WO1999049965A1 - Heat treated fischer-tropsch catalyst particles - Google Patents

Heat treated fischer-tropsch catalyst particles Download PDF

Info

Publication number
WO1999049965A1
WO1999049965A1 PCT/GB1998/003004 GB9803004W WO9949965A1 WO 1999049965 A1 WO1999049965 A1 WO 1999049965A1 GB 9803004 W GB9803004 W GB 9803004W WO 9949965 A1 WO9949965 A1 WO 9949965A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst particles
fischer
tropsch
heat treatment
particles
Prior art date
Application number
PCT/GB1998/003004
Other languages
French (fr)
Inventor
Rafael Luis Espinoza
Philip Gibson
Jan Hendrik Scholtz
Original Assignee
Sasol Technology (Proprietary) Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AU93577/98A priority Critical patent/AU743613B2/en
Priority to JP2000540924A priority patent/JP3839666B2/en
Priority to EP98946574A priority patent/EP1068008A1/en
Priority to US09/601,076 priority patent/US6716790B1/en
Application filed by Sasol Technology (Proprietary) Limited filed Critical Sasol Technology (Proprietary) Limited
Priority to APAP/P/2000/001954A priority patent/AP2000001954A0/en
Priority to EA200001011A priority patent/EA003416B1/en
Priority to BR9815753-1A priority patent/BR9815753A/en
Priority to CA002326440A priority patent/CA2326440C/en
Priority to PL98343169A priority patent/PL343169A1/en
Priority to NZ507418A priority patent/NZ507418A/en
Publication of WO1999049965A1 publication Critical patent/WO1999049965A1/en
Priority to NO20004710A priority patent/NO323981B1/en
Priority to US10/677,878 priority patent/US7547657B2/en
Priority to US10/677,588 priority patent/US6951893B2/en
Priority to NO20054635A priority patent/NO326275B1/en

Links

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

Definitions

  • This invention relates to catalysts. More particularly the invention relates to a
  • Fischer-Tropsch catalyst particles to a method of making self-supported
  • the annealing step i.e. the heating and gradual controlled cooling, converts the
  • the catalyst may be activated and used.
  • the annealing does not lead to a breakage resistant
  • South African Patent No. 90/7530 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.
  • catalyst particle of this patent does not have superior synthesis performance and is expected to hydrothermally sinter at about 300°C.
  • 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.
  • 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 performance 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.
  • the invention provides a method of producing self-supported
  • the said particles being breakage resistant and thus inhibiting the
  • the heat treatment may be calcination of the said particles at a temperature of at
  • the heat treatment of the said catalyst particles may be carried out at a
  • 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
  • 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.
  • 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 including the use of the catalyst particles as described above.
  • synthesis of syncrudes and/or chemicals for example, waxes
  • the process comprising the step of contacting a suitable synthesis gas, at suitable
  • 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.
  • the catalyst was fed from a hopper at room
  • 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
  • Standard pilot plant prepared catalyst particles, and standard commercially prepared catalyst particles were used as reference materials.
  • 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.
  • the size of the primary particles was estimated as between 2 and 4 nm.
  • This example illustrates that removal of residual moisture from freshly prepared catalyst particles does not lead to mechanically stronger catalyst particles.

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. South African Patent No. 90/7530 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 performance 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.
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. 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.
DETAILED DESCRIPTION OF THE INVENTION
The invention will now be illustrated by means of the following non-limiting examples: EXAMPLE 1
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.
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=2.1 m, diameter=0.47m, inciination=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 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.
EXAMPLE 2
This example illustrates that heat treatment of standard self-supported
precipitated iron based Low Temperature Fischer Tropsch slurry bed catalyst
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
Mόssbauer spectroscopy at 4.2 K. The parameters are presented in Table 3.
Both samples can be described as highly dispersed Fe(lll)oxide. The Fe-phase
has been identified as α-Fe2O3. The particles display superparamagnetic
behaviour 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 Δ 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.
EXAMPLE 3 This example illustrates that heat treatment of the catalyst particles results in a
major improvement of the solid separation system performance 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 Graph 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 Graph
2. The average liquid product recovery rate is clearly above 1000 relative units
per hour.
EXAMPLE 4
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.
10 Particle size distributions of representative on 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.
Scanning electron micrographs of the above mentioned untreated and heat treated on-line catalyst particle samples are presented in Micrographs 1 and 2 respectively. The absence of fine catalyst particles in the heat treated sample is once again obvious for the heat treated version.
EXAMPLE 5
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 Graph 3. The catalyst activity shows a continuous increase after the change to heat treated catalyst particles which is indicated by a vertical bar in Graph 3.
n EXAMPLE 6
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 (Jl) test in order to measure their mechanical strength. The results are compared with a heat treated example in Table 5.
12

Claims

1. 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, in-use, inhibiting the formation of catalyst
fines, the method including the heat treatment of the said particles at a
temperature of at least 300┬░C.
2. A method as claimed in claim 1 wherein the heat treatment of the said
catalyst particles is carried out at a temperature of between 320 ┬░C and 500 ┬░C.
3. A method as claimed in claim 2, wherein the heat treatment of the said
catalyst particles is carried out at a temperature of between 360 ┬░C and 390 ┬░C.
4. A method as claimed in claim 3, wherein the heat treatment of the said
catalyst particles is carried out at a temperature of 380 ┬░C.
5. A method of producing self-supported precipitated iron-based Fischer- Tropsch catalyst particles for use in a Fischer-Tropsch slurry-bed process, the said catalyst particles having superior synthesis performance or activity under
low temperature Fischer-Tropsch operating conditions, the method including the
heat treatment of the said catalyst particles at a temperature of at least 300 ┬░C.
13
6. A method as claimed in claim 5, wherein the heat treatment temperature
is between 320 ┬░C and 500 ┬░C.
7. A method as claimed in claim 6, wherein the heat treatment temperature
is between 360 ┬░C and 390 ┬░C.
8. A method as claimed in claim 6, wherein the heat treatment temperature
is 380 ┬░C.
9. A method as claimed in any one of the preceding claims, in which the
said catalyst particles are maintained at the heat treatment temperature for at
least 0.1 hours.
10. A method as claimed in claim 9, in which the said catalyst particles are
maintained at the heat treatment temperature for between 0.5 and 4 hours.
11. A method of producing self-supported precipitated iron-based catalyst
particles for use in a Fischer-Tropsch slurry-bed process, the said catalyst particles having superior synthesis performance or activity under low
temperature Fischer-Tropsch operating conditions and being breakage resistant
and thus, in-use, inhibiting the formation of catalyst fines, the method including
the heat treatment of the said particles at a temperature of at least 300┬░C.
14
12. A method as claimed in claim 11 , wherein the heat treatment temperature
is between 320 ┬░C and 500 ┬░C.
13. A method as claimed in claim 12, wherein the heat treatment temperature
is between 360 ┬░C and 390 ┬░C.
14. A method as claimed in claim 13, wherein the heat treatment temperature
is 380 ┬░C.
15. Self-supported precipitated iron-based Fischer-Tropsch catalyst particles
for use in a Fischer-Tropsch slurry-bed process, which particles are produced according to a method as claimed in any one of claims 1 to 14.
16. A method of maintaining the performance of a solid separation system of
a Fischer-Tropsch process slurry-bed reactor where reduction in performance is
caused by an increase in catalyst particle fines in the slurry-bed reactor, the
method including the use of the said catalyst particles as claimed in claim 15.
15
17. A process for synthesis of syncrudes and/or chemicals, 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 claimed
in claim 15.
18. 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, in-use, inhibiting the formation of catalyst fines, as claimed in claim 1, substantially as herein described and illustrated.
19. A method of producing self-supported precipitated iron-based Fischer- Tropsch catalyst particles for use in a Fischer-Tropsch slurry-bed process, the said catalyst particles having a superior synthesis performance or activity under low temperature Fischer-Tropsch operating conditions, as claimed in claim 5, substantially as herein described and illustrated.
20. Self-supported precipitated iron-based Fischer-Tropsch catalyst particles for use in a Fischer-Tropsch slurry-bed process as claimed in claim 15, substantially as herein described and illustrated.
16
21. A method for maintaining the performance of a solid separation system of
a Fischer-Tropsch process slurry-bed reactor as claimed in claim 16,
substantially as herein described and illustrated.
22. A process for synthesis of syncrudes and/or chemicals, substantially as
herein described and illustrated.
23. A new method of producing self-supported precipitated iron-based
catalyst particles for use in a Fischer-Tropsch slurry-bed, new self-supported
iron-based catalyst particles, a new process for synthesis of syncrudes and/or
chemicals, or a new method of maintaining the performance of a solid separation
system of a Fischer-Tropsch process slurry bed reactor, substantially as herein described.
17
PCT/GB1998/003004 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles WO1999049965A1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
EA200001011A EA003416B1 (en) 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles
EP98946574A EP1068008A1 (en) 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles
US09/601,076 US6716790B1 (en) 1998-04-01 1998-10-07 Heat treated Fischer-Tropsch catalyst particles
CA002326440A CA2326440C (en) 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles
APAP/P/2000/001954A AP2000001954A0 (en) 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles.
JP2000540924A JP3839666B2 (en) 1998-04-01 1998-10-07 Heat treated Fischer-Tropsch catalyst particles
BR9815753-1A BR9815753A (en) 1998-04-01 1998-10-07 Method for producing heat treated catalytic particles
AU93577/98A AU743613B2 (en) 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles
PL98343169A PL343169A1 (en) 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles
NZ507418A NZ507418A (en) 1998-04-01 1998-10-07 Heat treated Fischer-Tropsch catalyst particles
NO20004710A NO323981B1 (en) 1998-04-01 2000-09-20 Process for preparing self-precipitated, precipitated, iron-based catalyst particles in a Fischer-Tropsch slurry bed process.
US10/677,878 US7547657B2 (en) 1998-04-01 2003-10-02 Heat treated Fischer-Tropsch catalyst particles
US10/677,588 US6951893B2 (en) 1998-04-01 2003-10-02 Heat treated Fischer-Tropsch catalyst particles
NO20054635A NO326275B1 (en) 1998-04-01 2005-10-10 Process for synthesizing a Fischer-Tropsch product

Applications Claiming Priority (2)

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.

Related Child Applications (4)

Application Number Title Priority Date Filing Date
US09601076 A-371-Of-International 1998-10-07
US09/601,076 A-371-Of-International US6716790B1 (en) 1998-04-01 1998-10-07 Heat treated Fischer-Tropsch catalyst particles
US10/677,588 Division US6951893B2 (en) 1998-04-01 2003-10-02 Heat treated Fischer-Tropsch catalyst particles
US10/677,878 Continuation US7547657B2 (en) 1998-04-01 2003-10-02 Heat treated Fischer-Tropsch catalyst particles

Publications (1)

Publication Number Publication Date
WO1999049965A1 true WO1999049965A1 (en) 1999-10-07

Family

ID=25586926

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/003004 WO1999049965A1 (en) 1998-04-01 1998-10-07 Heat treated fischer-tropsch catalyst particles

Country Status (18)

Country Link
US (3) US6716790B1 (en)
EP (2) EP1506811A3 (en)
JP (1) JP3839666B2 (en)
KR (1) KR100396325B1 (en)
CN (2) CN1235683C (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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001097968A2 (en) * 2000-06-20 2001-12-27 Sasol Technology (Pty) Ltd Hydrocarbon synthesis catalyst and process
US7259286B2 (en) * 2000-08-28 2007-08-21 Research Triangle Institute Attrition resistant bulk iron catalysts and processes for preparing and using same
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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2010028995A1 (en) * 2008-09-10 2010-03-18 Basf Se Integrated method for producing carbonyl iron powder and hydrocarbons
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
EA201890127A1 (en) * 2013-02-13 2018-09-28 Рес Сша, Ллс CATALYST FOR LOW-TEMPERATURE SYNTHESIS OF FISHER TRIPS WITH SUSPENSION LAYER

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (14)

* Cited by examiner, † Cited by third party
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
EP0115188B1 (en) 1982-12-30 1986-12-03 Geoffrey Alan Ozin Metal zeolite catalyst preparation
US4552855A (en) * 1982-12-30 1985-11-12 Ozin Geoffrey A Metal zeolite catalyst preparation
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
US4618597A (en) * 1983-12-20 1986-10-21 Exxon Research And Engineering Company High surface area dual promoted iron/managanese spinel compositions
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
US5645613A (en) * 1992-04-13 1997-07-08 Rentech, Inc. Process for the production of hydrocarbons
US5621155A (en) * 1986-05-08 1997-04-15 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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001097968A2 (en) * 2000-06-20 2001-12-27 Sasol Technology (Pty) Ltd Hydrocarbon synthesis catalyst and process
WO2001097968A3 (en) * 2000-06-20 2002-04-25 Sasol Tech Pty Ltd Hydrocarbon synthesis catalyst and process
US6844370B2 (en) 2000-06-20 2005-01-18 Sasol Technology (Pty) Ltd. Hydrocarbon synthesis catalyst and process
CN100384964C (en) * 2000-06-20 2008-04-30 Sasol技术股份有限公司 Hydrocarbon synthesis catalyst and process
US7259286B2 (en) * 2000-08-28 2007-08-21 Research Triangle Institute Attrition resistant bulk iron catalysts and processes for preparing and using same
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

Also Published As

Publication number Publication date
KR100396325B1 (en) 2003-09-03
ZA982737B (en) 1999-11-24
EP1068008A1 (en) 2001-01-17
MY118560A (en) 2004-12-31
NO20054635D0 (en) 2005-10-10
AP2000001954A0 (en) 2000-12-31
NO20004710L (en) 2000-11-16
CN1284898A (en) 2001-02-21
EA200001011A1 (en) 2001-02-26
NO20054635L (en) 2000-11-16
EA003416B1 (en) 2003-04-24
JP2002509789A (en) 2002-04-02
CN1108188C (en) 2003-05-14
CA2326440A1 (en) 1999-10-07
KR20010071127A (en) 2001-07-28
NO20004710D0 (en) 2000-09-20
CN1235683C (en) 2006-01-11
NO326275B1 (en) 2008-10-27
US7547657B2 (en) 2009-06-16
US20040072918A1 (en) 2004-04-15
US20040072917A1 (en) 2004-04-15
CA2326440C (en) 2006-01-10
AU743613B2 (en) 2002-01-31
BR9815753A (en) 2000-11-07
AR018034A1 (en) 2001-10-31
US6951893B2 (en) 2005-10-04
US6716790B1 (en) 2004-04-06
NZ507418A (en) 2002-07-26
JP3839666B2 (en) 2006-11-01
EP1506811A2 (en) 2005-02-16
NO323981B1 (en) 2007-07-30
AU9357798A (en) 1999-10-18
EP1506811A3 (en) 2008-12-31
PL343169A1 (en) 2001-07-30
ID22355A (en) 1999-10-07
CN1515359A (en) 2004-07-28

Similar Documents

Publication Publication Date Title
AU666265B2 (en) Structurally modified alumina supports, and heat transfer solids for high temperature fluidized bed reactions
JP4263597B2 (en) Production of waxes by Fischer-Tropsch synthesis
CA2898413C (en) Strengthened iron catalyst for slurry reactors
NO326275B1 (en) Process for synthesizing a Fischer-Tropsch product
US9327273B2 (en) Catalysts
WO2010059660A2 (en) Method for activating strengthened iron catalyst for slurry reactors
EP2155837A2 (en) Catalysts
EA020729B1 (en) Method of producing a catalyst precursor, method of producing a catalyst
Urruchurto et al. Spray-drying for the preparation of Al–Co–Cu pillared clays: A comparison with the conventional hot-drying method
MXPA00009681A (en) Heat treated fischer-tropsch catalyst particles
CA2122159C (en) High surface purity heat transfer solids for high temperature fluidized bed reactions
CN107429167A (en) Hydrocarbon synthesis catalyst, Its Preparation Method And Use
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
Ray et al. Dehydration-rehydration characteristics of gibbsitic bauxite under equilibrium condition
US4963343A (en) Stable k2 fe22 o34 potassium ferrite phase
JP2892033B2 (en) Method for producing catalyst for coal liquefaction by sulfuration of acicular goethite
AU2013242856B2 (en) Strengthened iron catalyst for slurry reactors

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 98813709.7

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)

Free format text: (EXCEPT GD)

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: PV2000-3444

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: 1020007010761

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2326440

Country of ref document: CA

Ref document number: 2326440

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/2000/009681

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 507418

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 93577/98

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1998946574

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 200001011

Country of ref document: EA

WWP Wipo information: published in national office

Ref document number: 1998946574

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 09601076

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: PV2000-3444

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1020007010761

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: CA

WWG Wipo information: grant in national office

Ref document number: 93577/98

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 1020007010761

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: PV2003-2347

Country of ref document: CZ

WWW Wipo information: withdrawn in national office

Ref document number: 1998946574

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: PV2000-3444

Country of ref document: CZ

WWR Wipo information: refused in national office

Ref document number: PV2003-2347

Country of ref document: CZ