Cobalt-based catalyst applied to carrier

FIELD: cobalt-based catalysts used in Fisher-Tropsh reaction in reactors with gas-liquid-solid agent fluidized bed.

SUBSTANCE: diameter of particles of cobalt-based catalyst applied to carrier is measured by means of Coulter LS230 in interval of from 70 to 250 mcm, area of surface exceeds 175 m2/g and volume of pores exceeds 0.35 cm3/g as measured by BET method. Specification contains also description of Fisher-Tropsh method in reactor with gas-liquid-solid agent fluidized bed. This method includes chemical interaction of CO with H2 for obtaining C5+ hydrocarbons in presence of said catalyst.

EFFECT: enhanced activity of catalyst; facilitated procedure.

8 cl, 3 dwg, 10 tbl, 6 ex

 

This invention relates to a catalyst based on cobalt, which can be used in the reaction of the Fischer-Tropsch reactor with a fluidized bed gas-liquid-solid substance.

On the activity of the catalysts of the Fischer-Tropsch process can influence all the physical factors that affect the rate of mass transfer of reactants and products between different phases and on the heat transfer. In the result, one can observe that in terms of the diffusion regime not only get a lower reaction rate, but also change the selectivity to different products, jeopardizing the course of the process as a whole, both from a qualitative and quantitative point of view.

In the catalytic reaction processes of mass transfer and heat between the fluid medium and the catalyst depend on the hydrodynamic regime, where the reagents and reaction products, and the geometry of the reactor, that is, from the decision of the reactor.

In synthesis the Fischer-Tropsch you can apply reactors, fixed bed, reactors with fly ash, fluidized bed reactor, as described in U.S. patent 4670472 (Dyer et al.). The last time a fluidized bed system gas-liquid-solid (slurry bubble column) prefer other types of reactors. The rate of flow of fluid in these cases should be such that the s to guarantee a more or less homogeneous suspension of the catalyst throughout the reaction volume and to facilitate the removal of heat, formed by an exothermic reaction, thus improving the heat exchange between the reaction zone and the corresponding heat exchanger is introduced into the column. As for the catalyst, the solid particles should have a size large enough to ensure that they can be easily separated from the liquid products, but small enough to minimize internal diffusion limitations for a particle.

Restrictions on transfer processes (chemicals and/or heat) can be divided into external (between particles) diffusion mode and internal (intra-particle) diffusion mode. The essence of the phenomena associated with the external diffusion depends on the hydrodynamics and the geometry of the system, i.e. on the speed and characteristics of the fluid reagent and the surface area of the partition between the phases (the shape and size of the catalyst particles). On the other hand, the phenomenon of internal diffusion depend on the chemical and morphological structure of the catalyst (pore size, surface area, density of active sites) and the size of the molecules of the particles in question.

Multiphase reactors suspension type typically use small catalyst particles (20-150 μm), which do not create problems of internal diffusion, but may be subject to limitations of external mass transfer due to the low rate of diffusion of gases in fluid is x hydrocarbons and a relatively low rate of flow of the fluid. Conversely, the relatively high conductivity of the liquid allows to neglect the constraints on external heat transfer (J.M.Smith, "Chemical engineering Kinetics", McGrawHill Int. D., 1988, Chapter 10, page 415).

On the other hand, internal transport phenomena associated with the morphological parameters of the porous material used as a carrier of the active phase, which determines the diffusion capacity within the catalyst particles. The effect of transport limitations inside the particles is to create a negative of the gradient of the concentration of the reactants within the catalyst particles, which eventually leads to a fall in the rate of reaction.

In the same way you can observe the temperature gradients, which in exothermic reactions, such as Fischer-Tropsch synthesis, creating a temperature increase towards the center of the catalyst particles, increasing the reaction rate, thus, in contrast to mass transfer, improving the selectivity to liquid hydrocarbons. And in the case of reactions with reducing the number of moles of formed the gradient of the total pressure, is able to create streams of reactants towards the center of the particle. While, on the one hand, this phenomenon increases the diffusion of the reactants into the catalyst, on the other hand, it slows down the diffusion of the reaction products out.

In mn Giannou reaction, such as the Fischer-Tropsch synthesis, the migration of the reactants and products formed due to the presence of liquid hydrocarbons. More specifically, the different diffusion coefficients of the reactants (CO, H2in liquid hydrocarbons, which is about 103-104times lower than the diffusion coefficients in the gas, creating a low concentration of CO in the direction towards the center of the particles, resulting in gradually increasing the ratio of N2/FROM inside the catalyst. This condition favors the formation of light hydrocarbons and the flow of secondary reactions of major products. From the studies presented in the literature in this direction, it can be seen that catalysts based on cobalt, deposited on various substrates used in the Fischer-Tropsch synthesis, it is possible to neglect the internal diffusion limitations when working with particles having a diameter less than 200 μm (Iglesia et al., Computer-aided Design of Catalysts (Designing catalysts with the aid of a computer) ED. Becker-Pereira, 1993. Chapter 7).

With the more General items for any catalytic reaction of the phenomenon of internal migration become less important with decreasing particle size of the catalyst. For example, in the case of a fluidized bed or suspension of restrictions on the heat transfer inside the particle is usually negligible (J.M.Smith, "Chemical Engineering Kinetics", McGraw-Hill It. D., 1988, Chapter 11, page 451).

The ideal case when there are no restrictions on mass and heat transfer, are homogeneous catalysts. However, these homogeneous systems are not applied in many processes because of the difficulties and costs associated with the separation of the catalyst from the reaction medium. In fact, these costs often exceed the benefits associated with the absence of diffusion limitations.

Thus, the size of the catalyst particles are of fundamental importance and must be sufficiently small to avoid complications on mass and heat transfer due to internal diffusion limitations, but at the same time large enough that they can be easily separated from the liquid suspension.

The use of a slurry bubble reactor in the form of columns (SPCR) for multiphase systems gas-liquid-solid substance in the Fischer-Tropsch synthesis is one of the preferred solutions. More specifically, in SPCR the catalyst suspended in the liquid hydrocarbon, often in the reaction product. Synthesis gas consisting of CO, H2N2, CO2served with a corresponding distributing device capable of generating gas bubbles dispersed in the suspension. The gas bubbles migrate to the suspension from the bottom up, being exposed to the phenomena of coalescence and breakup. Thus the om creates a distribution of bubble diameters in a wide range (3-80 mm), which determines the mixing and distribution of the catalyst within the bubble column. The efficiency of mixing and, hence, the degree distribution of solids in liquids, mainly associated with the hobby of large gas bubbles (20-80 mm) at a rate of about 1-2 m/S.

Gaseous products are moved towards the upper part of the reactor and are then processed from the outside, while the liquid products are separated by filtration of the catalyst.

Despite the advantages recognized when using SPCR in the reaction of the Fischer-Tropsch (see links provided in US-A-5939350, col. 2), the aspects related with filtering is a critical aspect of using the process as a whole because of the reduced average size of the particles used solids. Therefore, to facilitate the operations of filtering you want to work with catalyst particles having a sufficiently large diameter. The upper limit of the average diameter of the particles obviously depends on the earnings performance of the catalyst, which, as mentioned above, should not affect the limitations of the diffusion type, can reduce the effectiveness of the catalyst in relation to the efficiency that can be obtained in the kinetic mode.

The element of novelty in this invention is associated is the establishment of media with appropriate morphological characteristics, which would be used in the reactor with a fluidized bed gas-liquid-solid (SPKR)that can facilitate the separation of the phases, the liquid/solid due to the preferred particle size of the carrier itself and does not impact negatively on the efficiency of the catalyst due to the limitations on mass and heat transfer.

Accordingly, this invention relates to a catalyst based on cobalt on the carrier, wherein the carrier, preferably comprising at least 80% of the aluminum oxide has an average particle diameter, measured using a Coulter LS230, in the range from 70 to 250 μm, preferably from 120 to 180 μm, a surface area in excess of 175 m2/g, preferably from 185 to 210 m2/g, and pore volume exceeding 0,35 cm3/g, preferably more than 0,40 cm3/g measured by the BET method (Brunauer, Emmett, teller).

In a preferred implementation of the media consists mainly (>80%) of aluminum oxide in any combination of phases selected from: ETA, gamma, Delta, theta, alpha, and their mixtures, in the presence or in the absence of activator stability of the structure of the media itself, such as Si, Zr, TA, Zn, Sn, Mn, Ba, Ca, La, CE. Adding these elements or their mixtures perform the usual well-known ways using precursors such as nitrates, oxalates, that the expenses, the halides, alkoxides. For example, additives such as Si, Ba, Ce, La, Ca, reduce the sintering and slow phase transition aluminium oxide without affecting porosimetric the specifications of the original aluminum oxide (R.J.Ferrauto, C.H.Bartolomew in "Fundamentals of Industrial Catalytic Process", Blackie Academic &professional, 1997).

The active phase of this group of catalysts should consist primarily (>80%) of cobalt in the presence or in the absence of amp activity different effect on the performance of the catalyst, as described in the literature (see, for example, B.Jager, R.Espinoza in "Catalysis Today", 23, 1995, 21-22). Such activators as K, Na, Mg, Sr, Cu, Mo, TA, W, and metals of group VIII, significantly increase the activity. Ru, Zr, oxides of rare earth metals (OPM), Ti increase the selectivity to hydrocarbons with high molecular weight. EN, ORME, Re, Hf, CE, U, Th promote regeneration of cobalt catalysts.

Catalysts based on cobalt on the media according to this invention produce the most conventional methods known to experts in this field, such as ion exchange, impregnation before moisture, precipitation of cobalt, coprecipitation of cobalt and activator, gelation and mechanical mixing. In a preferred implementation of the catalysts obtained by impregnation method before moisturizing.

Another object of this innovation is about the invention relates to a method of Fischer-Tropsch, which includes chemical interaction WITH and H2possibly diluted CO2and/or N2with the formation of predominantly5+hydrocarbons, characterized in that it occurs in the presence of the catalyst according to this invention described above.

the Fischer-Tropsch process is a well-known method and reaction conditions described in literature. For example, the temperature can vary from 170 to 400°C, preferably from 180 to 250°C, while the pressure can vary from 105up to 107PA (from 1 to 100 bar, preferably from 1.5·106up to 4·106PA (15 to 40 bar). The ratio of CO/H2may vary from 0.5/1 to 4/1, preferably from 1.7/1 to 2.5/1, preferably is the stoichiometric ratio (±3%). The catalyst according to this invention preferably is used in a slurry bubble reactor with an average hourly rate of gas flow in the range from 4000 to 20000.

The following examples are presented for a better understanding of this invention.

EXAMPLES

In the examples of this invention used catalysts obtained as described in EP-A-857513 in obtaining catalyst precursor containing one cobalt. In the experimental examples as a carrier was used gamma-alumina having characteristics which, shown in Table 1.

Table 1
Morphological characteristics of native oxide of aluminum.
The media (Al2O3)AndInDE
Crystalline phasegammagammagammagammagamma
Surface area (m2/g)170175192120205
The specific pore volume (cm3/g)0,430,350,480,250,53
The average particle size (µm)6065165165165
Designation of catalystSAT-ASAT-InSAT-CAT-DSAT-E

All the examples, the catalysts comprise 14% of the mass. cobalt and obtained well-known specialists in this field by the method of impregnation to the beginning of the hydration carrier on the basis of aluminum oxide with an aqueous solution of cobalt nitrate Co(NO3)2·6N2O. These catalysts is s used in the test for reactivity in 2-liter reactor with continuous stirring, which was continuously applied to the mixture of CO and H2 under the conditions specified below:

Table 2
Operating conditions when tested catalysts.
The reaction temperature:230-240°
Total pressure:2,1·106PA (21 absbr)
The ratio of N2/FROM:2/1
The volumetric rate:1,3-3,0 Art. l /g cat./hour

Description of the test catalysts.

The catalyst was loaded into a predefined number in a tubular reactor with a fixed bed activated by recovery in hydrogen (2000 Art. l/h/l cat.) and nitrogen (1000 Art. l/h/l cat.) at a temperature in the range of 320-450°and a pressure of 105PA (1 bar) for 16 hours. Activated in such a way catalyst is moved in the absence of air and the flow of nitrogen into the autoclave with stirring (the reactor with continuous stirring)containing n-paraffin, liquefied at a temperature of about 130°in the presence of a stream of nitrogen for 30 Art. l/h. Then turn with a speed of 1000 rpm blade mixing system and supported her under these conditions for 16 hours. During this phase the system is brought up to a final working pressure of 2·10 6- 3·106PA (20-30 bar). At the end of this phase is injected with a mixture of reactants consisting of H2and in the stoichiometric ratio of 2:1, by gradual introduction of the CO-N2reducing the supply of N2. This operation was completed within the 4 hour time interval at a temperature of 130°S, as shown in Table 3.

Table 3
Nutrition in the activation phase.
Time (hours)The feed rate of N2(Art. l/h/l cat.)Feed rate (Art. l/h/l cat.)The feed rate of N2(Art. l/h/l cat.)
03301651170
2770385500
411175580

It turns out that at the end of this phase, the activation system is fully exempt from the diluent gas (Na) and is in terms of pressure, flow rate and ratio of N2/CO, are shown in Table 2. Then the temperature was raised for about 15 hours to the reaction temperature. The liquid level inside the reactor is automatically maintained constant through a system of regulation based on the differential pressure between the top of the her lower and upper part of the autoclave. The resulting paraffin is removed from the reactor through a filter system that can hold the catalyst, and stored at a temperature of 150°C. Leaving the reactor, the gas passes through two consecutive traps at temperatures of 30°s and 0°s, respectively. The gas coming out of the traps, passes through the measuring device and the subsequent sampling system for gas chromatography analysis. Facing solid and liquid substances analyzed using the appropriate gas chromatographic apparatus for the quantitative analysis.

In order to normalize the data on the catalytic activity of different tests in relation to the actual content of cobalt, as a parameter of comparison using the output of products containing carbon (hydrocarbons and CO2), normalized by the actual number of moles of cobalt present in the catalyst, and on time: it is expressed as Cow (exit cobalt-time) = the number of reacted moles CO/total number of moles of CO per hour.

Example 1 (comparative 1).

Catalyst CAT-And deposited on Al2O3type a, characterized by the following morphological parameters: gamma crystalline phase, surface area equal to 170 m2/g, specific pore volume of 0.43 cm3/g, average particle size 60 MK is.

Testing of catalytic activity conducted with the above catalyst, can be considered as the base case, for which we can obtain data on the intrinsic catalyst activity, ignoring the limitations of diffusive nature. Data on catalytic activity obtained at two different temperatures, are shown in Table 4.

Example 2 (comparative 2).

Catalyst CAT-deposited on Al2O3type, characterized by the following morphological parameters: gamma crystalline phase, surface area equal to 175 m2/g, specific pore volume of 0.35 cm3/g, average particle size of 65 μm. Test on the catalytic activity obtained at different average velocities of the gas and the ratio of H2/CO, are given in Table 5.

Example 3 (comparative 3).

Catalyst CAT-deposited on Al2O3type, characterized by the following morphological parameters: gamma crystalline phase, surface area equal to 175 m2/g, specific pore volume of 0.35 cm3/g, average particle size of 65 microns.

Tests on catalytic activity differed from that of example 2, other working conditions and amount of catalyst. These data are shown in Table 6.

Example 4.

Catalyst CAT-deposited on Al2 O3type, characterized by the following morphological parameters: gamma crystalline phase, surface area equal to 192 m2/g, specific pore volume of 0.48 cm3/g, average particle size of 165 μm.

Data on catalytic activity are shown in Table 7.

Example 5 (comparative 5).

Catalyst CAT-D inflicted on Al2O3type D is characterized by the following morphological parameters: gamma crystalline phase, surface area equal to 120 m2/g, specific pore volume of 0.25 cm3/g, average particle size of 165 μm.

Data on catalytic activity are shown in Table 8.

Example 6.

Catalyst CAT-E deposited on Al2O3type E is characterized by the following morphological parameters: gamma crystalline phase, surface area equal to 205 m2/g, specific pore volume of 0.53 cm3/g, average particle size of 165 μm, the presence of 1.5% of the mass. SiO2.

Tests on catalytic activity was characterized by using a catalyst supported on alumina, containing 1.5% of the mass. SiO2. Data on catalytic activity are shown in Table 9.

Example 7. The effect size of the catalyst particles on the separation of liquids and solids.

It is known that with increasing particle diameter can be easier and more ek is with efficiency to separate solid from liquid.

Figure 1 (taken from W.Leung, Industrial Centrifugation Technology, McGraw-Hill Inc., March 1998) shows the classification of equipment for separating solids from liquids, the type of equipment with solid walls, depending on the particle size. This equipment is classified according to two different principles: dynamic decanting (which significantly accelerate attached to particles) and static decanting (in which a substantial surface characteristics of the decanter). It is evident from Fig. 1 you can see that with increasing particle size required gravitational acceleration (R) or required surface accordingly. The reduction in the number of R means reducing the speed of rotation and therefore saving energy. The lower surface means reducing the size of the apparatus. Fig. 2 (taken from W.Leung. Industrial Centrifugation Technology, McGraw-Hill Inc., March 1998) shows the classification of equipment for separating solids from liquid filtration-type depending on the particle size. This equipment is classified according to two different principles of operation: filtration under pressure (in which a substantial pressure difference created between the flow above and below the filter) and the filter centrifugation (in which significantly accelerate attached to particles). From figure 2 one can see that HC is the increase of the particle size decreases accordingly necessary pressure or required gravitational acceleration (number R). The reduced pressure or the number of R means a reduction in the necessary work and therefore energy savings.

Figure 3 (taken from commercial publishing Dorr-Oliver, The DorrClone Hydrocyclone, Bulletin DC-2, 1989) shows the range of commercial applications of hydrocyclones of different sizes depending on the power (rpm), differential operating pressure and particle size. The hydrocyclone is a static device which uses the difference in the densities of the solid and liquid phases and the resulting centrifugal force to separate solid particles from the liquid in which they are suspended. When the performance of 680 m3per hour to be processed slurry solid-liquid, which corresponds to a power of approximately 3000 rpm (density : solids: 2,7, the concentration of solids: 25% of the mass. and the separation efficiency: 95%), as can be seen, by increasing the particle size of the solids can be applied to a smaller number of hydrocyclones, but with a larger diameter in accordance with Table 10

Table 10
The particle diameterThe diameter of the hydrocycloneOverall performance/performance of a hydrocycloneThe required number of hydrocyclonesDrop manometric. pressure KPa (psi)
5 µm10 mm3000/0,93333275,79 (40)
44 microns76 mm

(3 inches)
3000/2015068,95(10)
100 mm610 mm

(24 inches)
3000/700434,47 (5)
150 microns1219 mm

(48 inches)
3000/3000134,47 (5)

From the above Table 10 clearly you can see that during the transition from a solid to a particle size of 5 microns to a particle size of 150 μm, the number of hydrocyclones varies from 3000 to 1. This enables a huge reduction in costs for two reasons: the first is that it reduces the required number of hydrocyclones, and the second is that reduced structural complexity, increasing with decreasing diameter of the hydrocyclone.

Discussion of example 7.

Example 7 described above, aims to show that:

So as to favor the separation unit of the liquid and solid phases, it is preferable to work with solid particles having a larger average diameter, for example more than 100 microns (in fact, with the increase of the diameter of the particles at the same concentration of solids reduces the volume required at the stage of separation, as well as reduced construct the main complexity), in the case of catalysts which are not included in the scope of the present invention, it is impossible to operate without regulatory process limitations on internal diffusion. The use of the catalyst, deposited on the particles with the morphological characteristics defined in this invention, allows to reduce the weight at the division, without compromising the effectiveness of the catalyst.

Discussion of examples 1-6.

The use of the catalyst, deposited on the particles on the basis of aluminum oxide with an average diameter in the range from 70 to 250 microns, a surface area above 175 m2/g, pore volume higher than 0.35 cm3/g allows you to obtain the operating characteristics of the catalyst are comparable, if not surpassing, the characteristics obtained with the same catalyst consisting of a carrier of aluminum oxide, having a smaller average particle sizes; thus, the behavior of the catalyst potentially less dependent on morphological issues that are outside the above interval.

Example 4 shows, as in the case of SAT, characterized in that its bearer has morphological parameters (average particle size of 165 microns, a surface area of 192 m2/g, specific pore volume of 0.48 cm3/g) in the range of the present invention, have higher values of Sow (table 7, test-a-)than in the case is utilizator comparison of the SAT-A (table 4, test-a-) under similar reaction conditions. It was unexpectedly found that in the case of the SAT-With selectivity for CH4lower than that described in comparative example: CH4(%S) = 8,90 for the SAT-C and CH4(%S) = 10,32 for the SAT-And, while performance liquid C5+much higher Production. C5+=203 g/h/kg cat. for the SAT-and With Production. C5+= 151 g/h/kg cat to CAT-A. This clearly indicates that the SAT-With this invention promotes the formation of hydrocarbon products with a higher molecular weight, thus providing an additional advantage for the conversion processes of the product in the Fischer-Tropsch synthesis (for example, hydroisomerization, hydrocracking). Moreover, the selectivity for methane may be further limited to a small decrease in the ratio of N2/WITH food, as it shows the test-b in Table 7. To obtain similar levels of Sow it is necessary to increase the temperature of the catalyst of comparison And to 235°With (see Table 4, test b, in comparison with Table 7). However, although these conditions and lead to an increase in the degree of conversion of the reactants and, therefore, Sow, they do not favor the selectivity for methane and the production of liquid products.

Example 5 (table 8) demonstrates how the use of native aluminum oxide with an average of diameter the particles 165 μm is not effective, if other morphological parameters lie outside the interval specified by this invention. In fact, in the case of the catalyst of comparison, CAT-D performance of the catalyst is much worse than in the case represented by example 4(CAT-C). Values of Sow not exceed 3.7 h-1and performance With2+and C5+approximately 110 and 75 g/h/kg cat. accordingly, that is, 43% and 37%, respectively, of the performance obtained with the catalyst CAT-D.

Examples 2 and 3, are shown in Tables 5 and 6 represent two different experimental tests conducted with the catalyst of comparison SAT In different media consisting of particles having an average diameter of 65 μm, a surface area of 175 m2/g and a specific pore volume of 0.43 cm3/year performance characteristics of the catalyst obtained with this catalyst, even lower than the features obtained with the catalyst supported on alumina (SAT-C). More specifically, it appears that the case, which is representative of the present invention is more active (Sow >7,0 h-1even if you are a higher flow rate (average hourly rate of gas supply).

Example 6 (table 9) refers to the catalyst test conducted with catalyst CAT-E relevant for this invention and obtained about what adenium cobalt in the media, consisting of 98.5% of the mass. γ-Al2O3and 1.5% of the mass. SiO2. Show about 6.2, obtained at an average hourly rate of gas supply, equal to 1.85 h-1indicates higher activity from the point of view of transformation in moles per hour per mol With respect to the SAT-Century, in fact, the values of Sow obtained with SAT-In at lower space velocities (Tables 5 and 6), Show=5.2 h-1for an average hourly rate of gas supply = 1.35 h-1and Sow=4.2 h-1for an average hourly rate of gas supply = 1.5 h-1indicate the fact that Saw decreases with increase in flow rate. As for the selectivity for methane with a catalyst CAT-E obtained values of about 8%C.

Table 4
The catalyst for comparison of SAT-A.
Test-a--b-
MediaAndAnd
Surface area (m2/g)170170
The specific pore volume (cm3/g)0,430,43
The average particle size (µm)6060
The amount of catalyst (g)46,8046,50
Average hourly soon the be of gas supply (Art. l/g cat./h)2,352,35
Temperature (°)230235
Test pressure, PA (absbr)2,1·106(21)2,1·106(21)
The actual ratio of N2/CO2,002,00
The degree of conversion of CO (%)48,355,0
The degree of transformation of H2(%)54,458,6
Sow (mol WITH diareah./h/mol Co)6,97,9
The average number of received N2O (g/h/kg cat.)294,16330,54
Selectivity for CH4(% carbon)10,3212,56
Performance With2+(g2+/h/kg cat.)208,95236,28
The performance of C5+(g5+/h/kg cat.)150,55176,88

Table 5
The catalyst for comparison of SAT-Century
Test-a--b-
MediaInIn
Surface area (m2/g) 175175
The specific pore volume (cm3/g)0,350,35
The average particle size (µm)6565
The amount of catalyst (g)64,7064,70
Hourly average gas flow rate (tablespoons/g cat./h)1,501,50
Temperature (°)230230
Test pressure, PA (absbr)2,1·106(21)2,1·106(21)
The actual ratio of N2/CO2,251,65
The degree of conversion of CO (%)50,843,8
The degree of transformation of H2(%)51,645,9
Sow (mol WITH diareah./h/mol Co)4,24,2
The average number of received N2O (g/h/kg cat.)198,09159,13
Selectivity for CH4(% carbon)of 10.58at 9.53
Performance With2+(g2+/h/kg cat.)136,39116,17
The performance of C5+(g5+/h/kg cat.)105,87to 9.93

Table 6
The catalyst for comparison of SAT-Century
Test-a--b-
MediaInIn
Surface area (m2/g)175175
The specific pore volume (cm3/g)0,350,35
The average particle size (µm)6565
The amount of catalyst (g)73,0073,00
Hourly average gas flow rate (tablespoons/g cat./h)1,351,35
Temperature (°)230230
Test pressure, PA (absbr)2,1·106(21)2,1·106(21)
The actual ratio of N2/CO2,002,07
The degree of conversion of CO (%)61,2to 59.4
The degree of transformation of H2(%)61,359,8
Sow (mol WITH diareah./h/mol Co)5,2a 4.9
The average number of received N2O (g/h/kg cat.) 222,83201,52
Selectivity for CH4(% carbon)8,649,66
Performance With2+(g2+/h/kg cat.)164,01142,47
The performance of C5+(g5+/h/kg cat.)140,24118,37

/tr>
Table 7
Catalyst CAT-S.
Test-a--b-
Media
Surface area (m2/g)192192
The specific pore volume (cm3/g)0,480,48
The average particle size (µm)165165
The amount of catalyst (g)43,5043,50
Hourly average gas flow rate (LNU./g cat./h)2,352,35
Temperature (°)230230
Test pressure, PA (absbr)2,1·106(21)2,1·106(21)
The actual ratio of N2/CO2,001,92
The degree of conversion of CO (%)45.046,6
The degree of transformation of H2(%)47,047,0
Sow (mol WITH diareah./h/mol Co)7,27,3
The average number of received N2O (g/h/kg cat.)353,33279,02
Selectivity for CH4(% carbon)8,90to 7.77
Performance With2+(g2+/h/kg cat.)255,95241,99
The performance of C5+(g5+/h/kg cat.)203,23189,94

Table 8
The catalyst comparison CAT-D
Test-a--b-
MediaDD
Surface area (m2/g)120120
The specific pore volume (cm3/g)0,250,25
The average particle size (µm)165165
The amount of catalyst (g)42,3042,30
Average hourly feed rate g is for (LNU./g cat./h) 2,352,35
Temperature (°)230230
Test pressure, PA (absbr)2,1·106(21)2,1·106(21)
The actual ratio of N2/CO2,001,95
The degree of conversion of CO (%)24,024,7
The degree of transformation of H2(%)27,628,6
Sow (mol WITH diareah./h/mol Co)3,63,7
The average number of received N2O (g/h/kg cat.)153,90161,47
Selectivity for CH4(% carbon)11,0910,88
Performance With2+(g2+/h/kg cat.)109,16113,82
The performance of C5+(g5+/h/kg cat.)72,3076,93

Table 9
Catalyst CAT-E.
Test-a--b-
MediaEE
Surface area (m2/g)20520
The specific pore volume (cm3/g)0,530,53
The average particle size (µm)165165
The amount of catalyst (g)54,4054,70
Hourly average gas flow rate (LNU./g cat./h)1,851,85
Temperature (°)230230
Test pressure, PA (absbr)2,1·106(21)2,1·106(21)
The actual ratio of N2/CO2,001,95
The degree of conversion of CO (%)53,254,3
The degree of transformation of H2(%)58,459,5
Sow (mol WITH diareah./h/mol Co)6,26,3
The average number of received N2O (g/h/kg cat.)251,65250,27
Selectivity for CH4(% carbon)8,07to 7.93
Performance With2+(g2+/h/kg cat.)194,96207,47
The performance of C5+(g5+/h/kg cat.)161,92175,73

p> 1. Supported on a carrier, the catalyst based on cobalt, characterized in that the carrier has an average particle diameter, measured using a Coulter LS230, in the range of 70-250 μm, the surface area above 175 m2/g and a pore volume above 0,35 cm3/g, measured way BET.

2. The catalyst according to claim 1, characterized in that the carrier consists of at least 80% aluminum oxide.

3. The catalyst according to claim 1, characterized in that the carrier has an average particle diameter in the range of 120-180 μm.

4. The catalyst according to claim 1, characterized in that the catalyst has a pore volume of more than 0,40 cm3/year

5. The catalyst according to claim 1, characterized in that the catalyst has a surface area in the range 185-210 m2/year

6. The catalyst according to claim 1, characterized in that the active phase consists predominantly, more than 80%, of cobalt.

7. The way the Fischer-Tropsch reactor with a fluidized bed gas-liquid-solid substance, which includes chemical interaction WITH and H2possibly diluted CO2and/or N2to obtain mainly With5+hydrocarbons, characterized in that it is carried out in the presence of a catalyst according to any one of paragraphs. 1-6.

8. The way the Fischer-Tropsch process according to claim 7, characterized in that it is carried out in a slurry bubble reactor in the form of columns.



 

Same patents:

FIELD: petrochemical process catalysts.

SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.

EFFECT: increased catalytic activity.

12 cl, 3 dwg, 1 tbl, 2 ex

FIELD: petrochemical processes catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.

EFFECT: increased selectivity and productivity.

2 cl, 3 tbl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on aluminum metal may additionally contain promoters selected from oxides ZrO2, La2O3, K2O and metals Re, Ru, Pd, and Pt.

EFFECT: increased heat conductivity and selectivity.

2 cl, 2 tbl, 2 ex

FIELD: hydrocarbon manufacturing.

SUBSTANCE: natural gas is brought into reaction with vapor and oxygen-containing gas in at least one reforming zone to produce syngas mainly containing hydrogen and carbon monoxide and some amount of carbon dioxide. Said gas is fed in Fisher-Tropsh synthesis reactor to obtain crude synthesis stream containing low hydrocarbons, high hydrocarbons, water, and unconverted syngas. Then said crude synthesis stream is separated in drawing zone onto crude product stream containing as main component high hydrocarbons, water stream, and exhaust gas stream, comprising mainly remained components. Further at least part of exhaust gas stream is vapor reformed in separated vapor reforming apparatus, and reformed exhaust gas is charged into gas stream before its introducing in Fisher-Tropsh synthesis reactor.

EFFECT: increased hydrocarbon yield with slight releasing of carbon dioxide.

7 cl, 3 dwg, 1 tbl, 5 ex

The invention relates to catalysts for obtaining hydrocarbons, including liquid synthetic fuels, olefins, solid hydrocarbons and their oxygenated derivatives, such as alcohols from a mixture of CO and hydrogen

The invention relates to the production of hydrocarbons from synthesis gas

The invention relates to a method of separation of olefins from saturated hydrocarbons, and more specifically to a method of separation of olefins from saturated hydrocarbons in the stream of the Fischer-Tropsch (FT)

FIELD: petrochemical process catalysts.

SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.

EFFECT: increased catalytic activity.

12 cl, 3 dwg, 1 tbl, 2 ex

FIELD: nitric acid production.

SUBSTANCE: invention relates to decomposition of N2O from nitric acid production emission gases. N2O is decomposed by contacting N2O-containing emission gas escaping absorption column with catalyst containing at least one cobalt oxide compound and at least one magnesium oxide compound under conditions favoring formation of N2O into nitrogen and oxygen gases, content of said cobalt oxide compounds ranging between 0.1 and 50% and that of magnesium oxide compounds between 50 and 99.9% based on the total weight of catalyst. At least 30% of cobalt in catalyst are in trivalent state. Preparation of catalyst envisages dry mixing of cobalt oxide and magnesium oxide compounds or corresponding precursors followed by compaction of the mixture under anhydrous conditions such that resulting catalyst has desired volume density.

EFFECT: enabled high degree of N2O decomposition at low temperatures and without disadvantages for nitric acid production process.

20 cl, 2 dwg

FIELD: petrochemical processes catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.

EFFECT: increased selectivity and productivity.

2 cl, 3 tbl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on aluminum metal may additionally contain promoters selected from oxides ZrO2, La2O3, K2O and metals Re, Ru, Pd, and Pt.

EFFECT: increased heat conductivity and selectivity.

2 cl, 2 tbl, 2 ex

FIELD: catalytic chemistry.

SUBSTANCE: the invention is dealt with the fields of catalytic chemistry. The invention offers a predecessor of the cobaltic catalyst, which contains a catalyst carrier impregnated with cobalt. All the restorable cobalt is present in the carrying agent in the form of a sustained cobalt oxide in accordance with a block formula CoOaHb, in which a ≥ 1.7 and b ≥ 0. The invention also offers alternatives of the method of preparation of the predecessor of the cobaltic catalyst. The technical result is production of a cobaltic catalyst with a higher activity.

EFFECT: the invention ensures production of a cobaltic catalyst with a higher activity.

20 cl, 10 ex, 12 tbl, 10 dwg

The invention relates to a method of obtaining-generatingcapacity of ethylbenzene oxidation of the latter with oxygen in the presence of a ternary catalyst system comprising a bis-acetylacetonate Nickel, electron-donor complexing compound, for example an alkali metal stearate - sodium or lithium, N-organic-2, hexamethylphosphorotriamide and phenol concentration (0,5-3,0)10-3mol/l,-generatingcapacity is used to obtain propylene oxide, the world production of which is more than 106tons per year, and 44% of production based on the use of EVP as epoxidised agent

The invention relates to the production of hydrocarbons from synthesis gas

FIELD: inorganic compounds technologies.

SUBSTANCE: invention provides porous composite particles containing alumina component and residue of at least one additional crystal growth inhibitor component dispersed within alumina component, wherein indicated composite particles have (A) specific surface area at least 80 m2/g; (B) average nitrogen-filled pore diameter 60 to 1000 Å; (C) total nitrogen-filled pore volume 0.2 to2.5 cm3/g and (D) average particle size 1 to 15 μm, and where, in indicated composite particles, (i) alumina component contains at least 70 wt % of crystalline boehmite with average crystallite size 20 to 200 Å, γ-alumina obtained from indicated crystalline boehmite, or mixture thereof; (ii) residue of additional is obtained from at least one ionic compound containing ammonium, alkali metal, alkali-earth metal cation, or mixtures thereof and wherein anion is selected from group comprising hydroxyl, silicate, phosphate, sulfate, or mixtures thereof and is present in composite particles in amounts between 0.5 and 10 % of the summary weight of alumina and additional components. Invention also provides a method to obtain composite particles, agglomerated particles prepared therefrom, and a method for hydroprocessing of petroleum feed using above-mentioned agglomerates.

EFFECT: avoided unnecessary calcination before addition of metals to increase average pore size and use of organic solvents for azeotropic removal of water.

36 cl, 2 tbl, 22 ex

Up!