Preparation of a cobalt-containing catalyst

Abstract

The present invention is directed to the preparation of a cobalt containing catalyst, a precipitate as an intermediate product, a Fischer-Tropsch catalyst and a process for producing normally gaseous, normally liquid and optionally normally solid hydrocarbons from synthesis gas. The precipitate and catalyst comprise crystalline Co(OH)(CO3)0.5, the crystals are needle shaped and have a surface area of at least 80 m.sup.2/g dry precipitate.

Claims

1. A process for the preparation of a cobalt-containing catalyst or catalyst precursor, comprising: (a) mixing: (1) water; (2) a first aqueous solution comprising carbonate and hydroxide ions; (3) a second aqueous solution comprising cobalt ions and ions of at least one promoter metal compound, selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium; to form a mixture; (b) obtaining from the mixture obtained in step (a) a precipitate consisting of needle shaped crystalline Co(OH)(CO.sub.3).sub.0.5 and X(OH)(CO.sub.3).sub.0.5 H.sub.2O wherein X is selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium, the precipitate having a surface area of at least 80 m.sup.2/g; wherein the pH of the mixture of step (a) during mixing is maintained within the range of 6.5 to 8.5 and the temperature of the water, first and second aqueous solution and the mixture obtained in step (a) is maintained within the range of 50 and 85 degrees Celsius; and (c) co-mulling of a carrier material and the precipitate to obtain a co-mulled material wherein prior to the co-mulling the precipitate is washed.

2. The process according to claim 1, wherein in step (a) the first and second aqueous solutions are admixed to the water.

3. The process according to claim 1, further comprising the step of: (d) shaping and drying of the co-mulled material obtained in step (c) to obtain a shaped material.

4. The process according to claim 3, further comprising the step of calcining or drying of the shaped material obtained in step (d).

5. A Fischer-Tropsch catalyst comprising a carrier material and crystalline Co(OH)(CO.sub.3).sub.0.5 H.sub.2O and X(OH)(CO.sub.3).sub.0.5 H.sub.2O wherein X is selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium, wherein the crystals are needle shaped and have a surface area of at least 80 m.sup.2/g dry precipitate.

6. The Fischer-Tropsch catalyst according to claim 5 wherein the carrier material is a refractory metal oxide or precursor thereof.

7. A process for producing normally gaseous, normally liquid and optionally normally solid hydrocarbons at ambient conditions of 20° C. and 1 bar from synthesis gas which process comprises the steps of: (i) providing the synthesis gas to a reactor comprising the catalyst; and (ii) utilizing a Fischer-Tropsch catalyst of claim 6, catalytically converting the synthesis gas of step (1) at temperature in the range from 125 to 350° C. and pressure from 1 to 200 bara to obtain the normally gaseous, normally liquid and optionally normally solid hydrocarbons.

8. A process for producing normally gaseous, normally liquid and optionally normally solid hydrocarbons at ambient conditions of 20° C. and 1 bar from synthesis gas which process comprises the steps of: (i) providing the synthesis gas to a reactor comprising the catalyst; and (ii) utilizing a Fischer-Tropsch catalyst of claim 7, catalytically converting the synthesis gas of step (i) at temperature in the range from 125 to 350° C. and pressure from 1 to 200 bara to obtain the normally gaseous, normally liquid and optionally normally solid hydrocarbons.

9. A precipitate consisting of crystalline Co(OH)(CO.sub.3).sub.0.5 and X(OH)(CO.sub.3).sub.0.5 H.sub.2O wherein X is selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium, wherein the crystals are needle shaped and have a surface area of at least 80 m.sup.2/g dry precipitate.

10. A Fischer-Tropsch catalyst precursor comprising a carrier material and crystalline Co(OH)(CO.sub.3).sub.0.5 H.sub.2O and X(OH)(CO.sub.3).sub.0.5 H.sub.2O wherein X is selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium, wherein the crystals are needle shaped and have a surface area of at least 80 m.sup.2/g dry precipitate.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) In an aspect of the invention the process comprises the steps of:

(2) (a) mixing: (1) water; (2) a first aqueous solution comprising carbonate ions; (3) a second aqueous solution comprising cobalt ions and optionally ions of at least one promoter metal compound, selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium; to form a mixture;

(3) (b) obtaining from the mixture obtained in step (a) a precipitate;

(4) wherein the pH of the mixture of step (a) during mixing is maintained within the range of 6.5 to 8.5 and the temperature of the water, first and second aqueous solution and the mixture obtained in step (a) is maintained within the range of 50 and 85 degrees Celsius.

(5) Optionally to (1) water, (2) a first aqueous solution comprising carbonate ions and/or (3) a second aqueous solution comprising cobalt ions and optionally ions of at least one promoter metal compound, selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium a surfactant is added.

(6) Surfactants are surface active substances. Types of surfactant suitable for the present invention are anionic, cationic, zwitterionic and/or nonionic surfactants. Examples of suitable anionic surfactants for the present invention, but not limited to this list, are: sulfates, sulfonate and phopshate esters; carboxylates. An example of suitable cationic surfactants for the present invention, but not limited to this surfactant, is quaternary ammonium salts. Examples of suitable nonionic surfactants for the present invention, but not limited to this list are ethoxylates; fatty acid esters; amine oxides; sulfoxides; phosphine oxides. Examples of a suitable zwitterionic surfactant, but not limited to these surfactants are amino acids.

(7) In an aspect of the invention the precipitate comprises crystalline Co(OH)(CO.sub.3).sub.0.5 having a surface area of at least 80 m2/g.

(8) In an aspect of the invention the Fischer-Tropsch catalyst or Fischer-Tropsch catalyst precursor comprises a carrier material and crystalline Co(OH)(CO.sub.3).sub.0.5.

(9) In an aspect of the invention the catalyst is used in a process for producing normally gaseous, normally liquid and optionally normally solid hydrocarbons from synthesis gas, said process comprises the steps of:

(10) (i) providing the synthesis gas to a reactor comprising the catalyst; and

(11) (ii) catalytically converting the synthesis gas of step (i) at an elevated temperature and pressure to obtain the normally gaseous, normally liquid and optionally normally solid hydrocarbons.

(12) The inventors found that the method of the present invention provides for small needle shaped cobalt containing crystals. The crystals comprise Co(OH)(CO.sub.3).sub.0.5 and have at least a surface area of at least 80 m.sup.2/g. The crystal preferably have at least a surface area of at least 100 m.sup.2/g. The surface area is determined with BET surface area measurements. The small crystals together with high surface area allow for a good distribution of the crystals in a catalyst. Further the high surface area provides for a high surface area for contact of the reactants and the catalytically active phase. This results in a higher activity of the catalyst compared to the prior art catalysts.

(13) In an aspect of the invention the second aqueous solution comprising cobalt ions further contains ions of at least one promoter metal compound, selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium.

(14) In an aspect of the invention the first aqueous solution comprises carbonate and hydroxide ions. In an aspect of the invention the carbonate and hydroxide ions are present in a 1:1 ratio.

(15) In an aspect of the invention the second aqueous solution further comprises one or more of the following anions: chloride, bromide, iodide, chlorate, perchlorate, nitrate, nitrite, sulfate or any other anion of which a cobalt salt is soluble in water.

(16) In an aspect of the invention the process, in step (a), the first and second aqueous solutions are admixed to the water. The inventors found that this allows for good pH control during mixing.

(17) Ph range of precipitation needs to be controlled between 6.5-8.5 to minimize solubility of Co salts. Outside the preferred pH range soluble Co salts are remain in the supernatant and are not used economically.

(18) In an aspect of the invention the process further comprising the step of:

(19) (c) co-mulling of a carrier material and the precipitate to obtain a co-mulled material, wherein prior to the co-mulling the precipitate is washed. The co-mulled material can be used as a Fischer-Tropsch catalyst in slurry reactors. Examples of these reactors are disclosed in WO2007069317, U.S. Pat. Nos. 8,722,748, 8,013,025 and 6,265,452. The co-mulled product can also be used as a catalyst in microchannel reactors such as disclosed in U.S. Pat. No. 7,084,180.

(20) In an aspect of the invention the process further comprises the step of:

(21) (d) shaping and drying of the co-mulled material obtained in step (c) to obtain a shaped material.

(22) Optionally the co-mulled material is shaped without drying or the co-mulled material is further used without shaping and drying.

(23) Typically, the ingredients of the mixture are mulled for a period of from 5 to 120 minutes, preferably from 15 to 90 minutes. During the mulling process, energy is put into the mixture by the mulling apparatus. The mulling process may be carried out over a broad range of temperature, preferably from 15 to 90° C. As a result of the energy input into the mixture during the mulling process, there will be a rise in temperature of the mixture during mulling. The mulling process is conveniently carried out at ambient pressure. Any suitable, commercially available mulling machine may be employed.

(24) To improve the flow properties of the mixture, it is preferred to include one or more flow improving agents 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, sulphoxonium, sulphonium, phosphonium and iodonium compounds, alkylated aromatic compounds, acyclic mono-carboxylic acids, fatty acids, sulphonated aromatic compounds, alcohol sulphates, ether alcohol sulphates, sulphated fats and oils, phosphonic acid salts, polyoxyethylene alkylphenols, polyoxyethylene alcohols, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyacrylamides, polyols and acetylenic glycols. Preferred additives are sold under the trademarks Nalco and Superfloc.

(25) To obtain strong extrudates, it is preferred to include in the mixture, prior to extrusion, at least one compound which acts as a peptising agent for the titania. Suitable peptising agents for inclusion in the extrudable mixture are well known in the art and include basic and acidic compounds. Examples of basic compounds are ammonia, ammonia-releasing compounds, ammonium compounds or organic amines. Such basic compounds are removed upon calcination and are not retained in the extrudates to impair the catalytic performance of the final product. Preferred basic compounds are organic amines or ammonium compounds. A most suitable organic amine is ethanol amine. Suitable acidic peptising agents include weak acids, for example formic acid, acetic acid, citric acid, oxalic acid, and propionic acid.

(26) Optionally, burn-out materials may be included in the mixture, prior to extrusion, in order to create macropores in the resulting extrudates. Suitable burn-out materials are commonly known in the art.

(27) In an aspect of the invention shaping is effected by extrusion of the co-mulled material. Extrusion may be effected using any conventional, commercially available extruder. In particular, a screw-type extruding machine may be used to force the mixture through the orifices in a suitable die-plate to yield extrudates of the desired form. The strands formed upon extrusion may be cut to the desired length.

(28) In an aspect of the invention the process further comprises the step of calcining or drying of the shaped material obtained in step (d). Calcination is effected 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 oxygen-containing atmosphere, preferably air. It will be appreciated that, optionally, the drying step and the calcining step can be combined.

(29) One or more aspects of the invention relating to the process can be combined.

(30) The method of the present invention provides as an intermediate product a precipitate. Said precipitate comprises crystalline Co (OH)(CO3)0.5 H.sub.2O and is an aspect of the invention.

(31) In an aspect of the invention the precipitate further comprises X(OH)(CO.sub.3).sub.0.5 wherein X is selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium or chromium, wherein the crystals are needle shaped and have a surface area of at least 80 m.sup.2/g dry precipitate.

(32) In an aspect of the invention the precipitate consists of Co(OH)(CO.sub.3).sub.0.5 and X(OH)(CO.sub.3).sub.0.5 wherein X is selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium, platinum or chromium, wherein the crystals are needle shaped and have a surface area of at least 80 m.sup.2/g dry precipitate. Preferably, the mol ratio of Co(OH)(CO.sub.3).sub.0.5 to X(OH)(CO.sub.3).sub.0.5 is at least 10:1.

(33) In an aspect of the invention the precipitate is obtainable by the process according to the invention. Preferably the precipitate is obtained by the process according to the invention.

(34) One or more aspects of the invention relating to the precipitate can be combined.

(35) In an aspect of the invention a Fischer-Tropsch catalyst or Fischer-Tropsch catalyst precursor comprises a carrier material and crystalline Co(OH)(CO.sub.3).sub.0.5. The crystalline Co(OH)(CO.sub.3).sub.0.5 is referred to as the active phase in the present invention.

(36) The term “a Fischer-Tropsch catalyst or Fischer-Tropsch catalyst precursor” as used herein typically refers to an active phase material, or a precursor thereof, with an inert carrier, such as a refractory oxide, present typically as nano-sized particles. The active phase material or precursor thereof may be a catalytically active metal or precursor thereof.

(37) The Fischer-Tropsch catalyst or Fischer-Tropsch catalyst precursor may, for example, be extrudates, pellets, or one or more particles comprising catalyst material on a support. Substrates for supporting Fischer-Tropsch catalyst or Fischer-Tropsch catalyst precursor can be one or more of a number of materials, which are known in the art. These include metals such as steel, preferably stainless steel. Others include ceramics and combinations thereof.

(38) In an aspect of the invention the Fischer-Tropsch catalyst comprises as a carrier material, a refractory metal oxide or precursor thereof.

(39) In an aspect of the invention the catalyst further comprises crystalline X(OH)(CO.sub.3).sub.0.5 wherein X is selected from the group consisting of manganese, vanadium, rhenium, ruthenium, zirconium, titanium, platinum or chromium, wherein the crystals are needle shaped and have a surface area of at least 80 m.sup.2/g dry precipitate.

(40) In an aspect of the invention the catalyst is an extrudated particle comprising the crystalline Co(OH)(CO.sub.3).sub.0.5 and preferably crystalline X(OH)(CO.sub.3).sub.0.5 as defined above. The extrudated particles can be used in fixed bed reactors.

(41) One or more aspects of the invention relating to the Fischer-Tropsch catalyst can be combined.

(42) In an aspect of the invention the catalyst is used in a process for producing normally gaseous, normally liquid and optionally normally solid hydrocarbons from synthesis gas. Said process comprises the steps of:

(43) (i) providing the synthesis gas to a reactor comprising the catalyst; and

(44) (ii) catalytically converting the synthesis gas of step (i) at an elevated temperature and pressure to obtain the normally gaseous, normally liquid and optionally normally solid hydrocarbons.

(45) For the present description normally gaseous, normally liquid and normally solid hydrocarbons means the state the respective hydrocarbons are in at ambient conditions (20° C. and 1 bar).

(46) Fischer-Tropsch synthesis is preferably carried out at a temperature in the range from 125-150 to 350° C., more preferably 175 to 275° C., most preferably 180 to 270° C. The pressure preferably ranges from 1-5 to 150-200 bar abs., more preferably from 10 to 70 bar abs. Preferably, a Fischer-Tropsch catalyst is used, which yields substantial quantities of paraffins, more preferably substantially unbranched paraffins. A part may boil above the boiling point range of the so-called middle distillates, to normally solid hydrocarbons. A most suitable catalyst for this purpose is a cobalt-containing Fischer-Tropsch catalyst. The term “middle distillates”, as used herein, is a reference to hydrocarbon mixtures of which the boiling point range corresponds substantially to that of kerosene and gas oil fractions obtained in a conventional atmospheric distillation of crude mineral oil. The boiling point range of middle distillates generally lies within the range of about 150 to about 360° C. The higher boiling range paraffinic hydrocarbons if present, may be isolated and subjected to a catalytic hydrocracking step, which is known per se in the art, to yield the desired middle distillates. The catalytic hydrocracking is carried out by contacting the paraffinic hydrocarbons at elevated temperature and pressure and in the presence of hydrogen with a catalyst containing one or more metals having hydrogenation activity, and supported on a carrier. Suitable hydrocracking catalysts include catalysts comprising metals selected from Groups VIB and VIII of the (same) Periodic Table of Elements. Preferably, the hydrocracking catalysts contain one or more noble metals from Group VIII. Preferred noble metals are platinum, palladium, rhodium, ruthenium, iridium, and osmium. Most preferred catalysts for use in the hydrocracking stage are those comprising platinum.

(47) The amount of catalytically active metal present in the hydrocracking catalyst may vary within wide limits and is typically in the range of from about 0.05 to about 5 parts by weight per 100 parts by weight of the carrier material. Suitable conditions for the catalytic hydrocracking are known in the art. Typically, the hydrocracking is effected at a temperature in the range of from about 175 to 400° C. Typical hydrogen partial pressures applied in the hydrocracking process are in the range of from 10 to 250 bar.

(48) The process may be operated in a single pass mode (“once through”) or in a recycle mode. Slurry bed reactors, ebulliating bed reactors and fixed bed reactors may be used, the fixed bed reactor being the preferred option.

(49) The product of the hydrocarbon synthesis and consequent hydrocracking suitably comprises mainly normally liquid hydrocarbons, beside water and normally gaseous hydrocarbons. By selecting the catalyst and the process conditions in such a way that especially normally liquid hydrocarbons are obtained, the product obtained (“syncrude”) may transported in the liquid form or be mixed with any stream of crude oil without creating any problems as to solidification and or crystallization of the mixture. It is observed in this respect that the production of heavy hydrocarbons, comprising large amounts of solid wax, are less suitable for mixing with crude oil while transport in the liquid form has to be done at elevated temperatures, which is less desired.

(50) The off gas of the hydrocarbon synthesis may comprise normally gaseous hydrocarbons produced in the synthesis process, nitrogen, unconverted methane and other feedstock hydrocarbons, unconverted carbon monoxide, carbon dioxide, hydrogen and water. The normally gaseous hydrocarbons are suitably C 1-5 hydrocarbons, preferably C1-4 hydrocarbons, more preferably C1-3 hydrocarbons. These hydrocarbons, or mixtures thereof, are gaseous at temperatures of 5-30° C. (1 bar), especially at 20° C. (1 bar). Further, oxygenated compounds, e.g. methanol, dimethyl ether, may be present in the off gas. The off gas may be utilized for the production of electrical power, in an expanding/combustion process such as in a gas turbine described herein, or recycled to the process. The energy generated in the process may be used for own use or for export to local customers. Part of an energy could be used for the compression of the oxygen containing gas. The process as just described may be combined with all possible embodiments as described in this specification.

(51) Steam generated by any start-up gas turbine and/or steam generated in step (i) may also be used to preheat the reactor to be used in step (ii) and/or may be used to create fluidization in the case that a fluidized bed reactor or slurry bubble column is used in step (ii).

(52) Any percentage mentioned in this description is calculated on total weight or volume of the composition, unless indicated differently. When not mentioned, percentages are considered to be weight percentages. Pressures are indicated in bar absolute, unless indicated differently.

(53) One or more of the aspects of the invention may be combined. The appended claims form an integral part of the description by way of this reference. The present disclosure is not limited to the embodiments as described above and the appended claims. Many modifications are conceivable and features of respective embodiments may be combined.