MXPA00006417A - Cobalt based fisher-tropsch catalyst - Google Patents

Abstract

A process for the preparation of a cobalt-containing catalyst or catalyst precursor, comprising (a) mixing (1) titania or a titania precursor, (2) a liquid, and (3) a cobalt compound, which is at least partially insoluble in the amount of liquid used, to form a mixture, (b) shaping and drying of the mixture thus-obtained, and (c) calcination of the composition thus-obtained. A catalyst or catalyst precursor obtainable by the process as defined, and a process for the preparation of hydrocarbons comprising contacting a mixture of carbon monoxide and hydrogen with the catalyst as defined.

Description

CATALYST OF FISCHER-TROPSCH BASED ON COBALT DESCRIPTION OF THE INVENTION The present invention relates to a novel process for the preparation of a catalyst or catalyst precursor, the catalyst or catalyst precursor thus obtained and a process for the preparation of hydrocarbons from synthesis gas using the catalyst or novel catalyst precursor. The preparation of hydrocarbons from a gas mixture comprising carbon monoxide and hydrogen (synthesis gas) by contacting the mixture with a catalyst at elevated temperature and pressure is known in the literature as Fischer-Tropsch synthesis. The catalysts used in the synthesis of Fischer-Tropsch frequently comprise one or more metals of Group VIII of the Periodic Table of the Elements, especially of the iron group, optionally in combination with one or more metal oxides and / or metals as promoters. Recently, particular interest has been given to catalysts comprising cobalt as the catalytically active component, in combination with one or more promoters selected from zirconium, titanium, chromium, vanadium and manganese, especially manganese, and supported on a titania carrier. Such catalysts are known in the art. REF.120959 and have been described, for example in the specifications of International Patent Application Publication No. WO 97/00231 and European Patent Applications No. 96203538.2 and 96202524.3. Typically, the catalysts in the prior art have been prepared by impregnating a porous carrier with one or more soluble cobalt salts and an amount of a solvent, followed by drying, calcination and optionally activation. In the case of pore impregnation of a porous carrier it will usually be possible to start with a mechanically strong extrudate. However, the maximum charge of cobalt that can be obtained by a single impregnation step is restricted by the pore volume of the carrier and the solubility of the cobalt salt. In practice, several impregnation steps are necessary to obtain the desired amount of cobalt. The need for such a number of steps is undesirable for the preparation of catalysts on a commercial scale. It has been described in the prior art that the suitable Fischer-Tropsch catalyst can also be prepared by mixing or kneading alumina (EP 0 455 307), silica (EP 0 510 771) or zirconia (EP 0 510 772) with a soluble or insoluble cobalt source. In this way a paste can be obtained which is extruded, dried and calcined to obtain a catalyst or catalyst precursor that can be used in the Fischer-Tropsch reaction. Especially in the case of using an insoluble cobalt source, a sufficiently high cobalt charge can be obtained with a relatively simple process, suitable for use on a commercial scale. However, to obtain mechanically strong catalysts, the extrudates have to be calcined at relatively high temperatures. The disadvantage of high calcination temperatures is that the performance of the catalyst is adversely affected. Thus, there is a need in the art for mechanically strong Fischer-Tropsch catalysts with a high charge of cobalt, obtained by a simple preparation process, which shows high performance. Surprisingly, it has now been found that mechanically strong catalysts with a high charge of cobalt and excellent performance can be prepared by a relatively simple process. In particular, it has been found that mixing a partially insoluble cobalt compound, a liquid, and titania before formation, drying and calcination results in a mechanically strong catalyst having a very good activity and C5 + selectivity when used in the processes for the preparation of hydrocarbons. Thus, the present invention relates to a process for the preparation of a catalyst or cobalt-containing catalyst precursor, comprising: (a) mixing (1) titania or a titania precursor, (2) a liquid, and (3) cobalt metal powder or a cobalt compound, powder or compound which is at least partially insoluble in the amount of liquid used, to form a mixture; (b) forming and drying the mixture thus obtained; and (c) calcination of the composition thus obtained. The process of the present invention advantageously provides a simple process for the preparation of a catalyst or cobalt-containing catalyst precursor, resulting in a mechanically strong catalyst, which has a high activity and C5 + selectivity when used in the synthesis of Fischer-Tropsch. The titania for inclusion in the mixture may further comprise up to 20% by weight of another refractory oxide, typically silica, alumina or zirconia, or a clay as a binder material, preferably up to 10% by weight based on the Total weight of refractory oxide and binder material. Preferably, the titania has been prepared in the absence of sulfur-containing compounds. An example of such a preparation method involves the flame hydrolysis of titanium tetrachloride. Titania is commercially available and is well known as a material to be used in the preparation of catalysts or catalyst precursors. The titania suitably has a surface area of 0.5 to 200 m2 / g, more preferably 20 to 150 m2 / g. As an alternative or in addition to the titania, the mixture may comprise a titania precursor. Titania can be prepared by heating titania hydroxide. As the heating progresses, the titania hydroxide is converted via a number of intermediate forms and the successive loss of a number of water molecules in the titania. For the purpose of this specification, the term "titania precursor" should be taken as reference to the titania hydroxide or any of the above-mentioned intermediate forms.The liquid can be any of the suitable liquids known in the art, for example water; ammonia, alcohols, such as methanol, ethanol and propanol, ketones, such as acetone, aldehydes, such as propanal and aromatic solvents, such as toluene, A more convenient and preferred liquid is water. which at least 50% by weight is insoluble in the amount of liquid used, can be used suitably in the process of the present invention, Preferably, at least 70% by weight of the cobalt compound is insoluble in the amount of liquid used, more preferably at least 80% by weight, still more preferably at least 90% by weight Examples of cobalt compounds Suitable are cobalt hydroxide, cobalt oxide or mixtures thereof, preferred cobalt compounds are Co (OH) 2 or C03O. The amount of cobalt compound present in the mixture can vary widely. Typically, the mixture comprises up to 60 parts by weight of cobalt per 100 parts by weight of refractory oxide, preferably 10-40 parts by weight. The above amounts of cobalt refer to the total amount of cobalt, based on the cobalt metal, and can be determined by known elementary analysis techniques. The catalyst or cobalt-containing catalyst precursor prepared by the process of the present invention may comprise one or more promoter metals. Suitable promoter metals are known to those skilled in the art. The preferred promoter metals are manganese, vanadium, rhenium, ruthenium, zirconium, titanium and chromium. A more preferred metal promoter is manganese. The metal promoter or precursor thereof can be added at any stage of the preparation process in the form of soluble or insoluble promoter metal compounds. Suitable promoter metal compounds are metal powders, hydroxides, oxides, salts (of organic acid) and mixtures thereof.

The amount of promoter metal in the catalyst or catalyst precursor can vary widely. Typically the catalyst or catalyst precursor comprises the promoter metal in an amount such that the atomic ratio of the cobalt and the promoter metal is at least 4, preferably at least 5, more preferably between 6 and 250. In In a preferred embodiment, at least one metal promoter compound is present in step (a), i.e. the mixing step, of the preparation process. The cobalt compound, which is at least partially insoluble in the liquid can be obtained by precipitation. Any method of preparation known in the art can be used. Preferably, the cobalt compound is precipitated by the addition of a base or a base-releasing compound to a solution of a soluble cobalt compound, for example by the addition of sodium hydroxide, potassium hydroxide, ammonia, urea or ammonium carbonate. Any soluble cobalt compound can be used, preferably cobalt nitrate, cobalt sulfate or cobalt acetate, more preferably cobalt nitrate. Alternatively, the cobalt compound can be precipitated by the addition of an acid or an acid-releasing compound to a complex of cobalt and ammonia. The precipitated cobalt compound can be separated from the solution, washed, dried and, optionally, calcined. Suitable separation, washing and calcination methods are commonly known in the art. In one embodiment of the process of the present invention, the cobalt compound and the promoter metal compound are obtained by coprecipitation, most preferably by coprecipitation at constant pH. Coprecipitation at constant pH can be effected by the controlled addition of a base, a base releasing compound, an acid or acid releasing compound to a solution comprising a soluble cobalt compound and a soluble metal promoter compound, preferably by the controlled addition of. ammonia to an acid solution and a cobalt compound and a metal promoter compound. The cobalt compound and, optionally, the metal promoter compound can be precipitated in the presence of at least a part of the titania or titania precursor, preferably in the presence of all the titania or titania precursor. In a preferred embodiment of the invention, cobalt hydroxide and manganese hydroxide are co-precipitated by the addition of ammonia to a solution comprising cobalt nitrate, manganese nitrate and titania particles. Cobalt hydroxide and manganese hydroxide and precipitated titania particles can be separated from the solution, washed, dried and optionally calcined by methods commonly known in the art. The solids content of the mixture formed in step (a) of the preparation process of the invention can be up to 90% by weight based on the total mixture. It will be appreciated that the mixing method depends to a large extent on the solids content of the mixture. The mixing of step (a) of the catalyst preparation process of the present invention can be carried out suitably by methods known to those skilled in the art, such as mixing, kneading or stirring. It will be appreciated. that the mixture obtained may not be of the desired size and shape to serve as a catalyst carrier. In this way, the forming step is required to prepare the catalyst or catalyst precursor. The forming techniques are well known to those skilled in the art and include agglomeration, granulation, extrusion, spray drying and hot oil dripping methods. The process of the present invention involves a drying step. Typically, the composition will be dried after the formation and before calcination. Optionally, the formation and drying can be combined in one step, for example by spray drying. Alternatively, the mixture can be dried before forming it, for example by drying a filter cake before crushing it. It will be appreciated that drying and calcination can be combined in one step. In one embodiment of the invention, the solids content of the mixture obtained in step (a) of the catalyst preparation process is relatively high and therefore mixing is carried out adequately by mixing or kneading, and the mixture thus obtained it is formed by agglomeration, extrusion, granulation or grinding, preferably by extrusion. In this embodiment, the solids content of the mixture is typically in the range of 30 to 90% by weight, preferably 50 to 80% by weight. Typically, the ingredients of the mixture are kneaded for a period of 5 to 120 minutes, preferably 15 to 90 minutes. During the kneading process, energy is fed to the mixture by means of the kneading apparatus. The kneading process can be carried out over a wide temperature range, preferably from 15 to 90 ° C. As a result of the energy introduced into the mixture during the kneading process, there will be an increase in the temperature of the mixture during kneading. The kneading process is carried out conveniently at ambient pressure. Any suitable commercially available kneading machine could be used.

To improve the flow properties of the mixture, it is preferred to include one or more agents to improve the flow and / or extrusion aids in the mixture prior to extrusion. Suitable additives for inclusion in the mixture include fatty amines, quaternary ammonium compounds, polyvinyl pyridine, sulfoxonium, sulfonium, phosphonium and iodonium compounds, alkylated aromatic compounds, acrylic monocarboxylic acids, fatty acids, sulfonated aromatic compounds, alcohol sulphates, ether sulfates alcohol, sulphated fats and oils, salts of phosphonic acid, polyoxyethylene alkylphenols, polyoxyethylene alcohols, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyacrylamides, polyols and acetylenic glycols. Preferred additives are sold under the Nalco and Superfloe brands. To obtain strong extrudates, it is preferred to include in the mixture, prior to extrusion, at least one compound that can act as a peptizing agent for titania. Peptising agents suitable for inclusion in the extrudable mixture are well known in the art and include basic and acidic compounds. Examples of basic compounds are ammonia, compounds that release ammonia, ammonium compounds or organic amines. Such basic compounds are removed after calcination and are not retained in the extrudates to impart the performance or catalytic performance of the final product. The preferred basic compounds are organic amines or ammonium compounds. A more suitable organic amine is ethanol amine. Suitable acidic peptizing agents include weak acids, for example formic acid, acetic acid, citric acid, oxalic acid and propionic acid. Optionally, calcined materials may be included in the mixture, prior to extrusion, to create macropores in the resulting extrudates. Suitable calcined materials are commonly known in the art. The total amount of agents to improve the flow / extrusion aids, peptizing agents, and calcined materials in the mixture are preferably in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on of the total weight of the mixture. The extrusion can be carried out using any commercially available, conventional extruder. In particular, a screw type extrusion machine can be used to force mixing through the holes in a plate in the form of a suitable matrix to produce extrudate of the desired shape. The strands formed after extrusion can be cut to the desired length. After extrusion, the extrudates are dried. The drying can be carried out at elevated temperature, preferably up to 500 ° C, more preferably up to 300 ° C. The period for drying is typically up to 5 hours, more preferably from 15 minutes to 3 hours. In another embodiment of the invention, the solids content of the mixture obtained in step (a) is such that a slurry or suspension is obtained, and the slurry or suspension thus obtained is formed and dried by spray drying. The solids content of the slurry / suspension is typically in the range of 1 to 30% by weight, preferably 5 to 20% by weight. The slurry or suspension thus obtained is formed and dried suitably by spray drying. The extruded and dried, spray-dried or otherwise formed and dried compositions are subsequently calcined. The calcination is carried out at elevated temperature, preferably at a temperature between 400 and 750 ° C, more preferably between 500 and 650 ° C. The duration of the calcination treatment is typically from 5 minutes to several hours, preferably from 15 minutes to 4 hours. Suitably, the calcination treatment is carried out in an atmosphere containing oxygen, preferably air. It will be appreciated that, optionally, the drying step and the calcination step can be combined. The present invention also relates to a catalyst or cobalt-containing catalyst precursor obtainable by a process as defined herein above.

The catalyst according to the present invention is typically used to catalyze a process for the preparation of hydrocarbons from synthesis gas. Typically, when used in such a process, at least a part of the cobalt is in its metallic state. Therefore, it is usually advantageous to activate the catalyst or catalyst precursor before using it by a reduction treatment, in the presence of hydrogen at an elevated temperature. Typically, the reduction treatment involves treating the catalyst at a temperature in the range of 100 to 450 ° C for 1 to 48 hours at elevated pressure, typically 1 to 200 bar abs. Pure hydrogen can be used in the reduction treatment, although it is usually preferred to apply a mixture of hydrogen and an inert gas, such as nitrogen. The relative amount of hydrogen present in the mixture can range from 0 to 100% by volume. According to a preferred embodiment, the catalyst is brought to the desired temperature and pressure level in a nitrogen gas atmosphere. Subsequently, the catalyst is contacted with a gas mixture containing only a small amount of hydrogen gas, the rest being nitrogen gas. During the reduction treatment, the relative amount of hydrogen gas in the gas mixture is gradually increased to 50% or even 100% by volume. If possible, it is preferred to activate the catalyst in situ, ie inside the reactor. International Patent Application Publication WO 97/17137 discloses a catalyst activation process in which you comprise contacting the catalyst in the presence of liquid hydrocarbon with a gas containing hydrogen at a hydrogen partial pressure of at least 15 bar abs., Preferably at least 20 bar abs., More preferably at least 30 bar abs. Typically, in this process the partial pressure of hydrogen is at most 200 bar abs. It is advantageous to rejuvenate the used catalyst, ie the catalyst that has lost at least part of the initial activity of an activated fresh catalyst, subjecting it to a ROR treatment. Typically, the ROR treatment involves the steps, in sequence, of reduction with a hydrogen-containing gas, oxidation with an oxygen-containing gas, and reduction with a hydrogen-containing gas. In a further aspect, the present invention relates to a process for the preparation of hydrocarbons, which comprises contacting a mixture of carbon monoxide and hydrogen at elevated temperature and pressure with a catalyst containing cobalt as described hereinabove. The process is typically carried out at a temperature in the range of 125 to 350 ° C, preferably 175 to 275 ° C. The pressure is typically in the range of 5 to 150 bar abs., Preferably 5 to 80 bar abs., In particular 5 to 50 bar abs. Hydrogen and carbon monoxide (synthesis gas) are typically fed into the process in an atomic ratio in the range of 0.5 to 2.5. The gas hourly space velocity (GHSV) of the synthesis gas in the process of the present invention can vary within wide ranges and is typically in the range of 400 to 10000 Nl / l / h, for example 400 to 4000 Nl / l / h. The term GHSV is well known in the art, and is related to the volume of synthesis gas in NI, ie liters at STP conditions (0 ° C and 1 bar abs), which is contacted in one hour with one liter of catalyst particles, that is, excluding interparticular empty spaces. In the case of a fixed catalyst bed, the GHSV can also be expressed per liter of catalyst bed, i.e., including the interparticular void space. The process for the preparation of hydrocarbons can be conducted using a variety of reactor types and reaction regimes, for example a fixed bed regime, a slurry phase regime or a boiling bed regime. It will be appreciated that the size of the catalyst particles may depend on the reaction regime that is intended. It is the knowledge of one skilled in the art to select the most appropriate particle size of the catalyst for a given reaction regime. further, it will be understood that one skilled in the art is able to select the most appropriate conditions for a specific reactor configuration and reaction regime. For example, the space velocity per hour of the preferred gas may depend on the type of reaction regime being applied. In this way, if you want to operate the synthesis process of. hydrocarbon with a fixed bed regime, preferably the space velocity per hour of the gas is chosen in the range of 500 to 2500 Nl / l / h. If it is desired to operate the hydrocarbon synthesis process with a suspended phase regime, the spatial velocity of the gas per hour is preferably chosen in the range of 1500 to 7500 Nl / l / h. The invention will now be better illustrated by means of the following Examples.

Example I (Comparative) A mixture containing 217 g of alumina powder, 44 g of commercially available Co (OH) 2 powder, 14 g of Mh (Ac) 2.4H20, 8 g of HN03 and 170 g of water was prepared. The mixture was kneaded for 15 minutes. The mixture was formed using a Bonnot extruder. The extrudates were dried for 16 hours at 120 ° C and calcined for 2 hours at 500 ° C. The resulting extrudates had 18% by weight of Co and 2% by weight of Mn.

Example II (Comparative) Titania extrudate was prepared as follows. Commercially available titania powder (P25 ex.Degussa) was mixed with water and ammonia. The mixture was formed using a Bonnot extruder. The extrudates were dried for 16 hours at 120 ° C and calcined for 2 hours at 500 ° C. A solution containing 100 g of Co (N03) 2.6H20 and 4 g of Mn (N03) 2.4H20 and 10 ml of water was prepared. 70 g of titania extrudates were impregnated with this solution in four impregnation steps. After each impregnation step the extrudates were dried at 120 ° C for 16 hours and calcined at 500 ° C for 2 hours. The resulting extrudates were impregnated and calcined.

EXAMPLE III A mixture was prepared containing 143 g of commercially available titania powder (P25 ex Degussa), 66 g of commercially available Co (OH) 2 powder, 10.3 g of Mn (Ac) 2 • 4H20 and 38 g of Water. The mixture was kneaded for 15 minutes. The mixture was formed using a Bonnot extruder. The extrudates were dried for 16 hours at 120 ° C and calcined for 2 hours at 500 ° C. The resulting extrudates had 20% by weight of Co and 1% of Mn.

Example IV A suspension containing 175 g of commercially available titania powder (P25 ex.Degussa) was prepared. To this suspension was added a solution containing 250 g of co (N03) 2.6H20 and 8 g of Mn (N03) 2.4H20 dissolved in 500 ml of water. Simultaneously, ammonia was added to the suspension to maintain the pH of the suspension between 7 and 8. After the addition of the metal solution to the titania suspension, the Co and Mn precipitated on the titania were filtered and washed with water. The filter cake was dried at 120 ° C. A mixture containing the dried filter cake, ammonia and water was prepared. The mixture was kneaded for 15 minutes. The mixture was formed using a Bonnot extruder. The extrudates were dried for 16 hours at 120 ° C and calcined for 2 hours at 500 ° C. The resulting extrudates had 20% Co and 0.8% by weight Mn.

Example V A suspension containing 175 g of commercially available titania powder (P25 ex.Degussa) was prepared. To this suspension was added a solution containing 250 g of Co (N03) 2.6H20 and 8 g of Mn (N03) 2 • 4H0 dissolved in 500 ml of water. Simultaneously, ammonia was added to the suspension to maintain the pH of the suspension between 7 and 8. After the addition of the metal solution to the titania suspension, the Co and Mn precipitated on the titania were filtered and washed with water. A suspension containing the filter cake and 500 g of water was prepared. The suspension was spray dried using a Niro Atomizer. The inlet temperature was 250 ° C and the outlet temperature was 120 ° C. The resulting particles were calcined for 1 hour at 500 ° C. The resulting catalyst particles had 20% by weight of Co and 1% of Mn.

Example VI (Comparative) A spray-dried titania powder was prepared as follows.

Commercially available titania powder (P25 ex.Degussa) was mixed with water. The mixture had 30% by weight of titania powder. The mixture was spray dried using a Niro Atomizer. The inlet temperature was 250 ° C and the outlet temperature was 117 ° C. The resulting product was calcined for 1 hour at 500 ° C. The dew-dried titania particles were impregnated with a concentrated solution containing cobalt nitrate and manganese nitrate. The solution was prepared by heating solid cobalt nitrate (co (NO3) 2-6H2 °) and solid manganese nitrate (Mn (N03) 2 • 4H20) at a temperature of 60 ° C, thereby making the metal nitrates they dissolved in their own crystal water. The impregnated titania particles were dried for 2 hours at 120 ° C and subsequently calcined in air for 1 hour at 400 ° C. The resulting catalyst particles had 20% by weight of Co and 1% of Mn.

Example VII Catalysts I, II, III and IV were tested in a process for the preparation of hydrocarbons. The microflow reas containing 10 ml of catalyst extrusions I, II, III and IV, respectively, in the form of a fixed bed of catalyst particles, were heated to a temperature of 260 ° C and pressurized with a continuous flow of Nitrogen gas at a pressure of 2 bar abs. The catalysts were reduced in situ for 24 hours with a mixture of nitrogen gas and hydrogen. During the reduction, the relative amount of hydrogen in the mixture gradually increased from 0% to 100%. The concentration of water in the discharge gas was kept below 3000 ppmv. After reduction the pressure was increased to 26 bar abs. The reaction was carried out with a mixture of hydrogen and carbon monoxide at an H2 / C0 ratio of 1.1: 1. The GHSV was 800 Nl / l / h. The reaction temperature was expressed as the weighted average bed temperature (WABT) in ° C. Temporal spatial yield (STY) was expressed as grams of hydrocarbon product per liter of catalyst particles (including voids between the particles) per hour, and selectivity for C5 +, expressed as a percentage by weight of the total hydrocarbon product , was determined for each experiment after 50 hours of operation. The results are shown in Table I.

TABLE I TABLE I (continued) It will be appreciated that the activity and selectivity of both catalyst III and IV, according to the invention, is much better than the activity and selectivity of catalysts I and II.

Example VIII Catalysts V and VI were tested in a process for the preparation of hydrocarbons. The microflow reas containing 10 ml of catalyst particles V and VI, respectively, were heated to a temperature of 260 ° C, and pressurized with a continuous flow of nitrogen gas to a pressure of 2 bar abs. The catalysts were reduced in-itself for 24 hours with a mixture of nitrogen gas and hydrogen. During the reduction the relative amount of hydrogen in the mixture gradually increased from 0% to 100%. The concentration of water in the discharge gas was kept below 3000 ppmv.

After reduction the pressure was increased to 26 bar abs. The reaction was carried out with a mixture of hydrogen and carbon monoxide at an H2 / C0 ratio of 1.7: 1. The GHSV was 2400 Nl / l / h. The reaction temperature was expressed as the weighted average bed temperature (WABT) in ° C. Temporal spatial yield (STY) was expressed as grams of hydrocarbon product per liter of catalyst particles (excluding voids between the particles) per hour, and selectivity for C5 +, expressed as a percentage by weight of the total hydrocarbon product , was determined for each experiment after 50 hours of operation. The results are shown in Table II.

TABLE II It will be appreciated that catalyst V shows a better performance than catalyst VI. In addition, the process for preparing the catalyst of Example V (according to the invention) is much simpler than the process for preparing the catalyst of Example VI (comparative). It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (17)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A process for the preparation of a catalyst or cobalt-containing catalyst precursor, characterized in that it comprises: (a) mixing (1) titania or a titania precursor, which is an intermediate form that is formed by heating titanium hydroxide to convert it to titanium, (2) a liquid, and (3) cobalt metal powder or a cobalt compound, powder or compound which is at least partially insoluble in the amount of liquid used to form a mixture; (b) forming and drying the mixture thus obtained; and (c) calcination of the composition thus obtained.

2. The process according to claim 1, characterized in that at least 50 percent by weight of the cobalt compound is insoluble in the amount of liquid used, preferably at least 70 percent by weight, more preferably at least 80 weight percent, still more preferably at least 90 weight percent.

3. The process according to claim 1 or 2, characterized in that the cobalt compound is cobalt hydroxide or a cobalt oxide, preferably Co (OH) 2 or Co30

4. 4. The process according to any of claims 1 to 3, characterized in that the cobalt metal powder or cobalt compound is used in an amount of up to 60 weight percent of the amount of refractory oxide, preferably between 10 and 40 percent by weight.

5. The process according to any of claims 1 to 4, characterized in that the catalyst or catalyst precursor comprises at least one promoter metal, preferably manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium promoters, so more preferably manganese, the promoter metal is preferably used in an amount such that the atomic ratio of the cobalt and the promoter metal is at least 4, preferably at least 5. The process according to claim 5, characterized because at least one metal promoter compound is present in step (a). The process according to any of claims 1 to 6, characterized in that the cobalt compound is obtained by precipitation, optionally followed by calcination. 8. The process according to any of claims 5 to 7, characterized in that the cobalt compound and at least one of the promoter metal compounds are obtained by coprecipitation, preferably by coprecipitation at constant pH. 9. The process according to claim 7 or 8, characterized in that the cobalt compound precipitates in the presence of at least a part of the titania or the titania precursor, preferably in the presence of all the titania or titania precursor. The process according to any of claims 1 to 9, characterized in that the mixing in step (a) is carried out by kneading or mixing and the mixture thus obtained is formed by agglutination, extrusion, granulation or grinding, preferably by extrusion. The process according to claim 10, characterized in that the mixture obtained has a solids content in the range of 30 to 90% by weight, preferably 50 to 80% by weight. The process according to any of claims 1 to 9, characterized in that the mixture formed in step (a) is a suspension and the suspension thus obtained is formed and dried by spray drying. 13. The process according to claim 12, characterized in that the suspension obtained has a solids content in the range of 1 to 30% by weight, preferably 5 to 20% by weight. The process according to any of claims 1 to 13, characterized in that the calcination is carried out at a temperature of between 400 and 750 ° C, preferably between 500 and 650 ° C. 15. A catalyst or catalyst precursor, characterized in that it can be obtained by a process according to any of claims 1 to 14. 1

6. An activated catalyst suitable for the production of hydrocarbons, characterized in that it is obtained by reduction with hydrogen at temperature of a catalyst or catalyst precursor according to claim 15. 1

7. The process for the preparation of hydrocarbons, characterized in that it comprises contacting a mixture of carbon monoxide and hydrogen with a catalyst according to claim 15 or 16. .