch catalyst | |
| CA1062642A (en) | Process for the conversion of hydrocarbons | |
| US4963343A (en) | Stable k2 fe22 o34 potassium ferrite phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |