WO2004047986A1 - Iron-based copper-containing catalyst - Google Patents

Iron-based copper-containing catalyst Download PDF

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Publication number
WO2004047986A1
WO2004047986A1 PCT/IB2003/005352 IB0305352W WO2004047986A1 WO 2004047986 A1 WO2004047986 A1 WO 2004047986A1 IB 0305352 W IB0305352 W IB 0305352W WO 2004047986 A1 WO2004047986 A1 WO 2004047986A1
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iron
catalyst
catalyst composition
copper
ole
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PCT/IB2003/005352
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French (fr)
Inventor
Andre Johan Van Zyl
Jacobus Lucas Visagie
Nilenindran Sundra Govender
David De Villiers
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Sasol Technology (Proprietary) Limited
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Priority to AU2003282271A priority Critical patent/AU2003282271A1/en
Publication of WO2004047986A1 publication Critical patent/WO2004047986A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01J23/72—Copper
    • 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying

Definitions

  • THIS invention relates to iron-based catalysts, in particular to iron-based catalysts and their use in the conversion of synthesis gas (CO and H 2 ) to alcohols and olefins.
  • WO 01/89689 discloses an iron-based Fischer-Tropsch catalyst composition wherein the main iron phase is the ferrihydrite.
  • the catalyst composition includes natural promoters which may be selected from manganese or chromium or a mixture thereof and chemical promoters selected from magnesium zinc, copper and alkaline or alkali earth metals.
  • the catalyst is best bound to refractory oxide support such as silica. According to the specification, the catalyst composition produces significant yield of higher paraffins, olefins and alcohols.
  • WO 03/043734 discloses an iron-based Fischer-Tropsch catalyst composition wherein the main iron phase is ferrihydrite, and the catalyst composition includes alumina, manganese and zinc as structural promoters. Although this catalyst composition has shown very good activity and selectivity for the production of alcohols and olefins, manganese and zinc are expensive and there is a need to find a catalyst composition with good selectivity for alcohols and olefins, which is also less expensive to produce.
  • an iron-based Fischer-Tropsch catalyst composition preferably wherein the main iron phase is ferrihydrite, wherein the catalyst composition includes more than 10% (by mass) copper, preferably 15% (by mass) or more copper, typically from 15% to 20% (by mass) copper.
  • iron-based is meant that Fe makes up at least 30% (by mass) of the composition.
  • the main iron phase is ferrihydrite means that at least 75% of the iron phase is ferrihydrite, as determined by X-ray diffraction using Co K alpha radiation.
  • the preferred catalyst compositions exhibit hyperfine interaction parameters similar to those of ferrihydrite, as determined by M ⁇ ssbauer absorption spectroscopy (MAS).
  • the composition includes from 20g to 60g copper per 100g iron.
  • the composition also includes K 2 O which may be present in an amount of from 0.1% to 2% (by mass) of the composition.
  • compositions are typically supported on silica or alumina.
  • the catalyst composition has a BET surface area of from 100 to 230 m 2 /g, and a total pore volume of from 0.2 to 0.5 cm 3 /g.
  • Figure 1 is a graph showing the activities of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc
  • Figure 2 is a graph which shows the productivity towards alcohols of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc;
  • Figure 3 is a graph which shows the productivity towards olefins of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc;
  • Figure 4 is a graph which shows the alcohol selectivities of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc;
  • this invention relates to a catalyst composition for selectively converting synthesis gas under Fischer-Tropsch conditions to olefins and alcohols in significant yields.
  • Catalyst compositions according to preferred embodiments of the invention are iron-based, have a high amount of copper (more than 10%, typically from 15% to 20% by mass) and the main iron phase is ferrihydrite.
  • the compositions also include K 2 O and are supported on silica or alumina.
  • the abovementioned catalyst compositions show a high activity and selectivity for alcohols and olefins. In fact they show similar activity and selectivity to a preferred composition catalyst as described in International patent publication no. WO 03/043734 which is an alumina bound catalyst and additionally contains manganese and zinc.
  • a catalyst composition of the invention performs as well as the catalysts described in International patent publication no. WO 03/043734, but need not include manganese and zinc.
  • the exclusion of manganese and zinc means that the catalyst composition is less expensive to produce, and it is not necessary to recover these metals from the spent catalyst composition.
  • the addition of the second solution to the first solution causes the formation of a precipitate, which is the catalyst composition of the invention.
  • the precipitate is then filtered, and washed and the filter cake then reslurried and spray-dried at an inlet temperature of 260°C and an outlet temperature of 120°C. Thereafter, on-spec catalyst is calcined at 450°C for 16 hours and sieved to a particle size of 38-150 ⁇ m.
  • a continuous process for the preparation of a silica supported catalyst composition is carried out in much the same manner as the process for producing an alumina support composition.
  • aluminium nitrate is not added to the first acidic solution.
  • the precipitate from the process is then filtered and reslurried and bound by adding silica (SiO 2 ) and then spray drying the resulting slurry at an inlet temperature of 260°C and an outlet temperature of 120°C. Thereafter, the on-spec catalyst is calcined at 450°C for 16 hours and sieved to a particle size of 38-150 ⁇ m.
  • Table 1 below shows typical catalyst compositions of high-copper catalysts of the invention after calcination at 450°C.
  • the table shows the amount of Fe, Cu, Zn, K 2 O, SiO 2 or AI 2 O 3 in the catalyst composition.
  • the rest of the composition is made up primarily by oxygen atoms.
  • the above catalyst compositions according to the invention so-formed are iron-based, and main iron phase is ferrihydrite, except for OLE 143 where only 60% of the iron phase is ferrihydrite.
  • the catalysts mentioned in Table 1 were tested using a standard procedure. Each catalyst (20g) was loaded in 350g molten wax before in- situ reduction at 240°C and 20 bar with a hydrogen space velocity of 6000 ml(n)/gr cat/hr for 16hrs. Lowering the temperature to 200°C, introducing APG (Arge Pure Gas, approximately 75% syngas) for 1 hour and thereafter increasing the temperature to 240°C and the pressure to 45 bar attained switchover to synthesis. First period TCD (Thermal Conductivity Detector used to analyse for CO 2 , CO, H 2 , CH 4 , Ar, N 2 ) analyses were used to adjust synthesis gas flow rates in order to operate at 35 to 45% CO+CO conversions.
  • TCD Thermal Conductivity Detector used to analyse for CO 2 , CO, H 2 , CH 4 , Ar, N 2
  • the catalyst OLE151 is a comparative example of a preferred catalyst as defined in International patent publication no. WO 03/043734.
  • the catalyst had the following elemental composition: Fe 42.9% by mass, Cu 3.56% by mass, Mn 14% by mass, Zn 5.41% by mass, K 2 O 0.27% by mass, and AI 2 O 3 3.57% by mass.
  • Two additional experiments were carried out.
  • the activity and selectivity of the OLE 155 catalyst was improved by impregnation with KNO 3 , followed by calcination to obtain K 2 O.
  • hydrogen is diluted with 10% Ar.
  • hydrogen was diluted with 20% Ar.
  • a further experiment was carried out on OLE 154 and activity and selectivity was improved by changing the reduction procedure (thereby increasing the amount of K 2 O from 0.23% to 0.8%).
  • OLE 174 series of catalysts (different Cu and Al levels) was prepared using the same procedure described in Example 1. These catalysts were optimised with regards to activity and selectivity. The optimum composition was OLE 174D2 (high copper containing catalyst). This catalyst is compared to a catalyst with the same Al and K 2 O level but with lower copper loading, namely OLE 142B2. The starting materials used for the preparation of the catalysts are presented in Table 5 and the final composition in Table 6. The testing results are shown in Table 6.
  • This Example 2 shows that the catalyst OLE 174D2 with a higher copper loading, i.e. above 20g Cu per 100g Fe results in a catalyst with much higher activity, a higher total production of alcohols and olefins, as well as a higher alcohol selectivity and a comparable olefin selectivity as compared to the catalyst OLE 174B2 having a copper loading of less than 10g copper per 10Og Fe.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

This invention relates to an iron-based Fischer-Tropsch catalyst composition wherein the main iron phase is ferrihydrite, where the catalyst composition includes a high amount of copper. Typically, the composition includes 15% to 20% (by mass) copper, replacing manganese and zinc in the composition. The catalyst compositions according to the invention having high amounts of copper show good productivity and selectivity towards alcohols and olefins in the Fischer-Tropsch reaction, and are comparable to catalysts containing manganese and zinc.

Description

IRON-BASED COPPER-CONTAINING CATALYST
BACKGROUND OF THE INVENTION
THIS invention relates to iron-based catalysts, in particular to iron-based catalysts and their use in the conversion of synthesis gas (CO and H2) to alcohols and olefins.
International patent publication no. WO 01/89689 discloses an iron-based Fischer-Tropsch catalyst composition wherein the main iron phase is the ferrihydrite. The catalyst composition includes natural promoters which may be selected from manganese or chromium or a mixture thereof and chemical promoters selected from magnesium zinc, copper and alkaline or alkali earth metals. The catalyst is best bound to refractory oxide support such as silica. According to the specification, the catalyst composition produces significant yield of higher paraffins, olefins and alcohols.
International patent publication no. WO 03/043734 discloses an iron-based Fischer-Tropsch catalyst composition wherein the main iron phase is ferrihydrite, and the catalyst composition includes alumina, manganese and zinc as structural promoters. Although this catalyst composition has shown very good activity and selectivity for the production of alcohols and olefins, manganese and zinc are expensive and there is a need to find a catalyst composition with good selectivity for alcohols and olefins, which is also less expensive to produce.
It is an object of this invention to provide a less expensive iron-based catalyst with good activity and selectivity towards alcohols and olefins. SUMMARY OF THE INVENTION
According to a first aspect of the invention there is provided an iron-based Fischer-Tropsch catalyst composition, preferably wherein the main iron phase is ferrihydrite, wherein the catalyst composition includes more than 10% (by mass) copper, preferably 15% (by mass) or more copper, typically from 15% to 20% (by mass) copper.
By "iron-based" is meant that Fe makes up at least 30% (by mass) of the composition. The term "the main iron phase is ferrihydrite" means that at least 75% of the iron phase is ferrihydrite, as determined by X-ray diffraction using Co K alpha radiation. The preferred catalyst compositions exhibit hyperfine interaction parameters similar to those of ferrihydrite, as determined by Mόssbauer absorption spectroscopy (MAS).
Advantageously, the composition includes from 20g to 60g copper per 100g iron.
Usually, the composition will comprise from 30% to 60% (by mass) iron.
Advantageously, the composition also includes K2O which may be present in an amount of from 0.1% to 2% (by mass) of the composition.
The compositions are typically supported on silica or alumina.
Advantageously, the catalyst composition has a BET surface area of from 100 to 230 m2/g, and a total pore volume of from 0.2 to 0.5 cm3/g.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph showing the activities of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc; Figure 2 is a graph which shows the productivity towards alcohols of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc;
Figure 3 is a graph which shows the productivity towards olefins of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc;
Figure 4 is a graph which shows the alcohol selectivities of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc; and
Figure 5 is a graph which shows the olefin selectivities of high copper containing catalysts of the invention, in comparison to a catalyst which contains manganese and zinc.
DESCRIPTION OF EMBODIMENTS
In broad terms this invention relates to a catalyst composition for selectively converting synthesis gas under Fischer-Tropsch conditions to olefins and alcohols in significant yields.
Catalyst compositions according to preferred embodiments of the invention are iron-based, have a high amount of copper (more than 10%, typically from 15% to 20% by mass) and the main iron phase is ferrihydrite. The compositions also include K2O and are supported on silica or alumina.
The abovementioned catalyst compositions show a high activity and selectivity for alcohols and olefins. In fact they show similar activity and selectivity to a preferred composition catalyst as described in International patent publication no. WO 03/043734 which is an alumina bound catalyst and additionally contains manganese and zinc. Thus, a catalyst composition of the invention performs as well as the catalysts described in International patent publication no. WO 03/043734, but need not include manganese and zinc. The exclusion of manganese and zinc means that the catalyst composition is less expensive to produce, and it is not necessary to recover these metals from the spent catalyst composition.
An alumina supported catalyst composition of the invention may be produced in a continuous process by making a first acidic solution containing Fe nitrate (Fe (NO3)3.9H2O), Cu nitrate Cu (NO3)2.3H2O), Al nitrate (Al (NO3)3.9H2O) and 10% oxylic acid, and heating the solution to 75°C. A second basic solution, containing 25%, by mass, KOH and a temperature of 45°C is then added to the solution. The rate at which the second solution is added to the first solution is adjusted so that the pH is maintained at a range of approximately 8 and the temperature at approximately 70°C. The addition of the second solution to the first solution causes the formation of a precipitate, which is the catalyst composition of the invention. The precipitate is then filtered, and washed and the filter cake then reslurried and spray-dried at an inlet temperature of 260°C and an outlet temperature of 120°C. Thereafter, on-spec catalyst is calcined at 450°C for 16 hours and sieved to a particle size of 38-150 μm.
A continuous process for the preparation of a silica supported catalyst composition is carried out in much the same manner as the process for producing an alumina support composition. However, aluminium nitrate is not added to the first acidic solution. The precipitate from the process is then filtered and reslurried and bound by adding silica (SiO2) and then spray drying the resulting slurry at an inlet temperature of 260°C and an outlet temperature of 120°C. Thereafter, the on-spec catalyst is calcined at 450°C for 16 hours and sieved to a particle size of 38-150 μm.
Instead of using a continuous process of preparation, the alumina can be included by co-precipitation by adding Al nitrate to the second basic solution, or it could be added to the washed precipitate by mixing a solution containing Al nitrate or Al hydroxide with the slurried precipitate and spray- drying and calcining the resulting mixture. The potassium can also be added in other ways, for example by impregnation after calcination of the composition.
Table 1 below shows typical catalyst compositions of high-copper catalysts of the invention after calcination at 450°C. The table shows the amount of Fe, Cu, Zn, K2O, SiO2 or AI2O3 in the catalyst composition. The rest of the composition is made up primarily by oxygen atoms.
TABLE 1
Figure imgf000006_0001
The above catalyst compositions according to the invention so-formed are iron-based, and main iron phase is ferrihydrite, except for OLE 143 where only 60% of the iron phase is ferrihydrite.
Table 2 below shows the surface area and total pore volume of the catalysts mentioned in Table 1 above. TABLE 2
Figure imgf000007_0001
Temperature reduction profiles for the catalysts mentioned in Table 1 were obtained and Table 3 below shows the maxima obtained from TPR reduction profiles.
TABLE 3
Figure imgf000007_0002
The catalysts mentioned in Table 1 were tested using a standard procedure. Each catalyst (20g) was loaded in 350g molten wax before in- situ reduction at 240°C and 20 bar with a hydrogen space velocity of 6000 ml(n)/gr cat/hr for 16hrs. Lowering the temperature to 200°C, introducing APG (Arge Pure Gas, approximately 75% syngas) for 1 hour and thereafter increasing the temperature to 240°C and the pressure to 45 bar attained switchover to synthesis. First period TCD (Thermal Conductivity Detector used to analyse for CO2, CO, H2, CH4, Ar, N2) analyses were used to adjust synthesis gas flow rates in order to operate at 35 to 45% CO+CO conversions. The following flow rates were used: OLE 151-35%, OLE 138- 36%, OLE143-35%, OLE 154-44%, OLE 154 (change reduction) - 39% and OLE 155 (K2O impregnated) - 35%. Mass balance calculations were performed on period 3 using TCD and FID GC (Flame lonisation Detector used to analyse gaseous products e.g. alcohols, olefins, paraffins etc.) analyses on the gas samples and GC analyses on oil and water samples. A repeat run of OLE154 was initialised in which reduction was obtained at much milder conditions to prevent excessive sintering. Reduction was attained using a 80% H2 and 20% Ar mixture at 2 bar and 240°C for 16 hours.
The results of the tests of the catalysts from Table 1 are shown in Figures 1-5. The catalyst OLE151 is a comparative example of a preferred catalyst as defined in International patent publication no. WO 03/043734. The catalyst had the following elemental composition: Fe 42.9% by mass, Cu 3.56% by mass, Mn 14% by mass, Zn 5.41% by mass, K2O 0.27% by mass, and AI2O3 3.57% by mass. Two additional experiments were carried out. The activity and selectivity of the OLE 155 catalyst was improved by impregnation with KNO3, followed by calcination to obtain K2O. In the other procedures, hydrogen is diluted with 10% Ar. In this procedure, hydrogen was diluted with 20% Ar. A further experiment was carried out on OLE 154 and activity and selectivity was improved by changing the reduction procedure (thereby increasing the amount of K2O from 0.23% to 0.8%).
Referring to Figure 1 , it can be seen that the iron-based catalyst compositions of the invention containing a high percentage of Cu (and no Mn or Zn) i.e. OLE 138, 143 and 154, and OLE 155 containing a high percentage of Cu and a low amount of Zn and no Mn, show comparable activities to OLE151 , which contains Mn and Zn. From Figure 1 it can also be seen that the activity of the catalyst can be increased by optimising the reduction procedure (see OLE 154 change reduction). Referring to OLE 155 (K2O impregnation), it may be necessary to impregnate the catalyst with KNO3 during the preparation step, should the catalyst have a low K2O. Figures 2-5 show that the catalyst compositions of the invention having a high amount of Cu also have good productivity and selectivity towards alcohols and olefins, which are comparable to the catalyst OLE151 containing manganese and zinc. From Figures 2-5 it can also be seen that the activity of the catalyst can be increased by optimising the reduction procedure (see OLE 154 change of reduction). Referring to OLE 155 (K2O impregnation), it may also be necessary to impregnate the catalyst with KNO3 during the preparation step, should the catalyst have a low K2O.
The invention will now be described with reference to the following non- limiting Examples.
Example 1. Preparation of catalysts OLE 138, 143, 154 and 155.
These catalysts were prepared using the co-precipitation method. Specific amounts of the starting materials are presented in Table 4 below.
Essentially, the method consists of feeding a heated stream of metal nitrates dissolved in water and another stream of a suitable precipitating agent, usually KOH, into a precipitation reactor. The rate at which the streams are fed is controlled such that the temperature in the reactor is 70°C and the pH is 8.
The precipitate which forms is filtered, washed thoroughly with water until the conductivity is below 1.OmS. The filter cake is then reslurried and spray dried at an inlet temperature of 260°C and outlet of 120°C. Thereafter the on-spec catalyst is calcined at 450°C for 16 hours and finally sieved between 38 and 150 microns before being characterised and tested.
Table 4. Amount of raw materials used in the preparation of OLE 138, 143, 154 & 155
Figure imgf000010_0001
promoter added before spray drying * promoter added before precipitation
Example 2. Effect of varying the Copper loading
An OLE 174 series of catalysts (different Cu and Al levels) was prepared using the same procedure described in Example 1. These catalysts were optimised with regards to activity and selectivity. The optimum composition was OLE 174D2 (high copper containing catalyst). This catalyst is compared to a catalyst with the same Al and K2O level but with lower copper loading, namely OLE 142B2. The starting materials used for the preparation of the catalysts are presented in Table 5 and the final composition in Table 6. The testing results are shown in Table 6.
Table 5. Amount of raw materials used in the preparation of OLE 172B2 & 172D2
Figure imgf000010_0002
promoter added before precipitation : promoter impregnated after calcinations
Table 6. Final elemental composition for OLE 174B2 & OLE 174D2
Figure imgf000011_0001
Table 7. Fischer-Tropsch synthesis results for OLE 174B2 & OLE 174D2
Figure imgf000011_0002
This Example 2 shows that the catalyst OLE 174D2 with a higher copper loading, i.e. above 20g Cu per 100g Fe results in a catalyst with much higher activity, a higher total production of alcohols and olefins, as well as a higher alcohol selectivity and a comparable olefin selectivity as compared to the catalyst OLE 174B2 having a copper loading of less than 10g copper per 10Og Fe.

Claims

1. An iron-based Fischer-Tropsch catalyst composition, wherein the catalyst composition includes more than 10% (by mass) copper.
2. The iron-based Fischer-Tropsch catalyst composition according to claim 1 , wherein the catalyst composition includes 15% (by mass) or more copper.
3. The iron-based Fischer-Tropsch catalyst composition according to claim 3, wherein the catalyst composition includes from 15% to 20% (by mass) copper.
4. The iron-based Fischer-Tropsch catalyst composition according to any one of the preceding claims, wherein the main iron phase is ferrihydrite.
5. The iron-based Fischer-Tropsch catalyst composition according to any one of the preceding claims, wherein the composition includes from 20g to 60g copper per 100g iron.
6. The iron-based Fischer-Tropsch catalyst composition according to any one of the preceding claims, wherein the composition also includes K2O which is present in an amount of from 0.1% to 2% (by mass) of the composition.
7. The iron-based Fischer-Tropsch catalyst composition according to any one of the preceding claims, wherein the catalyst composition is supported on silica or alumina.
8. The iron-based Fischer-Tropsch catalyst composition according to any one of the preceding claims, wherein the catalyst composition has a BET surface area of from 100 to 230 m2/g. The iron-based Fischer-Tropsch catalyst composition according to any one of the preceding claims, wherein the catalyst composition has a total pore volume of from 0.2 to 0.5 cm3/g.
PCT/IB2003/005352 2002-11-25 2003-11-24 Iron-based copper-containing catalyst WO2004047986A1 (en)

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CN103801307A (en) * 2014-02-27 2014-05-21 神华集团有限责任公司 Precipitated iron catalyst for Fischer-Tropsch synthesis and preparation method thereof
CN104399501A (en) * 2014-11-09 2015-03-11 复旦大学 High-activity iron-based low-temperature Fischer-Tropsch synthesis catalyst and preparation method thereof
US10974222B2 (en) 2015-04-28 2021-04-13 3M Innovative Properties Company Filter media for respiratory protection

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CN103801308A (en) * 2014-02-27 2014-05-21 神华集团有限责任公司 Precipitated iron catalyst for Fischer-Tropsch synthesis and preparation method thereof
CN103801307A (en) * 2014-02-27 2014-05-21 神华集团有限责任公司 Precipitated iron catalyst for Fischer-Tropsch synthesis and preparation method thereof
CN104399501A (en) * 2014-11-09 2015-03-11 复旦大学 High-activity iron-based low-temperature Fischer-Tropsch synthesis catalyst and preparation method thereof
US10974222B2 (en) 2015-04-28 2021-04-13 3M Innovative Properties Company Filter media for respiratory protection
US11331645B2 (en) 2015-04-28 2022-05-17 3M Innovative Properties Company Filter media for respiratory protection

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