EA041431B1 - COBALT-CONTAINING CATALYTIC COMPOSITION - Google Patents

Description

Field of invention

The invention relates to catalysts, in particular to a cobalt-containing catalyst composition. The present invention relates to a method for producing a cobalt-containing catalyst precursor, a method for producing a cobalt-containing catalyst, and a method for synthesizing hydrocarbons using such a catalyst.

State of the art

The synthesis of hydrocarbons from syngas (syngas) containing hydrogen and carbon monoxide in the presence of a Fischer-Tropsch (FT) synthesis catalyst is commonly known as FT synthesis. During FT synthesis, synthesis gas is contacted with an FT synthesis catalyst under FT synthesis conditions to produce hydrocarbons. One type of catalyst that is often used in low temperature FT synthesis (LTFT) contains an active catalyst component such as Co on a support and/or in a catalyst support such as alumina, silica, titania, magnesium dioxide, or the like, and the resulting hydrocarbons are typically in the form of a waxy hydrocarbon product.

It is known that during FT synthesis, the activity of supported catalysts such as Co typically decreases with time (ie, the catalyst is deactivated), resulting in less synthesis gas being converted to hydrocarbons. This characteristic of a catalyst, in that its activity may decrease over time during hydrocarbon synthesis, is called catalyst activity stability.

As stated above, the lack of stability of catalyst activity has the effect that the catalyst deactivates over time and then less hydrocarbons are formed. To counteract this effect, the temperature of the FT synthesis process can be increased to compensate for the loss of catalyst activity. However, the increased reaction temperature has the disadvantage that more undesirable methane is produced during FT synthesis. Other costly measures such as catalyst loading increase, catalyst recovery or catalyst reactivation can also be used to restore hydrocarbon production.

It is known in the art that many different components, such as modifiers, dopants, and promoters, can be incorporated into catalysts to improve certain aspects of the catalyst, such as improved hydrothermal stability, increased activity of the active component, increased catalyst activity, increased catalyst production selectivity, and increasing the stability of catalyst activity in the synthesis of FT. There is a long list of such components suitable for the purposes outlined above, for example Si, Ti, Zr, Cu, Zn, Ba, Co, Ni, La, W, Na, K, Ca, Sn, Cr, Fe, Li, Tl, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, Ta, Mn, Pt, Pd, Re and Ru. It has now been found that when Ti and Mn are included in combination in a cobalt-containing catalyst with a silica-supported catalyst where the average pore diameter of the catalyst is greater than 20 less than 50 nm, unexpected beneficial effects are obtained. W02014020507; W09961550; Applied Catalysis A: General, 419-420 (2012) 148-155; W02008104793; W02012107718; AU 2013203123; US 20120252665 A1; Fuel Processing Technology, 89 (2008) 455-459 and Catalysis Today, 197 (2012) 18-23 describe the incorporation of Ti into catalysts.

The incorporation of Mn into catalysts is described in Journal of Catalysis, 246 (2007) 91-99; Journal of Physical Chemistry B, 110 (2006), 8626-8639; EP 0966415A1; US 6333294 B1; US 20020010221 A1; Fuel Processing Technology, 90 (2009) 901-908; Journal of Catalysis, 288 (2012) 104-114; Journal of Catalysis, 237 (2006) 152161; US20080132589; US 20080064769 A1; US 20100099780 Al and US 20040127352 A1. The inclusion of both Ti and Mn in a silica support is described in PCT/IB2016/050745, where the application has not been published as of the priority date of this application. PCT/IB2016/050745 does not disclose an average pore diameter greater than 20 nm but less than 50 nm for silica substrates. Most surprisingly, it has been found that if a silica-supported cobalt catalyst, where the average pore diameter of the catalyst is greater than 20 nm but less than 50 nm, contains both titanium and manganese, the activity and/or activity stability and /or C5+ catalyst productivity and/or lower catalyst methane selectivity and/or support abrasion resistance are increased in hydrocarbon synthesis where synthesis gas is in contact with the catalyst. This is illustrated by the examples of the present invention given in the present invention below.

Description of the invention

Cobalt-containing catalyst composition.

According to a first aspect of the present invention, there is provided a cobalt-containing catalyst composition containing cobalt and/or a cobalt compound, which is supported on and/or in a silica support (SiO ₂ ) of the catalyst, where the average pore diameter of the catalyst is more than 20 nm but less than 50 nm; the catalytic composition also contains a titanium compound on and/or in the catalyst support and a manganese compound on and/or in the catalyst support.

The catalyst composition may be a hydrocarbon synthesis catalyst composition for synthesizing hydrocarbons and/or hydrocarbon oxygenates from at least hydrogen and carbon monoxide. Advantageously, the catalyst composition is a Fischer-Tropsch (FT) synthesis catalyst composition for Fischer-Tropsch synthesis. Synthesis of FT can be done in a reactor

- 1 041431 fixed bed, slurry bed reactor or fixed fluidized bed reactor. Preferably, FT synthesis is a three phase slurry bed FT synthesis process.

In one embodiment of the invention, the catalyst composition may contain a cobalt compound, in which case the catalyst composition may be a catalyst precursor. The cobalt compound may be cobalt salts, alternatively it is cobalt oxide. The cobalt salt may include any suitable cobalt salt such as cobalt hydroxide and/or cobalt nitrate. The cobalt oxide may be selected from the group consisting of CoO, CoO(OH), Co ₃ O ₄ , Co ₂ O ₃ and a mixture of two or more of them. Preferably, the cobalt oxide is Co ₃ O ₄ .

In another embodiment of the invention, the catalyst composition may contain zero valent cobalt, in which case the catalyst composition may be an active catalyst. The cobalt may be in the form of particles or, preferably, crystallites distributed on the surface of the substrate.

The catalyst precursor or catalyst may contain cobalt (Co) at a charge of 5 to 70 g Co/100 g catalyst support, preferably 20 to 40 g Co/100 g catalyst support, and more preferably 25 to 35 g Co/100 g catalyst support . The catalyst composition may also contain a dopant, preferably a dopant capable of enhancing the reducibility of the cobalt compound. The dopant may be in the form of a dopant that is a metal compound selected from the group consisting of palladium (Pd), platinum (Pt), ruthenium (Ru), rhenium (Re), and a mixture of two or more of these. The mass ratio of dopant metal (especially palladium metal or platinum metal) to cobalt metal can be from 1:300 to 1:3000.

The silica (SiO ₂ ) catalyst support may be a precipitated silica support. Preferably it is a colloidal (also called pyrogenic) silica support or a silica gel support. Preferably it is an amorphous silica support, especially an amorphous colloidal silica support or an amorphous silica gel support.

The silica catalyst support is a porous support and is preferably pre-shaped as well. Preferably, the silica support has an average pore diameter greater than 22 nm, preferably at least 25 nm, preferably less than 40 nm, preferably 25 to 35 nm, preferably 30 nm. The average pore diameter was determined using the Barett-Joyner-Halenda (BJH) nitrogen physical sorption method. It is understood that the average pore diameter is the average pore diameter of the substrate prior to the addition of any one or more titanium compounds, manganese compounds and cobalt compounds.

The pore volume of the support may be from 0.1 to 1 ml/g of catalyst support, preferably from 0.3 to 0.9 ml/g of catalyst support. The preformed substrate may be a particulate substrate, preferably with an average particle size of 1 to 500 µm, preferably 10 to 250 µm, even more particularly 45 to 200 µm.

Preferably, the catalyst composition contains more than 1 wt.% and not more than 10 wt.% Ti, based on the weight of the silica catalyst support (SiO ₂ ) (excluding the weight of Ti and Mn), and Ti is present in the form of one or more titanium compounds.

Preferably, the catalyst composition does not contain more than 5 wt.% Ti, preferably not more than 3.5 wt.% Ti. Preferably titanium in the form of one or more titanium compounds may be present in and/or on the catalyst support in an amount of more than 1.5 wt.%, preferably at least 2.0 wt.%, more preferably at least 2.4 wt.% Ti.

Preferably, titanium in the form of one or more titanium compounds may be present in and/or on the catalyst support in an amount of less than 3.5 wt.%, preferably not more than 3.0 wt.%, but preferably more than 2.0 wt.% Ti.

The preferred amount of titanium in the form of one or more titanium compounds present in and/or on the catalyst support is 2.6 wt% Ti. Ti is preferably present in the form of titanium oxide.

Preferably, Ti is included as a substrate modifier, i. e. as Ti which has been introduced onto and/or into the catalyst support (and preferably also calcined) before the cobalt compound has been introduced onto and/or into the catalyst support.

Alternatively, Ti may be included as a promoter, i. e. in the form of Ti which has been introduced onto and/or into the catalyst support during and/or after the introduction of the cobalt compound onto and/or into the catalyst support.

Preferably, the catalyst composition contains more than 0.5 wt% and less than 10 wt% Mn based on the weight of the silica (SiO2) catalyst support (excluding the weight of Ti and Mn), the Mn being present in the form of one or more manganese compounds.

Preferably the catalyst composition does not contain more than 7.5 wt.% Mn, preferably not more than 5 wt.% Mn. Preferably, manganese in the form of one or more manganese compounds may be present in and/or on the catalyst support in an amount of more than 1 wt.%, preferably over

- 2 041431 at least 1.5 wt.%, more preferably at least 1.8 wt.% Mn.

Preferably manganese in the form of one or more manganese compounds may be present in and/or on the catalyst support in an amount of less than 5 wt.%, preferably not more than 3.5 wt.%, but preferably more than 1.8 wt.% Mn.

The preferred amount of manganese in the form of one or more manganese compounds present in and/or on the catalyst support is 3.1 wt% Mn. The manganese is preferably present in the form of manganese oxide.

Mn may be included as a promoter, ie. in the form of Mn that has been introduced onto and/or into the catalyst support during and/or after the introduction of the cobalt compound onto and/or into the catalyst support. Alternatively, Mn may be included as a substrate modifier, ie. in the form of Mn which has been introduced onto and/or into the catalyst support (and preferably also calcined) before the cobalt compound has been introduced onto and/or into the catalyst support. In one embodiment of the invention, the catalyst composition is free or substantially free of Re. Preferably, if any Re is present in the catalyst composition, the weight ratio of Re to Co is less than 0.001:1.

In accordance with a second aspect of the present invention, there is provided a process for producing a cobalt-containing catalyst precursor, comprising introducing a cobalt compound on and/or into a silica (SiO ₂ ) catalyst support wherein the average pore diameter is greater than 20 nm but less than 50 nm; before and/or during and/or after the introduction of the cobalt compound on and/or into the catalyst support, the introduction of the titanium compound onto and/or into the catalyst support; and before and/or during and/or after the introduction of the cobalt compound onto and/or into the catalyst support, the introduction of the manganese compound onto and/or into the catalyst support, thereby providing a cobalt-containing catalyst precursor.

It is understood that when a compound is introduced onto and/or into a catalyst support, the compound may be in contact with the support precursor compound, or it may be in contact with the support itself.

The method preferably includes one or more calcination steps in which at least the titanium and manganese compounds introduced into and/or onto the catalyst support are converted to titanium oxide and manganese oxide, respectively.

The silica (SiO ₂ ) catalyst support is preferably a catalyst support as described herein above.

Obtaining a titanium-containing catalyst support.

The titanium compound can be introduced onto and/or into the catalyst support by producing a titanium-containing catalyst support material by contacting a silicon-based catalyst support material (preferably silica (SiO ₂ )) with a titanium compound; and calcining the titanium-containing catalyst support material at a temperature above 200° C. to obtain a silica (SiO ₂ ) catalyst support that contains Ti in the form of one or more titanium compounds.

Contacting the Catalyst Support Material with a Titanium Compound.

The silica catalyst support material may be selected from the group consisting of a silica catalyst support precursor that is converted to a silica (SiO ₂ ) catalyst support upon calcination; and silica (SiO ₂ ) substrates.

When the silica catalyst support material is a precursor of the silica catalyst support, the titanium compound is preferably added to and/or into the catalyst support (and preferably also calcined) prior to the introduction of the cobalt compound to and/or into the catalyst support. In this embodiment, titanium can serve as a substrate modifier. The catalyst support precursor may be formed in particulate form after the introduction of the titanium compound onto and/or into the catalyst support precursor, and preferably before it is calcined. Forming can, for example, be carried out by spray drying.

The catalyst support precursor may be partially dried before being molded. Then, the obtained shaped product can be subjected to calcination at a temperature above 200° C. to convert the catalyst support precursor into a catalyst support. The calcination may take place prior to the introduction of the cobalt compound onto and/or into the formed product. To achieve the desired particle size distribution, the product can be classified in particle form, for example using cyclones or sieves. However, the silicon-based catalyst support material is preferably a silica (S SiO2) catalyst support. The catalyst support is preferably suitable for use as a support in a catalyst for the synthesis of hydrocarbons and/or hydrocarbon oxygenates from at least hydrogen and carbon monoxide, in particular a Fischer-Tropsch (FT) synthesis catalyst.

The FT synthesis catalyst can be used in a process to be carried out in a fixed bed reactor, a slurry bed reactor, or even a fluidized bed fixed bed reactor. Preferably, the process should be carried out in a three-phase fluidized bed synthesis reactor. In a preferred embodiment of the invention, the catalyst support or catalyst support precursor may be contacted with the titanium compound (and preferably also calcined) prior to the introduction of the cobalt compound onto and/or into the catalyst support. In this embodiment, titanium can serve as a substrate modifier. Preferably, calcination of the titanium-containing catalyst support material also occurs prior to the introduction of the cobalt compound onto and/or into the catalyst support. In an alternative embodiment of the invention, the catalyst support or catalyst support precursor may be contacted with the titanium compound during and/or after the introduction of the cobalt compound onto and/or into the catalyst support. In this embodiment, titanium can serve as a promoter. Then, the calcination of the titanium-containing catalyst support material occurs after the introduction of the cobalt compound on and/or into the catalyst support.

The catalyst support may be as described herein above.

As stated above, the catalyst support material is in contact with the titanium compound. The titanium compound may be an inorganic titanium compound, but it is preferably an organic titanium compound.

As used herein, an organic titanium compound is to be understood as a titanium compound in which the titanium is bonded to at least one organic group via a bond, such as a covalent bond, metal ligand coordination, or ionic interaction.

Preferably, in the organic titanium compound, the titanium is bonded to at least one non-carbon atom of at least one organic group, in particular the oxygen atom of the organic group.

In one embodiment of the invention, at least one organic group of an organic titanium compound may be a chelate compound, preferably a chelate compound, which is bonded to titanium via at least one non-carbon atom, preferably an oxygen atom (preferably via two oxygen atoms). Preferably all groups associated with titanium are organic groups, and preferably all of these organic groups are associated with titanium through an oxygen atom.

In one embodiment of the invention, some, but preferably all, of the organic groups have the formula -(O)-R, where R is an organic group. R in different -(O)-R groups may be the same or different. The R -(O)-R group may or may not be associated with the R of another -(O)-R group.

R may be an acyl or hydrocarbyl group, or may be a heterohydrocarbyl group (i.e., an organic group consisting of carbon, hydrogen, and at least one atom that is not carbon or hydrogen), preferably a hydrocarbyl group, preferably an alkyl group, and preferably an alkyl group with no more than eight carbon atoms.

Alternatively, R may have the formula -OR ¹ where R ¹ may be a hydrocarbyl group or may be a heterohydrocarbyl group (i.e., an organic group consisting of carbon, hydrogen, and at least one atom that is not carbon or hydrogen ), preferably an alkyl group, preferably an alkyl group, and preferably an alkyl group with no more than eight carbon atoms.

In one embodiment of the invention, the organic titanium compound may be selected from the group consisting of titanium (IV) methoxide; titanium (IV) ethoxide; titanium (IV) propoxide; titanium (IV) isopropoxide; diisopropoxide bis(acetylacetonate) titanium (IV); 2-ethylhexoxide titanium (IV); titanium (IV) hexoxide; titanium (IV) butoxide; and bis-(ammonium lactato)titanium (IV) dihydroxide.

Contacting the catalyst support material with the titanium compound may be by any suitable method, including, for example, impregnation, precipitation, adsorption, or chemical vapor deposition.

Preferably, contacting the titanium compound with the catalyst support material is by impregnation. A suitable impregnation liquid medium can be used to bring the titanium compound and the catalyst support material into contact. The impregnation may be an initial wet impregnation, but is preferably a slurry phase impregnation. Preferably the liquid medium is a non-aqueous medium such as an organic liquid medium, and preferably it is an alcohol such as ethanol. Alternatively, the liquid medium is an inorganic liquid medium such as water. Preferably the liquid medium is a solvent for the titanium compound.

The impregnation is preferably carried out at a temperature above 25°C. The temperature can be 50-60°C. The impregnation can be carried out for 1 minute to 20 hours, preferably 1 minute to 5 hours. The impregnation can be carried out at atmospheric pressure. After impregnation, excess impregnating liquid medium can be removed, preferably by drying. Drying is preferably carried out under sub-atmospheric conditions, preferably from 1 to 90 kPa. Drying is preferably carried out at

- 4 041431 temperature above 25°C, more preferably at a temperature not exceeding 125°C.

Calcination of the Titanium-Containing Support Material The calcination of the titanium-containing catalyst support material can take place in a non-reducing environment, preferably in an oxidizing environment such as air. The calcination can be carried out either in a stationary calciner or in a fluidized bed calciner. Instead, the calcination can also take place in a rotary kiln. However, a rotary kiln is most preferred. Ignition can typically take place within 10 minutes to 10 hours.

During calcination of a titanium-containing catalyst support material obtained by contacting the catalyst support material with a titanium compound, the titanium compound in and/or on the catalyst support material may react and/or it may decompose and/or it may chemically bond to the catalyst support material; however, preferably, calcination converts the titanium compound to titanium oxide, preferably by decomposition and/or reaction.

If the titanium compound is introduced onto and/or into the catalyst support prior to the introduction of the cobalt compound onto and/or into the catalyst support, the calcination of the titanium-containing support material is preferably carried out at a temperature of 350° C. or higher, preferably at least 400° C., more preferably at a temperature of above 500°C, even more preferably at least 525°C. Preferably, the calcination is carried out at a temperature below 1200°C, preferably below 950°C. When the titanium compound is introduced onto and/or into the catalyst support during and/or after the introduction of the cobalt compound onto and/or into the catalyst support, the calcination of the titanium-containing support material is preferably carried out in the manner described below for calcination after the introduction of the cobalt compound onto and/or into the support. catalyst.

The level of Ti after calcination may be as described in this invention above.

In one preferred embodiment of the invention, the titanium compound may be introduced onto and/or into the catalyst support (and preferably also calcined) prior to the introduction of the cobalt compound onto and/or into the catalyst support. In this embodiment, titanium can serve as a substrate modifier. Alternatively, the titanium compound may be introduced onto and/or into the catalyst support during and/or after the introduction of the cobalt compound onto and/or into the catalyst support. In this embodiment, titanium can serve as a promoter.

Obtaining a manganese-containing catalyst support.

The manganese compound can be introduced onto and/or into the catalyst support by producing a manganese-containing catalyst support material by contacting a silicon-based catalyst support material (preferably silica (SiO ₂ )) with a manganese compound; and calcining the manganese-containing catalyst support material at a temperature above 180° C. to obtain a silica (SiO ₂ ) catalyst support that contains Mn in the form of one or more manganese compounds.

Contacting the Catalyst Support Material with a Manganese Compound.

The silicon-based catalyst support material may be selected from the group consisting of a silicon-based catalyst support precursor that is converted to a silica (SiO ₂ ) catalyst support when it is calcined; and silica (SiO ₂ ) substrates.

If the silicon catalyst support material is a silicon catalyst support precursor, the manganese compound is preferably added to and/or into the catalyst support (and preferably also calcined) before the cobalt compound is added to and/or to the catalyst support. In this embodiment, manganese can serve as a substrate modifier. The silicon-based catalyst support precursor can be particulated after the introduction of the manganese compound onto and/or into the catalyst support precursor, and preferably before it is calcined. Forming can, for example, be carried out by spray drying. The catalyst support precursor may be partially spray dried prior to shaping. The resulting shaped product may then be subjected to a calcination to convert the catalyst support precursor into a catalyst support. The calcination may take place prior to the introduction of the cobalt compound onto and/or into the shaped product. To achieve the desired particle size distribution, the product can be classified in particle form, for example using cyclones or sieves.

However, the silicon-based catalyst support material is preferably a silica (SiO ₂ ) catalyst support. The catalyst support is preferably as described herein above.

In one embodiment of the invention, the catalyst support or catalyst support precursor may be contacted with the manganese compound prior to the introduction of the cobalt compound onto and/or into the catalyst support. In this embodiment, manganese can serve as a substrate modifier. Preferably, the calcination of the manganese-containing catalyst support material also occurs prior to the introduction of the cobalt compound onto and/or into the catalyst support.

In an alternative embodiment of the invention, the catalyst support or catalyst support precursor may be contacted with the manganese compound during and/or after the introduction

- 5 041431 cobalt compounds on and/or in the catalyst support. In this embodiment of the invention, manganese can serve as a promoter. Then, calcination of the manganese-containing catalyst support material occurs after the introduction of the cobalt compound onto and/or into the catalyst support.

Preferably, the catalyst support or catalyst support precursor is brought into contact with the manganese compound after the titanium compound has been introduced onto and/or into the catalyst support. The catalyst support may be as described herein above.

As stated above, the catalyst support material is in contact with the manganese compound. The manganese compound may be an inorganic manganese compound such as manganese nitrate. Alternatively, it may be an organic manganese compound. In this specification, an organic manganese compound is a manganese compound wherein the manganese is bonded to at least one organic group via a bond, such as a covalent bond, a metal-ligand coordination bond, or ionic interaction.

Preferably, in the organic manganese compound, the manganese is bonded to at least one non-carbon atom of at least one organic group, in particular the oxygen atom of the organic group. Preferably all of the groups associated with manganese are organic groups, and preferably all of these organic groups are associated with manganese through an oxygen atom. The manganese compound may be selected from the group consisting of manganese(II) acetate tetrahydrate, manganese(II) ethoxide, and manganese(II) methoxide. Contacting the catalyst support material with the manganese compound may be by any suitable method including, for example, impregnation, precipitation, adsorption, or chemical vapor deposition.

Preferably, contacting the manganese compound with the catalyst support material is by impregnation. A suitable impregnation liquid medium can be used to bring the manganese compound into contact with the catalyst support material. The impregnation may be an initial wet impregnation. In a preferred alternative embodiment, the impregnation may be a slurry phase impregnation. Preferably the liquid medium is an inorganic liquid medium such as water. Preferably the liquid medium is a solvent for the manganese compound.

After impregnation, excess impregnating liquid medium can be removed, preferably by drying. Drying is preferably carried out under sub-atmospheric conditions, preferably from 1 to 90 kPa. Drying is preferably carried out at a temperature above 25°C, more preferably at a temperature not exceeding 125°C.

Calcination of a manganese-containing substrate.

The calcination of the manganese-containing catalyst support material may take place in a non-reducing environment, preferably in an oxidizing environment such as air. The calcination can be carried out either in a stationary calciner or in a fluidized bed calciner. Instead, the calcination may take place in a rotary kiln. In a preferred embodiment, the calcination is carried out in a fluid bed calciner. Ignition can typically take place within 10 minutes to 10 hours.

During calcination of a manganese-containing catalyst support material obtained by contacting the catalyst support material with a manganese compound, the manganese compound in and/or on the catalyst support material may react and/or it may decompose and/or it may chemically bond to the catalyst support material; however, preferably, calcination converts the manganese compound to manganese oxide, preferably by decomposition and/or reaction.

If the manganese compound is added to and/or the catalyst support before the cobalt compound is added to and/or the catalyst support, the calcination of the manganese-containing support material is preferably carried out at a temperature of 350°C or higher, preferably at least 400°C, more preferably , at temperatures above 500°C, even more preferably, the calcination is carried out at at least 525°C. Preferably, the calcination is carried out at a temperature below 1200°C, preferably below 950°C. When the manganese compound is introduced onto and/or into the catalyst support during and/or after the introduction of the cobalt compound into and/or into the catalyst support, the calcination of the manganese-containing support material is preferably carried out in the manner described below for calcination after the introduction of the cobalt compound into and/or into the catalyst support. . The level of Mn after calcination may be as described in this invention above.

In one embodiment of the invention, the manganese compound may be introduced onto and/or into the catalyst support (and preferably also calcined) prior to the introduction of the cobalt compound onto and/or into the catalyst support. In this embodiment, manganese can serve as a substrate modifier. Alternatively, the manganese compound may be introduced onto and/or into the catalyst support during and/or after the introduction of the cobalt compound onto and/or into the catalyst support. In this embodiment, manganese can serve as a promoter.

In a preferred embodiment of the invention, the titanium compound is introduced onto and/or into the catalyst support (and preferably also calcined) prior to the introduction of the cobalt compound onto and/or into

- 6 041431 catalyst support. In this embodiment, titanium can serve as a substrate modifier.

The titanium compound and the manganese compound can be introduced separately or simultaneously onto and/or into the catalyst support. In one embodiment, the manganese compound is added to and/or into the catalyst support before or with the addition of the titanium compound to and/or into the catalyst support. In another embodiment, the manganese compound is introduced onto and/or into the catalyst support after the titanium compound is introduced onto and/or into the catalyst support.

In one embodiment, the manganese compound may be introduced onto and/or into the catalyst support that contains the titanium compound, wherein the manganese compound is introduced during and/or after the introduction of the cobalt compound onto and/or into the catalyst support that contains the titanium compound. In the last mentioned embodiment, manganese can serve as a promoter.

Introduction of a cobalt compound onto and/or into the catalyst support.

The cobalt compound may be introduced onto and/or into the catalyst support by contacting the cobalt compound with the catalyst support in any suitable manner, but preferably this is by impregnation. Preferably, the impregnation is carried out by forming a mixture of the cobalt compound, the carrier liquid for the cobalt compound and the catalyst support. The liquid carrier may contain a solvent for the cobalt compound, and preferably said cobalt compound is dissolved in the carrier liquid. The liquid carrier may be water. The impregnation may be carried out by any suitable impregnation method, including initial wet impregnation or slurry phase impregnation. Slurry phase impregnation is preferred.

Preferably, the cobalt compound is dissolved in a carrier liquid so that the volume of the solution exceeds xy litres, which solution is then mixed with the catalyst support, and where x is the BET pore volume of the catalyst support in l/kg of support and y is the weight of the catalyst support impregnated , in kg. Preferably, the volume of the solution is greater than 1.5 liters (l), and preferably it is about 2 liters.

The impregnation may be carried out at subatmospheric pressure, preferably below 85 kPa, preferably at 20 kPa or below. Preferably, the impregnation is also carried out at a temperature above 25°C. The impregnation temperature may be above 40°C, preferably above 60°C, but preferably not above 95°C.

The impregnation may be followed by at least partial drying of the impregnated substrate, preferably at a temperature above 25°C. The drying temperature may be above 40°C, preferably above 60°C, but preferably not above 95°C. Preferably, drying can be carried out under subatmospheric conditions, preferably below 85 kPa, preferably at or below 20 kPa.

In one embodiment of the invention, the impregnation and at least partial drying of the catalyst support may be carried out using a procedure that includes a first step in which the catalyst support is impregnated (preferably slurry impregnated) with a cobalt compound at a temperature above 25°C and at pressure below atmospheric, and the resulting product is dried; and at least one subsequent stage, in which the resulting at least partially dried impregnated catalyst carrier of the first stage is subjected to processing at a temperature above 25°C and a pressure below atmospheric pressure, so that the temperature in the subsequent stage exceeds the temperature in the first stage and/or the subatmospheric pressure in the subsequent stage is lower than in the first stage. This two-stage impregnation procedure may be as described in WO 00/20116, which is incorporated into this invention by reference.

An additive capable of increasing the cobalt reducibility of the cobalt compound may also be incorporated onto and/or into the catalyst support. The additive may be added during or after the addition of the cobalt compound to and/or into the catalyst support. The dopant may be introduced in the form of a dopant mixture which is a compound of a metal selected from the group consisting of palladium (Pd), platinum (Pt), ruthenium (Ru), rhenium (Re), and a mixture of two or more of them. Preferably, the dopant is an inorganic salt. Preferably the dopant is water soluble. The weight fraction of the dopant metal in the cobalt metal may be as indicated above.

The cobalt compound introduced onto and/or into the catalyst support may be any suitable cobalt compound. Preferably it is an inorganic compound, more preferably an inorganic cobalt salt. The cobalt compound may be cobalt nitrate, and in particular it may be Co(NO ₃ ) ₂ -6H ₂ O. In an alternative embodiment of the invention, the cobalt compound may be introduced onto and/or into the catalyst support by contacting an insoluble cobalt compound (such as cobalt hydroxide) with a catalyst support, preferably by forming a suspension of insoluble cobalt compound particles with catalyst support particles in a carrier liquid; and removing the carrier liquid from the suspension to obtain a dried product, which is then calcined. The method may also include the step of adding the cobalt compound in the form of a soluble cobalt compound (such as cobalt nitrate). Preferably, the soluble cobalt compound is included in a suspension of insoluble cobalt compound particles with catalyst support particles in a carrier fluid.

- 7 041431

The method may also include the step of introducing an acid, preferably a carboxylic acid, preferably a multifunctional carboxylic acid, having the general formula

HOOC-C*RiC*R ₂ -COOH (1) or a precursor thereof, wherein C* in each of C*R ₁ and C*R2 is sp ² carbon, and R ₁ and R2 are the same or different, and each is selected from a group consisting of hydrogen and an organic group in and/or on a catalyst support before or simultaneously with the cobalt compound.

Preferably, the ratio of the amount of carboxylic acid used to the surface area of the catalyst support is at least 0.3 µmol carboxylic acid/m ² surface area of the support.

In principle, any multifunctional carboxylic acid according to formula (1) or its precursor, such as an anhydride, can be used. Non-limiting examples of carboxylic acids are maleic acid, mesaconic acid, cytaconic acid and fumaric acid. Preferably, maleic acid can be used. An example of a suitable acid precursor is maleic anhydride. Mixtures of acids of formula (1) or their precursors can also be used, as well as mixtures of acids of formula (1) or their precursors with acids or their precursors that do not correspond to formula (1).

The catalyst support with the cobalt compound on and/or in it may be calcined. Preferably, the calcination is carried out after the drying step. The calcination may be carried out to decompose the cobalt compound and/or to react with oxygen. During calcination, oxide or oxides of cobalt may be formed.

For example, a cobalt compound (eg, cobalt nitrate or cobalt hydroxide) can be converted to a compound selected from CoO, CoO(OH), Co ₃ O ₄ , Co ₂ O ₃ or a mixture of two or more of these.

The calcination may be carried out in any suitable manner, for example in a rotary kiln, but is preferably carried out in a fluidized bed reactor or in a calciner.

The calcination may be carried out in an inert atmosphere, but preferably it is carried out in an oxidizing atmosphere, preferably in the presence of oxygen, more preferably in air.

Preferably, the calcination is carried out at a temperature above 95°C, more preferably above 120°C, even more preferably above 200°C, but preferably not above 400°C, more preferably not above 300°C.

The calcination may be carried out using a heating rate and an airspeed that meet the following criteria:

(i) when the heating rate is < 1°C/min, the air space velocity is not less than 0.76 Nm ³ /(kg Co(NO ₃ ) ₂ -6H ₂ O)/4; and (ii) when the heating rate is above 1°C/min, the air volume velocity satisfies the relationship: log 20 - log 0.76 ^(space velocity) > log 0.76 +--------------- -log (heating rate)

Impregnation, at least partial drying, and calcination may be repeated to achieve higher loadings of the cobalt compound on and/or in the catalyst support. In one embodiment of the invention, the first impregnation, drying and calcination procedure may be followed by a partial reduction procedure for the calcined material; and the partially recovered material can then be subjected to a further impregnation, drying and calcination procedure. The partial reduction procedure can be performed with a final temperature between 100 and 300°C.

In one embodiment of the invention, the cobalt compound can be introduced onto and/or into the catalyst support by a method that includes, in a first preparation step, impregnating the catalyst support with an organic cobalt compound in a carrier liquid, at least partially drying the impregnated support, and calcining, at least partially dried impregnated substrate to obtain a calcined intermediate product; and in a second preparation step, impregnating the calcined intermediate from the first preparation step with an inorganic cobalt compound in the carrier liquid, at least partially drying the impregnated support and calcining the at least partially dried impregnated support to form a catalyst precursor.

Activation.

According to a third aspect of the present invention, there is provided a method for producing a cobalt-containing catalyst, comprising: obtaining a cobalt-containing catalyst precursor as set forth above in this invention; and reducing the catalyst precursor, thereby activating the catalyst precursor.

Recovery of the catalyst precursor preferably includes treating it with a reducing gas to activate it. Preferably the reducing gas is hydrogen or a hydrogen-containing gas. The hydrogen-containing gas may consist of hydrogen and one or more inert gases which are inert with respect to the active catalyst. The hydrogen-containing gas preferably contains at least 90 vol% hydrogen.

- 8 041431

The reducing gas may be contacted with the catalyst precursor in any suitable manner. Preferably, the catalyst precursor is provided in the form of a particulate bed, with the reducing gas flowing through the particulate bed. The particulate bed may be a fixed bed, but preferably it is a fluidized bed, and preferably the reducing gas acts as a fluidizing medium for the catalyst precursor particulate bed.

The reduction can be carried out at a pressure of 60 to 150 kPa, preferably 80 to 130 kPa. Alternatively, the pressure may be from 150 to 2000 kPa. Preferably, however, the pressure is approximately atmospheric pressure. The reduction is preferably carried out at a temperature above 25° C., at which the catalyst precursor is reduced to its active form. Preferably, the reduction is carried out at a temperature above 150°C and preferably below 600°C. Preferably, the reduction is carried out at a temperature below 500°C, more preferably below 450°C.

During the reduction, the temperature may vary, and preferably it is increased to the maximum temperature as indicated above. The flow of the reducing gas through the catalyst bed is preferably controlled to ensure that contaminants generated during the reduction are kept at a sufficiently low level. The reducing gas may be recycled, and preferably the recycled reducing gas is treated to remove one or more contaminants generated during the reduction. The contaminants may contain one or more of water and ammonia.

The reduction may be performed in two or more steps during which one or both of the heating rate and the space velocity of the reducing gas are changed.

In one embodiment of the invention, the active catalyst can be coated, preferably by introducing a mixture of active catalyst particles and a coating medium in the form of a molten organic substance which is at a temperature T ₁ and which solidifies or solidifies at a lower temperature, temperature T ₂ , such that T ₂ <T1, at least one shape; and at least partially immersing the mold in a coolant to cool the organic matter to a temperature T ₃ where T ₃ <T ₂ . During the reduction, the partial pressure of the water is preferably kept as low as possible, more preferably below 0.1 atmosphere. The space velocity of hydrogen can be from 2 to 4 l/h per 1 g of catalyst.

In one embodiment of the present invention, the method for producing a cobalt-containing catalyst may include, in the step of forming a carbide, treating the activated catalyst containing the catalyst support supporting zero-valent cobalt with a gas containing CO (preferably at a temperature T1, where T1 is from 200 to 280 ° C) , to convert cobalt to cobalt carbide, resulting in a catalyst precursor containing cobalt carbide; and in a subsequent activation step, subjecting the cobalt carbide-containing catalyst precursor to a hydrogen-containing gas (preferably at a temperature T ₂ where T ₂ is at least 300° C.) to convert the cobalt carbide to metallic cobalt, thereby activating the cobalt carbide-containing precursor catalyst and obtaining a cobalt-containing catalyst for the synthesis of hydrocarbons.

The catalyst is preferably a catalyst as described above in this invention.

Synthesis of hydrocarbons.

According to a fourth aspect of the present invention, there is provided a process for synthesizing hydrocarbons, which comprises contacting a cobalt-containing catalyst as described above in this invention with hydrogen and carbon monoxide at a temperature above 100° C. and a pressure of at least 1000 kPa to produce hydrocarbons, and optionally hydrocarbon oxygenates.

According to a fifth aspect of the present invention, there is provided a hydrocarbon synthesis process for producing hydrocarbons and optionally hydrocarbon oxygenates, which comprises contacting a synthesis gas containing hydrogen, carbon monoxide and N-containing pollutants selected from the group consisting of HCN, NH ₃ , NO, R _x NH ₃ _ _x where R is an organic group and x is 1, 2 or 3, where R is the same or different when x is 2 or 3, R1-CN where R ¹ is an organic group, and heterocyclic compounds containing at least one nitrogen atom as a ring member of the heterocyclic ring of the heterocyclic compound, wherein N-containing contaminants total at least 100 vppb but less than 1,000,000 vppb of the synthesis gas, at a temperature of at least 180 °C and a pressure of at least 1000 kPa with a catalyst as given above to produce hydrocarbons and optionally carbohydrate oxygenates orogens using the Fischer-Tropsch synthesis of hydrogen with carbon monoxide. Synthesis gas (syngas) may contain a total of at least 200 vppb N-containing pollutants. Preferably the synthesis gas contains at least 250 vppb of N-containing contaminants. More preferably, the synthesis gas contains at least 500 vppb of N-containing contaminants. As a rule, synthesis gas contains at least

- 9 041431 re 1000 vppb N-containing pollutants. Preferably, the synthesis gas contains no more than 100,000 vppb of N-containing contaminants. More preferably, the synthesis gas contains no more than 20,000 vppb of N-containing contaminants. As a general rule, synthesis gas may contain no more than 10,000 vppb of N-containing contaminants. For example, in one embodiment of the invention, the synthesis gas may contain approximately 2000 vppb of N-containing contaminants. However, in another embodiment, the synthesis gas may contain approximately 5000 vppb of N-containing contaminants. Typically, when synthesis gas is involved in a gas-liquid process, it contains HCN and NH ₃ as N-containing contaminants; when it comes to the process of converting coal into a liquid, it contains NH ₃ and NO as N-containing pollutants.

Preferably R in R _x NH ₃ _ _x is a hydrocarbyl group and/or an oxygenated hydrocarbyl group. More preferably R in R _x NH ₃ _ _x is an alkyl group and/or an alcohol. Preferably x is 1 or 2. In a preferred embodiment, R _x NH ₃ _ _x is dipropylamine (CH ₃ CH ₂ CH ₂ ) ₂ NH. Alternatively, R _x NH ₃ _ _x may be diethanolamine or methyldiethanolamine.

Preferably R ¹ in R 1 -CN is a hydrocarbyl group. More preferably, R ¹ in R 1 -CN is an alkyl group. In one preferred embodiment of the invention, R ¹ is methyl.

Heterocyclic compounds may include oxygen-containing groups. Examples of such oxygenated and non-oxygenated compounds are 4-piperidinoacetophenone (heterocyclic with oxygen), 1,4-bipiperidine (heterocyclic, no oxygen), 1-piperidine propionitrile (monocyclic), and 3-piperidino-1,2-propanediol (monocyclic with oxygen). Alternatively, the hydrocarbon synthesis process may be as described in this invention above, except that the synthesis gas contains at least or less than 100 vppbN-containing contaminants, as described in this invention above.

In one preferred embodiment of the invention, the catalyst can be obtained by including in the stage of formation of the carbide, the activated catalyst containing the catalyst support supporting zero valence cobalt is treated with a gas containing CO (preferably at a temperature T1, where T1 is from 200 to 280 ° C) , to convert cobalt to cobalt carbide, resulting in a catalyst precursor containing cobalt carbide; and in a subsequent activation step, subjecting the cobalt carbide-containing catalyst precursor to a hydrogen-containing gas (preferably at a temperature T ₂ where T ₂ is at least 300° C.) to convert the cobalt carbide to metallic cobalt, thereby activating the cobalt carbide-containing precursor catalyst and obtaining a cobalt-containing catalyst for the synthesis of hydrocarbons.

Preferably the hydrocarbon synthesis process is a Fischer-Tropsch process, preferably a three-phase Fischer-Tropsch process, more preferably a slurry-bed Fischer-Tropsch process to produce a wax product.

The partial pressure of water in the slurry layer can reach at least 500 kPa, preferably at least 800 kPa. The total molar ratio of H ₂ /CO in the feed may be from 1.4 to 2, preferably about 1.5, alternatively about 1.8. Alternatively, the partial pressure of water in the slurry layer may be below 500 kPa. The total H2/CO molar ratio in the feed may be from 1.4 to 2, preferably about 1.6. The hydrocarbon synthesis process may also include a hydroprocessing step to convert hydrocarbons and possibly their oxygenates into liquid fuels and/or other chemicals. According to another aspect of the present invention, products obtained from a hydrocarbon synthesis process as described herein above are provided. The catalyst, as described in this invention above, can be used to improve the stability of the activity or the activity or productivity of the hydrocarbon synthesis process. The improvement can be compared to a catalyst that does not contain titanium and manganese. The titanium and manganese present in the catalyst can reduce catalyst deactivation during hydrocarbon synthesis. Improved activity stability, activity, C5+ productivity and reduced deactivation can be measured after three and/or more days of hydrocarbon synthesis. The titanium and manganese present in the catalyst may serve to reduce methane selectivity and/or may reduce support dissolution during hydrocarbon synthesis. C5+ productivity is a unit mass of C5+ hydrocarbons per unit of catalyst per unit of time and is a function of the CO conversion rate and the selectivity of the catalyst for C5+ hydrocarbons.

Brief description of the drawings

The invention will now be described in more detail, by way of example only, with reference to the accompanying figures, in which:

fig. 1 is a graph showing the FT speed for examples 1, 2, 6-8, 10, 11 and 33 relative to example 9;

- 10 041431 fig. 2 is a graph showing the selectivity of methane compared to examples

1, 2, 6-8, 10, 11 and 33 with respect to example 9;

fig. 3 is a graph showing the cumulative dissolution of Al as a function of time for Mn-modified, Ti-modified, MnTi-modified, unmodified alumina, Si-Al ₂ O ₃ and MnSi-Al ₂ O ₃ substrates;

fig. 4 is a graph showing the FT speed for RCR Examples 33, 37, 38 and 39 versus SR Example 38;

fig. 5 is a graph showing the selectivity of CH4 relative to Examples 33, 37, 38 RCR and 39 relative to Example 38 SR;

fig. 6 is a graph showing the performance of C5+ compared to Example 38 SR;

fig. 7 is a graph showing FT speed vs. Examples 40, 41, 42, 44, 46, 47, 48, 49 and 50 vs. 38 SR examples; and also FIG. 8 is a graph showing the selectivity of CH4 relative to examples 40, 41, 42, 44, 46, 47, 48, 49 and 50 relative to examples 38 SR.

The foregoing and other objects, features and advantages of the present invention will become more apparent from the following description of some embodiments of the present invention through the following non-limiting examples.

Examples

Now the present invention will be described with reference to the following non-limiting experimental examples.

Example 1 (comparative) - 30 g Co/0.04 g Pt/100 g unmodified Al ₂ O ₃ .

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.04 g Pt/100 g support was prepared using an unmodified Al ₂ O ₃ (Puralox with a surface area of 150 m ² /g - hereinafter referred to as Puralox) support . In the first impregnation step, Co(NO ₃ ) ₂ -6H ₂ O (79.0 g) and (NH ₄ ) ₃ Pt(NO ₃ ) ₂ (0.026 g) were dissolved in distilled water (100 g). Maleic acid in an amount of approximately 0.03 mol/100 g of carrier was dissolved in this solution. Puralox (100 g) was then added to this mixture and excess water was removed under reduced pressure using the drying profile in Table 1. 1 to get free flowing powder.

Table 1

Drying profile for impregnated substrate

Temperature (°C) Pressure (kPa) Time(min) 60 25 15 75 25 thirty 85 25 thirty 85 25-13 120 85 13-5 15 85 5 180

The free-flowing powder was then calcined in a fluid bed calciner with a linear heating rate from 1°C/min to 250°C with a holding time of 6 hours using GHSV Nm ³ /kg Co(NO3)2-6H2O/4.

Then, in the second impregnation step, the above steps were repeated using Co(NO ₃ ) ₂ -6H ₂ O (56.8 g) and [Pt(NH ₄ ) ₄ (NO ₃ ) ₂ ] (0.042 g) dissolved in water (100 G). Pre-calcined material (100 g) was added to this mixture and excess water was removed under reduced pressure using the drying profile in Table 1. 1 to get free flowing powder. The free flowing powder was then calcined again in a fluidized bed calciner with a gentle heating rate from 1°C/min to 250°C with a holding time of 6 h using GHSV 2.5 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/ 4.

Example 2 (comparative) 30 g Co/0.04 g Pt/3.1 g Mn/100 g unmodified Al ₂ O ₃ (Mn as promoter).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor was prepared as described in Example 1.

In this example, manganese was added as a catalyst promoter. After the second impregnation step, Mn(NO ₃ ) ₂ -4H ₂ O (10.1 g) was dissolved in water (100 g) and added to the calcined material (100 g). Excess water was removed under reduced pressure using the drying profile in Table 1. 1 to get free flowing powder. The free flowing powder was then calcined again in a fluidized bed calciner with a gentle heating rate from 1°C/min to 250°C with a holding time of 6 hours using GHSV Nm7kg Co(NO ₃ ) ₂ -6H ₂ O/4.

Example 3 (comparative) - Ti-Al ₂ O ₃ (Puralox) substrate (Ti as modifier).

Titanium (IV) isopropoxide (17.2 g) was added to dry ethanol (78.9 g) and left to stir

- 11 041431 within 10 minutes. A12O3 (Puralox) (100 g) was added to this solution and allowed to stir for another minute. Thereafter, ethanol was removed under reduced pressure using the drying profile in Table 1. 2 to get free flowing powder.

table 2

Drying profile for Ti impregnated with Puralox

Pressure Temperature

Time(min) (kPa) (°C)

84.2 60 10 50 60 thirty 40 60 thirty thirty 60 thirty 20 60 60 10 60 60 5 60 60

After this fluidized bed calcination step, the substrate material was further calcined in a muffle furnace to 550° C. at a heating rate of 5° C./min and a final hold of 5 hours. The resulting modified substrate included 2.6 g Ti/100 g Al ₂ O3. After the drying step, the modified substrate was calcined in a fluid bed calciner with a GHSV of 2.5 Nm3/kg substrate/h using air as the calcination gas using a heating rate of 1°C/min to 425°C without a holding step at this temperature. . After this fluidized bed calcination step, the support material was further calcined in a muffle furnace to 550°C with a heating rate of 5°C/min and a final holding time of 5 hours. The resulting modified support contained 2.6 g Ti/100 g Al2O3.

Example 4 (comparative) - Mn-Al ₂ O3 (Puralox) support (Mn as modifier).

Manganese (II) acetate tetrahydrate (13.8 g) was dissolved in water (80-100 g) and stirred for 10 minutes. Al ₂ O ₃ (Puralox) (100 g) was added to this solution and stirred for another 10 minutes. The water was then removed under reduced pressure using the drying profile in Table 1. 3 to get free flowing powder.

Table 3

Drying profile for Mn-impregnated Puralox material

Pressure Temperature

Time(min)(kPa)(°C)

P0 8560

85180

After the drying step, the modified carrier was calcined in a fluidized bed calciner with a GHSV of 2.5 Nm ³ /hr/kg of substrate using air as the calcination gas using a heating rate of 1°C/min to 425°C without a holding step at this temperature. After this fluidized bed calcination step, the respective substrate material was subjected to further calcination in a muffle furnace to 550° C. with a heating rate of 5° C./min and a final holding time of 5 hours. The resulting modified substrate contained 3.1 g Mn/100 g Al ₂ O ₃ .

Example 5 (comparative) - MnTi-Al ₂ O ₃ (Puralox) substrate (Mn and Ti as modifiers).

The Ti-Al2O3 support prepared from Example 3 was impregnated with manganese (II) acetate tetrahydrate as described in Example 4. The resulting modified support contained 2.6 g Ti/3.1 g Mn/100 g Al ₂ O ₃ .

Example 6 (comparative) 30 g Co/0.075 g Pt/100 g Ti-Al ₂ O ₃ (Ti as modifier).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 1, however a TiAl2O3 support was used as described in Example 3.

Example 7 (comparative) 30 g Co/0.075 g Pt/100 g Mn-Al ₂ O ₃ (Mn as modifier).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 1. However, no maleic acid was added during catalyst preparation. A Mn-Al ₂ O ₃ substrate was used as described in Example 4.

Example 8 (comparative) 30 g Co/0.075 g Pt/100 g MnTi-Al ₂ O ₃ (Ti and Mn as modifiers).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 1. However, no maleic acid was added during catalyst preparation. A MnTi-Al2O3 substrate was used as described in Example 5.

Example 9 (comparative) 30 g Co/0.075 g Pt/3.1 g Mn/100 g Ti-Al ₂ O ₃ (Ti as modifier and Mn as promoter).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/3.1 g Mn/100 g support was prepared as described in Example 2, however, a Ti-Al ₂ O ₃ support was used as described in example 3.

- 12 041431

Example 10 (comparative) 30 g Co/0.04 g Pt/100 g Si-Al2O ₃ (Si as modifier).

Cobalt Based Fischer-Tropsch Synthesis Catalyst Precursor with 30g Composition

Co/0.04 g Pt/100 g support was prepared as described in Example 1. However, a 2.1 g Si/100 g Al ₂ O ₃ support was used using TEOS (tetraethoxysilane) as the starting material for modification of the support as described in US 6638889.

Example 11 (comparative) - 30 g Co/0.04 g Pt/3.1 g Mn/100 g Si-Al ₂ O ₃ (Si as modifier and Mn as promoter).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor was prepared as described in Example 10. However, during the second impregnation step, Co(NO ₃ ) ₂ -6H ₂ O (56.8 g), [Pt(NH ₄ ) ₄ ( NO ₃ ) ₂ ] (0.042 g) and Mn(NO ₃ ) ₂ 4H ₂ O (11.6 g) were dissolved in water (100 g) and the calcined material obtained in the first impregnation step (100 g) was added.

Example 12 (comparative) 30 g Co/0.075 g Pt/100 g Ti-Al ₂ O ₃ (Ti as modifier).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 1, however no maleic acid was added during catalyst preparation. Ti-Al ₂ O ₃ was used and prepared as described in Example 3.

Example 13 (comparative) 30 g Co/0.075 g Pt/100 g Ti-Al ₂ O ₃ (Ti as modifier).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor was prepared as described in Example 12. However, 5 g Ti/100 g Al ₂ O ₃ support was used and prepared as described in Example 3.

Example 14 (comparative) - 30 g Co/0.075 g Pt/ 100 g Ti-Al ₂ O ₃ (Ti as modifier).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor was prepared as described in Example 12. However, a 10 g Ti/100 g Al ₂ O ₃ support was used and prepared as described in Example 3.

Example 15 - recovery.

The calcined catalyst precursors were reduced prior to Fischer-Tropsch synthesis using pure H2 flowing at 2.0 Nm ³ /kg catalyst/hour at atmospheric pressure. The following heating profile was used: holding from 1°C/min to 110°C for 3 hours followed by holding from 1°C/min to 425°C for 10 hours. The recovered catalyst was cooled to room temperature and suspended in molten wax and loaded into the CSTR under an inert gas atmosphere (argon or nitrogen).

Example 16 - Fischer-Tropsch synthesis.

The activated and wax-protected catalysts as described in Example 15 were tested for their FTS slurry phase performance in a laboratory microsuspension CSTR at a reactor temperature of 230°C and a reactor pressure of approximately 2200 kPa, during which the feed gas mixture of pure H2 and CO and Ar was used with an Ar content of ~5% and an overall H2/CO feed molar ratio of approximately 1.8. This reactor was electrically heated and sufficiently high stirrer speeds were used to remove any restrictions on gas-liquid mass transfer. The gas space velocity was changed such that the synthesis gas conversion was approximately 78±1%. The partial pressure of water was approximately 1000 kPa.

Discussion.

Fig. 1 shows the percentage difference in FT speed for examples 1, 2, 6-8, 10, 11 and 33 relative to example 9 and can be calculated as (FT speed of examples 1, 2, 6-8, 10, 11 or 33 - FT speed example 9)/FT rate of example 9. As can be seen, example 2 (Co/3.1 g Mn/100 g unmodified Al ₂ O ₃ ) demonstrates that the addition of manganese as a catalyst promoter did not improve the stability of the catalyst activity compared to example 1 (unmodified catalyst sample without promoter), online over time. This trend was also observed when comparing catalysts containing Si-modified support Al ₂ O ₃ promoted with manganese as in example 11 (Co/3.1 g Mn/100 g Si-Al ₂ O ₃ ) with example 10 (Co/100 g Si-Al ₂ O ₃ ). Example 9 (Co/3.1 g Mn/100 g Ti-Al ₂ O ₃ ) showed deactivation of the original catalyst, however, after five days on-line, the performance of the catalyst stabilized and remained stable for 50 days.

Example 6 (Co/100 g Ti-Al2O3) and Example 7 (Co/100 g Mn-Al2O3) showed that titanium and manganese as an Al2O3 support, respectively, as a modifier, resulted in increased activity and activity stability compared to example 1, an unmodified catalyst sample without a promoter.

Referring to example 7, this example showed black wax, which indicates the decomposition of the catalyst. This was not observed for catalysts containing a combination of titanium and manganese support modifications (example 8, Co/100 g MnTi-Al ₂ O ₃ ).

Catalysts containing a combination of titanium and manganese, either manganese added as a support as a modifier (example 8) or a catalyst promoter (example 9), showed a significant increase in activity and activity stability compared to examples 1, 2, 6, 7, 10 and 11.

The percentage difference in methane selectivity of Examples 1, 2, 6-8, 10, 11 and 33 relative to Example 9 is shown in FIG. 2 and can be calculated as (% selectivity CH ₄ relative to examples 1, 2, 6-8, 10, 11 or 33% selectivity CH ₄ example 9)/% selectivity CH ₄ example 9. As can be seen, examples 8 and 9 containing the Mn/Ti combination showed lower methane selectivity compared to the rest of the catalyst samples tested over time. Example 7 containing the Mn-modified Al ₂ O3 showed an initial low methane selectivity which increased to the methane selectivity observed for Example 6 containing the Ti-modified Al ₂ O ₃ support.

In the table below. 4 shows the performance of the FT with respect to examples 12-14 with respect to initial activities. These samples were prepared using Ti-modified Al ₂ O ₃ with various levels of Ti modification. As can be seen, increasing the Ti content from 2.6 g Ti/100 g Al ₂ O ₃ to 10 g Ti/100 g Al ₂ O ₃ did not lead to a relative improvement in the activity stability of the catalysts compared to example 12. Catalysts containing higher loading Ti, led to a decrease in the stability of activity over time.

Table 4

Relative speed FT ¹ relative to examples 12-14 tested under conditions as described in example 16

Time in the stream, days Example 12, (2.6 rTi/100 gA1 ₂ O ₃ ) Example 13 (5 g Ti-Al ₂ O ₃ ) Example 14 (10 g Ti-Al ₂ O ₃ ) 1 1 1 1 19 0.53 0.38 0.37

¹ Relative to the initial rate FT ((CO+CO ₂ ) µmol/CO/gf)) and the error is 5% eg 1±0.05.

Example 17 - Fischer-Tropsch synthesis.

The activated and wax-protected catalysts as described in Example 15, with respect to Examples 8 and 9, were tested for their FTS slurry phase performance in a laboratory microsuspension CSTR at a reactor temperature of 230° C. and a reactor pressure of approximately 1900 kPa, during which a pure mixture was used. source gases H ₂ , CO and Ag with an Ar content of 10% and a molar ratio of the total raw material H ₂ /CO ~ 1.5.

This reactor was electrically heated and sufficiently high stirrer speeds were used to remove any restrictions on gas-liquid mass transfer. The gas space velocity was changed such that the synthesis gas conversion was approximately 72+1%. The partial pressure of water was approximately 600 kPa. Examples 8 and 9 were tested under the conditions described in example 17. As can be seen from the table. 5, Example 8 containing the MnTi support modification and Example 9 (containing Mn as a promoter and Ti as a support as a modifier) showed comparable relative values. FT activity and methane selectivity over time showed a positive effect from the combination of MnTi and the addition of Mn as a catalyst promoter or support as a modifier under FT conditions.

Table 5

FT performance relative to examples 8 and 9 over time in on-line mode under conditions as described in example 17

Time in the stream, days Relative FT speed ¹ Relative CH ₄ selectivity ² Example 8 Co/MnT1-A1 ₂ Oz 1 1 1 9 0.8 0.88 thirty 0.71 0.86 Example 9, CoMn/Ti-Al ₂ O ₃ 1 1 1 8 0.78 0.89 thirty 0.67 0.84

¹ Relative to the initial rate FT ((CO+CO ₂ ) µmol/CO/gf)) and the error is 5%, eg 1±0.05.

² Selectivity deviations %CH ₄ relative to day 1; C% excluding the formation of CO ₂ and the error is 0.3 percentage points, for example 5.8±0.3.

Example 18 (comparative) - 30 g Co/0.075 g Pt/ΙΟΟ g Mn-A1 ₂ O ₃ .

- 14041431

Cobalt Based Fischer-Tropsch Synthesis Catalyst Precursor with 30g Composition

Co/0.075 g Pt/100 g support was prepared as described in Example 1. However, no maleic acid was added during the preparation of the catalyst. A Mn-Al2O ₃ substrate was used as described in example 4.

However, the resulting modified substrate consisted of 2.1 g Mn/100 g Al ₂ O ₃ .

Example 19 (comparative) 30 g Co/0.075 g Pt/100 g Mn-Al ₂ O ₃ .

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 1. However, no maleic acid was added during catalyst preparation. A Mn-Al ₂ O ₃ substrate was used as described in Example 4. However, the resulting modified substrate consisted of 7.5 g Mn/100 g Al ₂ O ₃ .

Example 20 (comparative) 30 g Co/0.075 g Pt/100 g Mn-Al ₂ O ₃ .

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 1. However, no maleic acid was added during catalyst preparation. A Mn-Al2O3 substrate was used as described in Example 4. However, the resulting modified substrate consisted of 10 g Mn/100 g Al ₂ O ₃ .

Example 21 - Fischer-Tropsch synthesis.

The activated and wax-protected catalysts as described in Example 15 for Examples 1820 were tested for their performance in the FTS slurry phase in a laboratory microsuspension CSTR. The pressure was raised to 1800 kPa and the temperature to 230°C, where after the synthesis was introduced.

The synthesis source gas consisted of hydrogen, carbon monoxide and contained 10% argon as an internal standard with a total molar ratio of H2/CO to the source material ~ 1.6. This reactor was electrically heated and sufficiently high stirrer speeds were used to remove any restrictions on gas-liquid mass transfer. The %H2+CO conversion was maintained at 60%±2 by controlling the feed flow with Brooks mass flow controllers. The partial pressure of water was approximately 500 kPa. Tab. 6 shows the relative performance of FT relative to examples 18-20. These samples were prepared using Mn-modified Al ₂ O ₃ with various levels of Mn modification. No positive effect was observed when the Mn content was increased from 2.1 g Mn/100 g Al ₂ O ₃ to 10 g Mn/100 g Al ₂ O ₃ . The increase in Mn levels resulted in a significant fluctuation (decrease) in FT velocities with time in the flow.

TABLE 6 Relative Velocity of FT ¹ vs. Examples 18-20 Tested Under the Conditions As Described in Example 21

Time on-line Example 18, (2.1 g Mn/100 g A1 ₂ 0h) Example 19 (7.5 g Mn/100 g Al ₂ O ₃ ) Example 20, (10 g Mn/100 g Al ₂ Oz) 1 1 1 1 5 0.94 0.72 0.45

¹ Relative to the initial rate FT ((CO+CO ₂ ) µmol/CO/gs)) and the error is 5% eg 1±0.05.

Example 22 (comparative) - MnSi-Al ₂ O ₃ (Puralox) substrate.

The Si-Al ₂ O ₃ substrate as described in Example 10 was impregnated with manganese(II) acetate tetrahydrate as described in Example 4. The resulting modified substrate consisted of 3 g Mn/100 g SiAl2O3.

Example 23 (comparative) - MnSi-Al ₂ O ₃ (Puralox) substrate.

The Si-Al2O3 substrate as described in Example 10 was impregnated with manganese acetate tetrahydrate as described in Example 4. The resulting modified substrate consisted of 5 g Mn/100 g Si-Al ₂ O ₃ .

Example 24 (conductivity measurements).

Aluminum oxide dissolves in an aqueous medium at low pH values. The dissolution of aluminum oxide leads to the formation of aluminum ions. As more and more alumina dissolves, the concentration of aluminum increases over time. The conductivity was monitored by increasing the amount of aluminum over time at a constant pH of 2. The pH was kept constant by automatically adding a 10% nitric acid solution. The results are shown in FIG. 3 for modified and unmodified Al ₂ O ₃ .

Modified Al ₂ O ₃ substrates modified with Ti (Example 3), Mn (Example 4) and Si showed very similar Al dissolution behavior over time. Modification of MnSi Al ₂ O ₃ (example 22) led to a decrease in the dissolution of Al. However, a further increase in the Mn loading (Example 23) nullified the suppression of Al dissolution and resulted in Al dissolution behavior similar to the Si-modified Al2O3 substrate. Surprisingly, it can be seen that compared to the MnTi-modified substrate (Example 5), Al dissolution was significantly suppressed compared to the MnSi-modified Al ₂ O ₃ (Example 22).

Example 25 (comparative) 30 g Co/0.075 g Pt/3.1 g Mn/100 g (2.6 g Ti/100 g Al ₂ O ₃ ) (Co hydrolysis, Ti as modifier and Mn as promoter ), C4639.

- 15 041431

Cobalt Based Fischer-Tropsch Synthesis Catalyst Precursor with 30g Composition

Co/0.075 g Pt/3.1 g Mn/100 g (2.6 g Ti/100 g Al ₂ O ₃ ) usually as described in example 9, however, the substrate

Al ₂ O ₃ used in example 9 was replaced by a titanium-containing support, which was prepared by co-hydrolysis of titanium (IV) 2-ethylhexoxide and Al-hexanolate, as described in example 37 of WO 2014020507.

Example 26 (comparative) - 30 g Co/0.075 g Pt/3.1 g Mn/100 g (2.6 g Ti/100 g Al ₂ O ₃ (calcined PURAL 200™ as support impregnated with Ti slurry as modifier and Mn as a promoter), C4685.

A cobalt-based Fischer-Tropsch synthesis catalyst precursor was prepared with a composition of 30 g Co/0.075 g Pt/3.1 g Mn/100 g (2.6 g Ti/100 g Al ₂ O ₃ ) as described in Example 9, however, The Puralox used in Example 9 was replaced with a calcined PURAL 200™ with a pore diameter similar to that of the Example 25 substrate and a surface area of approximately 90 m ² /g.

Example 27 - Fischer-Tropsch reduction and synthesis (FTS).

The calcined catalyst precursors of Examples 25 and 26 are reduced and slurried into molten wax as described in Example 15. FTS performance for the activated and wax protected catalysts of Examples 25 and 26 was evaluated in a fixed bed reactor at 230° C. and a reactor pressure of approximately 1600 kPa s. using a feed gas mixture with an inlet H2/CO molar ratio of approximately 1.6. The space velocity of the gas supply was changed in such a way that the synthesis gas conversion was ~62-65%.

Discussion.

Tab. 7 shows that similar FTS catalyst results were obtained by comparing a Co/Pt/Mn/Ti-Al ₂ O ₃ catalyst sample obtained by co-hydrolysis of a Ti-modified support (Example 25) with Example 26 (Ti slurry impregnation), demonstrating that that the joint hydrolysis of the Ti-modified substrate is an alternative to the suspension impregnation of titanium on alumina.

Table 7

FT performance relative to examples 25 and 26 under conditions as described in example 27

CH ₄ selectivity ¹ Time on-line Example 25, C4639 ² Co/Pt/Mn/Ti-Al ₂ O ₃ with co-hydrolysis Example 26 C4685 ² Co/Pt/Mn/Ti-Al ₂ O ₃ impregnated with slurry % difference in absolute selectivity CH ₄ Examples 25 and 26 ³ 1 1.00 1.00 0.06 2 1.00 1.02 0.03 3 1.01 1.01 0.07 7 1.05 Relative speed FT ⁴ % difference in absolute speeds FT Examples 25 and 26 ⁵ 1 1.00 1.00 0.14 2 0.97 0.97 0.15 3 0.93 0.94 0.13 7 0.88

¹ C% excluding CO2 formation.

² Variation in %CH ₄ selectivity relative to day 1.

% difference CH ₄ selectivity (sel) of examples 25 and Ex. 26 = (%CH4 sel example 25 - %CH4 sel example 26)/%CH4 sel example 26.

⁴ Relative to initial velocity FT ((CO+CO2) µmol/CO/gf)).

⁵ % speed difference FT examples 25 26 = (FT speed example 25 -FT speed example 26)/FT speed example 26.

Example 28: (comparative) 30 g Co/0.075 g Pt/5 g Ni/100 g (2.6 g Ti/100 g (Ti as modifier and Ni as promoter), C4140.

- 16 041431

Co(NO3)2-6H2O (11.9 g), (NH3)4Pt(NO3)2 (0.0075 g) and Ni(NO3)2-6H2O (1.9 g) were dissolved in water (13 ml for Co , 2 ml for Pt, 2 ml for Ni). The pH of the solution was adjusted to 2.3 using dilute nitric acid. Added 15 g of Ti-modified Puralox substrate, as described in example 3, and excess water was removed under reduced pressure using the drying profile shown in table. 8 to obtain a free flowing powder.

Table 8

Drying profile

Pressure Temperature _ _{ζ λ} (kPa) (°C) Timemin)

atmospheric 60 10 28 60 thirty 28 75 90 28 85 60 5 85 60

g of bulk sample was calcined in a vertical oven using an air flow of 1000 ml/min and a heating rate from 1°C/min to 250°C with a holding time of 6 hours. The above steps were repeated in the second stage of impregnation, dissolving Co(NO ₃ ) ₂ - 6H ₂ O (6.8 g), (NH ₃ )4Pt(NO ₃ )2 (0.01 g) and Ni(NO ₃ ) ₂ -6H ₂ O (1.2 g) in water (9 ml for Co , 2 ml for Pt, 3 ml for Ni). Pre-calcined material (first stage impregnation) (12 g) was added to the mixture and excess water was removed under reduced pressure using the drying profile shown in Table 1. 8. 15 g of a free-flowing sample was calcined in a vertical oven using an air flow of 750 ml/min and a heating rate from 1°C/min to 250°C with a holding time of 6 hours.

Example 29: (comparative) - 30 g Co / 0.075 g Pt / 3.1 g Mn / 100 g (2.6 g Ti / 100 g Al ₂ O ₃ ) (Ti as modifier and Mn as promoter - similar to example 9, but with smaller quantities and a different drying profile), C4144.

Co(NO ₃ ) ₂ -6H ₂ O (13.3 g) and (NH ₃ ) ₄ Pt(NO ₃ ) ₂ (0.0075 g) were dissolved in water (13 ml for Co, 3 ml for Pt). The pH of the solution was adjusted to 2.3 using dilute nitric acid. 15 g of Puralox Ti-modified support as described in Example 3 was added and excess water was removed under reduced pressure using the drying profile shown in Table 1. 9 to get free flowing powder.

Table 9

Drying profile

Pressure (kPa) Temperature (°C) Time(min) Atmospheric 60 10 28 60 thirty 25 75 thirty 25 85 thirty 25-13 85 120 gradient 13-5 85 15 gradient 5 85 180

g of bulk sample was calcined in a vertical oven using an air flow of 1000 ml/min and a heating rate from 1°C/min to 250°C with a holding time of 6 hours. In the second stage of impregnation, the above steps were repeated using Co(NO ₃ ) ₂ - 6H ₂ O (5.75 g) and (NH ₃ ) ₄ Pt (NO ₃ ) ₂ (0.01 g) and also Mn (NO ₃ ) ₂ 4H ₂ O (1.4 g), dissolving it in water (10 ml for Co, 2 ml for Pt, 3 ml for Mn). 12 g of calcined material from the first stage of impregnation was added to the mixture and excess water was removed under reduced pressure using the drying profile shown in table. 9 to get free flowing powder. A 15 g bulk sample was calcined in a vertical oven using an air flow of 750 ml/min and a heating rate from 1°C/min to 250°C with a holding time of 6 hours.

Example 30 - Fischer-Tropsch reduction and synthesis (FTS).

The calcined catalyst precursors of Examples 28 and 29 were reduced and slurried into molten wax as described in Example 15. The FTS performance of the activated and wax protected catalysts from Examples 28 and 29 was evaluated in a fixed bed reactor at 230°C as described in Example 27.

Discussion.

It is known that Nickel can be used as an activity stability promoter [Ind. Eng. Chem. Res. 2010, 49, 4140-4148 and US 8,143,186]. However, the addition of Ni as a promoter to the Co/Pt/Ti-Al2O3 FTS catalyst did not show the same performance of the Co FTS catalyst as when using Mn as a promoter. Mn as a promoter resulted in lower methane selectivity with higher activity compared to Ni as a promoter. Tab. 10 illustrates the degree of deactivation of the catalysts, as indicated in example 28 and example 29, relative to their

- 17 041431 initial activity, as well as fluctuations in the selectivity to methane obtained on the catalysts prepared in examples 28 and 29 and activated and tested, as found in example 30 with respect to its initial selectivity to methane.

Table 10

FTS performance relative to Example 28 (Co/Pt/Ni//Ti-Al ₂ O ₃ ) and Example 29 (Co/Pt/Mn/Ti-Al ₂ O ₃ ) over time on-line under conditions ____________ as described in example 30____________

CH ₄ selectivity ¹ Time on-line Example 28, C4140 ² Co/Pt/Ni/Ti-A1 ₂ 03 Example 29, C4144 ² Co/Pt/Mn/Ti-A1 ₂ 03 % difference in absolute CH ₄ selectivity of Examples 28 and Ex. 29 ³ 1 1.00 1.00 0.78 3 0.94 1.03 0.64 5 0.93 1.04 0.59 10 1.04 Relative speed FT ⁴ % difference in absolute FT speeds of Examples 28 and Examples 29 ⁵ 1 1.00 1.00 -0.27 3 1.10 0.93 -0.14 5 1.17 0.92 -0.08 10 0.88

¹ C% except for the formation of CO ₂ .

² Variation in %CH ₄ selectivity relative to the day

1.

³ % difference CH4 selectivity (sel) of Examples 28 and 29 = (% _CH4sel of Example 28 - % _CH4sel of Example 29)/%CH4sel of Example 29.

⁴ Relative to initial FT rate ((CO+CO ₂ ) µmol/CO/gf)).

⁵ % difference in FT speeds of examples 28 and 29 = (FT speed of example 28 - FT speed of example 29)/FT speed of example 29.

Example 31: (comparative) 30 g Co/0.075 g Pt/3.1 g Mn/100 g (2.6 g Ti/100 g Al ₂ O ₃ ) with Ti as a modifier and Mn as a promoter using the hydrothermal precipitation method (HDM), C4585.

Co (NO ₃ ) ₂ -6H ₂ O (37.2 g), (NH ₃ ) ₄ Pt (NO ₃ ) ₂ (0.07 g), Mn (NO ₃ ) ₂ -4H ₂ O (7.06 g ) and maleic acid (1.25 g) was dissolved in 75 ml of water. Cobalt hydroxide (3 g) was added to the nitrate solution, after adding 50 g of Puralox Ti-modified support as described in Example 3. An additional 3 g of Co(OH) ₂ was added to the slurry and stirred at 95° C. in a rotary evaporator at 65 vol. /min An additional 3 g of Co(OH) 2 was added until the desired content of 11.8 g was reached. The mixture was stirred until complete absorption of Co(OH) ₂ (over approximately 3 hours). Excess water was removed under reduced pressure using the drying profile shown in Table 1. 11 to obtain a free flowing powder and calcined at 250°C at a heating rate of 1°C/min in air (2500 ml/min/gkat) for 6 hours.

Table 11

Drying profile

Pressure (kPa) Temperature (°C) Time (min) 50-13 95 180 5 100 120

The calcined catalyst precursor was reduced and slurried in molten wax as described in Example 15. The catalyst was tested for its performance in the FTS slurry phase in a laboratory CSTR microsuspension.

As can be seen from Table. 12, example 31, obtained using HDM, showed lower methane selectivity and higher activity compared to absolute selectivity.

- 18 041431 for CH4 and the reaction rates of example 9 (cobalt nitrate slurry impregnation method). The methane selectivity fluctuation in example 31 is slightly larger than in example 9, but the deactivation with respect to the 1st day over time in example 31 and example 9 are comparable.

Table 12

FTS performance relative to example 31 (Co/Pt/Mn/Ti-Al ₂ O ₃ - obtained using HDM) in on-line time mode under conditions as described in example 17)

Time on-line CH ₄ selective Example 31, C4585 ² Co/Pt/Mn/Ti-A1 ₂ 03 (HDM) ¹ Example 9, С2155 ² Co/Pt/Mn/Ti-А1 ₂ 0з % difference in absolute CH ₄ selectivity of Examples 31 and 9 ³ 1 1.00 1.00 -0.15 17 0.85 0.89 -0.19 31 0.76 0.86 -0.26 Relative speed FT ⁴ % difference in absolute FT speed of Examples 31 and 9 ⁵ 1 1.00 1.00 0.21 17 0.66 0.70 0.15 31 0.66 0.70 0.15

C% excluding CO2 formation.

² Variation in %CH ₄ selectivity relative to day 1.

³ % difference in CH4 selectivity (sel) between C4585 and C2155 = (% CH ₄ sel and C4585 - % CH ₄ sel and C2155)/% CH ₄ sel and C2155.

⁴ Relative to initial FT rate ((CO+CO ₂ ) µmol/CO/gf)).

⁵ % difference in FT speed between C4585 and C2155 = (FT speed C4585 - FT speed C2155)/FT speed C2155.

Example 32: (comparative) - MnTi-SiO ₂ (Mn and Ti as substrate as modifiers on silica substrate) - (FSQ-15).

Titanium (IV) isopropoxide (17.2 g) was added to dry ethanol (78.9 g) and allowed to stir for 10 minutes. Amorphous, preformed silica gel (100 g), CARiACT Q-15 (average pore diameter 15 nm) obtained from Fuji Silysia Chemical LTD was added to this solution and allowed to stir for another 10 minutes. Ethanol was removed under reduced pressure using the drying profile shown in Table 1. 2 to get free flowing powder.

Manganese (II) acetate tetrahydrate (13.8 g Mn(Ac) ₂ -4H ₂ O for loading 3.1 g Mn) was dissolved in water (80-100 g) and allowed to stir for 10 minutes. A free flowing powder prepared from Ti(OPr) ₄ modified silica (100 g) was added to this solution and allowed to stir for another 10 minutes. Water was removed under reduced pressure using the drying profile shown in Table 1. 3 to get free flowing powder. After the drying step, the modified carrier was calcined in a fluidized bed with a GHSV of 2.5 Nm ³ /kg substrate/hour using air as the calcination gas at a heating rate of 1°C/min to 425°C. The support material was additionally calcined in a muffle furnace to 500-550° C. at a heating rate of 5° C./min and a final holding time of 5 hours. The resulting modified support contained 3.1 g Mn/2.6 g Ti/100 g SiO ₂ .

Example 33: (comparative) 30 g Co/0.075 g Pt/100 g (3.1 g Mn/2.6 g Ti/100 g SiO ₂ ) (Mn and Ti as support as modifiers), (FSQ- 15), C4859.

In the first impregnation step, Co(NO ₃ ) ₂ -6H ₂ O (39.5 g) and (NH ₄ ) ₃ Pt(NO ₃ ) ₂ (0.025 g) were dissolved in water (50 g). The pH of the solution was adjusted to 2.3 using dilute nitric acid. To the mixture was added MnTi-SiO ₂ (50 g) the substrate described in example 32, and excess water was removed under reduced pressure using the drying profile shown in table. 1 to get free flowing powder. The free-flowing powder was calcined in a fluidized bed calciner with a linear heating rate from 1°C/min to 250°C with a holding time of 6 h using GHSV 2.5 Nm ³ /kg (Co(NO ₃ ) ₂ -6H ₂ O)/ 4. In the second impregnation step, Co(NO ₃ ) ₂ -6H ₂ O (28.4 g) and (NH ₄ ) ₃ Pt(NO ₃ ) ₂ (0.04 g) were dissolved in water (50 g). The pH of the solution was adjusted to 2.3 using dilute nitric acid. The calcined material from the first impregnation stage (50 g) was then added to this mixture and excess water was removed under reduced pressure using the drying profile in Table 1. 1 to get free flowing powder. The free-flowing powder was calcined in a fluidized bed calciner with a linear heating rate from 1°C/min to 250°C with a holding time of 6 h using GHSV 2.5 Nm ³ /kg (Co(NO ₃ ) ₂ -6H ₂ O)/ 4.

The calcined catalyst material was reduced and suspended in molten wax as described in Example 15. The catalyst was tested for its FTS slurry phase in CSTR laboratory microsuspension as described in Example 17.

Discussion.

As indicated in the present invention above, FIG. 1 shows the difference in FT rate for examples 1, 2, 6-8, 10, 11 and 33 relative to example 9. The Mn/Ti combination on a silica support (example 33) also showed a significant increase in activity compared to comparative examples that do not include Mn/Ti combination. As indicated in the present invention above, FIG. 2 shows the difference in percent methane selectivity for Examples 1, 2, 6-8, 10, 11, and 33 compared to Example 9. Example 33, containing a Mn/Ti combination on a silica support, showed the lowest methane selectivity over time compared to with the rest of the tested samples of catalysts.

Example 34: (comparative) - MnTi-SiO2 (FSQ-6).

A modified support with a composition of 3.1 g Mn/2.6 g Ti/100 g SiO2 was prepared as described in Example 32, however, the support was replaced with CARiACT Q-6 with an average pore diameter of 6 nm.

Example 35: (comparative) - MnTi-SiO2 (FSQ-30).

A modified support with a composition of 3.1 g Mn/2.6 g Ti/100 g SiO2 was prepared as described in Example 32, however, the support was replaced with CARiACT Q-30 with an average pore diameter of 30 nm.

Example 36: (comparative) - MnTi-SiO2 (FSQ-50).

A modified support with a composition of 3.1 g Mn/2.6 g Ti/100 g SiO2 was prepared as described in Example 32, however, the support was replaced with CARiACT Q-50 with an average pore diameter of 50 nm.

Example 37: (comparative) 30 g Co/0.075 g Pt/100 g MnTi-SiO2 (FSQ-6), C4881.

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 33, however, a MnTi-SiO2 (FSQ-6) support was used as described in Example 34.

Example 38: (according to the present invention) 30 g Co/0.075 g Pt/100 g MnTi-SiO2 (FSQ-30), C4812.

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 33, however, a MnTi-SiO2 (FSQ-30) support was used as described in Example 35.

Example 39: (comparative) 3ο g Co/0.075 g Pt/100 g MnTi-SiO2 (FSQ-50), C4860.

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as described in Example 33, however, a MnTi-SiO2 (FSQ-50) support was used as described in Example 36.

Example 40: (according to the present invention) 30 g Co/0.075 g Pt/2.5 g MAC/100 g MnTi-SiO2 (FSQ-30), C4987.

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g MnTi-SiO2 (FSQ-30) supports were prepared as described in Example 38, however, maleic acid (MAc) was added to the solution ( 1.25 g) during the first stage of impregnation.

Example 41: (comparative) 30 g Co/0.075 g Pt/100 g SiO2 (FSQ-30), C4408 (unmodified SiO2).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/100 g support was prepared as follows using FSQ-30 as support.

Co(NO ₃ ) ₂ -6H ₂ O (11.8 g) and (NH ₄ ) ₃ Pt(NO ₃ )2 (0.0075 g) were dissolved in distilled water (15 ml for Co, 2 ml for Pt). To this mixture was added FSQ-30 silica (15 g) and excess water was removed under reduced pressure using the drying profile shown in Table 1. 13 to obtain a free flowing powder.

- 20 041431

Table 13

Drying profile __________

Temperature (°C) Pressure (kPa) Time (min) 60 No vacuum 10 60 28 thirty 75 28 90 85 28 60 85 5 180

g of a free-flowing sample was calcined in a vertical oven using an air flow of 700 ml/min (GHSV = 2500 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/4) and a heating rate from 1°C/min to 250°C with holding time 6 h.

The above steps were repeated in a second impregnation step by dissolving Co(NO ₃ ) ₂ -6H ₂ O (6.8 g) and (NH ₃ ) ₄ Pt(NO ₃ ) ₂ (0.0098 g) in water (12 ml for Co , 2 ml for Pt). The pre-calcined (first impregnation stage) material (12 g) was added to the mixture and excess water was removed under reduced pressure using the drying profile shown in Table 1. 13. 15 g of a free-flowing sample was calcined in a vertical oven using an air flow rate of 680 ml/min (GHSV = 2,700 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/4) and a heating rate from 1°C/min to 250°C with a holding time of 6 hours.

Example 42 (comparative) 30 g Co/0.075 g Pt/3.1 g Mn/100 g SiO ₂ (FSQ-30), C4404, (Mn as promoter).

Co(NO ₃ ) ₂ -6H ₂ O (9.4 g), (NH ₄ ) ₃ Pt(NO ₃ ) ₂ (0.006 g) and Μπ(ΝΟ ₃ ) ₂ 4Η ₂ Ο (1.7 g) were dissolved in distilled water (10 ml for Co, 1 ml for Pt and 2 ml for Μπ). Unmodified silica FSQ-30 (12 g) was added to this mixture and excess water was removed under reduced pressure using the drying profile shown in Table 1. 13 to obtain a free flowing powder. A 15 g bulk sample was calcined in a vertical oven with an air flow of 620 ml/min (GHSV = 2,500 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/4) and a heating rate from 1°C/min to 250°C with holding time 6 h.

(GHSV = 2.700 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/4) and a heating rate of 1°C/min to 250°C with a holding time of 6 hours.

The above steps were repeated in the second impregnation step by dissolving Co(NO ₃ ) ₂ -6H ₂ O (5.7 g) and (NH ₃ ) ₄ Pt(NO ₃ ) ₂ (0.0081 g) in water (10 ml for Co , 1 ml for Pt). The pre-calcined (first impregnation step) material (10 g) was added to the mixture and excess water was removed under reduced pressure using the drying profile shown in Table 1. 13. 11 g of a free-flowing sample was calcined in a vertical oven using an air flow of 500 ml/min (GHSV = 2,700 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/4) and a heating rate from 1°C/min to 250 °С with a holding time of 6 hours.

Example 43 (comparative) 3.1 g Μπ/100 g SiO ₂ (FSQ-30) (Μπ as support as modifier).

The manganese-modified support in Example 4, however, used silica (FSQ-30) (100 g) as the support. The resulting modified substrate contained 3.1 g Μπ/100 g SiO ₂ .

Example 44 (comparative) - 30 g Co/0.075 g Pt/2.5 g MAC/100 g Mn-SiO ₂ (FSQ-30), C4998 (Μπ as support as modifier and MAC).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/2.5 g MAC/100 g support was prepared as described in Example 40, however, a Mn-SiO ₂ (50 g) modified support was used. , as described in example 43.

Example 45 (comparative) - 2.6 g Ti/100 g SiO ₂ (FSQ-30), (Ti as support as modifier).

A titanium-modified support was prepared as described in Example 3, however, FSQ-30 silica (100 g) was used as the support. The resulting modified substrate contained 2.6 g Ti/100 g SiO ₂ .

Example 46 (comparative) 30 g Co/0.075 g Pt/100 g Ti-SiO ₂ (FSQ-30), C4410.

Co(NO ₃ ) ₂ -6H ₂ O (11.8 g) and (NH ₄ ) ₃ Pt(NO ₃ ) ₂ (0.0075 g) were dissolved in water (15 ml for Co, 2 ml for Pt). To the mixture was added Ti-SiO ₂ (15 g) substrate as described in example 45, and excess water was removed under reduced pressure using the drying profile shown in table. 13 to get loose powder. 17 g of bulk sample was calcined in a vertical furnace with an air flow of 700 ml/min (GHSV = 2,500 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/4) and a heating rate from 1°C/min to 250°C with holding time 6 h.

The above steps were repeated in a second impregnation step by dissolving Co(NO ₃ ) ₂ -6H ₂ O (6.8 g) and (NH ₃ ) ₄ Pt(NO ₃ ) ₂ (0.0098 g) in water (12 ml for Co , 2 ml for Pt). The pre-calcined (first impregnation stage) material (12 g) was added to the mixture and excess water was removed under reduced pressure using the drying profile shown in Table 1. 13. 15 g of a free-flowing sample was calcined in

- 21 041431 vertical oven using an air flow of 680 ml/min (GHSV = 2,700 Nm ³ /kg Co(NO ₃ ) ₂ -6H ₂ O/4) and a heating rate of 1°C/min to 250°C with holding time 6 o'clock

Example 47 (comparative) 30 g Co/0.075 g Pt/2.5 g MAC/100 g Ti-SiO ₂ (FSQ-30), C4997.

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/2.5 g MAC/100 g support was prepared as described in Example 40, however, a Ti-modified silica support was used as described in example 45.

Example 48 (according to the present invention) 30 g Co/0.075 g Pt/2.5 g MAC/3.1 g Mn/100 g TiSiO ₂ (FSQ-30), C4991 (Mn as promoter in first impregnation) .

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/2.5 MAs/100 g Ti-SiO ₂ (FSQ-30) was prepared as described in example 47, however, in this example, manganese was added as a catalyst promoter in the first impregnation step before adjusting the pH by dissolving Mn(NO ₃ ) ₂ -4H ₂ O (7.1 g) in water (100 g).

Example 49 (according to the present invention) 30 g Co/0.075 g Pt/2.5 g MAC/3.1 g Mn/100 g TiSiO ₂ (FSQ-30), C4990 (Mn as promoter in second impregnation) .

A cobalt-based Fischer-Tropsch synthesis catalyst precursor with a composition of 30 g Co/0.075 g Pt/2.5 MAs/100 g Ti-SiO ₂ (FSQ-30) was prepared as described in example 47, however, in this example, manganese was added as a catalyst promoter in the first impregnation step before adjusting the pH by dissolving Mn(NO ₃ ) ₂ -4H ₂ O (7.1 g) in water (100 g).

Example 50 (according to the present invention) 30 g Co/0.075 g Pt/3.1 g Mn/100 g Ti-SiO ₂ (FSQ30), C4996 (Mn as promoter in first impregnation).

A cobalt-based Fischer-Tropsch synthesis catalyst precursor was prepared as described in Example 48, however, in this example, no maleic acid was added during catalyst preparation.

Example 51 - standard recovery (SR).

The calcined silica supported catalyst materials in Examples 33, 37-42, 44, and 4650 were reduced in situ prior to Fischer-Tropsch synthesis using pure H ₂ flowing at 2.0 Nm ³ /kg catalyst/hr at atmospheric pressure. The temperature was raised at a rate of 1°C/min to 385-425°C and maintained for 6 hours.

Example 52 - Recovery - Carbidization - Activation of Recovery (RCR).

The calcined silica-supported catalyst materials in Examples 33 and 37-39 were activated in situ prior to Fischer-Tropsch synthesis in a fixed bed reactor using the following procedure:

Increasing the temperature to 380° C. at 1° C./min in hydrogen (4500 ml/gkat/h) at atmospheric pressure and holding for 6 hours, followed by cooling to 200° C. in hydrogen.

Replacement of hydrogen with argon (2000 ml/gkat/h) and keeping for 20 min.

At the stage of carbide formation, replace the argon with CO (6000 ml/gkat/h) and start increasing the temperature to 230°C at a rate of 1°C/min and maintain for 6 h at 600 kPa CO.

When cooled in a CO atmosphere (1000 ml/gkat/h) from 230 to 170°C, the pressure drops to atmospheric pressure.

At 170° C. and atmospheric pressure, CO was replaced with argon (20 min; 2000 ml/gkat/h), where the argon was then replaced with hydrogen again.

In the activation step, raising the temperature to 425°C in a hydrogen atmosphere (8000 ml/gkat/h) at a rate of 1°C/min and holding time of 7 h, followed by cooling to 200°C in a hydrogen atmosphere, after which FT synthesis was started .

Example 53 - Fischer-Tropsch synthesis.

The FTS performance of the activated silica supported catalysts of Examples 33, 37-42, 44 and 46-50 was evaluated in a fixed bed reactor at 230° C. and a pressure of 1700 kPa. The H2/CO ratio at the inlet was ~1.6. The gas space velocity was changed as such to control the synthesis gas conversion by about 50-55%.

Discussion.

Pore Diameter: Standard Recovery (SR).

Fig. 4 and 5 show the difference in FT rates and percent CH4 selectivity for Example 33 (FSQ-15), Example 37 (FSQ-6) and Example 39 (FSQ-50) versus Example 38 (FSQ-30) (activated at 385° C with standard recovery as described in Example 51).

Example 38 with an average diameter of 30 nm, after standard reduction, showed the highest FT rates compared to other catalysts after standard reduction. Catalysts with large average support pore diameters of 30 nm and 50 nm had the lowest CH4 selectivity, however, from FIG. 6 shows that a better combination of FTS-activity/C5 + selectivity (C5 + productivity) is obtained compared to the Fischer-Tropsch catalyst as described in example 38 (FSQ-30). The C5+ productivity for the Fischer-Tropsch catalyst as described in Example 37 (FSQ-6) and Example 39 (FSQ-50) was significantly lower (see FIG. 6).

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As stated in this invention above, C5+ productivity is the specific gravity of C5+ hydrocarbons per unit of catalyst per unit of time and is a function of the rate of CO converted and the hydrocarbon selectivity of the C5+ catalyst.

Pore diameter: RCR activation.

Fig. 4 and 5 show the difference in FT rates and percent CH ₄ selectivity for Example 33 (FSQ-15), Example 37 (FSQ-6) and Example 39 (FSQ-50) relative to Example 38 (FSQ-30) (activated at 385 °C with standard recovery as described in example 51).

RCR activation of catalysts on a silica support further increased the activity and selectivity of the catalysts. The activated RCR Fischer-Tropsch catalyst showed even greater differentiation in C5+ performance for the catalyst, as shown in Example 38 with a support pore diameter of 30 nm (see FIG. 6).

Addition of maleic acid (MAc).

The CH ₄ selectivity obtained for the catalyst by adding maleic acid during the first impregnation step as described in Example 40 (30 g Co/0.075 g Pt/2.5 g MAC/100 g MnTi-SiO ₂ (FSQ30)) was comparable with a catalyst selectivity for CH ₄ as described in example 38 with similar pore diameters (FSQ-30) (see table. 14). However, the activity and stability of the activity of the catalyst, as indicated in example 40, was higher and may be the result of improved dispersion of the metal with the addition of maleic acid.

Table 14

Difference in FTS performance of Example 38 and Example 40 (same pore diameter) after standard reduction under conditions as described in Example 50

Relative selectivity CH ₄ , “/o ¹ Time on-line Example 40 C4987 ² Co/Pt/MAc/MnTi-SiO ₂ Example 38 C4812 ² Co/Pt/MnTi-SiO ₂ Difference CH ₄ selectivity of Example 40 relative to Example 38 ³ 1 1.00 1.00 -0.13 2 0.97 0.90 -0.05 3 0.99 0.91 -0.05 4 1.00 0.87 0.00 5 1.01 0.85 0.04 Relative speed FT ⁴ Time on-line Example 40 C4987 Co/Pt/MAc/MnTiSiO ₂ Example 38 C4812 Co/Pt/MnTi-SiO ₂ Speed difference FT of Example 40 relative to Example 38 ⁵ 1 1.00 1.00 -0.09 2 0.97 0.86 0.02 3 0.96 0.85 0.03 4 0.95 0.80 0.09 5 0.95 0.79 0.09

¹ C% except for the formation of CO ₂ .

² . Variation in %CH ₄ selectivity relative to day 1.

³ % CH ₄ sel selectivity difference of Example 40 and Example 38 = (%CH ₄ sel of Example 40 - %CH ₄ sel of Example 38)/%CH ₄ sel of Example 38.

⁴ Relative to initial FT rate ((CO+CO ₂ ) µmol/CO/gf)).

⁵ Difference of FT speed of examples 40 and 38 = ((FT speed of example 40 - FT speed of example 38)/FT speed of example 38).

Mn Ti-SiO ₂ substrate.

The combination of Ti and Mn is critical for high Fischer-Tropsch activity and low CH ₄ selectivity (see FIGS. 7 and 8). Modification of the silica support with Mn alone (Example 44) or as a promoter (Example 42) resulted in a catalyst with lower Fischer-Tropsch performance compared to the unmodified silica support (Example 41). The use of Ti as a support modifier (Example 46 and Example 47 (with MAC)) for Co Fischer-Tropsch catalyst demonstrated higher Fischer-Tropsch synthesis rates compared to unmodified support (Example 41). However, CH ₄ selectivity was not significantly improved using Ti as a modifier support compared to unmodified silica support. When using Ti as a support as a quality modifier in combination with Mn (either as a support as a modifier as in Example 38 and Example 40 (with MAC) or as a promoter as in Examples 48, 49 and 50), the CH4 selectivity obtained for these catalysts was the lowest. Using Mn as a support as a modifier (example 38 and example 40 (with MAC)) resulted in higher FT rates compared to using Mn as a promoter (examples 48, 49 and 50).

Example 54 - abrasion resistance.

The abrasion resistance of a MnTi-SiO2 (FSQ-30) catalyst support as described in Example 35 was compared with an unmodified FSQ-30 support to determine the physical strength of the modified catalyst support.

A Silverson homogenizer was used to perform a shear attrition test. A catalyst support (5 g) as described in example 35 was added to 170 ml of distilled water and stirred for 15 minutes at a stirrer speed of 1000 rpm at 25°C. After completion of the shear attrition test, the entire sample/mixture was decanted and PSD (particle size distribution) was measured using a Saturn digitizer, which is essentially a volume-based method used to determine PSD before and after shear testing.

Discussion.

The mechanical strength of the modified substrate, as described in example 35, is shown in table. 15. Mechanical abrasion tests showed that the Ti/Mn modified silica is mechanically stable compared to unmodified silica with the same pore diameter of 30 nm. Thus, Ti and Mn as a modifier improve mechanical integrity to resist particle breakage.

Table 15

Before and after shear test PSD indicating the relative change in mean volume value for Ti/Mn modified silica compared to unmodified counterpart

Unmodified silica (30 nm pore diameter) Ti/Mn modified silica (30 nm pore diameter) Average shift Δ 16.3 0.3

Example 55 - Fischer-Tropsch synthesis in suspension phase with poison gas NH ₃ .

Fischer-Tropsch catalyst: Catalyst performance as described in Example 40 (30 g Co/0.075 g Pt/2.5 g MAC/100 g MnTi-SiO ₂ (FSQ-30)) was tested in an N-polluting poison gas environment.

The calcined catalyst precursor was reduced under the conditions described in Example 51, cooled to room temperature, suspended in molten wax, and loaded into a CSTR under an inert gas (argon or nitrogen).

The catalysts as described in Example 40 were tested for slurry phase FTS performance in a laboratory microsuspension CSTR at a reactor temperature of 230°C and a reactor pressure of approximately 1700 kPa and a total H/CO feedstock molar ratio of approximately 1.63. The reactor was electrically heated and sufficiently high stirrer speeds were used to remove any restrictions on gas-liquid mass transfer. The gas space velocity was changed such that the synthesis gas conversion was approximately 63%. The partial pressure of water was less than 500 kPa. The synthesis gas feed contained 2000 vppb NH ₃ .

Example 56 - Fischer-Tropsch synthesis in slurry phase in poison gas NH ₃ (RCR activation).

The catalyst as described in Example 40 was tested for its slurry phase FTS performance in a laboratory microsuspension CSTR under similar conditions as described in Example 55. However, the catalyst was activated as described in Example 52.

Example 57 - Fischer-Tropsch synthesis in suspension phase in the poison gas HCN.

The catalyst as described in Example 40 was tested for its slurry phase FTS performance in a laboratory microsuspension CSTR under similar conditions as described in Example 55. However, the synthesis gas contained approximately 2000 vppb HCN instead of 2000 vppb NH ₃ .

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Claims (8)

Discussion. FT rate and selectivity for CH ₄ relative to the initial (day 3) FT rate and selectivity for CH ₄ obtained on the catalyst obtained in example 40 under the conditions described in example 55-57 are shown in table. 16. Table 16 FT performance relative to examples 40 in on-line time mode under conditions as described in examples 55-57 Relative selectivity for CH4 ¹ Online time Example 55, NH ₃ , SR Example 56, NH ₃ , RCR Example 56, HCN, SR 3 1.00 1.00 1.00 12 0.99 1.05 1.04 23 0.99 1.00 1.06 32 0.81 0.91 1.07 Relative speed FT ² Online time Example 55, NH ₃ , SR Example 56, NH ₃ , RCR Example 56, HCN, SR 3 1.00 1.00 1.00 12 0.89 1.08 0.89 23 0.77 0.95 0.87 32 0.82 0.96 0.83 ¹ Variation in %CH ₄ selectivity from baseline (day 3); C% excluding education _CO2 . ² Relative to initial (day 3) rate FT ((CO+CO ₂ ) mol/CO/gs)). From Table. 16, it can be concluded that the Co/Pt/MnTi-SiO ₂ (FSQ-30) catalyst also performed well under N-contaminated syngas conditions without significant variation in CH ₄ selectivity and significant variation in on-line time FT rates. CLAIM 1. A cobalt-containing catalyst composition containing cobalt and/or a cobalt compound on and/or in a silica (SiO ₂ ) catalyst support, characterized in that the average pore diameter of the catalyst support is greater than 20 nm but less than 50 nm, as defined with using the Barett-Joyner-Halenda (BJH) nitrogen physical sorption analysis method, the catalyst composition also contains a titanium compound on and/or in the catalyst support and a manganese compound on and/or in the catalyst support, where the composition comprises more than 1 wt.% and not more 10 wt.% Ti, based on the weight of the silica (SiO ₂ ) catalyst substrate, excluding the weight of Ti and Mn, and Ti is present in the form of one or more titanium compounds; and where the composition comprises more than 0.5 wt.% and less than 10 wt.% Mn, based on the weight of the silica (SiO ₂ ) catalyst support, excluding the weight of Ti and Mn, and Mn is present in the form of one or more manganese compounds. 2. Catalyst composition according to claim 1, characterized in that the silica catalyst support is an amorphous silica support. 3. Catalyst composition according to claim 1 or 2, characterized in that the silica catalyst support has an average pore diameter of more than 22 nm but less than 50 nm. 4. Catalyst composition according to claim 3, characterized in that the silica catalyst support has an average pore diameter of 25 to 35 nm. 5. Catalyst composition according to any one of claims 1 to 4, characterized in that the titanium compound is an organic titanium compound. 6. Catalyst composition according to claim 5, characterized in that the organic titanium compound is selected from the group consisting of titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide, bis(acetylacetonate) titanium (IV) diisopropoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) hexoxide, titanium (IV) butoxide, and bis(ammonium lactato)titanium (IV) dihydroxide. 7. Catalyst composition according to any one of claims 1 to 6, characterized in that the manganese compound is an organic manganese compound. 8. Catalyst composition according to any one of claims 1 to 6, characterized in that the manganese compound