Elongated mold particles; their application as catalyst or catalyst carrier
SUBSTANCE: description of the elongated mould particles is provided, the particles have two asperities which start from and end at the central position where it aligns the longitudinal axis of the particle, and the cross-section of the particle takes the space, that is surrounded by peripheral edge of six circles which are located around the central circle; each of the six circles contacts two adjacent circles, while two interlacing circles are located at the equal distance from them the central circle and can be connected to the central circle; at that, two circles adjacent to the interlacing circles (but not the common circle) contact the central circle, except for the space taken by four remained external circles, and four remained interstitial areas; the elongated mould particles have complementary one to four asperities which are connected, preferably one or two, to the existing end asperity in a way specified above, and the complimentary asperity is specified as described above, while existing end asperity becomes a new central circle and the initial central circle becomes another asperity; also, the description is provided for the mould catalyst or its precursor for hydrocarbon synthesis by Fischer-Tropsch, mould carrier, method for producing the mould carrier, matrix disk, method for producing the hydrocarbons and method for producing the fuel and basic oil from hydrocarbons.
EFFECT: method for producing hydrocarbons is improved.
14 cl, 1 tbl, 2 dwg, 4 ex
The technical field to which the invention relates.
The present invention relates to a new class of oblong shaped particles, and these particles can be used in a variety of processes, catalytic or non-catalytic.
Molded particles according to the invention are very effective media for catalyst or catalyst precursor, which can be used in the processes, limited by mass transfer or diffusion, such as the method of synthesis of hydrocarbons by the Fischer-Tropsch process.
In addition, the invention relates to a catalyst or catalyst precursor, the catalyst or catalyst precursor applied on specific molded carrier, to a method of preparation of the catalyst or catalyst precursor of the mouldable paste and the matrix disc used to produce the extrudate catalyst.
In addition, the invention relates to a method for producing fuels and base oils by hydrogenation, hydroisomerization and/or hydrocracking of hydrocarbons, which can be obtained in the Fischer-Tropsch synthesis using this catalyst.
The level of technology
In the past a very large number of works were devoted to the development of particles, in particular catalytically active particles, for various PR the processes. Significant efforts were also directed towards the clarification of advantages, and sometimes disadvantages when changing the form of particles, different from the traditional forms, such as pellets, rods, spheres, and cylinders, for use in catalytic and non-catalytic processes.
Examples of additional, well-known forms are the rings, the shape leaf clover, handleoversize and C-shaped particles. Considerable efforts have been devoted to the so-called "multi-leaf" molded particles. Many industrial catalysts are available in the form t (three fold) or MEMBER (four). They serve as alternatives to industrial cylindrical form, and often provide advantages due to their inherent high values of the ratio surface/volume, which leads to a greater availability of catalytic centers and, thus, to increased activity of the catalyst.
An example of a study on the impact of different forms of particles on the catalytic properties can be found in article I.Naka and A. de Bruijn (J.Japan Petrol. Inst., V.23 supported, No.4, 1980, pp.268-273), entitled "catalytic Activity with feasibility form hydrodesulphurization unit". This article describes the experiments which were tested feasibility extrudates of catalyst (12 wt.% Moo3and 4 wt.% Soo on gamma-alumina), it is either in the cross-section symmetric quatrefoil, single quatrefoil and trehlistnyj and cylindrical extrudates with a diameter of 0.8 mm, 1.6 mm and 2.1 mm; and testing of the catalyst activity (12 wt.% Moo3and 4 wt.% Soo on gamma-alumina) in relation to a hydrodesulphurization unit was performed in a small laboratory setting. In this article concluded that the activity in the hydrodesulphurization unit significantly correlated with the ratio of geometric volume to the surface of the catalyst particles, but does not depend on the form of the catalyst.
In document EP 0220933 described that the shape of the three catalysts of the type is important, in particular, in connection with the index, known as the pressure loss. From experimental data it follows that for asymmetric four-petalled particles, the pressure loss is less than for most close-to-symmetric four-petalled particles. Particles with asymmetric form described in the document EP 0220933 so that each pair of tabs separated by a groove, which the protrusions, in order to prevent the occurrence in them of the projections of the neighboring particles. In document EP 0220933 indicated that this form of particles prevents their "packaging" in the layer and leads to a low overall bulk density of the catalyst bed.
In document EP 0428223 described that the catalyst particles can be in the form of cylinders, hollow is elenkov, for example cylinders, in which there is a Central cavity having a radius in the range of 0.1-0.4 radius of the cylinder; straight or twisted shamrocks; or one of the other forms described in the patent US 4028221. It is noted that a three extrudates are preferred.
In document EP 0218147 disclosed multilobe extrudates with a spiral-like petals, with the outer shape of three or four coils, spiral twisted about the axis of the extrusion along the length of the particle; the application of the extrudate as catalyst or catalyst carrier, in particular as catalyst or catalyst carrier in Hydrotreating processes. It is noted that the spiral shape of the particles reduces the pressure loss along the fixed catalyst layer, through which the liquid and/or gaseous reagents. Therefore, in this constructive solution of the reactor can be used smaller catalyst particles that meet the requirements of the pressure loss.
Because many of the facts in this area are controversial and the problem of pressure loss remains relevant, especially when increasing the ratio of surface/volume of the particles by reducing their size, there is still considerable scope for alternative forms (optional catalytically active particles, which is ogli would weaken or even prevent such problems. In the present invention it has been unexpectedly found that specifically molded particles provide an obvious and significant advantages compared with traditional particle "three", cylindrical or four-petalled forms, as in catalytic and non-catalytic processes.
Disclosure of inventions
Elongated molded particles containing two protrusions, each protrusion extends from and is attached to the Central position, where the Central position is aligned along the longitudinal axis of the particles, and the cross-section of a particle occupies a space surrounded by the outer edges of six circles around a Central circle, each of these six circles for the two neighboring circles, while two alternating circle are equidistant from the centre circle with the possibility of connection to the Central circle and the two circles adjacent to two alternating circles (but not the total range), relate to the Central circle, minus the space occupied by the four remaining outer circles and including the four remaining region of the internode.
Detailed description of the invention
It is known that processes of the type which require a solid porous catalyst particles, is often limited by the speed of diffusion of the reactants in the particle can produce the RA or the diffusion rate of the formed products from the catalyst particles. Therefore, the best are the catalyst particles having a high value of the ratio surface/volume.
It is established that the catalyst particles according to the present invention, have a high ratio of surface to volume compared to traditional cylindrical or three particles of similar size and provide significantly less pressure loss than the corresponding traditional cylindrical or three particles.
Molded particles according to the invention, can be obtained from any suitable material provided that it can be processed in such a way as to achieve the desired particle shape. Methods of obtaining such forms include pressing, extrusion or other molding of granular or powdered catalyst material or catalyst precursor in various forms in some of the conditions that can ensure the preservation of forms received, both during the reaction and the regeneration process.
Preferred particles according to the present invention have a cross-section in which two alternating circles have a diameter in the range of values between 0.74 and 1.3 diameter of the Central circle, preferably, of 0.87-1.15 diameter of the Central circle.
More preferably the mi particles, according to the present invention are those which have a cross-section in which two alternating circles have the same diameter as the diameter of the Central circle. Greatest preference is given to particles which have a cross-section in which two alternating circle attached to the Central circle.
Figure 1 shows the cross-section of the preferred particles according to the invention. The cross-sectional area of the particles is limited by the solid line) can be described in the main claim. From this drawing depicting a cross section of the preferred particles) shows that in the layout of the six outer circles of equal size, arranged around the Central circle of the same size, each of the outer circle is bordered by two neighboring circles and the Central circle, while two alternating circle are equidistant from the Central circle and may be attached to the Central circle. These two circles adjacent to alternating circles (but not the total range), relate to the Central circle.
The cross-section of the particles is preferably composed of three circles (the Central circle and two alternating outer circles), together with four fields (3), formed due to the inclusions of the Central circle and five on uinyh circles, among them are two alternating outer circle, each of which covers two adjacent outer circles, minus the space occupied by the remaining four circles. In the framework of this invention enable the Central circle and five outer circles, among which are two alternating outer circle, called "interstitial areas". Two alternating outer circle are equidistant from the Central circle.
Used herein, the term "equal distance" refers to the fact that the distance between the center of the Central circle and the center of one of the outer circles is equal to the distance between the center of the Central circle and the center of any one of the remaining outer circles.
In the framework of this invention, the term "equidistant" may include deviations up to 20% from the specified distance, preferably up to 10%, more preferably up to 5%. In the most preferred embodiment, these deviations are not available.
Condition preferred form of particles according to the present invention, means that they do not contain sharp edges.
The two tabs and the Central position together form a cross-section of the molded particles. The main part of each lug is formed by one of the alternating circles. The main part of the Central position generates the I Central circle. Interstitial region are distributed between the Central position and the projection of a line perpendicular to the straight line connecting the center point of the center circle and the center point of the striped circle. This perpendicular line crosses the straight line to a point located exactly in the middle between two points of the centers (see figure 1). The present invention relates to an elongated molded particles, or catalyst, or catalyst precursor, in which any of the Central circles has three or more protrusions. Thus, excluded three -, four-petalled and other particles.
Molded particles of the present invention include particles containing from one to four additional protrusions, preferably from one to two additional protrusions, each attached to an existing end projection, as defined in paragraph 1, and the additional ledge defined in the same way as in paragraph 1, the existing limit protrusion becomes the new Central circle, and the original Central circle becomes another ledge. The cross-section of the particles, including additional tabs, shown in figure 2. These additional tabs are not attached to each Central position, that is, in the invention are not included multilobe patterns, such as t phlebectasia.
An alternative way of describing the preferred particles of the present invention is a representation of a cross section of these particles, composed of three or more circles, in which the angle between two lines connecting the centers of the three adjacent circles is the interval 90-180 or 180-270°; preferably 110-150 or 210-250°more preferably 120 or 240°.
Molded particles according to the invention may include particles having only one additional protrusion, or particles having at least two additional tabs, or a mixture of both types of particles.
It can be understood that minor deviations from the above forms are included in the scope of the present invention. In the case when the catalyst or catalyst precursor, according to the invention, obtained using the extrusion process uses a matrix discs. Professionals in this area of technology known production matrix disks for receiving particles according to the present invention, which contain one or more holes in its structure and for which you can expect the permissible deviations of dimensions with practical obtaining such a matrix drive. In this regard, it is noted that the pressure relief immediately after extrusion can lead to deformation of the extrudates. Usually small Atlanticists up to 10%, preferably up to 5%, more preferably up to 2%, relative to the diameter of the circles of the ideal form, as defined in the present invention.
In a typical method of obtaining particles of the catalyst or catalyst precursor, according to the invention, in the interval 10-100% of the number of obtained particles should have a nominal diameter with a deviation of less than 5% from the ideal form, which is defined in the present invention. Preferably, at least 50% of the catalyst particles should have a nominal diameter with a deviation of less than 5% from the ideal form, which is defined in the present invention.
According to the present invention it is possible to obtain catalyst particles that also contain one or more holes along the length of the particle. For example, these particles may contain one or more holes in the field, presents the Central cylinder (the Central circle in cross-section, is shown in figure 1) and/or one or more holes in one or more alternating cylinders (striped circles in cross-section, is shown in figure 1).
The presence of one or more of the holes leads to the increase of the ratio surface/volume, which in principle allows a greater availability of catalytically active centers and, in any case, greater availability comes the future of raw materials, which can more efficiently be processed from the point of view of catalysis. Because with decreasing particle size becomes difficult to obtain hollow particles, it is preferable to use porous particles without holes, when for some assignments it is desirable to use particles of a smaller size.
It is established that the porosity of the layer of catalytic particles according to the invention, significantly higher than 50% (porosity is defined as the volume fraction of empty space available in the layer between the particles, i.e. the pore volume within a particle is not included in the value of porosity). The particles used in the experiment, described below, have porosity, typically in excess of 58%, which is significantly higher than the porosity map "three" particles, which is slightly higher than 43%.
Catalytic particles according to the invention, can be described as particles having a length to diameter (L/D), is at least equal to 1. The particle diameter defined as the diameter of one of the circles shown in figure 1.
The length of the particles containing from one to four additional tabs, defined as the distance between the tangent line that touches the first protrusion, and a line parallel to this tangent and on the second ledge. This second protrusion is a protrusion, the most is remote from the first protrusion, as shown in figure 2.
Particles according to the present invention may have a ratio L/D in the range 1-25. Preferably the particles according to the invention have a value of L/D in the range of 1.5 to 20, more preferably in the range of 2-10. For example, the particles used in the following experiment, have a ratio L/D is approximately equal to 2.5.
The length of the particles according to the present invention, it is in the range 1-25 mm, preferably in the range of 2-20 mm, depending on the type intended application.
Molded particles according to the invention, it is obtained from porous media. This porous carrier may be selected from any suitable refractory oxides or silicates of metals or their combinations, which are known from the prior art. Specific examples of preferred porous carriers include silica, alumina, titanium dioxide, zirconium dioxide, cerium oxide, gallium oxide and mixtures thereof, especially silicon dioxide, aluminum oxide, titanium oxide, usually TiO2. These particles can contain one or more catalytically active metals or their predecessors.
In one embodiment of the present invention molded particles can be used as a carrier for catalyst for Fischer-Tropsch synthesis. Obtaining ug is avodarto from a gaseous mixture, containing carbon monoxide and hydrogen by contacting this mixture with the catalyst at elevated temperature and pressure is known from the literature as the Fischer-Tropsch synthesis. Get the fuel and base oil from hydrocarbons by hydrogenation, hydroisomerization and/or hydrocracking, these hydrocarbons obtained by contacting a mixture of carbon monoxide and hydrogen with a catalyst, which is described in claim 6 of the formula, and this catalyst is not necessarily trigger.
Used in the Fischer-Tropsch synthesis catalysts often contain one or more metals from group VIII of the Periodic table of elements, not necessarily in combination with one or more metal oxides and/or other metals as promoters.
The most desirable to use a highly effective catalyst. In connection with the Fischer-Tropsch synthesis high-performance catalyst is a catalyst which possesses not only a high level of activity in the conversion of carbon monoxide and hydrogen into hydrocarbons, but also has a high selectivity of the formation of hydrocarbons with a higher molecular weight, in particular of hydrocarbons5and above, in the following referred to as "hydrocarbons5+".
In the prior art it is known that the efficiency of the catalyst usually is about increases with decreasing particle size of the catalyst. In addition, the catalysts should have a high stability, i.e. a drop of activity should be negligible.
The Fischer-Tropsch synthesis can be performed using a variety of modes of process, e.g., fluidized bed or in a layer in the form of a suspension.
When using the process in terms of a fixed catalyst layer main parameter considered in the calculation process is the pressure drop over the layer of catalyst. Most preferably, the pressure difference was as little as possible.
However, the prior art it is well known that for a given shape of the catalyst particles with reduced particle size in a fixed bed of catalyst, there has been increasing pressure drop in the catalyst bed.
Thus, when calculating the fixed catalyst layer there is a contradiction between the desire for a satisfactory level of activity and maintaining a minimum pressure drop over the layer of catalyst.
Except as provided above, the catalyst particles should have sufficient strength in order to avoid undesirable abrasion and/or destruction of particles. The value of crushing strength should be very high in a fixed bed of catalyst, as in industrial reactors are used, the layers up to 15 meters. the particularly high pressure is realized in the lower part of the layer, where the strength of the catalyst particles is of great importance. This further complicates the problem further improvement of the catalyst particles.
Another complicating factor is the method of producing catalyst particles. There is a need for a relatively quick, cheap and convenient method of obtaining, which can provide large-scale production of catalyst particles. One example of such industrially available method of obtaining is the extrusion process.
When modeling using molded particles of the present invention as a carrier of the catalyst during Fischer-Tropsch synthesis of hydrocarbons shows that diffusion limits for CO and/or H2be substantially less than when using particles of a traditional three-petal shape, which leads to increased selectivity.
When using the molded extrudate according to the invention as catalyst carrier can be expected to improve performance in other processes, for which there are limitations to mass transfer.
When using the molded particles according to the invention, as the carrier of the catalyst during Fischer-Tropsch synthesis of hydrocarbons is an important advantage is a significant reduction in pressure drop in slo the catalyst. This reduction of pressure drop provides significant advantages because most preferably, the value of the differential pressure as low as possible.
In addition, the particles of the molded extrudate of the present invention have a high crushing strength compared to a three particles molded extrudate.
Moreover, achieves a good selectivity for C5+ and good stability. In addition, the particles are strong enough and can be easily obtained by extrusion.
The catalysts of the present invention, especially when used in the Fischer-Tropsch process, contain as catalytically active component, a metal of group VIII of the Periodic table of elements. Specifically, the catalytically active metals include ruthenium, iron, cobalt and Nickel, more preferably cobalt. In addition, the possible combinations of two or more components. Preferably used is a catalyst for Fischer-Tropsch synthesis, which results in a significant release of paraffins, more preferably almost unbranched paraffins.
The most suitable catalytic composition for this purpose includes a cobalt containing catalyst Fischer-Tropsch process. Such catalysts are described in the literature, see, for example, documents AU 698392 and WO 99/34917.
P is impactfully hydrocarbon feedstock to produce synthesis gas is natural gas or associated gas. Because these feedstocks usually lead to a synthesis gas having a ratio of H2/CO, close to two, the cobalt is a very good catalyst for Fischer-Tropsch synthesis, as for this type of catalyst is used, the ratio of N2/, Also close to 2.
Preferably, when the catalytically active metal is applied on a porous carrier. This porous carrier may be selected from any suitable refractory oxides, or silicates of metals, or combinations thereof, known in the prior art. Specific examples of preferred porous carriers include silica, alumina, titanium dioxide, zirconium dioxide, cerium oxide, gallium oxide and mixtures thereof, especially silicon dioxide, aluminum oxide, titanium oxide, usually TiO2.
The amount of catalytically active metal on the carrier for optimal catalyst is preferably in the range from 3 to 300 parts by weight per 100 parts by weight of the material of the carrier, more preferably from 10 to 80 parts by weight, especially from 20 to 60 parts by mass.
In addition, if desired, the catalyst may contain one or more metals or metal oxides as promoters. Suitable promoters - metal oxides can be selected from groups IIA, IIIB, IVB, VB, VIB or group VIIB of the Periodic table of elements is of actinides and lanthanides.
In particular, very suitable promoters include oxides of magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, cerium, thorium, uranium, vanadium, chromium and manganese. Particularly preferred promoters of the metal oxide to the catalyst used in the preparation of heavy paraffin hydrocarbons, are the oxides of manganese, vanadium and zirconium.
Suitable metal promoters can be selected from groups VIIB or VIII of the Periodic table of elements. Specifically are suitable rhenium, silver and the noble metals of group VIII, particularly preferred are platinum and palladium.
The amount of promoter present in the catalyst, expediently in the range from 0.01 to 100 parts by weight, preferably from 0.1 to 40 parts by weight, more preferably from 1 to 20 parts by weight to 100 parts by mass media. The most preferred promoters are selected from vanadium, manganese, rhenium, zirconium, and platinum, with regard to their ability to enhance the formation of n-paraffins with a long chain.
The catalytically active metal and the promoter, if present, can be deposited on the material of the carrier in any suitable treatment such as impregnation, mixing/kneading and mixing/extrusion.
After deposition of the metal and, if appropriate, promoter on the material media "loaded" the media usually subjected to calcination.
Processing by annealing allows to remove the water of crystallization, to decompose organic compounds and convert inorganic compounds into the corresponding oxides.
Obtained after calcination the catalyst may be activated by contacting the catalyst with hydrogen or a hydrogen-containing gas at a typical temperature of from about 200 to 350°C.
Other methods for producing catalysts for Fischer-Tropsch synthesis include kneading/dispersion, followed by extrusion, drying/calcination and activation.
A suitable material for a molded catalyst particles must be processed in such a way as to obtain particles of a given shape.
One example of the processing method is the extrusion process, in which the mouldable paste, preferably containing one or more catalytically active elements, and optionally one or more sources of one or more promoters, and finely ground refractory oxides or precursors of refractory oxides are dispersed together in a suitable solvent. Then dispergirovannoyj the mixture is extruded through the holes in the matrix disk. Product extrusion is subjected to drying.
Time to relax is Amy in the mixture, the solvent can be any suitable solvent, known from the prior art. Examples of suitable solvents include water; alcohols such as methanol, ethanol and propanol; ketones, such as acetone; aldehydes, such as propanol; aromatic solvents such as toluene. The most convenient and preferred solvent is water, optionally in combination with methanol.
The use of special matrix drive provides reception of catalytic particles of a given shape. Matrix disks are well known in the prior art, and they can be made of metal or polymeric material, especially a thermoplastic material.
The process of catalytic conversion can be carried out in the traditional conditions of synthesis known from the prior art.
Typically, the catalytic conversion may be carried out at a temperature in the range from 150 to 300°C, preferably from 180 to 260°C.
Typically, the total pressure of the catalytic conversion is in the range from 1 to 200 bar (absolute), more preferably from 10 to 70 bar (abs.).
In the process of catalytic transformations occur usually more than 75 wt.% hydrocarbons With5+, preferably more than 85 wt.% hydrocarbons With5+.
Depending on the catalyst and conditions of the transformation of quantity of heavy paraffin hydrocarbons (C20+) mo is et up to 60 wt.%, sometimes up to 70 wt.%, and sometimes even up to 85 wt.%.
Preferably applies a cobalt catalyst, a low ratio of N2/WITH (especially 1.7 or less), and there is a low temperature 190-230°C.
In order to prevent the formation of coke, preferably using gas with respect to H2/WITH, at least, of 0.3. Particularly preferably, when the Fischer-Tropsch synthesis is carried out in such conditions that the resulting products having at least 20 carbon atoms, the amount of alpha in the distribution of the Schulz-Flory was at least 0,925, preferably at least 0,935, more preferably at least 0,945, even more preferably at least 0,955. Preferably the flow of hydrocarbons from the Fischer-Tropsch synthesis contains at least 35 wt.% With30+, preferably 40 wt.%, more preferably 50 wt.%.
The Fischer-Tropsch synthesis can be carried out in the mode of the layer in the form of a suspension or fixed layer, especially in novotrubnom a fixed bed of catalyst.
It is established that in the layers of particles according to the invention, when a random packing of particles contains more voids than the layers containing the traditional three-particles, when packaging with the use of so-called technology "boot from toe".
The porosity value, is received when using particles of a traditional three-form, comes to about 45%, while when using particles according to the present invention, the value of porosity is at least 55%, making such particles attractive for use in processes with low pressure drop, for example, in the Fischer-Tropsch synthesis.
Described in this invention, the catalyst particles can also be molded in the form of particles with a spiral-like petals.
The term "particles spiral petals"used in this description, refers to an elongated molded particles containing two protrusions, each protrusion extends from and is attached to the Central position, where the Central position is aligned along the longitudinal axis of the particles, and the cross-section of the particle occupies the space surrounded by the outer edges of six circles around a Central circle, each of these six circles for the two neighboring circles, while three alternating circle are equidistant from the Central circle and may be connected to the Central circle, minus the space occupied by the four the remaining outer circles and including the four areas of internodes, and these protrusions are distributed along as retinue spiral around the longitudinal axis of the particles.
The term particles spiral petals used is in the description also can refer to the elongated molded particles containing from one to four additional tabs, each attached to an existing projection, as defined in paragraph 1, and the additional ledge defined in the same way as in paragraph 1, and the existing ledge becomes the new Central circle, and the original Central becomes another steep ledge, and these protrusions are distributed along as retinue spiral around the longitudinal axis of the particles.
By using particles with a spiral petals can be used in larger diameter particles spiral petals, which provide the specified selectivity, compared with the use of particles with direct petals, which leads to a significant reduction of the pressure loss on the layer of catalyst than might have been expected from the prior art.
Alternative for a given configuration of the fixed layer with a preset pressure loss due to the use of particles with a spiral-like petals in the Fischer-Tropsch synthesis can be achieved significantly higher selectivity than the corresponding particles with direct petals that are required for compliance with the requirements of the pressure loss.
The invention will now be illustrated using the following the existing non-limiting examples.
Experiments were carried out to compare the selectivity to hydrocarbons, C5+ in the Fischer-Tropsch synthesis for catalytic particles, prepared from a traditional three-petal (in the following referred to as TL) particles and particles having a shape according to the invention.
All three types of particles obtained by extrusion of the same material containing a catalytically active element, a promoter, a refractory oxide carrier and photometering mixture, using the appropriate matrix disk.
Example 1. Receiving catalyst particles of a three-form (comparative)
The catalyst particles of a three-form is obtained as follows.
Prepare a mixture of 143 g industrially available powder of titanium dioxide (P25 warehouse company Degussa), 66 g of available industrial powder Co(OH)2, 10.3 g of the diacetate tetrahydrate of manganese and 38 g of water. This mixture and mix for 15 minutes. The mixture is molded using a Bonnot extruder. The resulting extrudate is dried and calcined; the extrudate contains 20 wt.% Co and 1 wt.% Mn. The formed catalyst particles have a three-form, nominal diameter equal to 1.7 mm (catalyst A).
Example 2. Receiving catalyst particles according to the invention
Prepare a mixture of 143 g of available industrial dioxide powder is titanium (P25 warehouse company Degussa), 66 g industrially available powder of Co(OH)2, 10.3 g of the diacetate tetrahydrate of manganese and 38 g of water. This mixture and mix for 15 minutes. The mixture is molded using a Bonnot extruder, equipped with a suitable matrix drive, in order to obtain a desired shape, which is specified in paragraph 2 of the claims. The resulting extrudate is dried and calcined. The formed catalyst particles contain 20 wt.% Co and 1 wt.% Mn and have the form specified in paragraph 2, and the number of additional tabs is one (the catalyst) or two (catalyst C).
Catalysts a, b and C have in the method of producing hydrocarbons. Three microphotonic reactor containing 10 ml of the respective extrudates of catalysts a, b and C in the form of a stationary layer of particles is heated to a temperature of 280°and create an absolute pressure of 2 bar continuous flow of nitrogen gas. Catalysts restore in the reactor for 24 hours a mixture of gases, nitrogen and hydrogen. During recovery the relative concentration of hydrogen is gradually increased from 0%to 100%. The water concentration in the exhaust gas is maintained below 3000 ppm (by volume).
After restoring the pressure increased to 32 bar (capacity 130) or 57 bar (capacity 150). The process is carried out, feeding a mixture of hydrogen and monoxi the and carbon. Performance calculated in grams of the hydrocarbon product obtained per hour per 1 liter of the catalyst particles (including the voids between particles). In each experiment after 50 hours of operation determine the selectivity With5+which is expressed in wt.% from the amount of hydrocarbon products, and the selectivity With1expressed in wt.% from the amount of hydrocarbon products. The results are shown in the table.
|Productivity, g/[l(cat.)·h]||The relative selectivity With5+, %||The relative selectivity of C1, %|
|The catalyst In||130||102,2||74,2|
In the table the results related to the selectivity With5+obtained using catalysts b and C, expressed relative to the results obtained when using catalyst A (comparative catalyst), that is, for the catalyst And the selectivity of C5+ was taken as 100%.
From these results it is clear that the catalyst particles according to the invention (b and C) possess more than the high selectivity of the formation of hydrocarbons With 5+ in the Fischer-Tropsch synthesis compared with traditional three-particles (catalyst A).
In addition, the selectivity relative to unwanted products C1in the Fischer-Tropsch synthesis using the catalyst particles according to the invention, significantly lower than the selectivity for C1when using the comparative catalyst.
Selectivity With5+ for catalyst and the catalyst is greater than the selectivity With5+ for catalyst a, And the selectivity for C1lower than that of catalyst A. the Performance of catalysts b and C better, despite the lower amount of active metal in the reactor volume for these catalysts compared with the catalyst And, because of their higher porosity. Thus, the specific shape of the particles of catalysts b and C provides the best use of expensive catalytic material.
Example 4. Experimental determination of pressure loss
The pressure loss in the catalyst layer filled with catalyst particles of the catalyst, the average length of the particles is equal to 4.5 mm is mapped to a pressure loss in the catalyst layer filled with catalyst particles of the catalyst And, when the average length of the particles is equal to 4.5 mm, the pressure Loss in the catalyst layer filled with particles of a catalyst, was), the governmental below: in the column, filled with catalyst, the pressure loss is equal 79,9% of the pressure loss in the column filled with catalyst A. From this result it is clear that the molded catalyst particles according to the invention provide advantages in terms of pressure loss in comparison with the known molded catalyst particles.
1. Elongated molded particles containing two protrusions, each protrusion extends from and is attached to the Central position, where the Central position is aligned along the longitudinal axis of the particles, and the cross-section of the particle occupies the space surrounded by the outer edges of six circles around a Central circle, each of these six circles for the two neighboring circles, while two alternating circle are equidistant from the Central circle and may be connected to the Central circle and the two circles adjacent to two alternating circles (but not General circle) relate to the Central circle, minus the space, employed four remaining outer circles and including the four remaining region of the internode, elongated molded particles additionally contain one to four additional protrusions, preferably one or two additional tabs, each attached to an existing end projection, as defined, is Elena above, moreover, the additional protrusion defined in the same way as above, the existing limit protrusion becomes the new Central circle, and the original Central circle becomes another ledge.
2. Elongated molded particles according to claim 1, having a cross section in which two alternating circle and additional tabs, if they exist, have a diameter in the range of values of 0.74 and 1.3 of the diameter of the Central circle, preferably, of 0.87-1.15 diameter of the Central circle.
3. Elongated molded particles according to claim 1, in which the angle between two lines connecting the centers of the two circles and the Central circle is the value 90-180° or 180-270°; preferably 110-150° or 210-250°more preferably 120-240°.
4. Elongated molded particles according to any one of claims 1 to 3, having a cross section in which two alternating circle and additional tabs, if they exist, have the same diameter as the Central circle.
5. Elongated molded particles according to any one of claims 1 to 3, with the ratio L/D (in mm), where D represents the diameter of the Central circle, as defined in claim 1, in the interval of values 1-25, preferably, 2-10, or having a length (L) in the range of 0.5-15 mm, preferably 1-5 mm
6. A molded catalyst or catalyst precursor for sin is ESA hydrocarbons by Fischer-Tropsch, containing a catalytically active component or precursor supported on a carrier, which represents an elongated molded particles according to any one of claims 1, 2 or 3, and referred to a catalytically active component selected from elements of group VIII of the Periodic table.
7. A molded catalyst or a catalyst precursor according to claim 6, in which the catalytically active component selected from Fe, Co or Ni and combinations thereof, preferably With.
8. A molded catalyst or a catalyst precursor according to claim 7, in which the carrier is a refractory oxide, preferably silicon dioxide, aluminum oxide, titanium dioxide, preferably titanium dioxide.
9. A molded catalyst or a catalyst precursor according to claim 7 or 8, containing an element selected from groups IIA, IIIB, IVB, VB, VIB, VIIB or VIII of the Periodic table of the elements or their compounds, preferably selected from V, Zr, Mn, Ru, Re, Pt, Pd or Ag.
10. Molded carrier having elongated molded particles according to any one of claims 1 to 3, in which the carrier is produced by extrusion.
11. The method of receiving media having elongated molded particles according to any one of claims 1 to 3, by pressing, extrusion or other spray granulated or powdered material in various forms in some of the conditions that both is that the preservation of the forms received, as during the reaction, as well as in the regeneration process, preferably by extrusion.
12. Matrix ROM, designed for use when receiving media of claim 10, where the matrix disk contains one or more holes having a cross-sectional shape of the particles of the medium.
13 a Method of producing hydrocarbons by contacting a mixture of carbon monoxide and hydrogen with a catalyst, which is described in claim 6, and this catalyst does not necessarily trigger.
14. The method of obtaining fuel and base oil from a hydrocarbon, described in item 13, by hydrogenation, hydroisomerization and/or hydrocracking.
FIELD: chemistry, organic, processing of hydrocarbons.
SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.
EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.
14 cl, 1 ex
FIELD: petroleum processing.
SUBSTANCE: catalyst is characterized by that content of rare-earth elements in crystalline lattice of Y-zeolite, based on RE2O3, is 4 to 15 wt %, initial size of elementary cell is 2.450 to 2.458 nm, and size of equilibrium structure of elementary cell after its treatment with 100% steam at 800°C for 17 h exceeds 2.430 nm. Also described is a method for preparation of above catalyst for hydrocarbon cracking comprising (1) drying Y-zeolite with rare-earth element ions to water level below 10%, then, at a weight ratio SiCl4/Y-zeolite, interacting zeolite with gaseous SiCl4 supplied with dry air at 150-600°C for a period of time from 5 min to 2 h after reaction followed by removing residual soluble by-products in zeolite by washing with decationized water; (2) mixing and suspending 10-50% Y-zeolite with rare-earth element ions prepared in step (1), 10-60% binder, and 2-75% clay followed by forming catalyst by spray drying and using it.
EFFECT: increased catalytic activity, hydrothermal stability, degree of heavy oil conversion, and selectivity with respect to gasoline, dry gas, and coke, and considerably reduced content of olefin in produced gasoline.
33 cl, 3 dwg, 17 tbl, 36 ex
FIELD: petroleum processing.
SUBSTANCE: invention relates to technologies of obtaining feedstock sources such as crude oil, high-boiling petroleum fractions, petroleum residues, coal liquefaction and by-product-cock plant products, spent lubricating oils, household and industrial wastes of various hydrocarbon fuels, and hydrocarbon raw materials for basic and petrochemical synthesis. Method according to invention comprises: provision and/or synthesis hydrogen donors; hydrocarbon, hydrogen donor, and catalyst stirring step; separation of resulting mixture; isolation of light and heavy fractions; and recycling of heavy fraction together with catalyst to mixing step and hydrogenation of light fraction followed by recovering synthesized hydrogen donors, which are also directed to mixing step.
EFFECT: enhanced process efficiency.
9 cl, 1 dwg, 4 ex
FIELD: petroleum processing.
SUBSTANCE: petroleum feedstock hydrocracking catalyst is prepared by compounding zeolite Y with aluminonickel(cobalt)-molybdenum(tungsten) oxide system. Specifically, low-alkalinity zeolite Y having silicate modulus 5.5-7.0 and crystallinity at least 70% is mixed with aluminum hydroxide having pseudoboehmite structure in proportion (1-9):1. Thus obtained mix is molded, dried, and calcined under water steam atmosphere to give molded thermally treated zeolite. The latter is impregnated with aqueous Ni(Co) and Mo(W) salt solutions or ground and compounded with aluminonickel(cobalt)-molybdenum(tungsten) oxide system by mixing with aluminum hydroxide and Ni(Co) and Mo(W) salts, after which follow molding and impregnation with aqueous Ni(Co) and Mo(W) salt solutions.
EFFECT: expanded catalyst preparation possibilities.
2 cl, 5 tbl, 4 ex
FIELD: petrochemical processes.
SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.
EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.
12 cl, 3 tbl, 22 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalyst (water-soluble silicon compound) solution is added to hydrocarbons, which are then subjected to cracking in presence of hydrogen at temperature and overpressure providing explosive transfer of catalyst solution into vapor phase. Motor fuel components are predominantly obtained. Yearly processing of 0.5 to 1.0 million ton petroleum is thus envisaged.
EFFECT: simplified process, increased yield of commercial products, and enabled creation of mediate-scale cracking plants.
5 cl, 2 tbl, 3 ex
FIELD: petroleum processing.
SUBSTANCE: at least part of heavy feed is supplied to deasphalting section in presence of hydrocarbon solvents to form two streams, of which one stream is composed of deasphalted petroleum products and the other of asphalts. The latter is mixed with hydrogenation catalyst and optionally with the rest of heavy feed not directed to deasphalting section. Resulting mixture is fed to hydrofining reactor, to which also hydrogen or H2/H2S mixture is supplied. Stream containing hydrofining reaction product and dispersed catalyst is routed to one or more distillation or evaporation stages, by means of which most volatile fractions, including hydrofining gases, are separated. At least 60 wt % of bottom residue (goudron) or liquid leaving evaporation unit containing dispersed catalyst, sulfide-rich metals obtained in feed demetallization stage, and optionally coke is recycled to deasphalting zone.
EFFECT: simplified technology.
18 cl, 2 dwg, 4 tbl, 3 ex
FIELD: petroleum processing.
SUBSTANCE: blend composed of vacuum distillate and distilled fraction of secondary destruction processes is subjected to hydrogenation processing at elevated temperature and pressure in presence of catalyst, said secondary destruction process fraction containing sulfur up to 1% and being taken in amount 2 to 25% based on total weight of feedstock, while vacuum distillate boils up to 560°C. More particularly, secondary destruction process fraction is catalytic cracking, visbreaking, or retarded coking gas oil fraction. Process is carried out at 340-415°C, pressure 4-10 MPa, and feedstock supply volume flow rate 0.5-2.0 h-1.
EFFECT: improved purification degree of residue and enabled involvement of heavy vacuum distillate.
2 cl, 3 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: to crude oil with 2-10% water content is added catalyst followed by activation of hydrogen donors and hydrogenation of crude oil. Catalyst is used in the form of water-soluble group VI and VIII element compounds, which dissolves in water contained in crude oil to form true solution. Hydrogen donors are own crude oil fractions and products obtained from own crude oil fractions.
EFFECT: simplified and deepened oil processing.
10 cl, 1 dwg, 1 tbl
SUBSTANCE: catalyst for Fischer-Tropsch synthesis is described, with metal from group VIII of the periodic table as an active component and carrier containing the oxide constituent and scale shaped metallic aluminum. The method for preparation of catalyst for Fischer-Tropsch synthesis is also described which consists in application of the active component upon the carrier by use of pipette; the carrier is prepared from paste by extrusion, the extrudates are exposed to air, dehumidified and baked and the used paste contains the oxide constituent, scale shaped metallic aluminium, binding agent and plasticiser.
EFFECT: catalyst's activity and selectivity in regard to high molecular hydrocarbons are increased.
15 cl, 1 tbl, 15 ex
FIELD: petroleum chemistry.
SUBSTANCE: invention relates to petroleum chemistry, gas chemistry, coal chemistry. It refers to synthetic petroleum, that features the following content of the components: content of alkanes - at least 80 W%, C5-C10 fractions- at least 50 W%, content of aromatic compounds - not over 0.5 W%.The catalyst to produce synthetic petroleum was also applied for containing a carrier and an active component. Zeolite HBETA is used as a catalyst containing 1-2 W% of extralattice aluminium while the active component is represented by cobalt with the content of 10-60 W% of the catalyst weight The invention refers also to the method of catalyst production, and to that of synthetic petroleum production.
EFFECT: invention relates to petroleum chemistry, gas chemistry, coal chemistry.
8 cl, 7 ex, 1 tbl
FIELD: chemistry; petrochemistry; gas chemistry.
SUBSTANCE: catalyst for Fischer Tropsch synthesis and its carrying agent are described. Said catalyst contains metal of VIII group of Periodic Table as active component; said carrying agent contains oxide component and carbon fiber. Method of aforesaid catalyst preparation is also described, it consists in infiltration of active component to carrying agent. The carrying agent is produced by extrusion of the paste and then extrudates are exposed on the air, dried and calcinated. The processed paste contains oxide component, binder, plastifier and carbon fiber.
EFFECT: increasing of catalyst selectivity.
17 cl, 1 tbl, 15 ex
FIELD: catalytic gas treatment.
SUBSTANCE: invention proposes catalyst for treating hydrogen-rich gas mixtures to remove carbon monoxide via methanation of carbon monoxide, said catalyst containing nickel-cerium oxide system. Catalyst is prepared by reaction of nickel compounds with cerium compound. Methanation of carbon monoxide is conducted at temperature not below 20°C and pressure not below 0.1 atm in presence of above-indicated catalyst.
EFFECT: enhanced removal of carbon monoxide to level below 10 ppm.
8 cl, 5 tbl, 9 ex
FIELD: chemical industry; natural gas industry; methods of production of the hydrocarbons out of the gaseous hydrocarbon raw materials.
SUBSTANCE: the invention presents the method of production of the hydrocarbons out of the gaseous hydrocarbon raw with usage of Fischer-Tropsch catalyst including the following phases: i) transformation by means of the partial oxidization of the gaseous hydrocarbon raw material and the oxygen-containing gas into the synthesis gas at the heightened temperature and pressure; ii) the catalytic conversion of the synthesis gas of the phase (i) with usage of Fischer-Tropsch catalyst on the basis of cobalt on zirconium oxide into the stream containing the hydrocarbon; iii) division of the hydrocarbons-containing stream of the phase (ii) into the stream the hydrocarbon product and the recycling stream; and iv) withdrawal of the carbon dioxide from the recycling stream and return of the carbon dioxide depleted recycling stream into the phase (i).
EFFECT: the invention ensures effective production of the hydrocarbons out of the gaseous hydrocarbon raw materials.
6 cl, l tbl, 1 ex
FIELD: synthesis gas reaction catalysts.
SUBSTANCE: invention relates to catalyst for producing hydrocarbon from synthesis gas, which is suitable for hydrogenating carbon monoxide and obtaining hydrocarbon from carbon monoxide. Catalyst is composed of carrier, on which metal compound is deposited, catalyst containing impurities within a range from 0.02 to 0.15 wt %. Preparation of catalyst comprises preliminarily treating catalyst support to reduce concentration of impurities followed by depositing metal on support. Catalytic production of hydrocarbon from synthesis gas is also described.
EFFECT: increased activity, strength, and abrasion resistance of catalyst.
59 cl, 1 dwg, 1 tbl, 7 ex
FIELD: chemical engineering.
SUBSTANCE: invention relates to chemical process and catalytic reactors suitable for carrying out the process. In particular, Fischer-Tropsch synthesis is described involving compact block of catalytic reactor (10) forming passages wherein gas-permeable catalyst structure (16) is present, said passages extending between manifolds (18). Synthesis is performed in at least two steps since reactor block provides at least two consecutive passages (14, 14a) for Fischer-Tropsch synthesis process interconnected through manifold wherein gas flow velocity in the first passages is high enough to limit conversion of carbon monoxide to 65%. Gases are cooled in manifold between two steps so as to condense water steam and then passes through the second passage at flow velocity high enough to limit conversion of the rest of carbon monoxide to 65%.
EFFECT: reduced partial pressure of water steam and suppressed oxidation of catalyst.
17 cl, 3 dwg
FIELD: disproportionation reaction catalysts.
SUBSTANCE: invention relates to Fischer-Tropsch catalyst containing cobalt and zinc, to a method for preparation thereof, and to Fischer-Tropsch process. Catalyst according to invention containing co-precipitated cobalt and zinc particles, which are characterized by volume-average size below 150 μm and particle size distribution wherein at least 90% of the catalyst particle volume is occupied by particles having size between 0.4 and 2.5 times that of the average particle size and wherein zinc/cobalt atomic ratio within a range of 40 to 0.1. Catalyst is prepared by introducing acid solution containing zinc and cobalt ions at summary concentration 0.1 to 5 mole/L and alkali solution to reactor containing aqueous medium wherein acid solution and alkali solution come into contact with each other in aqueous medium at pH 4-9 (deviating by at most 0.2 pH units) at stirring with a speed determined by supplied power between 1 and 300 kW/L aqueous medium and temperature from 15 to 75°C. Resulting cobalt and zinc-including precipitate separated from aqueous medium, dried, and further treated to produce desired catalyst. Employment of catalyst in Fischer-Tropsch process is likewise described.
EFFECT: enhanced strength and separation properties suitable for Fischer-Tropsch process.
13 cl, 2 dwg, 1 tbl, 5 ex
FIELD: production of pigments and catalysts based on titanium dioxide, in particular, process for treatment of titanium dioxide for removal of sulfur, in particular sulfates.
SUBSTANCE: method involves treating calcined titanium dioxide at elevated temperatures using aqueous solution containing one or more ammonium compounds; separating titanium dioxide from aqueous solution and drying titanium dioxide. Ammonium compounds preferably used in treatment process are ammonium acetate or ammonium chloride.
EFFECT: increased efficiency in cleaning of titanium dioxide from sulfur, in particular sulfates.
9 cl, 5 tbl, 5 ex
FIELD: petrochemical process catalyst.
SUBSTANCE: invention relates to a method of preparing catalyst for use in Fischer-Tropsch process and to catalyst obtained according present invention. Preparation of catalyst suitable for conversion at least one synthesis gas component comprises: providing aqueous solution of organic acid; adding iron metal to acid solution; passing oxidant through the solution until iron metal is consumed and iron-containing slurry formed; grinding resulting slurry to achieve average particle size less than about 2 μm; adding at least one promoter to ground iron-containing slurry to form product suspension, concentration of said promoter being such as to obtain said product suspension containing solid phase constituting from about 10 to about 40% of the weight of suspension, including said promoter; performing spray drying of suspension to obtain particles; and calcining these particles to obtain desired catalyst.
EFFECT: optimized catalyst preparation procedure.
23 cl, 2 dwg, 1 tbl, 12 ex
FIELD: petrochemical processes and catalysts.
SUBSTANCE: invention relates to the area of production of olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5-paraffin hydrocarbons and can be applied in chemical and petrochemical industries. C3-C5-Paraffin hydrocarbon dehydrogenation catalyst is described containing chromium oxide, alkaline metal oxide, transition metals, and carrier, said carrier being nanostructured oxygen-containing aluminum compound of general formula: Al2O3-x(OH)x*nH2O, wherein x=0-0.28 and n=0.03-1.8, consisting of nanostructured primary particles 2-5 nm in size and characterized by disordered/imperfect layered structure similar to byerlyte structure. Method of preparing this catalyst as well as process of dehydrogenating C3-C5-paraffin hydrocarbons into olefins are also described, the latter being conducted in fluidized bed of described catalyst, which is recycled within the circuit: dehydrogenation reactor - regeneration reactor.
EFFECT: increased mechanical strength at high catalytic activity and stability.
20 cl, 1 dwg, 2 tbl, 10 ex