Method of preparing catalyst precursor, catalyst preparation method, and a process for production of hydrocarbons using thus prepared catalyst

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

 

The technical field to which the invention relates.

The present invention relates to a catalyst carrier, the catalyst based on a metal of group VIII on a carrier and the catalyst precursor based on a metal of group VIII on a carrier. The invention also relates to methods for the specified carrier, catalyst and predecessor, and also to the use of a catalyst based on a metal of group VIII on a carrier, in particular, in the method of producing hydrocarbons from synthesis gas.

The level of technology

Catalytic preparation of hydrocarbons from synthesis gas, i.e. a mixture of carbon monoxide and hydrogen, it is well known from the prior art, as the Fischer-Tropsch synthesis.

Typically, the catalysts used in the Fischer-Tropsch synthesis, contain a catalytically active metal of group VIII of the Periodic table of the elements (Handbook of chemistry and physics, 68thedition, CRC Press, 1987-1988)deposited on such refractory oxides as alumina, titanium dioxide, zirconium dioxide, silicon dioxide or mixtures of these oxides. It is well known that as the catalytically active metals such catalysts are used, mainly iron, Nickel, cobalt and ruthenium. As these links can be mentioned EP-A-398420, EP-A-178008, EP-A-167215, EP-A-168894, EP-A-363537, EP-A-498976, EP-A-71770 and WO-99/34917.

In the Fischer-Tropsch synthesis, as and when PR is doing many other chemical reactions, the catalyst on the carrier, the reagents and solvent, if used, are in contact with each other, usually form a three-phase system consisting of gas, liquid and solid phase. Such three-phase systems can be used in the reactor nozzle or in the slurry reactor. The reactor nozzle may include a fluidized bed of particles of the solid catalyst, through which pass the gaseous and liquid reagents. Slurry reactor may include a dispersive phase from the liquid in which the suspended solid catalyst and gaseous reagents held in the form of bubbles through the liquid. In all of these operations one of the most important issues is the mechanical strength of the catalyst on the carrier, ensuring the integrity of the catalytic particles during the entire process. The stronger catalyst carrier or catalyst on the carrier, the greater the height of the used catalyst layer in the reactor with a fluidized bed or the greater the residence time of the catalyst in the slurry reactor.

In addition, it should be noted continuous interest in the search for new catalysts for Fischer-Tropsch synthesis, which can provide enhanced activity and improved selectivity in the conversion of carbon monoxide into valuable hydrocarbons, in particular in uglev dorogy, containing 5 or more carbon atoms (hereinafter describe "With5+hydrocarbons"), and to minimize the formation of carbon dioxide, which is of little value or even harmful carbon-containing by-product.

In accordance with the present invention can be obtained catalyst carriers and catalysts, suddenly having improved strength, and such catalysts have better performance in the Fischer-Tropsch synthesis, related to their activity and selectivity. The method according to the present invention, includes the following stages: reducing the size of particles of refractory oxide carrier by grinding a mixture of refractory carrier and liquid to a paste, mixing the resulting paste with an additional amount of fluid to the formation of the slurry, molding and drying the slurry and calcining the resulting material. The catalytically active metal may be introduced at any stage of the process or after it in the form of metal as such or in the form of its predecessor.

The catalysts obtained in accordance with the present invention have improved characteristics compared to catalysts prepared by the methods disclosed in WO-99/34917. The methods described in WO-99/34917 include molding paste without adding additional is sustained fashion liquids and the formation of the suspension without the use of an intermediate stage of grinding paste.

Additional technical result obtained by carrying out the present invention is that the particles have a high density, resulting in a given volume of reactor can be used more catalyst.

Another aspect of the present invention is that the improved catalytic properties can be achieved without the introduction of additional, i.e. another element in the carrier or the catalyst. This is favorable, because the presence of an additional element may unpredictably affect the properties of the catalyst, and in a negative direction.

Thus, the present invention relates to a method for producing a catalyst carrier or catalyst based on a metal of group VIII on a carrier or catalyst precursor based on a metal of group VIII on a carrier, including:

(a) the application of mechanical energy to the mixture containing refractory oxide and the first liquid, to obtain paste,

(b) mixing the resulting paste with the second fluid with the formation of the suspension,

(c) shaping and drying of the suspension, and

(d) annealing, -

considering the fact that if you get a catalyst based on a metal of group VIII on a carrier or its predecessor, at the stage of (a) or (b) as additionally what about the component is the precursor of the metal of group VIII or a metal of group VIII.

The present invention also relates to the media, the catalyst based on a metal of group VIII on the media and their predecessor, which receive the specified method. In addition, the invention relates to the use of a catalyst based on a metal of group VIII in a three-phase chemical process, in particular in the process of obtaining hydrocarbons, which consists in contacting a mixture of carbon monoxide and hydrogen at elevated temperature and pressure with a catalyst on a carrier according to the present invention.

In the present invention is used refractory oxide. Examples of suitable refractory oxides can serve as aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide or mixtures thereof such as silica-alumina, or physical mixtures such as a mixture of silica and titanium. The preferred refractory oxides are titanium dioxide, zirconium dioxide or a mixture, especially of titanium dioxide.

In accordance with a preferred embodiment of the invention, the refractory oxide comprising titanium dioxide, zirconium dioxide or mixtures thereof, may optionally contain up to 50 wt%. another refractory oxide, typically silicon dioxide or aluminum oxide, calculated on the total weight of the refractory oxide. More preferably, when the number of additional tuhopuu the CSO oxide, in his presence, up to 20 wt. -%, and even more preferably up to 10% of the mass. calculated on the total weight of the refractory oxide.

The most preferred refractory oxide comprises titanium dioxide, in particular titanium dioxide, obtained in the absence of sulfur-containing compounds. An example of such a method of obtaining can serve as flame hydrolysis of titanium tetrachloride.

Titanium dioxide may be treated rutile type, but preferably it contains an anatase. It is desirable that at least 50%, better still at least 90% of titanium dioxide was an anatase. Most preferably, when titanium dioxide is an exceptionally anatase.

The preferred refractory oxide is a material with a large surface area. Typically, the surface area is at least 0.5 m2/g, preferably at least 10 m2/g, in particular at least 25 m2/g, and most preferably at least 35 m2/g, in accordance with the measurement of surface area by the BET method according to ASTM D3663-92. The maximum value of surface area is 400 m2/g, in particular 200 m2/, Preferred values of surface area lying in the range of 40-100 m2/year

The particle size of the refractory oxide is not a Ki is the subject of the present invention and may be selected from a wide range of values, for example less than 1 mm, usually from the range of 0.1 to 100 μm, preferably in the interval of 0.5-50 μm.

The particle sizes referred to in this description represent the diameters of the particles of the average volume defined using device MASTERSIZER MICRO PLUS (trade name of the company Malvern Instruments, Ltd., United Kingdom; uses calculation method "5THD"supplied by Malvern Instruments, Ltd.); the material from which evaluations were carried out, was diluted with additional liquid, a already used the liquid (water in Examples I, II and III below) in order to achieve a certain value of optical density, and within 30 seconds was measured particle size.

The first and the second fluid, independently of one another, can be an organic liquid such as a lower alcohol, a lower ketone, lower ester with a lower or a simple ester, for example ethanol, acetone, methyl ethyl ketone, ethyl acetate, diethyl ether or tetrahydrofuran. In the text of the present description, the term "lower" as applied to name organic compounds, it is understood that this term refers to an organic compound containing a maximum of six carbon atoms, in particular four carbon atoms. The preferred first and second fluids are of FDS the aqueous liquid, for example, the mixture of organic liquid and water, preferably containing at least 50 wt%. water and less than 50 wt%. organic liquid based on the total weight of the liquid. Consider liquid water can be a water. Preferably, the first and the second liquid have the same compositions. Especially useful when the first and second liquid use water.

At stage (a) of the method according to the present invention, a mixture of lead mechanical energy to obtain paste. Mechanical energy can be fed to the mixture by methods known to the expert, for example in the result of plastilinovaya or crushing. Suitable devices can serve as a Z-blade mixer or Sigma-blade mixer, and a rotary wheel runners.

Usually the mechanical energy supplied to the mixture over a period of time from 5 minutes to 2 hours or more, for example up to 5 hours, but preferably within 15-90 minutes. This stage can be carried out in a wide temperature range, preferably at 15-90°C. In the power supply there is an increase in the temperature of the mixture.

The content of solid material in the paste obtained in stage (a)is not critical and can be chosen in a wide range of values. Typically, the solids content of the material is, at the ore, 60 wt. -%, for example 65-90 wt. -%, calculated on the total weight of the paste. The preferred solids content is 65-85% of the mass. In accordance with the present description of the content of solids in the mixture (paste or slurry) is defined as the mass of the residue formed after heating the mixture for 2 hours at 600°and if it is desirable, prior to heating, it is possible to carry out drying under more mild conditions.

Particles of solid material present in the toothpaste, typically have a size up to 5 μm, for example in the range of 0.05-3 μm, preferably in the range of 0.1 to 1 μm. Reducing the size of the particles resulting from the supply of mechanical energy on the stage (a) can be quantified by the ratio of particle size after finishing the step (a) to the particle size of the first stage (a). This ratio usually is 0.02 to 0.5, preferably from 0.05 to 0.02.

The amount of the second liquid, primitively at the stage (b), is not decisive. A suitable amount of the second fluid is at least 0.1 mass part (machine hours) per M.Ch. paste, and the maximum amount of the second fluid is usually 60 M.Ch. in M.Ch. paste. For example, the amount of the second liquid may be 0.5-20 machine hours per M.Ch. paste, preferably 1-10 M.Ch. in M.Ch. paste.

Regardless of the above, may used such a quantity of liquid, when the content of solid material in the suspension obtained in stage (b), will be a maximum of 55 wt. -%, for example 1-45% of the mass. based on the weight of the suspension. A suitable quantity is chosen in accordance with the method of molding used in stage (C). For example, if the molding is conducted by a sputtering technique, for example when carrying out the spray drying, the solids content in the suspension is usually 5-35 wt. -%, preferably 15-30 wt%. based on the weight of the suspension.

Phase mixing (b) can be accomplished in any suitable way known to the expert in this area. Expert it is clear that it is preferable to obtain a homogeneous mixture paste with the second fluid, for example, a mixture that does not contain large pieces. Mixing can be done using a radial turbine, anchor stirrers or marine impeller. Usually mixing time is 5-120mm minutes, preferably 15-90 minutes. Mixing can be carried out in a wide temperature range, preferably at 15-90°C.

At the stage (C) can be any suitable methods of forming and drying. For example, the slurry can be dried with the formation of the hardened material and continue to grind. Drying may be conducted at elevated temperature, for example at 30°C, preferably at temperatures up to 500°S,more preferably up to 300° C. Typically, the drying is carried out in a period of not more than 5 hours, preferably a period of time from 15 minutes to 3 hours.

Molding and drying preferably takes place in a single operation, for example by spray drying.

Before extrusion of suspension it is preferable to include one or more substances selected from modifiers fluidity and/or accelerators extrusion, accelerators peptization and burnable materials. Such additives and their use are known from the prior art, see, for example, WO-99/34917. Suitable patiserie agents for the method according to the present invention can serve as a weak acid, in particular acid with a pKa value, measured in water at 25°equal to at least 0, max 8, preferably 0.5 to 6. The greatest interest for the use of such carboxylic acids as formic acid, acetic acid, citric acid, oxalic acid and propionic acid.

Molded and dried composition from step (C) is subjected to calcination at a stage (d). The calcination is carried out at elevated temperatures, preferably at temperatures in the range of 400-750°S, more preferably 450-650°C. Typically, the calcination is carried out in a period of time from 5 minutes to several hours, preferably from 15 minutes to 4 hours. The calcination is conveniently carried out in color soderjashie atmosphere, preferably the air. If desired, the drying and the calcination can be carried out in one stage.

It should be noted that the most preferred variant of the method may vary, for example, depending on the desired size and shape of catalyst particles. The selection of the most appropriate method for a given set of conditions and requirements is the prerogative of the person skilled in the technical field.

It is preferable to obtain the catalyst in powder form and in this case, the spray drying is the preferred method of application at the stage (s).

The powder particles obtained after molding, drying and calcination, usually have a size in the range of 5-200 μm, preferably 10-100 μm. The catalyst in the form of such a powder is advantageously used in a chemical process conducted in a suspension mode, for example in a slurry reactor.

Alternative forms are granules, a saddle shape and cylinders, and they can be used in a chemical process conducted in a mode using a fixed catalyst layer, for example, in the reactor nozzle. Less preferably, to obtain the catalyst in the form of bulk material indefinite form.

Can be obtained a catalyst on the carrier or its predecessor, containing a catalytically active metal or preds the factory worker catalytically active metal. The catalytically active metal is a metal of group VIII, as in many chemical reactions, such as Fischer-Tropsch synthesis and hydrogenation reactions, uses a catalyst based on a metal of group VIII on a carrier.

In the Fischer-Tropsch synthesis, it is preferable to use a metal of group VIII selected from iron, Nickel, cobalt and ruthenium. More preferably, when the metal of group VIII choose cobalt or ruthenium as catalysts based on cobalt and ruthenium provide a relatively high yield of hydrocarbon, C5+. The most preferred metal of group VIII is cobalt. To improve the catalyst activity or selectivity in the conversion of synthesis gas into hydrocarbons can be used for more metal. Suitable additional metals can be selected from manganese, vanadium, zirconium, rhenium, scandium, and ruthenium. Preferred additional metal is manganese or vanadium, in particular manganese.

The amount of metal of group VIII present in the metal catalyst on the carrier may vary within wide limits. Typically, the catalyst based on a metal of group VIII on a carrier contains 1-50% of the mass. metal of group VIII, in particular, when using the catalyst in the Fischer-Tropsch synthesis is preferably 3-40 wt. -%, more PR is doctitle 5-30% of the mass. in the calculation of the mass of metal of group VIII by weight of catalyst based on a metal of group VIII on a carrier. The number of additional metal, if present, is typically 0.05 to 60 wt. -%, as a rule 0.1 to 25 wt%. based on the weight of the additional metal to the weight of catalyst based on a metal of group VIII on a carrier. The atomic ratio between the metal of group VIII and an additional metal, if present in the catalyst is at least 5:1 and a maximum of 200:1.

The catalyst based on a metal of group VIII on a carrier can be obtained using methods known to the expert.

Preferably the catalytically active components or their predecessors in the form of an additional component on the stage (b), or more preferably already at the stage (C). Less preferred alternative consists of applying the catalytically active components or their precursors to the media after the annealing in stage (d). The term "catalytically active components" means any catalytically active metal, i.e. a metal of group VIII and any additional metal present in the metal catalyst on the carrier. The term also refers to the precursors of the catalytically active metal. It is not excluded also, that in addition to the catalytically active component and the carrier, the metal is cue the catalyst on the carrier includes additional components.

Suitable catalytically active components include salts of catalytically active metal, such as nitrates, carbonates, and acetates, hydroxides and oxides catalytically active metal, as well as the catalytically active metal. The catalytically active components may be soluble or insoluble in the first or second fluid or they may be partially soluble in the first and second fluids.

The introduction of the catalytically active component or precursor in the carrier after the calcination stage (d) can be carried out in traditional ways. These traditional methods include precipitation of the catalytically active components or their precursors to the media; plastilinovaya and/or impregnation of the carrier of the catalytically active components or precursors; and/or co-extrusion of one or more catalytically active components or precursors with the carrier to obtain extrudates.

The traditional method of preparation of the catalyst based on a metal of group VIII on a carrier is the carrier impregnated with aqueous solutions of catalytically active components or precursors. In the preparation of cobalt and mn containing catalysts on the media it is most preferable to use a highly concentrated solution. Order to obtain that the CSOs are concentrated solution can use a mixture of molten nitrates of cobalt and manganese. After the operation, the impregnation is usually carried out drying and optional calcination. Drying and calcination is usually carried out as described above.

Returning to the question about the use of a catalyst based on a metal of group VIII on a carrier, it should be recalled that this catalyst can be used in the process of obtaining hydrocarbons from carbon monoxide and hydrogen. Usually when used in a specific process, at least part of the metal of group VIII is in the form of metal.

Therefore, it is often useful before use to activate the catalyst based on a metal of group VIII on a carrier by a recovery in the presence of hydrogen at elevated temperature. As a rule, the restoration includes the handling of catalyst within 1-200 hours at a temperature in the range of 100-450°and With increased pressure, usually when 1-200 bar abs. For recovery, you can use pure hydrogen, but usually prefer to use a mixture of hydrogen with an inert gas such as nitrogen. The relative amount of hydrogen in the mixture may be 0.1-100% vol.

In accordance with the preferred option of carrying out the reaction of recovery, the first catalyst in an atmosphere of inert gas lead to the desired temperature and pressure. Thereafter, the catalyst is brought into contact with a gas mixture containing only some m is large amount of hydrogen in nitrogen. During recovery the relative amount of hydrogen in the gas mixture is gradually increased up to 50% on. or even up to 100% vol.

Sometimes it is preferable to activate the catalyst based on a metal of group VIII on a carrier in situ, i.e. directly in the reactor obtain hydrocarbons from synthesis gas. For example, in WO-97/17137 describes how the activation of the catalyst in situ, in which the contacting of the catalyst, in the presence of a hydrocarbon liquid with a hydrogen-containing gas at a partial pressure of hydrogen of at least 15 bar abs., preferably, at least 20 bar abs., more preferably, at least 30 bar abs. Usually this method is used in the partial pressure of hydrogen of up to 200 bar abs.

Usually the process of obtaining hydrocarbons from synthesis gas is carried out at a temperature in the range of 125-350°C, preferably 175-275°C. Typically use a pressure in the range of 5-150 bar abs., preferably 5-80 bar abs., in particular 5-50 bar abs.

Hydrogen and carbon monoxide (synthesis gas) is usually injected into the reactor in a molar ratio of 0.7 to 2.5. Low molar ratio of hydrogen-carbon monoxide promote With5+the selectivity, i.e. the selectivity of hydrocarbon formation With5+.

However, according to this embodiment of the present invention, in which the metal of group VIII made the focus of a cobalt, and the additional metal is manganese and/or vanadium present in the atomic ratio of cobalt/manganese + vanadium), equal to at least 12:1, the catalyst exhibits an exceptionally high5+selectivity even when using a synthesis gas with a high atomic ratio of hydrogen: carbon monoxide. In this embodiment of the invention can be used in the molar ratio of hydrogen: carbon monoxide is found in the range of 1.5 to 2.5.

Hourly average gas flow rate ("GHSV") can vary within wide ranges and is typically 400-10000 nl/l/h, for example 400-4000 nl/l/h.

The term "GHSV" well known from the literature and refers to the average hourly rate of gas supply, i.e. the volume of the synthesis gas in the IO (i.e. at standard temperature 0°C and a standard pressure of 1 bar (100000 PA))in contact for one hour with one liter of catalytic particles, i.e. excluding the blank space between the particles. In the case of a process with a fixed bed of catalyst GHSV is usually expressed per liter of catalyst layer, i.e. taking into account the blank space between the particles. In this case, the value GHSV 1600 nl/l/h for catalyst particles corresponds to about 1000 nl/l/h for catalytic layer.

A method of producing hydrocarbons may be carried out in which eactor of different types and in different reaction modes, for example, using a fixed bed catalyst in a slurry phase or fluidized bed of catalyst. It should be borne in mind that the size of the catalyst particles may vary depending on the mode of carrying out the reaction. The choice of the most suitable size of the catalyst particles for a given mode of carrying out the reaction is the prerogative of the specialist in this field.

In addition, it should be stated that the specialist will not be difficult to choose the most suitable conditions for a particular configuration of the reactor, the reaction and the processing circuit. For example, the preferred value is an average hourly rate of gas supply may depend on the actual mode of the reaction. So, if you want the process of synthesis of hydrocarbons using a fixed bed catalyst, the preferred value is an average hourly rate of gas supply is selected from the interval 500-2500 nl/l/h If the process of synthesis of hydrocarbons preferably carried out in a slurry phase, the preferred value is an average hourly rate of gas supply is chosen from the interval 1500-7500 nl/l/h

An important feature of the invention is the fact that the catalyst carrier and the catalyst based on a metal of group VIII on the media has increased strength. Therefore, if PR is the management of chemical process using a fixed bed catalyst, can be used the high catalytic layer, and with the suspension phase or fluidized bed of catalyst is provided a lower attrition of catalyst particles. Less abrasion increases the residence time of the applied catalyst in the reactor and/or to reduced formation of dust particles. When reducing the number of small particles decreases the risk of leakage through the filter at a stage filtration trapping catalytic particles. The metal catalyst on the carrier according to the present invention is preferably used in the suspension mode of carrying out the reaction.

Information confirming the possibility of carrying out the invention

Further, the present invention is illustrated by the following Examples.

Example 1

A paste was prepared by mixing and stirring in a kneading machine 120 mass parts (machine hours) commercially available powder of titanium dioxide (P25 ex. Degussa, surface area according to BET 50 m2/g (ASTM D3663-92), particle size 7 μm), 50 M.Ch. commercially available powder of Co(OH)2(particle size 4 μm), 5,3 M.Ch. Mn(AC)2·4H2O ("AC" denotes acetate; soluble in water) and 50 M.Ch. water. Stirring is continued until the formation of solid material with a particle size of 3 μm. To the paste was added water (650 M.Ch.) and the resulting mixture homogenizer the Wali using a turbine stirrer with formation of a suspension. The particle size of the solid material in the resulting suspension has not changed. The suspension was spray dried using a spray nozzle. The resulting particles for 1 hour progulivali in air at 600°C. the particle Size of the obtained powder was 30 μm. Thus obtained catalyst precursor was subjected to various tests.

The density of particles was of 2.38 g/ml.

The particles were tested for strength, subjecting the suspension containing 5% by vol. particles in the water, to the action of high shear forces within 30 minutes using a high speed stirrer rotating at a speed of 5700 Rev/minutes the Temperature of the suspension was maintained at a level of significance 20°C. Measured the size of the original particles and particles after exposure to shear forces. It was found that shear effects during the test leads to the reduction of particle size by 5%.

The catalyst precursor was recovered and tested in the process of obtaining hydrocarbon. The flow-through microreactor containing 10 ml of particles in the form of a stationary layer was heated to a temperature of 260°and by continuously feeding nitrogen gas was blown therein a pressure up to 2 bar abs. The catalyst precursor was recovered in situ for 24 hours using a mixture of nitric. During recovery the relative amount of hydrogen in the mixture gradual the NGOs increased from 0% vol. up to 100% vol. The water content in the exhaust gas was maintained at a value below 3000 million shares in volume.

After restoring the pressure was increased to 31 bar abs. The synthesis of hydrocarbons was carried out using a mixture of hydrogen and carbon monoxide at a ratio of H2/CO equal to 1.1:1. The GHSV value reached 7700 nl/l/h the reaction Temperature, expressed as the weighted average bed temperature was 232°C. After 40 hours was determined volumetric capacity, expressed in grams of hydrocarbon product per liter of catalyst particles (including the voids between particles) per hour; the selectivity for methane, expressed in mol%. methane, based on the number of moles converted WITH; and the selectivity to hydrocarbons containing 5 or more carbon atoms (C5+selectivity), expressed as a mass percentage of the total hydrocarbon product. The results are shown in the Table.

Example II (comparative)

Repeating the procedure of Example 1 with the following changes:

(1) the Amount of water present during mixing of the catalytic ingredients, amounted to 620 ppm instead of 50 ppm, then instead of pasta received directly suspension, which were crushed using a ball mill until the particle size of 2 microns;

(2) the reaction of the hydrocarbon synthesis was carried out at 23° Instead 232°C.

The particle size of the powder after calcination was 30 μm. The density of the particles had a value of 1.31 g/ml the Effect of shear forces resulted in 80% reduction of particle size. Additional results are presented in the Table.

Table
ExampleIII*)
Volumetric capacity (g/LC)1130510
The selectivity for methane (mol%)4,811,0
C5+selectivity (% mass)90,180,7
*) comparative

Example III (comparative)

The catalyst precursor was prepared according to the method described in Example I except that the paste obtained according to the method of example I, ectodermal getting extrudate, which is then dried, progulivali (as in Example I), and crushed to a particle size of 58 μm instead of adding water to the paste to obtain a suspension, spray drying and calcination.

It was found that the density of the obtained particles was 2.14 g/ml of the test on the shift following the procedure described in Example I, led to a decrease in particle diameter weighted average volume by 83%.

Whichis data, you can see the catalyst of Example I, i.e., the catalyst according to the present invention, in many respects superior to the catalysts of Examples II and III, i.e. the catalysts of comparison. The present invention provides a more durable catalyst and a catalyst with a higher density. When using the catalyst according to the present invention achieves higher performance for hydrocarbons at lower temperatures. Achieved higher performance for hydrocarbons in the calculation of both the mass and volume of the catalyst. In addition, achieved a higher selectivity to hydrocarbons containing 5 or more carbon atoms, which, apparently, is only partially associated with the use of low temperatures.

In the preparation of precursors of the catalyst by mechanical energy on the refractory oxide in Example I and Example II were obtained particles of the same size. Although the particle size was the same, after molding, drying and calcination of the catalyst according to the present invention showed better properties than the catalyst of comparison.

1. The method of preparation of the catalyst precursor based on a metal of group VIII on a carrier is a refractory oxide, including

(a) the application of mechanical energy to the mixture containing refractory of the led, the connection of the catalyst precursor and water to obtain a paste, which contains at least 60 wt.% solids, and the ratio of the size of particles present in the system by the end of stage (a), the size of particles present in the early stage (a)is in the range of 0.02 to 0.5;

(b) mixing the paste obtained in stage (a)with water to form a slurry containing not more than 55 wt.% solids;

(c) shaping and drying of the suspension obtained in stage (b), and

(d) calcination.

2. The method according to claim 1, wherein the refractory oxide comprises titanium dioxide.

3. The method according to any one of claims 1 and 2, in which the paste obtained in stage (a)has a solids content in the range of 65-90 wt.%, preferably in the range of 65-80 wt.% calculated on the total weight of the paste.

4. The method according to any one of claims 1 to 3, in which the amount of water primitively at the stage (b)is 0.5 to 20 parts by weight per parts by weight of the paste, preferably 1-10 parts by weight to parts by weight of paste.

5. The method according to any one of claims 1 to 4, in which the particle size of the refractory oxide used in stage (a)is 0.1-100 μm, preferably 0.5 to 50 μm.

6. The method according to any one of claims 1 to 5, in which the ratio of the size of particles present in the system by the end of stage (a), the size of particles present in the early stage (a)is 0.05 to 0.2.

7. The method according to any one of claims 1 to 6, in which oterom stage (C) is the process of spray drying.

8. The method of preparation of a catalyst to obtain a hydrocarbon-based metal of group VIII on a carrier is a refractory oxide using the catalyst precursor and subsequent restoration, characterized in that use, the precursor of the metal of group VIII, which is obtained by the method according to any one of claims 1 to 7.

9. The method according to claim 8, in which the metal of group VIII is a cobalt.

10. The method according to claim 8 or 9, in which the metal of group VIII, at least partially present in the catalyst in the metallic form.

11. A method of producing hydrocarbons, comprising contacting a mixture of carbon monoxide and hydrogen at elevated temperature and pressure with a catalyst based on a metal of group VIII on a carrier is a refractory oxide, characterized in that the use of the catalyst obtained according to any one of p-10.



 

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1 ex

FIELD: petroleum processing.

SUBSTANCE: invention, in particular, relates to purification of vacuum gas oils, mazuts, and/or dewaxed products used further as feedstock for hydrocracking and catalytic cracking as well as high-quality fuel oils and marine oils. Purification contemplates removal of polycyclic aromatic hydrocarbons, heteroatomic compounds, resins, asphaltenes, and heavy metal compounds. Process consists in liquid extraction of undesired components with two mutually immiscible solvents: polar N-methylpyrrolidone with 3-5% water at 40-60°C and nonpolar n-undecane or undecane fraction forming azeotropic mixtures with N-methylpyrrolidone having minimal boiling temperature (about 179°C). Weight ratio of nonpolar solvent to raw material is (0.4-0.5):1.

EFFECT: increased selectivity of process in reduced risk of thermooxidative and hydrolytic decomposition of N-methylpyrrolidone as well as corrosion of equipment.

1 dwg, 4 tbl, 4 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention, in particular, relates to removing at least some trace impurities from liquid hydrocarbon fuels and to a method for clearing gasoline hydrocarbon fuel. Invention especially concerns those impurities selected from inanes, naphthalenes, phenantrenes, pyrene, alkylbenzenes, and mixtures thereof. At least a part of liquid hydrocarbon fuel, which is gasoline, is brought into contact with decolorizing activated carbon according to method disclosed in the present application. Employment of resulting gasoline in spark-ignition engines or at least in one zone in engine intake system is also described.

EFFECT: reduced formation of deposits in engines.

18 cl, 1 dwg, 2 tbl, 2 ex

FIELD: crude oil treatment and petroleum processing.

SUBSTANCE: removal of hydrogen sulfide and mercaptans from crude oil and gas condensate is accomplished by directly heating oil well produce in hydrocyclone and treating released gases together with steam-gas mixture by hydrogen sulfide- and mercaptan-selective reagent: aqueous solution of 1-hydroxy-2[1,3-oxazetidin]-3-yl-ethane (C4H9O2N) followed by cooling at temperature not higher than 15°C and separation at pressure at least 1.3 excessive atm. Installation has stilling manifold, depulser, separators, hydrocyclone, condenser-cooler, gasoline separator, discharge pumps, buffer vessel, and tanks. Accumulation tank for cleaned product is provided with heated hydrocyclone having diminishing cone angle and steam-gas line exit connected to gasoline separator equipped with mass-exchange bulk attachment.

EFFECT: considerably improved quality of well produce and reduced loss of raw material.

2 cl, 3 dwg

FIELD: crude oil treatment.

SUBSTANCE: invention relates to removal of hydrogen sulfide and mercaptans from petroleum and gas condensate. Process is conducted through oxidation of impurities with air oxygen dissolved in petroleum under pressure up to 2.5 MPa at 20 to 70°C in presence of solution of ammonium salts of cobalt sulfophthalocyanines in 20-30% aqueous ammonia solution. Reagents are used in following amounts calculated per 1 mole hydrogen sulfide: 0.1-1.6 mole NH4OH, 0.05-0.1 g phthalocyanine catalyst, and 0.05-0.1 m3 air. More specifically, ammonium salts of cobalt sulfo-, disulfo-, tetrasulfo-, dichlorodisulfo-, and dichlorodioxydisulfophthalocyanine are used. Part of exhausted ammonia catalyst solution is separated from cleaned raw material and returned into process.

EFFECT: minimized consumption of reagents and power, and enabled carrying out the process directly under oil-field conditions.

10 cl, 1 dwg, 2 tbl, 3 ex

FIELD: crude oil treatment.

SUBSTANCE: to remove hydrogen sulfide and mercaptans, 3-30% solution of urotropin in technical-grade formalin or in formalin/aqueous ammonia is added to crude material in amounts corresponding to 0.8-3.5 mole formaldehyde and 0.009-0.3 mole urotropin per 1 mole hydrogen sulfide and mercaptan sulfur. Reaction is carried out at 15 to 70°C. Method is applicable for oil and gas production and petroleum processing industries.

EFFECT: reduced consumption of reagents at high degree of purification of raw material.

5 cl, 3 tbl

FIELD: crude oil treatment.

SUBSTANCE: to remove hydrogen sulfide and mercaptans, 3-30% solution of urotropin in technical-grade formalin or in formalin/aqueous ammonia is added to crude material in amounts corresponding to 0.8-3.5 mole formaldehyde and 0.009-0.3 mole urotropin per 1 mole hydrogen sulfide and mercaptan sulfur. Reaction is carried out at 15 to 70°C. Method is applicable for oil and gas production and petroleum processing industries.

EFFECT: reduced consumption of reagents at high degree of purification of raw material.

5 cl, 3 tbl

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to synthesis of C5-C100-hydrocarbons from CO and H2, which catalyst contains carrier based on alumina prepared from gibbsite-structure aluminum hydroxide and cobalt in concentration of 15 to 50%. Carrier is prepared by mixing dry cobalt compound with dry gibbsite-structure aluminum hydroxide at cobalt-to aluminum molar ratio between 1:1 and 1:30, followed by calcination, impregnation (in two or more steps) with aqueous cobalt salt solution, and heat treatment. Invention also discloses process of producing C5-C100-hydrocarbons using above catalyst.

EFFECT: increased selectivity of catalyst regarding production of high-molecular hydrocarbons at reduced yield of methane.

7 cl, 1 tbl, 10 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: method involves carrying out the preparing synthesis gas by the gaseous oxidative conversion of natural gas with air oxygen, catalytic conversion of synthesis gas to a catalyzate followed by its cooling and separating and feeding a liquid phase into reactor for synthesis of gasoline. For aim reducing the cost of manufacturing catalytic preparing methanol is carried out in the synthesis reactor wherein methanol is fed into reactor for preparing high-octane components of gasoline that are stabilized and separated for liquid components and fatty gas that is fed into reactor for preparing oligomer-gasoline. Then liquid components from reactors wherein high-octane components of gasoline and oligomer-gasoline are prepared and then combined, and the mixture is stabilized. Water formed in all synthesis reactions after separating is removed separately, combined and fed to the fresh water preparing block and formed nitrogen is fed for storage with partial using in technological cycle and in storage of synthetic fuel. The unreacted depleted synthesis gas from block wherein methanol is prepared is used for feeding methanol into reactor sprayers for preparing high-octane component of gasoline, and unreacted gases from reactor for preparing oligomer-gasoline are fed into generator for synthesis gas. Also, invention claims the device for realization of the method. The device consists of blocks for preparing synthesis gas, catalytic conversion of synthesis gas to catalyzate and preparing gasoline and made of two separate reactors for preparing high-octane additive of gasoline and oligomer-gasoline. The device is fitted additionally by block for preparing fresh water and nitrogen collector. The reactor sprayers are connected with intermediate capacity for collection of methanol and with reactor for synthesis of methanol and block for preparing methanol, and reactor for preparing oligomer-gasoline is connected pneumatically with block for preparing synthesis gas. Invention provides the development of method for the combined preparing the fuel and fresh water.

EFFECT: improved preparing method.

2 cl, 6 dwg, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

FIELD: industrial inorganic synthesis and catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing VII group and group VIB metal compound nitrides. Ammonia is produced from ammonia synthesis gas by bringing the latter into contact with proposed catalyst under conditions favoring formation of ammonia.

EFFECT: increased ammonia synthesis productivity.

8 cl, 2 tbl, 19 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.

EFFECT: increased CO conversion.

2 tbl, 8 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting a mixture of carbon monoxide and hydrogen at increased temperature and pressure with a catalyst comprising manganese and cobalt on a carrier wherein cobalt, at least partially, presents as metal and catalyst comprises also inorganic phosphate in the amount at least 0.05 wt.-% as measure for elementary phosphorus relatively to the catalyst weight. Also, catalyst can comprise vanadium, zirconium, rhenium or ruthenium additionally. Method provides selectivity in formation (C5+)-hydrocarbons and decrease in formation of CO2.

EFFECT: improved preparing method.

7 cl, 1 tbl, 2 ex

FIELD: chemical industry; conversion of synthesis gas into alcohols and hydrocarbons.

SUBSTANCE: proposed catalyst contains the following constituents, mass-%: active component in terms of CO; promoter-fluorine, 0.1-1.0; the remainder being carrier-aluminum oxide.

EFFECT: enhanced conversion of CO.

1 dwg, 2 tbl, 6 ex

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbons are produced via contacting synthesis gas with catalytic composition consisting of mixture of iron-containing Fischer-Tropsch synthesis catalyst and acid component at elevated pressures and temperatures and specified iron-containing catalyst reduction conditions. Specifically, said iron component is a mixture of neodymium and cerium silicates at weight ratio between 1:9 and 9:1 and weight ratio of acid component to iron-containing catalyst ranges from 1:1 to 6:1.

EFFECT: increased selectivity and productivity of catalyst and reduced level of aromatic hydrocarbons in product.

3 cl, 1 tbl, 15 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing mainly C5+-hydrocarbons. Method involves contacting carbon monoxide with hydrogen at temperature 180-270°C and under increased pressure in the presence of catalytic composition comprising as measure for the total mass of catalytic composition from 5 to 30 wt.-% of cobalt, from 0.01 to 5 wt.-% of manganese and at least from 0.01 to 0.9 wt.-% of rhenium and/or ruthenium on a carried made of titanium dioxide. Invention provides reducing amount of carbon dioxide evolved in the process of hydrocarbons synthesis by Fisher-Tropsh to the level 2% vol./vol., not above, but preferably to 1% vol./vol., not above, and without reducing C5+-selectivity.

EFFECT: improved preparing method.

7 cl, 2 tbl, 4 ex

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to catalytic chemistry and, in particular, to preparation of deep-oxidation supported palladium catalysts, suitable, for example, in afterburning of motor car exhaust. Preparation involves depositing palladium from aqueous solution of palladium precursors followed by drying and calcination. Precursors are selected from nitrite anionic or cationic palladium complexes [Pd(NO2-)(H2O)3]Anx or [Pd(NO2-)n(H2O)m](Kat)y, wherein An are anions of acids containing no chloride ions, Kat is proton or alkali metal cation, n=3-4, m=0-1, x=1-2, and y=1-2. Nitrite ions are introduced into impregnating solution in the form of nitrous acid salts or are created in situ by reducing nitrate ions or passing air containing nitrogen oxides through impregnating solution. Ratio [Pd]/[NO2-] in impregnating solution is selected within a range 1:1 to 1:4.

EFFECT: eliminated chlorine-containing emissions, increased stability of chlorine-free impregnating solutions, reduced their acidity and corrosiveness, and increased catalytic activity in deep oxidation reactions.

2 cl, 1 tbl, 16 ex

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