Fischer-tropsch catalyst, method for producing catalyst and method for producing hydrocarbons

FIELD: engineering of Fischer-Tropsch catalysts, technology for producing these and method for producing hydrocarbons using said catalyst.

SUBSTANCE: catalyst includes cobalt in amount ranging from 5 to 20 percents of mass of whole catalyst on argil substrate. Aforementioned substrate has specific surface area ranging from 5 to 50 m2/g. Catalyst is produced by thermal processing of argil particles at temperature ranging from 700 to 1300°C during period of time from 1 to 15 hours and by saturating thermally processed particles with cobalt. Method for producing hydrocarbon is realized accordingly to Fischer-Tropsch method in presence of proposed catalyst.

EFFECT: possible achievement of high selectivity relatively to C5+ at low values of diffusion resistance inside particles.

3 cl, 9 ex, 9 dwg

 

The present invention relates to catalysts for the Fischer-Tropsch (f-T), their use in the Fischer-Tropsch synthesis (FT-synthesis), to methods of their use and of their reception.

Turning natural gas into liquid hydrocarbons (the process of "gas to liquid" or "GUI") based on the 3-step procedure consisting of: 1) a synthesis gas; 2) conversion of synthesis gas using FT-synthesis and 3) processing the products of FT synthesis (wax and naphtha/distillate) in the finished products, such as naphtha, kerosene, diesel fuel, or other products, for example, based lubricating oil.

Catalysts based on cobalt are preferred catalysts for holding the FT-synthesis. The most important properties of cobalt FT-catalyst are activity, selectivity, usually aimed at With5+and more heavy products, and resistance to deactivation. Known catalysts of this kind are usually as a substrate of titanium, silicon or alumina (aluminum oxide), the promoters, as shown, may be used various metals and metal oxides.

The recently released series of works by Iglesia et al. ("Selectivity values Control and Catalyst Design in the Fischer-Tropsch Synthesis: Sites, Pellets and Reactors, Vol. 39, 1993, p.221-302) contains a description of the sequence of reactions leading to the formation of various coal is Ogorodnik products and the methodology of optimization of the properties of the catalyst in the direction of synthesis of the desired heavy hydrocarbons. The maximum selectivity for C5+observed during the development of the granules of the catalyst with optimal diffusion resistance inside the particles. The objective is achieved by increasing the resistance of the diffusion inside the particles to the value which gives the maximum secondary reactions build the circuit of the primary products (alpha-olefins) without any significant resistance to the diffusion of the reactants (H2, CO), since the latter leads to a lower selectivity. It was shown that this principle is generally applicable to all the above substrates. When graphing, describe the behavior of various catalysts with different physical properties (particle size, porosity, content of cobalt dispersion of cobalt), get a typical picture of the graph in the shape of a volcano and the maximum selectivity for C5+determine for intermediate values of the parameter "χ", which is a function of the above parameters and is a measure of the resistance of the diffusion inside the particles at a given set of reaction conditions.

The definition of χ:

χ=R02Wθ/rp(1)

where R0is the radius of the catalyst particles, m,

ø is the porosity rolled atora,

θ - density catalytic centers (including centers/m2),

rp- the average radius of the pores, M.

According to the Iglesia, the optimal value χ for a typical set of conditions PB-reaction (200°C, 20 bar, H2/CO=2.1 a; 50-60% conversion) is of the order of 500-1000·1016m-1regardless of the nature of the substrate used for the catalyst. From the definition of χ it follows that any of the considered parameter (the radius of the particles, the porosity, the pore radius or density centres) can be modified to achieve the desired values χ. However, this view may be somewhat mistaken in connection with the existence of a known relationship between the specific surface area, the pore radius and porosity (or specific volume of the pores). Given these relationships, you can see that χ can be described by parameters such as particle size, binder content, the dispersion of cobalt and porosity. Thus, it can be seen that the parameter χ not actually depends on the pore radius and the density centres and is determined only by the indicator (option) bulk migration, which is controlled only by the particle size, the content of cobalt dispersion of cobalt and porosity.

Following well-known equations are valid for long ideal cylindrical structure:

rp=2Vg/Sg(2)
Vg=W/ρp(3)
ρp=(1-W)ρs(4)

where Vgspecific pore volume, cm3/g

Sg- specific surface area, m2/g

ρpis the particle density, g/cm3,

ρsis the material density, g/cm3.

Parameter density centers in equation (1) (θ=centers cobalt/m2) can be expressed by the following equation:

θ=number of centers With/m2surface area=XCoDCoA/SgMCo(5),

where XCo- the total concentration of Co in the catalyst (gCo/gcat),

DCo- dispersion (available part of the total cobalt)

A - Avogadro's number = 6,23·1023atoms/mol

MComolecular weight of cobalt = 58,9 g/mol.

When combining equations (2)-(5) with equation (1) we can see that the parameter χ can be described as follows:

χ=R02XCoDCoA(1-W)ρs/2MCo(6)

From equation (6) shows that χ not actually depends on the pore radius and depends only on volumetric density centres in the free pore volume of the catalyst. It is also obvious that due to the presence of the dependence of the second order of the size of the particles is a relatively simple way of monitoring parameter χ is the variation of the particle size.

If the catalyst based on cobalt is used in the reactor reactor type fixed bed, it is necessary to use particles with a size of 1 mm or more, in order to avoid unacceptable pressure drop in the reactor. However, the value χ consequently becomes too high in order to achieve optimal selectivity, due to the high resistance diffusion of reagents. To some extent this may be due to the use of so-called catalysts of the type "eggshell" or catalysts toroidal type, in which the phase containing the active cobalt, placed on a relatively thin area in the outer layer (shell) of the substrate. However, in the suspension-type reactors it is necessary to use smaller particles, usually about the size of 10-100 μm. It is easy to see that this will be extremely difficult to obtain parameter values χ in a desirable range. For example, a catalyst with a content of 10 wt.% cobalt with a 5% dispersion of cobalt, 50%porosity and particle size of 50 microns will have χ=13·1016m-1.

It should also be borne in mind that the parameters in equation (6) normally may not vary independently, that is, the higher the content of cobalt, the harder it is to achieve a high dispersion. Moreover, the lower the porosity, the eating becomes more difficult to use a catalyst with a high content of cobalt. The combination of 20 wt.% cobalt content at 10% of the variance and 30% porosity gives a higher bulk density cobalt, than you can find in any work known to the applicants and listed as references. The corresponding value χ for a particle size of 50 μm (which is acceptable for operation in the reactor suspension type) will be 75·1016m-1that is still much lower than the optimum value, the above-mentioned Iglesia.

Therefore, there is no clear guidance on obtaining catalysts with high selectivity to use them at small particle sizes, such as those that occur in the reactors of the suspension type.

Applicants conducted a series of experiments to study the influence of values χ selectivity using promoted with rhenium catalyst based on cobalt on alumina substrate. They showed only a limited capacity optimization by modifying χ by changing the particle size. The results are shown in figure 1. Figure 1 shows the effect of χ selectivity when using a catalyst based on 20%, Co1%Re/γ-Al2O3(8% dispersion, 60% porosity, the average particle size (microns): 46, 113, 225, 363, 638). Test reactor with a porous layer was conducted under the following conditions: 200°C, 20 bar, H2/CO=2,1; 50-0% conversion, >24 hours in the stream. All data obtained in the two or more repetitions.

The Iglesia assumes that the selectivity for C5+can be increased by reducing the relative density or reactivity centers hydrogenation of olefins relative to the centers of readable olefins. This effect is a direct consequence of the development and preparation of the reaction chain. However, there is no indication as to how such a change can be introduced in real catalyst.

The aim of the present invention is to provide a FT-catalyst for use in the suspension-type reactors with improved selectivity for C5+of hydrocarbons.

One of the requirements for the catalyst intended for use in the suspension reactor type, is that the size of the catalyst particles should retain its structural integrity. Catalysts that have the substrate titanium dioxide, a relatively weak, although from the point of view of selectivity were obtained encouraging results in the case of cobalt catalysts on the titanium substrate, they may tend to decay with long-term use. Alumina has an inherent higher resistance against abrasion and destruction of part of the catalyst, than titanium, and therefore is a preferable material as the substrate from the point of view of its mechanical properties.

In accordance with one aspect of the present invention provides catalysts for use in the reaction of the Fischer-Tropsch synthesis, which include cobalt on alumina substrate, in which the alumina substrate has a specific surface area of <50 m2/g, preferably <30 m2/g, but preferably not lower than 5 m2/year

Preferably the alumina is at least 50% alpha-alumina, and the balance represented the gamma and/or theta-alumina, preferably and predominantly theta-alumina. Preferably, it was at least 80% or even essentially pure alpha-alumina.

Preferably the cobalt ranges from 3 to 35 wt.% catalyst, more preferably from 5 to 20 wt.%. The catalyst may also include up to 2 wt.% rhenium, for example from 0.25 to 1 wt.% or from 0.25 to 0.5 wt.% rhenium. May also include other known metal promoters/additives, such as platinum, rhodium, iridium and palladium, preferably in the same quantities, as well as oxide promoters/additives such as oxides of alkaline-earth metals and oxides of alkali metals.

Accordingly, another aspect of the present invention proposes a method of preparation of the catalyst Fischer-Tropsch, which includes the processing of alumina particles at a temperature in the range from 700 to 1300°during the period of time from 1 to 15 hours, and impregnation of the alumina particles after the heat treatment of cobalt and desirable promoters/additives. The preferred treatment temperature is in the range from 900 to 1200°and the processing time is from 5 to 10 hours.

The invention also covers the use of the catalysts according to the first aspect of the invention in the reaction of FT-synthesis. It can be carried out in a suspension-type reactor column with bubbling.

The invention also relates to a method of transforming natural gas into hydrocarbons With5+that includes handling incoming flow of natural gas to the reaction of the reforming process of obtaining the original stream of synthesis gas comprising hydrocarbon and carbon monoxide, the introduction of the original stream of synthesis gas in the reaction of FT-synthesis in the presence of a catalyst in accordance with the first aspect of the invention and separating the product stream comprising hydrocarbons With5+.

The method of deposition of the active metal, a metal promoter, alkaline and rare earth oxide on a substrate of alumina is not critical and may be selected from a variety of different methods well known to the person skilled in the art. Was IP is alsoan one of the acceptable ways known as impregnation with (initial) minimum wet. Under this method, metal salts dissolved in such a quantity of a suitable solvent, which is just enough to fill the pores of the catalyst. According to another method, the oxides or hydroxides of metals together precipitated from aqueous solution by adding a precipitating agent. In another method, the metal salt is mixed with the moist substrate in an appropriate mixer with obtaining essentially of a homogeneous mixture. In the present invention in the case of impregnation with a minimum moisture content of catalytically active metals and promoters may be deposited on the substrate using an aqueous or organic solution. Suitable organic solvents include, for example, acetone, methanol, ethanol, dimethylformamide, diethyl ether, cyclohexane, xylene and tetrahydrofuran.

Suitable compounds include cobalt, such as cobalt nitrate, cobalt acetate, cobalt chloride and cobalt carbonate, the most preferred in the case of impregnation using an aqueous solution is a nitrate. Suitable rhenium compounds include, for example, oxide, rhenium chloride, rhenium and perrenial acid. Perriniana acid is the preferred connection in the case of the manufacture of the catalyst IP is the use of an aqueous solution. Suitable platinum, iridium and rhodium compounds include nitrates, chlorides and their complexes with ammonia. Alkaline salts, suitable for inclusion alkaline component in the catalyst include nitrates, chlorides, carbonates and hydroxides. The promoter oxide of rare earth metal may be appropriately included in the catalyst in the form of, for example, nitrate or chloride.

After the water impregnation the catalyst is dried at a temperature of from 110°to 120°over time from 3 to 6 hours. In the case of impregnation with the use of organic solvents, the catalyst is preferably first dried in a rotary evaporator at a temperature of from 50°C to 60°at low pressure, and then dried for several hours at 110°S-120°C.

The dried catalyst was annealed in air at a slow temperature rise to the upper limit, the component 200°500°C, preferably in the range from 250°With up to 350°C. the Rate of temperature rise is preferably from 0.5°to 2°per minute, while the catalyst is maintained at a higher temperature for a time from 1 to 24 hours, preferably from 2 to 16 hours. The impregnation procedure is repeated as many times as necessary to obtain a catalyst with the desired metal content. If prisutstvie the promoter oxide of cobalt, rhenium, alkaline and rare earth metal impregnation may be performed together or in separate stages. In the case of separate stages in the order of impregnation of the active components can be varied.

Before using annealed catalyst restore preferably hydrogen. This procedure can be appropriately carried out by blowing hydrogen with a spatial velocity of at least 1000 NCM3/, the Temperature is slowly increased from ambient temperature to a maximum level of 250°With up to 450°C, preferably in the range from 300°With up to 400°and maintain the maximum level during the time from 1 to 24 hours, more preferably 5-16 hours.

The reactor used for the synthesis of hydrocarbons from synthesis gas, can be selected from different types of reactors are well known to experts in the art, such as, for example, a reactor with a fixed bed reactor with a fluidized bed, the fluidized bed reactor or a slurry reactor. The size of the catalyst particles in the case of a reactor with a fixed or fluidized bed is preferably from 0.1 to 10 mm and more preferably from 0.5 to 5 mm For other specified types of transactions, the preferred particle size of from 0.01 to 0.2 mm

Synthesis gas is a mixture the carbon monoxide and hydrogen and it can be obtained from any source, well-known experts in this field, such as, for example, the conversion of natural gas steam or partial oxidation of coal. The molar ratio of H2:CO is preferably from 1:1 to 3:1 and more preferably from 1.5:1 to 2.5:1. Carbon dioxide is not a desirable source component for use with the catalyst according to the present invention, but it does not have a deleterious effect on the catalyst activity. On the other hand, all sulfur-containing compounds should be present in the incoming flow in very low quantities, preferably in quantities of less than 100 h/bn

A suitable reaction temperature is from 150°to 300°and more preferably is in the range from 175°, 250°C. the Total pressure may range from atmospheric to about 100 ATM, preferably in the range from 1 to 50 ATM. Hourly average gas flow rate in relation to the total amount of synthesis gas is preferably from 100 to 20000 cm3gas per gram of catalyst per hour and more preferably from 1000 to 10000 cm3/g/h, while average hourly volume-mass gas flow rate is defined as the volume of synthesis gas (measured at standard temperature and pressure)supplied per unit mass of catalyst per hour.

The reaction products are a complex mixture, but the reaction can be illustrated by the following equation:

nCO+2nH2→(-CH2-)n+nH2O

where (-CH2-)n denotes a linear chain hydrocarbon with carbon number n. Carbon number represents the number of carbon atoms constituting the main skeleton of the molecule. When FT-synthesis products are mainly or paraffins or olefins or alcohols. The products are characterized by carbon number from one to 50 or higher.

In addition, in the case of many catalysts, for example catalysts based on iron, the reaction conversion of water gas is a known side reaction:

CO+H2O→H2+CO2

In the case of catalysts based on cobalt speed of the last mentioned reaction is usually very low.

Hydrocarbon products in the reaction of the Fischer-Tropsch synthesis include range from methane to high-boiling compounds, which describes the so-called distribution Schulz-Flory, well-known experts in this field. The distribution of the Schulz-Flory is expressed mathematically by the equation Schulz-Flory: Wn=(1-α)2n-1where n is the carbon number, α denotes the distribution coefficient Schulz-Flory, which represents the ratio of the speed naradeva the Oia circuit to the speed increasing circuit plus the rate of chain termination, and Wndenotes the mass fraction of the product with carbon number n. This equation shows that the increase α leads to a higher average carbon number of the product. Higher values α desirable in those cases where more heavy products, such as diesel fuel, relatively more valuable than lighter products, such as naphtha and light gases.

The present invention in this regard relates to the production and use of FT-synthesis catalyst based on cobalt on a substrate of alumina with a small surface area to optimize selectivity in regard With the5+. This purpose is preferably achieved by heat treatment of alumina with high surface area to produce the desired surface area, but it should be understood that any method of obtaining materials with such properties are also covered by the scope of the present invention. Another advantage of the invention is unexpectedly high activity and high stability of the described materials to decontamination.

The present invention describes catalytic materials that can be used in any type FT-reactor, suitable for the synthesis of heavy hydrocarbons (for example, in a reactor with a fixed bed and slurry reactor). It should be understood that either the combination of cobalt and appropriate promoters (such as Re, Pt or other suitable components) will give a more significant benefit when using substrates of alumina with a small surface area, including cobalt catalysts without promoters.

The catalysts according to the present invention opens the way to achieve high selectivity in relation With5+at low values χi.e. at low values of resistance to the diffusion inside the particles. Thus, in the case of these catalysts are able to work around the limitations inherent in the approach of the Iglesia. It was found that cobalt on a substrate of alumina with a low surface area can significantly improve the selectivity for C5+in the FT-synthesis in comparison with the option of using alumina with high surface area, even at low values χ. This goal was achieved by heat treatment of alumina with high surface area to obtain products with desired surface area. The results of the tests show that the increase in selectivity in regard With the5+may at least partially be related to decreased activity of the hydrogenation of olefins in comparison with the main activity of the FT-synthesis.

It was also found that these catalysts, despite the low surface area, DOS is available for impregnation of active components, demonstrate the activity, which is higher than that of similar catalysts with high surface area (MLA) in conditions simulating high conversion in a suspension-type reactor column with bubbling (that is, at high and homogeneous values of the partial pressure of water). In fact, the activity of the catalyst with a low surface area close to the activity of the catalyst with high surface area and a higher content of cobalt.

The catalyst with a low surface area is not affected by the loss of activity per unit of time, but in the case of the catalyst with a low surface area is reversible phase changes in the direction of increased activity, which is not observed at the off-catalyst.

An additional advantage compared with the known technology is that because the composition of the wax becomes more severe (higher value α), this leads to an increase in the overall yield of the middle distillate or base lubricating oils, when the wax is subjected to hydrocracking or hydroisomerization in the subsequent process. The consequence of this in General GUI process is that the return nekovertirovannoe gas back into the conversion zone natural gas can be reduced, the overall efficiency of the process can be improved (t is, there can be reduced the production of CO 2) and can be lowered oxygen consumption. And it was further found that the catalysts according to the present invention show reduced activity in the process of conversion of water gas, which leads to a decrease unwanted formation of CO2.

The present invention can be implemented in different ways and below it is illustrated by the following examples.

On the accompanying drawings:

Figure 1 is a graph showing the influence of the value χ the selectivity for C5+;

Figure 2 is a graph showing the influence of the surface area of the substrate on the selectivity for C5+;

Figure 3 is a graph showing the selectivity for C5+as a function of % α-Al2O3in the substrate;

Figure 4 is a graph showing the influence of the value χ the selectivity for C5+when using catalysts based on cobalt on a substrate of Al2O3;

Figure 5 is a graph showing the effect of cobalt content on the selectivity for C5+when using cobalt catalysts on a substrate of Al2O3;

6 is a graph showing the effect of cobalt content on productivity is ü catalyst when using cobalt catalysts on a substrate of Al 2O3;

Fig.7 is a graph showing the selectivity towards propene and propane as a function of the surface area of the substrate; and

Fig and 9 are graphs showing selectivity for propane and propene, respectively, as a function of the value of χ for cobalt catalysts on a substrate of Al2O3.

Example 1. Obtaining catalyst

The catalysts prepared as follows: prepare a solution by dissolving a given amount of cobalt nitrate Co(NO3)2·6H2O and in case of some catalysts also perrenial acid HReO4or nitrate tetraammineplatinum Pt(NH3)4(NO3)2in a given quantity of distilled water. The entire solution is added with stirring to a specified quantity of alumina Condea Puralox SCCa 45/190 marks treated in air at different temperatures before impregnation, the number of the specified solution is taken to be sufficient to achieve the initial (minimal) degree of hydration. The resulting catalyst is dried for 3 h in a drying Cabinet at a temperature of 110°C. the Dried catalyst is then annealed in air by raising their temperature with a heating rate of 2°/min to 300°and keeping at the same temperature for 16 hours After annealing floor is secured sieve catalysts to achieve the desired particle size. In table 1A summarizes the amounts used in the preparation of the ingredients and composition of the obtained catalysts.

Catalysts 9-13 have different particle sizes of the same catalyst, and these particle sizes are achieved by pelletizing powder before crushing and screening. The catalyst (2x5 kg) get through the initial moisture in the mixer, drying at 120°C for 2 h and annealing at 300°C for 3 hours

Example 2. Cobalt catalysts on a substrate of alumina with high surface area having different particle sizes

Catalysts 9-13 table 1A examined in isothermal micro-reactor with a fixed bed. The specified reactor has a length of 25 cm and an inner diameter of 1 cm Each catalyst is subjected to pre-treatment consisting of recovery by passing hydrogen over the catalyst in the heat of the specified catalyst at a rate of 1°C/min up to 350°and maintaining at this temperature for 16 h under a pressure of 1 bar. In these tests, a synthesis gas consisting of a mixture of N2:CO ratio of 2.1:1 (+3% vol. N2), skip over 1-2 g of catalyst diluted with SiC in the ratio of 1:5 under a pressure of 20 bar and at the desired temperature and the lending rate. The volumetric rate usually varies to maintain the CO conversion in the range from 40 to 70%. Products from the reactor is directed into the gas chromatograph detector FID and accident analysis, as the basis for the calculations using the methane content, specified by both detectors.

To study the effect of χ the selectivity for C5+catalysts 9-13 experience in the same reaction conditions as were used with Iglesia soaltee the results are shown in table 1b and illustrated graphically in figure 1 and compared with results of Iglesia et al. Figure 1 shows the effect χ the selectivity for C5+using catalyst 20%Co1%Re-1RE/γ-Al2O3(8% dispersion, 60% porosity, the average particle size (microns): 46, 113, 225, 363, 638).

A sharp decrease in selectivity in regard With the5+at values χ above approximately 1000·1016m-1caused by diffusion limitations for H2and inside the particles, which is consistent with the explanation of the Iglesia et al. However, in the present context it is more important to note that the selectivity for C5+catalysts on a substrate of alumina with high surface area could not be significantly improved by variations χ (particle size) from low (<100·106 m-1) to medium (500-1000·1016m-1the level of value and that, obviously, need other ways to the necessary degree of selectivity of the cobalt catalysts on a substrate of alumina in regard With the5+.

Table 1b

Properties and testing of catalysts on the basis of the materials described in table 1. Reaction conditions: Reactor with a fixed layer when 200°C, 20 bar, original blend of N2/CO=2,1; conversion of 50-70%; >24 hours in the stream.
CatalystThe composition of

(wt.%)
The processing temperatures of the substrate (°)Phase of alumina (%α)Surface area (m2/g)PorosityDispersion (%)The average particle size (µm)χ m-1< / br>
(·1016)
GHSV2)< / br>
(h-1)
Conversion

CO (%)
The rate of the reaction3)< / br>
(g/g/hour)
The selectivity of1)(%)
CH4C2-C4C5+
920%Co-1%Re*) 50001820,60846292650570,3610,4to 83.5
1020%Co-1%Re*)50001820,6081121772380570,276,110,883,1
1120%Co-1%Re*)50001820,6082257072500620,315,99,884,2
1220%Co-1%Re*)50001820,60836318362750630,347,59,982,7
1320%Co-1%Re*)50001820,60863856783300530,3512,98,8to 78.3
*)The catalysts also contain 1% oxide redkozemelnye (La 2O3).

1)Selectivity for carbon, CO2in does not count (<1%CO2in all experiments).

2)Rate: MNC3(H2+WITH+inert gas)/g of catalyst/hour (3% vol. inert gas (N2) was used in all experiments).

3)grams of hydrocarbons With a1+on g catalyst per hour.

Example 3. Cobalt catalysts on a substrate of alumina with different surface area and composition of phases

A substrate of alumina with different surface area and phase composition of alumina receive through heat treatment at different temperatures, as described in example 1. The catalysts also contain variable amounts of cobalt and promoter. The catalysts tested in reactors with a fixed layer, using the same equipment and the same techniques described in example 2. The test results of all of the catalysts are presented in table 2 and illustrated in figure 2, 3 and 4.

Figure 2 and 3 shows that the selectivity for C5+for all of these catalysts with value χ<150·1016m-1(that is, all of the catalysts with small particles) is a function of the surface area of the substrate or the content α-alumina. Although there is some distribution of the data, polnocenno, that catalysts with a low surface area/high content of α-alumina show a significantly higher selectivity for C5+than the catalyst with a large surface area and with the backing of γ-alumina. It is also clear that this effect is more significant when the values of surface area less than about 50 m2/g and the content α-alumina above about 10%.

It should also be noted that the parameter growth Schulz-Flory (α) increases for catalysts that use alumina with a small surface area and a high content of α-alumina (see catalysts 2, 3 and 4 in table 2). This increase value α from 0.92 to 0.94 leads to increased output of the wax (C19+) (in % of the total production of hydrocarbons) more than 10% of units (less than 50% to more than 60%).

Figure 4 shows a graph of selectivity in regard With the5+as a function of χ for catalysts listed in table 2. You can see the presence of two parallel curves describing findings: one - to substrates γ-alumina with a large surface area, and the other for substrates with low surface area and with a high content of α-alumina. The last shows on average 4-6% units greater selectivity for C5+than marked for all levels C7; in the first case. Visible data scatter in figure 2-4 will be further explained in the examples 4 and 5.

0,61
Table 2

Properties and testing of catalysts on the basis of the materials described in table 1. Reaction conditions: reactor with a fixed bed at 210°C, 20 bar, original blend of N2/CO=2,1; conversion of 40-70%, about 100 hours in the stream.
CatalystComposition (wt.%)The processing temperatures of the substrate (°)Phase of alumina (% α)Surface area (m2/g)PorosityDispersion (%)The average particle size (µm)χ m-1(·1016)GHSV2)(h-1)Conversion of CO (%)The rate of the reaction3)(g/g/hour)The selectivity of1)(%)
CH4C2-C4C5+α4)α
120%Co-1%Re50001830,658,346277100438,8the 10.181,1-
212%Co-0.5%of the Re50001910,7511,264305100490,509,19,281,80,92
2b12%Co50001910,759,872334700460,439,4the 10.180,9-
2c20%Co50001910,757,572436200450,55the 9.710,879,5-
2d20%Co-1%Re50001910,7510,572438400460,779,39,981,2-
312%Co-0.5%of the Re11007660,6412,472605500500,54 8,48,783,00,92
412%Co-0.5%of the Re115086160,2410,264833900550,436,8of 5.4of 87.80,94
4a12%Co-0.5%of the Re115086160,2410,2841394300530,456,05,388,7-
4b12%Co115086130,196,872743100480,308,28,0is 83.8-
55%Co-0,25%Re115086130,198,572381700450,157,56,386,2-
68%Co-0,4%Re115086130,198,672622900450.26 6,6of 5.488,0-
710%Co-0.5%of the Re115086130,199,672873700480,366,86,187,1-

820%Co-1%Re115086160,24the 5.772984600470,437,66,985,5-
920%Co-1%Re*)50001820,60846294800540,516,89,4is 83.8-
1020%Co-1%Re*)50001820,6081121773800550,417,1the 9.783,1-
1120%Co-1%Re*)50001820,608 2257074500560,497,18,184,8-
1220%Co-1%Re*)50001820,60836318365000620,6210,48,181,5-
1320%Co-1%Re*)50001820,60863856784500560,5016,88,674,6-
13b12%Co-0.5%of the Re11508670,1171132073000520,316,94,888,3-
13c12%Co-0.5%of the Re11508660,116,62257813000490,296,7a 4.988,4-
13d12%Co-0.5%of the Re11508670,08 7,761369783400490,34the 13.4680,6-
1412%Co and 0.3%Pt115086130,197,772843400510,347,36,885,9-
1512%Co and 0.3%Pt50001910,758,872304300460,3910,310,4to 78.3-
*)The catalysts also contain 1% of the oxide of rare earth metal (La2O3).

1)Selectivity for carbon, CO2in does not count (<1%CO2in all experiments).

2)Rate: MNC3(H2+WITH+inert gas)/g of catalyst/hour (3% vol. inert gas (N2) was used in all experiments).

3)grams of hydrocarbons With a1+on g catalyst per hour.

4)Factor in the probability of increasing chain Schulz-Flory, measured in the range From30-C50.

5)The dispersion was measured With chemisorption of H for catalysts 9-13.

The dispersion From all other catalysts were calculated, assuming the same values output from the catalytic center in a unit of time, as for catalysts 9-13.

Example 4. The effect of cobalt content on a substrate of alumina with different surface area and composition of phases

Test example 4 was performed in the reactor with a fixed bed under the following conditions: 210°C, 20 bar, N2/CO=2,1; conversion of 45-50%; about 100 hours in the stream.

The results indicate the presence of an optimum cobalt content for a given value of the surface area of the alumina. A more detailed consideration of the results of example 3 shows that in the case of some substrates of alumina with a low surface area/high content of α-alumina, which have a low selectivity for C5+specified low selectivity associated with too high content of cobalt. The above situation is illustrated in figure 5 and 6. Figure 5 illustrates the effect of cobalt content on the selectivity for C5+and 6 is its impact on the performance of the catalyst on a substrate of Al2O3with different surface area/different content α-alumina.

If 20% of content observed With a smaller gain selek is Yunosti in regard With the 5+in the case of substrates with a low surface area/high content of α-alumina (figure 5). This is also clearly observed in the study of the influence of Co on the catalyst activity, which can be seen in the rate of hydrocarbon formation under these conditions, reaction (6). Despite the much lower surface area and pore volume of the catalysts according to the present invention, the use of cobalt as effectively as for substrates with a developed surface area until the Co content of 12%, then clearly it is noted that the substrate cannot effectively distribute more active metal.

However, these results should not be considered as limiting the invention, the Co content below 12%, they simply illustrate the fact that there is an optimal level for each set of properties of the substrate. It is well known that the distribution of the active metal substrate may vary and can be optimized accordingly impregnation method, the type of the cobalt precursor, solvent used, the number of stages of impregnation and conditions pre-treatment of the catalyst when specifying only some of the important parameters for that.

Example 5. The influence of the promoter metal

Although the obtained results demonstrate irout pronounced effect size surface area/content α -alumina for all the studied catalysts, it is clear that there is a synergy between the use of the promoter metal, such as Re or Pt, and the properties of the substrate. This provision is illustrated in table 3, which shows that the influence of substrates with a low surface area/high content of α-alumina is clearly higher for catalysts with Pt and Re in as promoters compared to catalysts without promoter.

In order to ensure that the observed effect of promoters is not caused by secondary factors (χ) due to higher activity (variance) of these catalysts were also conducted experiments using catalyst with a promoter-based Re and lower content With having thus lower activity (and χ). The results obtained are shown in table 4, demonstrate the positive impact of Re for catalysts with a virtually constant activity (and value χ).

Table 3

Differences in selectivity with respect to C5+(ΔC5+between catalysts based on substrates With low surface area/high content of α-alumina and a large surface area/γ-alumina containing and not containing the promoter. The number of samples cat who lyst corresponds to those shown in tables 1 and 2. Testing is carried out in a reactor with a fixed bed in the conditions: 210°C, 20 bar, N2/CO=2,1; conversion of 45-55%, about 100 hours in the stream.
Catalysts (No.)ΔC5+(%)
12%Co (2b/4b)3,5
12%Co-0.5%of Re (2/4)6,0
12%Co and 0.3%Pt (15/14)7,6

Table 4

The reaction rate and the selectivity for C5+for catalysts with a substrate of alumina with a low surface area/high content of α-alumina with an almost constant value χ. The number of samples of the catalyst corresponds to those shown in tables 1 and 2. Testing is carried out in a reactor with a fixed bed in the conditions: 210°C, 20 bar, N2/CO=2,1; conversion of 45-55%, about 100 hours in the stream.
CatalystComposition (wt.%)χ (m-1·1016)The reaction rate (g NS/g of catalyst/ hour)The selectivity for C5+(%)
4b12%Co740,30is 83.8
412%Co-0.5%of the Re830,43of 87.8
68%to 0.4%Re620,2688,0
710%-0,5%Re870,3687,1

Example 6. The activity of the conversion of water gas

The reaction of the conversion of water gas (CO+H2O=CO2+H2) basically is an undesirable side reaction in relation to the main reaction for the synthesis of hydrocarbons. The activity of the conversion of water gas for most of the catalysts was tested by adding water (steam) in the initial mixture in the process of experiments for testing the catalysts in the reactor with a fixed bed, while the other conditions for these experiments were similar to those described in example 2. The above modification has the advantage that the partial pressure of water is higher and more uniform throughout the reactor and thus facilitates the interpretation of the obtained results.

Table 5 presents typical results for catalysts with a substrate of alumina with a low surface area/high content of α-alumina and with a large surface area/γ-alumina.

Although most of the catalysts based on cobalt is characterized by relatively low activity of conversion of water gas, the obtained results show that the catalysts according to the present invention have the school much more reduced (by a factor of 2) the rate of formation of CO 2compared to catalysts with a substrate of alumina with high surface area/γ-alumina.

Table 5

The selectivity for CO2for catalysts based on Co-Re with a substrate of alumina with a low surface area/high content of α-alumina and with a large surface area/γ-alumina. The number of samples of the catalyst corresponds to those shown in tables 1 and 2. Testing is carried out in a reactor with a fixed bed in the conditions: 210°C, 20 bar. The composition of the initial mixture (molar): 50.5% of N2; 24%, 22-23% N2About; the balance of N2; conversion of 40-50%, 100-200 hours in the stream.
CatalystComposition (wt.%)The surface area of the substrate (m2/g)% α-Al2O3The selectivity for CO2(%)The rate of formation of CO2(mmol/g of catalyst/ hour)
212%Co-0.5%of the Re19100,560,156
412%Co-0.5%of the Re16860,280,087

Example 7. Experiments in a suspension reactor

The catalyst according to the present invention was also tested in suspension the m reactor to confirm the benefits in terms of selectivity and also in terms typical reactors of the specified type. The results are presented in table 6.

In virtually identical reaction conditions the catalyst with the substrate of alumina with a low surface area/high content of α-alumina shows a nearly 7% increase selectivity in regard With the5+(in comparison with typical catalyst on a substrate of alumina with high surface area/γ-alumina), which is even greater than that observed in experiments with reactor fixed bed. Tests in a suspension reactor also confirm the difference in selectivity towards CO2as described in example 6.

With2-C4
Table 6

The results of the tests of catalysts based on Co with a substrate of Al2O3(particle size 38-53 μm) in 2-liter stirred slurry reactor (CSTR). T=220°S; P=20 bar; the original mixture of N2/CO=2.0 with 3% inert carrier (N2). The results obtained after >100 hours in the stream.
CatalystThe surface area of the catalyst (m2/g)Conversion of CO (%)Selectivity (%, excluding CO2)The selectivity for CO2(%)
CH4With5+
12%Co-1%Re-1%RE*14077,48,37,883,92,7
12%Co-0.5%of the Re2577,75,3the 3.890,81,1
* RE - Oxide of rare earth metal (La2O3).

Example 8. The influence of water

The following example shows that the positive effects of the present invention on the selectivity for C5+does not depend on the concentration of water (water vapour partial pressure) in the reactor. Water is a reaction product of a Fischer-Tropsch, and its partial pressure in the reactor in this regard depends on the level of conversion. The following experiments were conducted to study the effect of level conversion on selectivity of the catalyst according to the present invention and the comparative sample. In addition, experiments were carried out with the addition of water (steam) into the reactor to further study the influence of water. Experiments carried out in a reactor with a fixed bed using the same experimental procedures as described in example 2, except for adding water and deliberate variations in flow velocity for impact on the level the conversion. The results are shown in table 7.

It is seen that the effect of the use of a substrate of aluminum oxide with a small surface area/high content of α-alumina does not depend on the partial pressure of water.

0
Table 7

The influence of the partial pressure of water on the selectivity for C5+catalysts based on Co-Re on the substrate with a low surface area/high content of α-alumina and a large surface area/γ-alumina. The number of samples of the catalyst corresponds to those shown in tables 1 and 2. Testing is carried out in a reactor with a fixed bed at: 210°C, 20 bar, a mixture of N2/CO=2,1; 500-600 hours in the stream.
Catalyst No.Description catalystConversion FROMThe partial pressure of H2On inputThe average partial pressure of H2AboutThe selectivity for C5+The selectivity of1)ΔC5+
(%)(bar)(bar)(%)(%)
412%Co-0.5%of the Re 16 m2/g 86% α-alumina2400,986,4of 5.4
502,288,44,6
7604,290,05,3
304,65,891,45,6

212%Co-0.5%of Re 191 m2/g 0% α-alumina2100,881,0-
5002,2is 83.8-
7404,084,7-
224,65,385,8-
1)The advantage of selectivity in regard With the5+catalyst 4 in comparison with catalyst 2 in the same conditions.

Example 9. Hydrogenating activity against olefins

Iglesia et al. (Iglesia et al.) showed that the olefins and paraffins are the primary products of the FT reaction, and secondary hydrogenation of olefins is an undesirable side reaction, since in this case olefins begin to interfere with the further growth of the chain. Reduction hydrogenating activity against olefins without reducing the output of the main production of hydrocarbons will be presented the ü a desirable property of the catalyst. However, at that level of technology there is no guidance on how this property should be given to the working catalyst.

A more detailed analysis of the test results in the reactor with a porous layer as described in examples 2 and 3, and data from other tests indicate that the improved catalyst according to the present invention associated with a reduction of activity in the hydrogenation of olefins, although it cannot be completely excluded the simultaneous decline in the edge of the growing chains.

The above conclusions are based on the results, illustrated in figure 7, and 9. 7 shows selectivity towards propene and propane as a function of the surface area of the substrate catalysts Co-Re/Al2O3c particle size <100 microns (χ<150·1016m-1). Co/Re=20-24, 5-20 wt.% Co. These tests are tests in the reactor with a fixed bed under the following conditions: 210°C, 20 bar, N2/CO=2.1 a, the conversion level of 45-55%, for about 100 hours in the stream.

On Fig shows the effect of cobalt catalysts on a substrate of Al2O3with different surface area/content α-alumina. This chart nezakislennye symbols indicate the large surface area of the substrate from γ-alumina, blackened symbols represent m is small, the surface area of the substrate from α -alumina. These tests are performed in a reactor with a fixed bed under the following conditions: 210°C, 20 bar, N2/CO=2.1 a, the conversion rates of 40-70%, for >24 hours in the stream.

Figure 9 shows the effect χ selectivity for propane when using a cobalt catalyst with a substrate of Al2O3with different surface area/content α-alumina. This chart nezakislennye symbols indicate the large surface area of the substrate from γ-alumina, blackened symbols represent small area of a surface of the substrate from α-alumina. These tests are performed in a reactor with a fixed bed under the following conditions: 210°C, 20 bar, N2/CO=2.1 a, the conversion rates of 40-70%, for >24 hours in the stream.

Thus, these figures show a decrease of the selectivity in respect of a light paraffin in catalysts with a low surface area/high content of α-alumina and indicate that activity in the hydrogenation of olefins reduced in catalysts according to the present invention. (Propene/propane index was selected as representative of light olefin/paraffin products. A similar effect was also observed in the case of other light products). From Fig.7. it is seen that although the selectivity towards propene catalysts reduced in the substrate with a low surface area/high content of α -alumina, this phenomenon is not accompanied by an increased formation of the corresponding paraffin (propane).

A similar effect is observed with the increase χ by increasing the size of the particles (Fig and 9). In the case of increasing value χ by increasing the particle size selectivity for olefins (propene) is continuously decreasing in the conversion of olefins into secondary products. Selectivity for propane begins to rise with value χ approximately 1000·1016m-1, indicating that light olefins into the corresponding paraffin. The mentioned phenomenon is the result of resistance to the diffusion of the reactants (H2WITH), leading to low concentrations of CO in the pores of the catalyst and, thus, to more favorable conditions for secondary hydrogenation of olefins. Although the results imply that this reaction cannot be entirely blocked by use of the catalysts according to the present invention, the tendency of formation of propane is lower for all values of χ.

Thus, the present invention describes a method of reducing the activity of the catalyst Fischer-Tropsch process for the hydrogenation of olefins without substantial changes in activity in the primary process of synthesis of hydrocarbons.

In addition to the above indirect evidence, the nternet evidence of reduced activity of the catalysts according to the present invention for the hydrogenation of olefins was obtained in experiments on individual hydrogenation of the olefin. Selected catalysts, manufactured and subjected to pre-treatment according to the methods of examples 1 and 2, are examined in the reactor with a fixed bed in the presence of activity in the hydrogenation of propene. The results are shown in table 8. The level of hydrogenation of the olefins in the case of catalyst-based substrate with a low surface area/high content of α-alumina was reduced by more than 2-fold, relative to the catalysts included in the test for comparison.

Table 8

Activity for olefin hydrogenation catalysts based on 12%Co-0.5%of Re/Al2O3with different surface area and composition of the phases. T=120°C, P=1 ATM, the feed stream includes 0,2% vol. of propene, 1,3% vol. H2and Not (thinner) - else.
CatalystSurface areaα-Al2O3The rate of formation of propane
(m2/g)(%)(g/g catalyst/ hour)
219101,1
36671,1
416860,4

1. The catalyst for use in the synthesis reaction f the Fischer-Tropsch process, which includes cobalt on a substrate of alumina, characterized in that the alumina substrate has a specific surface area of 5 to 50 m2/g and the content of cobalt is from 5 to 20% by weight of the total catalyst.

2. The catalyst according to claim 1, characterized in that the alumina substrate contains at least 10% alpha-alumina.

3. The catalyst according to any one of the preceding paragraphs, characterized in that the specific surface area of the alumina is <30 m2/year

4. The catalyst according to any one of claim 2 and 3, characterized in that the alumina is at least 50% and preferably at least 80% alpha-alumina.

5. The catalyst according to claim 4, characterized in that the alumina is an essentially pure alpha-alumina.

6. The catalyst according to any one of the preceding paragraphs, further comprising a promoter.

7. The catalyst according to claim 6, characterized in that the promoter is a rhenium, platinum, rhodium and/or iridium.

8. The catalyst according to claim 7, characterized in that the promoter is a rhenium content of which is from 0.5 to 50% of the amount of cobalt.

9. The catalyst according to claim 7, characterized in that the promoter is platinum, rhodium and/or iridium and its contents status is made from 0.1 to 50% of the amount of cobalt.

10. The catalyst according to claim 6, comprising up to 2 wt.% the promoter.

11. The method of producing catalyst for Fischer-Tropsch defined in claim 1, which includes heat treatment of alumina particles at a temperature of from 700 to 1300°C for from 1 to 15 h, and the impregnated heat-treated particles with cobalt.

12. The method according to claim 11, further comprising a stage of impregnation of the alumina particles with cobalt together with the promoter/additive.

13. The method according to item 12, characterized in that the promoter is a rhenium, platinum, iridium and/or rhodium.

14. A method of producing hydrocarbons, which carry out the reaction of synthesis gas in the presence of a catalyst according to any one of claims 1 to 10.

15. The method according to 14, characterized in that the above reaction is carried out in a suspension reactor bubble column.

16. The method according to item 15, wherein the reaction temperature is in the range from 150 to 300°C.

17. The method according to item 16, wherein the reaction temperature is in the range from 175 to 250°C.

18. The method according to any of PP-17, characterized in that the pressure of the reaction is in the range from 1 to 100 bar.

19. The method according to p, characterized in that the pressure of the reaction is in the range from 10 to 50 bar.



 

Same patents:

FIELD: organic chemistry.

SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.

EFFECT: improved method for production of linear olefins.

12 cl, 3 tbl, 1 dwg, 2 ex

FIELD: organic synthesis catalysts.

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

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

FIELD: petrochemical process catalysts.

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

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

7 cl, 1 tbl, 10 ex

FIELD: catalyst preparation methods.

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

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: petroleum chemistry, chemical technology.

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

EFFECT: improved preparing method.

2 cl, 6 dwg, 2 ex

FIELD: petrochemical process catalysts.

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

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

10 cl, 1 tbl, 3 ex

FIELD: industrial inorganic synthesis and catalysts.

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

EFFECT: increased ammonia synthesis productivity.

8 cl, 2 tbl, 19 ex

FIELD: industrial organic synthesis catalysts.

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

EFFECT: increased CO conversion.

2 tbl, 8 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

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

EFFECT: improved preparing method.

7 cl, 1 tbl, 2 ex

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

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

EFFECT: enhanced conversion of CO.

1 dwg, 2 tbl, 6 ex

FIELD: structural chemistry and novel catalysts.

SUBSTANCE: invention provides composition including solid phase of aluminum trihydroxide, which has measurable bands in x-ray pattern between 2Θ=18.15° and 2Θ=18.50°, between 2Θ=36.1° and 2Θ=36.85°, between 2Θ=39.45° and 2Θ=40.30°, and between 2Θ=51.48° and 2Θ=52.59°, and has no measurable bands between 2Θ=20.15° and 2Θ=20.65°. Process of preparing catalyst precursor composition comprises moistening starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent in liquid carrier and a metal compound; ageing moistened starting material; drying aged starting material; and calcining dried material. Catalyst includes carrier prepared from catalyst composition or catalyst precursor and catalytically active amount of one or several metals, metal compounds, or combinations thereof. Catalyst preparation process comprises preparing catalyst carrier from starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent and catalytically active amount of one or several metals, metal compounds, or combinations thereof in liquid carrier, ageing starting material; drying and calcinations. Method of regenerating used material involves additional stage of removing material deposited on catalyst during preceding use, while other stages are carried out the same way as in catalyst preparation process. Catalyst is suitable for treating hydrocarbon feedstock.

EFFECT: improved activity and regeneration of catalyst.

41 cl, 3 dwg, 8 tbl, 10 ex

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to sorption engineering and can be used for regeneration of different kinds of hopcalite lost catalytic activity during long-time storage. Regenerated sorbents can be used un respiratory masks and in processes or removing carbon monoxide from industrial emissions. Invention provides a method for activating carbon monoxide oxidation catalyst involving heat treatment thereof and characterized by that activation is conducted by heating catalyst bed 2-3 cm thick to 180-380°C at temperature rise velocity 10-20°C/min while constantly carrying away reactivation products.

EFFECT: enabled restoration of catalytic activity.

3 ex

FIELD: catalyst preparation.

SUBSTANCE: invention relates to supported catalysts and provides a method for preparing catalyst-containing solid product comprising step, wherein ceramic carrier is applied onto metallic surface, and depositing catalytically active material onto ceramic carrier, which was preliminarily coated with supporting porous metallic material, ceramic carrier being applied onto and/or into supporting porous metallic material. Invention also describes device used in preparation of catalyst-containing solid product for applying supporting porous material onto inside or outside metallic surfaces of the hollow body.

EFFECT: increased stability of catalyst.

7 cl, 2 dwg

FIELD: production of carbon carrier for catalysts.

SUBSTANCE: proposed method includes heating of moving layer of granulated furnace black used as backing, delivery of gaseous or vaporous hydrocarbons into soot layer followed by their thermal decomposition on soot surface forming layer of pyrocarbon at forming of layer of pyrocarbon and activation of material compacted by pyrocarbon at temperature of 800-900°C and unloading of finished product. Granulated furnace black at specific surface of 10-30 m2/g and adsorption rate of 95-115 ml/100 g is used as backing for compacting with pyrocarbon. Then, product is subjected to activation for obtaining total volume of pores of 0.2-1.7 cm3/g. Black is compacted by pyrocarbon at two stages: at first stage, granulated black is compacted to bulk density of 0.5-0.7 g/cm3, after which material is cooled down and screened at separation of fraction of granules of 1.6-3.5 mm; at second stage, this fraction is subjected to repeated pyrolytic compacting to bulk density of granules of 0.9-1.1 g/cm3.

EFFECT: enhanced economical efficiency; increased productivity of process.

3 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods of preparing catalysts based on sulfurized styrene/divinylbenzene copolymer and thermoplastic polymer material, which are used in processes for preparing alkyl tert-alkyl ethers, hydration of olefins, dehydration of alcohols, preparation of esters, and the like. Invention provides molded ionite catalyst consisted of sulfurized styrene/divinylbenzene copolymer in the form of mixture of powdered copolymers with macroporous and gel structure and, as thermoplastic material, propylene polymers and propylene/ethylene copolymers. Preparation of catalyst is accomplished by extrusion at temperature of heating extruder cylinder 140-200°C and temperature of forming head equal to temperature of the last heated zone of heating cylinder.

EFFECT: increased catalytic activity.

10 cl, 3 tbl, 15 ex

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: catalyst constitutes cements formed during heat treatment and depicted by general formula MeO·nAl2O3, where Me is at least one group IIA element and n is number from 1.0 to 6.0, containing modifying component selected from at least one oxide of magnesium, strontium, copper, zinc, indium, chromium, manganese, and strengthening additive: boron and/or phosphorus oxide. The following proportions of components are used, wt %: MeO 10.0-40.0, modifying component 1.0-5.0, boron and/or phosphorus oxide 0.5-5.0, and alumina - the balance. Catalyst is prepared by dry mixing of one group IIA element compounds, aluminum compounds, and strengthening additive followed by mechanochemical treatment on vibromill, molding of catalyst paste, drying, and calcination at 600-1200°C. Modifying additive is incorporated into catalyst by impregnation and succeeding calcination. Method of pyrolysis of hydrocarbon feedstock producing C2-C4-olefins is also described.

EFFECT: increased yield of lower olefins.

3 cl, 2 tbl, 18 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides reforming catalyst containing Pt and Re on oxide carrier, in particular Al2O3, wherein content of Na, Fe, and Ti oxides are limited to 5 (Na2O), 20 (Fe2O3), and 2000 ppm (TiO2) and Pt is present in catalyst in reduced metallic state and in the form of platinum chloride at Pt/PtCl2 molar ratio between 9:1 and 1:1. Contents of components, wt %: Pt 0.13-0.29, PtCl2 0.18-0.04, Re 0.26-0.56, and Al2O3 99.43-99.11. Preparation of catalyst comprises impregnation of alumina with common solution containing H2PtCl6, NH4ReO4, AcOH, and HCl followed by drying and calcination involving simultaneous reduction of 50-90% platinum within the temperature range 150-550оС, while temperature was raised from 160 to 280оС during 30-60 min, these calcination conditions resulting in creation of reductive atmosphere owing to fast decomposition of ammonium acetate formed during preparation of indicated common solution.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 3 ex

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

FIELD: structural chemistry and novel catalysts.

SUBSTANCE: invention provides composition including solid phase of aluminum trihydroxide, which has measurable bands in x-ray pattern between 2Θ=18.15° and 2Θ=18.50°, between 2Θ=36.1° and 2Θ=36.85°, between 2Θ=39.45° and 2Θ=40.30°, and between 2Θ=51.48° and 2Θ=52.59°, and has no measurable bands between 2Θ=20.15° and 2Θ=20.65°. Process of preparing catalyst precursor composition comprises moistening starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent in liquid carrier and a metal compound; ageing moistened starting material; drying aged starting material; and calcining dried material. Catalyst includes carrier prepared from catalyst composition or catalyst precursor and catalytically active amount of one or several metals, metal compounds, or combinations thereof. Catalyst preparation process comprises preparing catalyst carrier from starting material containing silicon dioxide-aluminum oxide and amorphous aluminum oxide by bringing it into contact with chelating agent and catalytically active amount of one or several metals, metal compounds, or combinations thereof in liquid carrier, ageing starting material; drying and calcinations. Method of regenerating used material involves additional stage of removing material deposited on catalyst during preceding use, while other stages are carried out the same way as in catalyst preparation process. Catalyst is suitable for treating hydrocarbon feedstock.

EFFECT: improved activity and regeneration of catalyst.

41 cl, 3 dwg, 8 tbl, 10 ex

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