Fischer-tropsch catalyst prepared using high-purity iron-containing precursor (variations)

FIELD: petrochemical process catalyst.

SUBSTANCE: invention relates to a method of preparing catalyst for use in Fischer-Tropsch process and to catalyst obtained according present invention. Preparation of catalyst suitable for conversion at least one synthesis gas component comprises: providing aqueous solution of organic acid; adding iron metal to acid solution; passing oxidant through the solution until iron metal is consumed and iron-containing slurry formed; grinding resulting slurry to achieve average particle size less than about 2 μm; adding at least one promoter to ground iron-containing slurry to form product suspension, concentration of said promoter being such as to obtain said product suspension containing solid phase constituting from about 10 to about 40% of the weight of suspension, including said promoter; performing spray drying of suspension to obtain particles; and calcining these particles to obtain desired catalyst.

EFFECT: optimized catalyst preparation procedure.

23 cl, 2 dwg, 1 tbl, 12 ex

 

Background of the invention

The present invention relates to a method for producing a catalyst intended for use in the Fischer-Tropsch process, and a catalyst obtained by the method of the invention. The catalyst of the present invention contains iron and at least one promoter. The catalyst was prepared using a method that includes obtaining high-purity iron precursor and in which upon receipt of the catalyst used nominal amount of water. The catalyst particles obtained with the use of high-purity iron precursor, essentially do not contain impurities and are characterized by an essentially spherical particle shape and a relatively small range distribution of particle sizes.

The Fischer-Tropsch synthesis involves the catalytic conversion of synthesis gas (a mixture of mainly carbon monoxide and hydrogen) to produce a wide range of saturated and unsaturated hydrocarbons ranging from methane to heavy wax. Using the Fischer-Tropsch synthesis can also be obtained and oxygenated compounds such as alcohols, ketones, aldehydes and carboxylic acids. The first commercial catalysts for Fischer-Tropsch were catalysts based on cobalt, and they were used back in 1935 in Germany. The wound is in the development of the Fischer-Tropsch synthesis interest is the development of catalysts, containing metals, less expensive than cobalt. The obvious choice was iron; however, commercial use of the catalysts of the Fischer-Tropsch iron-based was not implemented until the 1950's. Since that time, the South African company Sasol catalysts for Fischer-Tropsch-based iron has been used successfully on a commercial scale reactor with a fixed catalyst bed, fluidized bed and slurry reactors.

The activity and selectivity of catalysts for Fischer-Tropsch iron-based significantly improved by adding small amounts of promoters. Classic catalyst for Fischer-Tropsch iron-based promotirovat using copper and a metal of group I, such as sodium, potassium, rubidium, cesium, or combinations thereof. The catalysts of the Fischer-Tropsch iron-based active only when subjected to recovery under the action of hydrogen, carbon monoxide or synthesis gas. As it was found that copper can significantly reduce the temperature of the recovery of iron oxide and, thus, to prevent sintering of the catalyst. Promotion using a metal of group I, such as potassium, reduces the acidity of the iron oxide and, thereby, reduce the selectivity in respect of the receipt of n is desirable methane and increase the selectivity in respect of the receipt of alkenes and waxes. Can also be used and the metals of group II; however, the metals of group I are more effective promoters. To improve the integrity of the structure and lifetime of the catalysts based on iron and the use of a binder, such as SiO2and Al2O3; however, in General they exhibit acidic properties, and this will result to an increase in the selectivity in respect of the receipt of methane.

There are several methods used to obtain catalysts for Fischer-Tropsch iron-based. The earliest catalysts obtained by Fischer, was an iron shavings treated with alkali. At high pressure liquid product was enriched with oxygen-containing compounds, and at lower pressures received hydrocarbons. However, the obtained in this way catalysts based on iron quickly deaktivirovana.

The most common method of obtaining catalysts of the Fischer-Tropsch iron-based is settling. Usually a solution of iron salts such as iron nitrate (III)is treated with base, such as aqueous ammonia or sodium carbonate. The resulting precipitate in the form of oxyhydroxide iron repeatedly washed and filtered to remove salts - ammonium nitrate or sodium nitrate formed during the process osuzhdeni is. The washed precipitate on the filter is then dried and calcined. At any time before or after the stages of drying and calcination can be carried out promotion of precipitated iron catalyst with the use of copper and a metal of group I. the Final catalyst is typically formed by iron oxide (α-Fe2O3or hematite) phase corundum with high value of specific surface area.

Other types of catalysts based on iron include the catalyst on the basis of fused iron, iron-containing catalyst supported on a carrier, and the sintered alloy based on iron. Catalysts based on molten iron produced by fusing iron ore and one or more promoters, such as SiO2, Al2O3, CaO, MgO and K2O. the Resulting catalyst usually consists mostly of magnetite (Fe3O4) and is characterized by very low value of specific surface area. Active catalysts based on molten iron can be obtained only in the recovery of oxide to metallic iron under the action of hydrogen. Subjected to restore the catalyst may have a specific surface area up to approximately size in the range from 10 to 15 m2/, Catalysts based on dps who go iron are characterized by a high degree of integrity of the structure and, as such, are well suited for operations with the use of fluidized bed (Sasol); however, the relatively low value of specific surface area results in obtaining catalyst for Fischer-Tropsch worst activity compared to conventional precipitated iron catalysts. Iron-containing catalysts supported on a carrier, usually produced by impregnating with a solution of iron salts refractory metal oxide, such as Al2O3, SiO2, TiO2or ZrO2. Impregnation may be conducted by methods initial moisture or as a result of excessive moisture with subsequent drying in vacuum. Supported on a carrier of iron catalysts in the Fischer-Tropsch synthesis may have activity similar to the activity of precipitated iron catalysts based on the weight of iron; however, they usually have the worst characteristics per volume of catalyst. Supported on a carrier of iron-containing catalysts will inevitably suffers the effects of acid properties of the media based on metal oxides, which will increase the selectivity in respect of unwanted methane.

In the General case of precipitated iron catalysts are catalysts for Fischer-Tropsch,superior to other types of iron-containing catalysts, described in this document. The main disadvantages of obtaining precipitated iron catalysts include high cost, the method requires high labor costs, and by-products have a negative impact on the environment. The preferred source of iron precipitated iron catalysts is the nitrate of iron, as contamination by chloride and sulfur arising in the case of ferric chloride or ferric sulphate will have a negative impact on the activity of the resulting catalyst f, the iron Nitrate produced by dissolving metallic iron in nitric acid, which leads to the production of oxides of nitrogen that must be removed by way of wet gas cleaning system. This necessary stage wet gas purification introduces additional costs in the cost method. In addition, the deposition method tends to result in the obtaining of very viscous and gel-like precursor in the form of iron hydroxide or iron oxyhydrate. This viscous predecessor with great difficulty can be molded in a spherical and abrasion-resistant catalyst designed for use in applications fluidized bed.

Attractive would be the way to obtain catalysts for Fischer-Tropsch on cos the ve iron, which would reduce or even eliminate the stage of washing and filtration and characterized by a minimum level of emissions into the environment. From a commercial point of view, the logical way would be promotion, molding, drying and calcining commercially available iron oxide, which is characterized by a high degree of purity and high specific surface area. Commercial iron oxides readily available; however, usually it is a result of the processing of steel in chloride-hydrogen acid or sulfuric acid. These oxides contain significant amounts of impurities, including chloride and sulfur, which makes them unacceptable as raw materials for preparation of catalysts of the Fischer-Tropsch process. As is known from the prior art, the content of impurities in the commercial iron oxides (red or yellow iron oxides) can be reduced to very low levels when using the method of etching at very high temperatures. However, due to the use in the method of etching extreme conditions specific surface area of the iron oxide in the General case will be less than 10 m2/g, which makes the iron oxide is unacceptable for applications using as a catalyst.

Summary of the present invention

Catalysis is Thor Fischer-Tropsch, containing iron and at least one promoter, get in the way, which includes the obtaining of metallic iron of high purity iron oxide. The catalyst particles obtained from high-purity iron oxide, essentially do not contain contaminants, in particular, Halogens, nitrogen and sulfur species, and are characterized by an essentially spherical particle shape, a relatively narrow range of distribution of particle sizes and values of the specific surface area of up to approximately 100 m2/g, which is suitable for various applications using as a catalyst.

The method comprises conducting the reaction between metallic iron and a weak organic acid and air in the presence of minimal amounts of water. Intake of water in this invention is significantly less than the value used in the conventional deposition method, and the result of this method is the minimum number or not performed at all wastewaters containing sulfate, nitrate or chloride. Then grind the resulting suspension of iron oxide and add the promoters. The suspension is subjected to spray drying and receive the final catalyst. Because the method uses metallic iron, the amount of content potential pollution is affected impurities, such as sulfur and chlorine, can be maintained at a minimum level, if the raw material is pure metal. In addition, in the case of raw materials in the form of metallic iron will be no residual compounds that must be removed in the washing filtrate formed by iron oxide, so that the quantity of wastewater will be much smaller compared with the methods of preparation of the catalyst of the prior art. In addition, because there is no need for multiple washing and filtering the suspension, the period of manufacture of the catalyst will be shorter in comparison with the methods of preparation of the catalyst of the prior art.

Brief description of figures

Figure 1 is an image obtained with a scanning electron microscope, representing the image of the secondary electrons with an increase of 100 X measured when receiving image on a sheet of paper 216×280 mm (8.5"×11) for a catalyst containing iron oxide, the catalyst was prepared according to the method of deposition of the prior art described in example 1; and

Figure 2 is an image obtained with a scanning electron microscope, representing the image of the secondary electrons with an increase of 100 X measured at recip the Institute of image on the sheet of paper 216× 280 mm (8.5"×11) for a catalyst containing iron oxide, the catalyst was prepared according to the method corresponding to this development, described in example 2.

A detailed description of the preferred implementation options

The catalyst of the present invention is intended for use in the method of Fischer-Tropsch (f-T). The composition of the catalyst similar to catalyst f-T of the prior art and contains iron and at least one promoter. However, the way in which get the catalyst is new, and the catalyst of the present invention contains less impurities, such as sulfur and chlorine, and can be obtained with greater efficiency than the catalysts for f-T prior art.

The way the Fischer-Tropsch process is a catalyzed on the surface of the polymerization, which can convert synthesis gas (a mixture of gaseous hydrogen and carbon monoxide) into hydrocarbons with a wide range of lengths of chains and functionality. Typically, the catalysts used in the method of Fischer-Tropsch contain at least one metal, which is an effective adsorbent for carbon monoxide and which is effective in hydrogenation reactions, such as iron, cobalt and Nickel. To obtain a wide range of hydrocarbons are preferred kata is history, containing iron or cobalt; catalysts based on Nickel tend to produce large quantities of methane; and catalysts based on ruthenium mainly lead to the formation of methane or high-melting waxes depending on the reaction conditions. The catalyst of the present invention contains iron in an amount in the range of from about 35% (wt.) up to about 70% (wt.) the total weight of the catalyst including iron; and in a more preferred implementation, the catalyst contains iron in an amount in the range of approximately 56% (mass.) up to about 70% (wt.).

The catalysts of the Fischer-Tropsch process, in particular, iron-containing catalysts, also typically contain at least one promoter, which is added to improve selected properties of the catalyst or to modify the activity and/or selectivity of the catalyst. However, to obtain catalyst particles characterized by an essentially spherical shape and a relatively narrow distribution of particle size, adding a promoter is not required. In the prior art shown that in the case of catalysts based on iron effective promoters are copper, alkali metals and alkaline-earth metals such as sodium, potassium, rubidium, cesium, magnesium, calcium is, strontium, barium, and combinations thereof. To modify the properties of the catalyst or to modify the activity and/or selectivity of the catalyst optionally, the user can enter other metals. For example, the catalysts of the Fischer-Tropsch received with use of promoters selected from the group consisting of boron, cerium, chromium, copper, iridium, iron, lanthanum, manganese, molybdenum, palladium, platinum, rhenium, rhodium, ruthenium, strontium, tungsten, vanadium, zinc, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, magnesium oxide, titanium oxide, zirconium oxide and other rare earth metals such as scandium, yttrium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, the holmium, erbium, thulium, ytterbium, lutetium, and combinations thereof. Promoters in General add at concentrations lower than the concentrations of iron, and in the present invention promoters preferably include a number in the range from about 0.002 per cent (mass.) to approximately 40% (mass.), and more preferably include a number in the range from about 0.01% (wt.) to about 1% (mass.) the total weight of the catalyst.

The catalyst is also influenced by the physical structure of the catalyst Fischer-Tropsch, and, as is known from the prior art, for commercial buildings, the ski manufacturer the choice of the appropriate structure of catalyst for a particular type of reactor can be transformed in a relatively high production rates and relatively low cost of conducting technical service. The properties of the structure or mechanical properties of the catalyst, including the strength of the particles and abrasion resistance, depend on the chemical resistance of the catalyst, and are influenced by the size and shape of catalyst particles. The shape and size of the catalyst particles can also have an impact on properties such as flow distribution and pressure drop.

Although the composition of the catalyst in the present invention is similar to the composition of the catalysts of the Fischer-Tropsch prior art method, which receives the catalyst, resulting in the receipt of a catalyst which essentially does not contain impurities and which is characterized essentially spherical particle shape, a relatively narrow range of distribution of particle size and high specific surface area. In General view, the method of obtaining the preferred embodiments of the catalyst of the present invention includes the direct processing of metallic iron is a weak organic acid and air with obtaining suspensions of iron oxide, after intensive grinding of the suspension to obtain the small size of the micron range, then adding to the suspension one or more promoters, and then spray drying the slurry with what ispolzovaniem circular spray. The water in the process add only as needed to allow the materials to mix. In accordance with how it is used in the present description, the term "impurities" refers to elements or compounds, which, as is known from the prior art, have a negative impact on the performance of the catalyst Fischer-Tropsch process. Representatives of widely known pollutants are sulfur and chlorine.

More specifically, for obtaining a catalyst Fischer-Tropsch process of the present invention the metallic iron is injected into the interaction of with a weak organic acid in aqueous media at ambient conditions, and then the mixture aeronaut. Metallic iron can be a powder, granules, spheres, sawdust, or have another shape with an average diameter in the range from approximately 1 μm to approximately 500 μm. In one embodiment, the implementation of metallic iron has microspheroidal shape with an average diameter in the range from about 40 microns to about 150 microns. In addition, metal hardware shall essentially contain no contaminants, although trace amounts of carbon, manganese, Nickel, copper, silicon, and combinations thereof may be present. In accordance with how it is used in the present the invention, "trace amounts" are defined as quantities that are less than approximately 1.5% (mass.) for all items together. The organic acid is preferably a carboxylic acid having at least one carboxylic acid group with PKawhen the ambient temperature is in the range of from about 0.5 to about 6. For example, in the reaction may use formic acid, acetic acid, glycolic acid, oxalic acid, pyruvic acid, malonic acid, propionic acid and combinations thereof.

The organic acid is added to deionized water under stirring and get the acid solution. At ambient temperature and while maintaining the stirring or mixing the acid solution is slowly added metallic iron. As the iron reacts with the acid, the temperature of the reaction mixture increases, but the rate of addition should be sufficiently low, such that the temperature would not exceed approximately 38°With (100°F). It seems that when the solution of organic acid added metallic iron, the iron is oxidized acid and secreted gaseous hydrogen (H2). Hydrogen gas may be diluted in the exhaust duct with air to a concentration less PR is approximately 4%, that is less than the lower explosive limit, or it can be bypassed in the secondary combustion chamber to generate heat used during the drying or calcination.

After the metallic iron is added to the acid solution, the solution add an additional oxidant, such as air, compressed air, oxygen, hydrogen peroxide, organic peroxide, ozone or a combination of both. In one embodiment, the implementation of the oxidizing agent is compressed air, which is passed through the solution through the diffuser, made of stainless steel, mounted inside the mixing tank, however, for ozonation of air through a solution of iron/acid may be used and a wide range of other methods known from the prior art. The supply air flow is not interrupted, and the temperature of the reaction mixture incubated least approximately 38°until then, until it is worked out essentially all of the free iron and will not receive iron-containing suspension. Suspension seems, contains hydrate iron oxide, iron oxide, iron hydroxide, oxyhydroxide iron or a combination of both. The total time of the formation of iron may be in the range of from about 24 hours to about 48 hours or more depending on the source of iron. During the reaction OK the ASKA suspension changes, becoming from a drab brown. Usually the change of color will become apparent after a period of time ranging from about 45 minutes to about 6 hours after the start of the airflow. Unreacted iron can be determined using the diffraction of x-rays.

Iron suspension grind to obtain small particle size, such that the average particle size of less approximately 40 microns, preferably to a particle size of less approximately 10 μm. In the examples presented in this invention, using a Netzsch mill with ceramic balls SEPR, ER 120A 0,8/1,25 mm However, in the prior art there are several different methods of grinding, and instead of Netzsch mill can they be used.

Using standard methods known from the prior art, to define the content in the suspension of iron and suspension type promoters. Specific added promoters and concentration with which the promoters add, can vary depending on the application. If the promoter is added in the form of crystals, then before adding to the suspension of the crystals can be dissolved in a small amount of water. After adding promoters suspension of the product shall have a solids content in the range from about 10% to when listello 40%.

After that, the suspension is subjected to spray drying using a circular spray. The inlet temperature is set to approximately 260°and an outlet temperature withstand approximately 148,9°C. the Preferred average particle size in the range from approximately 50 μm to 80 μm (speed range is approximately 13000 rpm). After spray drying, the specific surface area of the catalyst is in the range from approximately 10 m2/g to about 40 m2/, the Catalyst was subjected to spray-dried, then calcined and sieved to remove large particles. After annealing in a chamber furnace with a temperature set equal to approximately 350° (662°F), for about 4 hours, the catalyst is characterized by a specific surface area in the range from approximately 10 m2/g to about 80 m2/, Subjected to spray drying, the catalyst was essentially has a spherical shape.

The following examples illustrate and explain the present invention, but they must in no way be construed as limiting the present invention. Example 1 describes obtaining catalyst Fischer-Tropsch process using a conventional deposition method. Examples 2-8 describe Varian is s preparation of catalysts of the Fischer-Tropsch process using a method with a minimum number of wastewater relevant to the present invention.

Example 1. A comparative sample of catalyst Fischer-Tropsch received by the deposition method of the prior art as follows.

Approximately 13.6 kg (30 pounds) of iron oxide was obtained by adding approximately 133,55 kg of a solution of nitrate of iron (7% Fe (wt./mass.); commercially available from Shepherd Chemical company, Cincinnati, Ohio) in stainless steel tanks with a capacity of 170 liters (45 gallons). Deionized water was added to until the total amount has not been equal to approximately 159 liters (42 gallons). The solution of iron nitrate were thoroughly stirred.

After this, the solution of iron nitrate was applied at a feed rate of approximately 890 cm3/min, made of stainless steel settling tank with a volume of approximately 8 liters, with a hole cut at the level corresponding approximately 6.5 liters. Essentially simultaneously in a precipitation tank at an initial feed rate of approximately 400 cm3/min, was applied an aqueous solution of ammonia (29% (wt./mass.)). The combined solution was in the tank for sedimentation during the residence time of approximately 5 minutes. The solution in the vessel for deposition was stirred using a stirrer with large SD is howami efforts, and the feed rate of the aqueous solution of ammonia was adjusted so that the combined solution in the vessel for deposition was characterized by a pH value approximately equal to 10.0. Formed suspension, which had the opportunity to flow through the upper level of containers for deposition in stainless steel tank for draining excess liquid with a capacity of approximately 416 liters (110 gallons), where she continued to stir. When the solution of iron nitrate was depleted, the flow of an aqueous solution of ammonia was stopped, and in the tank for draining excess liquid was approximately 180 liters (50 gallons) of suspension.

The suspension was filtered through a filter press and received the filtrate, and the conductivity of the filtrate was measured using standard techniques known from the prior art. The filtrate or residue on the filter was subjected to treatment with air until, until it became solid. The precipitate on the filter was loaded into the stainless steel tank with a capacity of approximately 416 l, and added approximately 136 l (36 gallons) of deionized water. The precipitate on the filter and the water are thoroughly mixed, and the filtering process was repeated. Stage washing and filtration were repeated until then, until the conductivity of the filtrate became approximately 00 µs. (This may require, for example, about 7 washes and 8 filtrowanie.)

Using standard methods known from the prior art, content was determined in a suspension of iron and to the suspension was added promoters. Added crystals of Cu(NO3)2·2H2O (commercially available from Aldrich, Milwaukee, Wisconsin) or a solution of Cu(NO3)2(28% Cu, mass./about. (enterprise products company SCI)) was added potassium nitrate (commercially available from Aldrich, Milwaukee, Wisconsin) so that approximately 100 g of iron in suspension to enter approximately 0.5 g of copper and enter approximately 0.2 g2O. If the promoters were added in the form of crystals, then before putting them into a suspension of crystals was dissolved in minimum amount of water.

The suspension is then subjected to spray drying using a circular spray (spray dryer APV Anhydro). The inlet temperature was set equal to approximately 500°F and the outlet temperature was kept equal to about 300°F. the Preferred average particle size in the range from 50 to 60 microns (13000 rpm). Subjected to a spray-dried catalyst was then progulivali at approximately 662°F for 4 hours in a chamber furnace. Got about 20 pounds of produce is RA.

Example 2. A sample of catalyst Fischer-Tropsch received by the comparative method shown in example 1, except that after the stages of washing and filtration to approximately 25 pounds filtercake was then added approximately 25 cm3nitric acid and carried out a thorough mixing so that the filter cake would be flowing under the action of mixing. To facilitate stirring as needed, you can add water. The solids content in the solution should be in the range from approximately 15% to approximately 20%. After it was determined the iron content, was added to the promoters and subjected to the suspension was spray-dried as in example 1.

Example 3. A sample of catalyst Fischer-Tropsch received by the comparative method shown in example 1, except that after the stages of washing and filtration, the product was grinded, passing through a Netzsch mill with ceramic balls SEPR, ER 120A of 0.8/1.25 mm, and received an average particle size of less approximately 2 μm. After it was determined the iron content, was added to the promoters and subjected to the suspension was spray-dried as in example 1.

Example 4. A sample of catalyst Fischer-Tropsch received by the comparative method presented in example 2, except that p is after adding nitric acid product was grinded, passing through a Netzsch mill with ceramic balls SEPR, ER 120A of 0.8/1.25 mm, and received an average particle size of less approximately 2 microns.

Example 5.A sample of catalyst Fischer-Tropsch received by the method of the invention presented in the present description, as follows.

In the lower part of the drum Nalgene volume of 50 gallons was installed stainless steel diffuser. The drum was added and thoroughly mixed for approximately 36 gallons of deionized water and approximately 16.5 pounds of formic acid (90%, commercially available from the company's Specialty Chemical Co. LCC, Cleveland, Tennessee, USA). In a solution of formic acid under stirring was added about 40 pounds of iron powder (commercially available from the company Pyron, Niagara falls, new York, USA, indicated by the product code AC-325). Iron powder was added slowly enough to withstand the reaction temperature, less approximately 100°F.

After adding the iron powder and the formation of the suspension through the diffuser missed compressed air. The airflow is not interrupted, and the reaction temperature was kept approximately 100°F as long, has not yet been developed essentially all free iron, or within about 24 hours. Unreacted glands which can be identified by the method of x-ray diffraction analysis.

Iron suspension grinded, passing through a Netzsch mill with ceramic balls SEPR, ER 120A of 0.8/1.25 mm, and received an average particle size of less approximately 2 μm. Using standard methods known from the prior art, content was determined in a suspension of iron and to the suspension was added promoters. Added crystals of Cu(NO3)2·2H2O (commercially available from Aldrich, Milwaukee, Wisconsin) or a solution of Cu(NO3)2(28% Cu, mass./about. (enterprise products company SCI)) was added potassium nitrate (commercially available from Aldrich, Milwaukee, Wisconsin) so that approximately 100 g of iron in suspension to enter approximately 0.5 g of copper and enter approximately 0.2 g2O. If the promoters were added in the form of crystals, then before putting them into a suspension of crystals was dissolved in minimum amount of water.

The suspension is then subjected to spray drying using a circular spray (spray dryer APV Anhydro). The inlet temperature was set equal to approximately 500°F and the outlet temperature was kept equal to about 300°F. the Preferred average particle size in the range from 50 to 60 microns (13000 rpm). Subjected to a spray-dried catalyst was then progulivali about p and 662° F for 4 hours in a chamber oven and sieved to remove large particles (mesh - 100 or 60). Got about 40 pounds of catalyst.

Example 6. A sample of catalyst Fischer-Tropsch received by the method of the invention shown in example 5, except that iron powder AC-325 replaced with Höganäs AB ASC-300 (Höganäs, Sweden), and the aeration was increased to approximately 48 hours.

Example 7. A sample of catalyst Fischer-Tropsch received by the method of the invention shown in example 5, except that iron powder AC-325 replaced with Höganäs ASC-300 (Höganäs, Sweden), and the aeration was increased to approximately 48 hours.

Example 8. A sample of catalyst Fischer-Tropsch received by the method of the invention shown in example 5, except that formic acid was replaced by acetic acid, and the aeration was increased to approximately 30 hours.

Example 9. A sample of catalyst Fischer-Tropsch received by the method of the invention shown in example 5, except that formic acid was replaced by oxalic acid, and the aeration was increased to approximately 36 hours.

Example 10. A sample of catalyst Fischer-Tropsch received by the method of the invention shown in example 5, except for the receiving, that formic acid was replaced with pyruvic acid, and the aeration was increased to approximately 36 hours.

Example 11. A sample of catalyst Fischer-Tropsch received by the method of the invention shown in example 5, except that formic acid was replaced with glycolic acid, and the aeration was increased to approximately 32 hours.

Example 12. A sample of catalyst Fischer-Tropsch received by the method of the invention shown in example 5, except that formic acid was replaced by propionic acid, and the aeration was increased to approximately 37 hours.

As previously noted, the amount of water used in the present invention, significantly less than the number used in a conventional deposition method. This can be demonstrated, after the mapping, for example, the amount of water used in example 4 (deposition method) and in example 5 (method of the invention). As shown in table 1, for the preparation of the catalyst according to the method of example 4, you need to enter the water in a quantity equal to approximately 4836 pounds. For the preparation of the catalyst according to the method of example 5 requires approximately 300 pounds of water, or approximately 16 times less water compared with the amount used in the method of example 4.

Table 1
Example 4Example 5
InputPoundsLb-moleInputPoundsLb-mole
Nitrate iron (III) Fe(NO3)3173,200,72Iron (Fe)40,000,72
The source of ammonia (NH4OH)71,562,04Formic acid (CH2About2)16,500,36
Dilution water (H2Oh)835,7746,43Water (H2Oh)299,7716,65
Water for washing (N2Oh)4000,26222,24The oxygen (O2)17,191,07
Nitric acid (HNO3)0,540,01
Total5081,33271,44Total373,4618,80
OutputPoundsLb-moleOutputPoundsLb-mole
Iron oxide (Fe2O3)57,19 0,72Iron oxide (Fe2O3)57,190,72
Ammonium nitrate (NH4NO3)163,572,04Waste water (H2Oh)0,000,00
Waste water (H2Oh)4594,86255,27Water vapor (H2Oh)299,7716,65
Water vapor (H2Oh)260,5414,47Hydrogen (H2)0,720,36
NO25,170,11CO215,780,36
Total5081,33272,62Total373,4618,09
Complete consumption of the introduced N2About4836,03268,67Complete consumption of the introduced N2About299,7716,65
The total number of H2On the output4855,40269,40The total number of H2On the output299,7716,65

In addition, as for the method of the invention on the sign in process requires less water compared to its number in the deposition method, is formed substantially lower the e wastewater. For example, in example 5, is formed 299,77 pound wastewater in comparison with example 4, which is formed 4855 pounds of wastewater. Moreover, the waste water of the present invention more clear, that is, they essentially do not contain sulfates, nitrates or chlorides.

1 and 2 are obtained using scanning electron microscope images of the catalyst obtained in accordance with what is described in examples 1 and 6, respectively. As is known from the prior art, the shape of the particles can affect the physical properties of the catalyst, such as the strength of the particles and abrasion resistance. Spherical particles have a tendency to greater strength of the particles and to increase the resistance to abrasion compared to non-spherical particles. The particle size may have an impact on catalyst properties as flow distribution and pressure drop, and for commercial operations preferred particles within a relatively narrow range. As shown in figure 2, the catalyst obtained from iron powder, characterized by an essentially spherical shape and a relatively narrow range of distribution of particle sizes. In order mappings can be said that, in accordance with that shown in figure 1, the catalyst obtained by the method of deposition of the preceding ur is VNA equipment, characterized by different shapes and particle sizes.

The catalyst of the present invention is intended for use in the method of Fischer-Tropsch, and its composition similar to the composition of the catalysts for f-T of the prior art. However, in the way that get the catalyst, use less water, it also produces less wastewater, it is more efficient and leads to a final product that essentially does not contain impurities and characterized by an essentially spherical particle shape and a relatively small range distribution of particle sizes. You must understand that, without leaving the scope of this project, it is possible to vary the composition of the catalyst and the specific process conditions.

1. A method of producing a catalyst for converting at least one component of the synthesis gas, including

a) obtaining an aqueous solution of organic acids;

b) adding to said acid solution of metallic iron;

c) passing through the above-mentioned acid solution of oxidizer until then, until it is consumed mentioned metallic iron, and is not formed of iron-containing suspension;

d) grinding the aforementioned iron containing slurry to obtain an average particle size of smaller about 2 microns;/p>

e) adding to the above ground iron containing suspension, at least one promoter with obtaining a suspension of the product, these add promoter of this concentration for the suspension of the product contained solid phase in the range of from about 10 to about 40%, including the above-mentioned promoter;

f) spray drying said slurry to obtain particles; and

g) calcining the above-mentioned particles with obtaining the above-mentioned catalyst.

2. The method according to claim 1, in which the aforementioned organic acid is a carboxylic acid having at least one carboxyl group with PKandwhen the ambient temperature is in the range of from about 0.5 to about 6.

3. The method according to claim 1, in which the aforementioned organic acid selected from the group consisting of formic acid, acetic acid, glycolic acid, oxalic acid, pyruvic acid, malonic acid and propionic acid, and combinations thereof.

4. The method according to claim 1, in which the aforementioned metal iron is a powder, granules, spheres, sawdust or other shape with an average diameter in the range from about 1 to about 500 microns.

5. The method according to claim 1 in which the said promoter selected from the group consisting of copper, is Christmas, metal, alkaline earth metal and combinations thereof.

6. The method according to claim 5, in which the mentioned alkaline metal chosen from the group consisting of sodium, potassium, rubidium, cesium, and combinations thereof.

7. The method according to claim 5, in which the aforementioned alkaline earth metal selected from the group consisting of magnesium, calcium, strontium, barium and combinations thereof.

8. The method according to claim 1, in which said suspension is subjected to spray drying using a circular spray.

9. The method according to claim 1 in which the said catalyst contains iron in an amount in the range of from about 35 to about 70 wt.% and the promoter in amounts in the range from about 0.002 to about 40 wt.%.

10. The method according to claim 9 in which the said catalyst is characterized essentially spherical particle shape and a relatively small range distribution of particle sizes.

11. The method according to claim 1 in which the said oxidant is air, compressed air, oxygen, hydrogen peroxide, organic peroxide, ozone, and their combination.

12. A method of producing a catalyst for converting at least one component of the synthesis gas, including

a) receiving iron containing suspension, essentially, does not contain impurities, the interaction between metallic iron and an aqueous solution of organic the acid and oxidizer;

b) grinding the aforementioned iron containing slurry to obtain an average particle size of smaller about 2 microns;

c) adding to the above ground iron containing suspension, at least one promoter with obtaining a suspension of the product;

d) spray drying said slurry to obtain particles; and

e) calcining the above-mentioned particles with obtaining the above-mentioned catalyst.

13. The method according to item 12, in which said suspension is subjected to spray drying using a circular spray.

14. The method according to item 12, in which said slurry contains a solid phase in the range from approximately 10 to approximately 40%.

15. The method according to item 12, in which the said catalyst contains iron in an amount in the range of from about 35 to about 70 wt.% and the promoter in amounts in the range from about 0.002 to about 40 wt.%.

16. The method according to item 12, in which the said catalyst is essentially spherical shape of the particles and relatively small range distribution of particle sizes.

17. The method according to item 12, in which the said source of iron is a formed metal iron powder, granules, spheres, sawdust, or other shape with an average diameter in the range from about 1 to approx the positive 500 microns.

18. The method according to item 12, in which the said solution of organic acid obtained from the water and carboxylic acid having at least one carboxyl group with PKawhen the ambient temperature is in the range of from about 0.5 to about 6.

19. The method according to item 12, in which the said solution of organic acid produced from water and acid selected from the group consisting of formic acid, acetic acid, glycolic acid, oxalic acid, pyruvic acid, malonic acid and propionic acid, and combinations thereof.

20. The method according to item 12, in which the said oxidant is air, compressed air, oxygen, hydrogen peroxide, organic peroxide, ozone, and their combination.

21. The method according to item 12, in which the said promoter selected from the group consisting of copper, alkali metal, alkaline earth metal and combinations thereof.

22. The method according to item 12, in which the said promoter selected from the group consisting of copper, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium and combinations thereof.

23. Catalyst for converting at least one component of the synthesis gas, which is produced by the interaction between source of iron and organic acid and air with obtaining suspensions of iron oxide, grinding mentioned suspension oxide glands is to obtain an average particle size of, a smaller about 2 microns, adding to the suspension of iron oxide of one or more promoters with obtaining a suspension of the product of the spray drying, the above-mentioned product suspension to form particles, calcining the above-mentioned particles with the formation of the above-mentioned catalyst, with the said catalyst contains iron in an amount in the range of from about 35 to about 70 wt.% and the promoter in amounts in the range from about 0.002 to about 40 wt.%.



 

Same patents:

FIELD: alternate fuel production.

SUBSTANCE: invention relates to synthesis of hydrocarbons from CO and H2, in particular to catalysts and methods for preparation thereof in order to carrying out synthesis of hydrocarbons C5 and higher according to Fischer-Tropsch reaction. Method resides in that non-calcined zeolite ZSM-12 in tetraethylammonium-sodium form is subjected to decationation at pH 5-9, after which decationized zeolite (30-70 wt %) is mixed with alumina binder while simultaneously adding cobalt (7.5-11.5 wt %) as active component and modifier, in particular boron oxide (3-5 wt %). Proposed method allows catalyst preparation time to be significantly reduced owing to combining support preparation and deposition of active component and modifier in one stage with required catalytic characteristics preserved. In addition, method is environmentally safe because of lack of waste waters, which are commonly present when active components are deposited using impregnation, coprecipitation, and ion exchange techniques.

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: synthesis gas is subjected to conversion to produce liquid hydrocarbons in sequentially connected reactors containing catalytic slurry of at least one solid catalyst in a liquid phase. Reactors are triphase bubble column-type reactors provided with virtually full stirring characterized by liquid Peclet number below 8, gas Peclet number below 0.2, and diameter larger than 6 m. Last reactor at least partially receives at least part of at least one of the gas fractions collected at the outlet of at least one of other reactors. At least one reactor is supplied with stream of catalytic slurry coming directly out of another reactor, and at least one stream of catalytic slurry coming out of reactor is at least partially separated so as to receive liquid product substantially free of catalyst and catalyst-rich catalytic slurry, which is then recycled.

EFFECT: improved process technology.

10 cl, 8 dwg, 7 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention provides fischer-tropsch process catalyst comprising at least one metal suitably absorbing carbon monoxide and at least one promoter, said metal and said promoter being dispersed on a substrate to form catalytic particle having BET surface area between 100 and 250 m2/g so that size of metal oxide crystallites ranges from 40 to 200 while said metal and said promoter are different compound and said particle has predominantly smooth and uniform morphology of surface. substrate is characterized by particle size between 60 and 150 μm, surface area 90 to 210 m2/g, pore volume 0.35 to 0.50 mL/g, and pore diameter 8 to 20 nm. Described are also catalyst and a method of preparing catalyst including cobalt dispersed onto substrate to form catalyst particle.

EFFECT: increased surface of catalyst, improved uniformity in distribution of metal, and reduced size of metal crystallites.

33 cl, 9 dwg, 1 tbl, 10 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of alcohol comprising synthesis of olefins by the Fischer-Tropsch process followed by the hydroformylation reaction and isolation of mixture of alcohols. Hydrocarbon fraction with the content of linear olefins 10-45 wt-% is separated from products reaction synthesized by the Fischer-Tropsch process with using cobalt catalyst by distillation followed by its hydroformylation with carbon monoxide and hydrogen taken in the molar ratio hydrogen to carbon monoxide = 1.0-5.0. The reaction of synthesis is carried out in the presence of cobalt-base catalyst and a substituted or unsubstituted monophosphocycloalkane ligand followed by steps of hydrogenation and distillation. Invention provides preparing a composition with the content of linear (C7-C12)-alcohols 60 wt.-%, not less, high rate of reaction and high selectivity of the process.

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

FIELD: method for separating at least a fraction of non-acidic chemical products from at least a fraction of raw gaseous product received in Fischer-Tropsch reaction, or from condensate of said product.

SUBSTANCE: in accordance to method at least a fraction of raw gaseous product or its condensate is fed into feeding plate of distillation column, liquid flow is drained from aforementioned column from plate, positioned above feeding plate of the column. Received liquid flow is divided on water phase and saturated non-acidic chemical product phase and water phase is returned to distillation column onto plate positioned below plate from which liquid flow is drained.

EFFECT: increased efficiency of cleaning method.

23 cl, 1 dwg

FIELD: petroleum chemistry.

SUBSTANCE: method involves preparing synthesis gas, catalytic conversion of synthesis gas in reactor for synthesis of dimethyl ether (DME) at enhanced temperature and pressure wherein synthesis gas is contacted with catalyst followed by cooling the gaseous mixture and its separation for liquid and gaseous phases. Dimethyl ether is isolated from the liquid phase that is fed into catalytic reactor for synthesis of gasoline and the gaseous phase containing unreacted components of synthesis gas is fed to repeated catalytic conversion into additional reactor for synthesis of DME being without the parent synthesis gas. Residue of gaseous phase containing components of synthesis gas not reacted to DME after repeated catalytic conversion in additional reactor for synthesis of DME are oxidized in reactor for synthesis of carbon dioxide. Then carbon dioxide is separated and mixed its with natural gas at increased temperature and pressure that results to preparing synthesis gas that is fed to the catalytic conversion into reactor for synthesis of DME. Invention provides increasing yield of gasoline fraction and decrease of carbon dioxide waste in atmosphere.

EFFECT: improved method of synthesis.

4 cl, 1 tbl, 1 dwg, 1 ex

FIELD: chemical industry; petrochemical industry; methods of production of the catalysts and hydrocarbons with their use.

SUBSTANCE: the invention is pertaining to the method of production of the catalyst for production of hydrocarbons and to the method for production of hydrocarbons at the presence of the catalyst on the basis of the metal of VIII group on the carrier - the refractory oxide. The presented method of production of the catalyst for production of hydrocarbons on the basis of the metal of VIII group on the carrier - the refractory oxide provides for mixing of the refractory oxide with the surface area of no less than 0.5 m2 /g with the solution of the precursor of this refractory oxide and with the metal or with the precursor of this metal till production of the suspension, drying of the suspension and its calcination. The invention also presents the method of production of the hydrocarbons providing for contacting of the mixture of the hydrocarbon monoxide with hydrogen at the heightened temperature and pressure at presence of the catalyst produced by the method described above. The technical result is production of the catalyst with higher activity in the synthesis of the hydrocarbons at conservation of high selectivity.

EFFECT: the invention ensures production of the catalyst with the higher activity in the synthesis of the hydrocarbons at conservation of the high selectivity.

8 cl, 1 tbl, 1 ex

FIELD: alternate fuel production and catalysts.

SUBSTANCE: synthesis gas containing H2, CO, and CO2 is brought into contact, in first reaction zone, with bifunctional catalyst consisting of (i) metal oxide component containing 65-70% ZnO, 29-34%, Cr2O3, and up to 1% W2O5 and (ii) acid component comprised of zeolite ZSM-5 or ZSM-11, beta-type zeolite or crystalline silica-alumino-phosphate having structure SAPO-5 at silica-to-alumina molar ratio no higher than 200, whereas, in second reaction zone, multifunctional acid catalyst is used containing zeolite ZSM-5 or ZSM-11 and having silica-to-alumina molar ratio no higher than 200.

EFFECT: increased selectivity with regard to C5+-hydrocarbons and increased yield of C5+-hydrocarbons based on synthesis gas supplied.

7 cl, 2 tbl, 15 ex

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

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: petrochemical processes and catalysts.

SUBSTANCE: invention provides high-silica zeolite catalyst comprising molybdenum and a second modifying element, namely nickel, content of the former in catalyst being no higher than 4.0 wt % and that of the latter from 0.1 to 0.5 wt %. Preparation of the catalyst involves modifying zeolite with molybdenum and second promoting element, the two being introduced into zeolite in the form of nano-size metal powders in above-indicated amounts.

EFFECT: enhanced efficiency of non-oxidative methane conversion process due to increased activity and stability of catalyst.

3 cl, 1 tbl, 7 ex

FIELD: alternate fuel production.

SUBSTANCE: invention relates to synthesis of hydrocarbons from CO and H2, in particular to catalysts and methods for preparation thereof in order to carrying out synthesis of hydrocarbons C5 and higher according to Fischer-Tropsch reaction. Method resides in that non-calcined zeolite ZSM-12 in tetraethylammonium-sodium form is subjected to decationation at pH 5-9, after which decationized zeolite (30-70 wt %) is mixed with alumina binder while simultaneously adding cobalt (7.5-11.5 wt %) as active component and modifier, in particular boron oxide (3-5 wt %). Proposed method allows catalyst preparation time to be significantly reduced owing to combining support preparation and deposition of active component and modifier in one stage with required catalytic characteristics preserved. In addition, method is environmentally safe because of lack of waste waters, which are commonly present when active components are deposited using impregnation, coprecipitation, and ion exchange techniques.

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

FIELD: petrochemical processes.

SUBSTANCE: catalyst, containing high-silica zeolite of the H-ZSM-5 type having silica modulus SiO2/Al2O3 = 20 to 160 in amount 60.0-90.0%, contains (i) as modifying component at least one oxide of element selected from group: boron, phosphorus, magnesium, calcium, or combination thereof in amount 0.1-10.0 wt %; and (ii) binding agent: alumina. Catalyst is formed in the course of mechanochemical and high-temperature treatments. Described is also a catalyst preparation process comprising impregnation of decationized high-silica zeolite with compounds of modifying elements, dry mixing with binder (aluminum compound), followed by mechanochemical treatment of catalyst paste, shaping, drying, and h-temperature calcination. Conversion of methanol into olefin hydrocarbons is carried out in presence of above-defined catalyst at 300-550°C, methanol supply space velocity 1.0-5.0 h-1, and pressure 0.1-1.5 mPa.

EFFECT: increased yield of olefin hydrocarbons.

3 cl, 1 tbl, 15 ex

FIELD: carbon monoxide conversion catalysts.

SUBSTANCE: preparation of middle-temperature carbon monoxide conversion catalysts, which can be used in industrial production of ammonia synthesis destined nitrogen-hydrogen mixture, comprises mechanical activation of iron-containing component with calcium and copper oxides, mixing with water to form plastic mass, extrusion forming, drying, and calcination, said iron-containing component being iron metal powder and said mechanical activation of components being accomplished by passing air enriched with oxygen to 30-100%. Under these circumstances, catalyst activity rises by 19.4-23.1%.

EFFECT: increased catalyst activity, eliminated formation of waste waters and emission of toxic nitrogen oxides, and reduced (by 30%) number of process stages.

1 tbl, 3 ex

FIELD: gas treatment processes and catalysts.

SUBSTANCE: invention relates to catalyst for selectively oxidizing hydrogen sulfide to sulfur in industrial gases containing 0.5-3.0 vol % hydrogen sulfide and can be used at enterprises of gas-processing, petrochemical, and other industrial fields, in particular to treat Claus process emission gases, low sulfur natural and associated gases, chemical and associated petroleum gases, and chemical plant outbursts. Catalyst for selective oxidation of hydrogen sulfide into elementary sulfur comprises iron oxide and modifying agent, said modifying agent containing oxygen-containing phosphorus compounds. Catalyst is formed in heat treatment of α-iron oxide and orthophosphoric acid and is composed of F2O3, 83-89%, and P2O5, 11-17%. Catalyst preparation method comprises mixing oxygen-containing iron compounds with modifying agent compounds, extrusion, drying, and heat treatment. α-Iron oxide used as oxygen-containing iron compound is characterized by specific surface below 10 m2/g, while 95% of α-iron oxide have particle size less than 40 μm. Orthophosphoric acid is added to α-iron oxide, resulting mixture is stirred, dried, and subjected to treatment at 300-700°C. Hydrogen sulfide is selectively oxidized to elemental sulfur via passage of gas mixture over above-defined catalyst at 200-300°C followed by separation of resultant sulfur, O2/H2S ratio in oxidation process ranging from 0.6 to 1.0 and volume flow rate of gas mixture varying between 900 and 6000 h-1.

EFFECT: increased yield of elemental sulfur.

9 cl, 5 tbl, 9 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: group of inventions relates to conversion of hydrocarbons using micro-mesoporous-structure catalysts. A hydrocarbon conversion process is provided involving bringing hydrocarbon raw material, under hydrocarbon conversion conditions, into contact with micro-mesoporous-structure catalyst containing microporous crystalline zeolite-structure silicates composed of T2O3(10-1000)SiO2, wherein T represents elements selected from group III p-elements and group IV-VIII d-elements, and mixture thereof, micro-mesoporous structure being characterized by micropore fraction between 0.03 and 0.40 and mesopore fraction between 0.60 and 0.97. Catalyst is prepared by suspending microporous zeolite-structure crystalline silicates having above composition in alkali solution with hydroxide ion concentration 0.2-1.5 mole/L until residual content of zeolite phase in suspension 3 to 40% is achieved. Thereafter, cationic surfactant in the form of quaternary alkylammonium of general formula CnH2n+1(CH3)3NAn (where n=12-18, An is Cl, Br, HSO4-) is added to resulting silicate solution suspension and then acid is added formation of gel with pH 7.5-9.0. Gel is then subjected to hydrothermal treatment at 100-150°C at atmospheric pressure or in autoclave during 10 to 72 h to produce finished product.

EFFECT: enlarged assortment of hydrocarbons and increased selectivity of formation thereof.

16 cl, 2 dwg, 2 tbl

FIELD: oil refining; methods of production of cracking globular catalysts.

SUBSTANCE: proposed method includes mixing aqueous suspension of zeolite Y in cation-exchange form with alumina suspension in aqueous solution of sodium silicate and aluminum sulfate solution, introducing platinum into aluminum sulfate solution or into aqueous suspension of zeolite fed for molding, forming catalyst granules in column filled with mineral oil, successive activation with solutions of aluminum sulfate and mixture of nitrates of rare-earth elements, washing-off with condensate water containing cations of iron, calcium and magnesium for removal of salts and calcination of granules in atmosphere of flue gases and water steam. For obtaining catalyst possessing enhanced activity, mechanical strength and bulk density, type Y zeolite is added into catalyst in hydrogen or hydrogen-rare-earth form; alumina is also added in the amount of 3-65 mass-%: with size of particles lesser than 10 mcm, 95-100 mass-%; lesser than 5 mcm, 40-80 mass-%. Catalyst has following composition in terms of oxides, mass-%: aluminum, 10.0-67.0; rare-earth elements, 0.5-3.5; platinum, 0.0001-0.01; iron, 0.01-0.2; calcium, 0.01-0.2; magnesium, 0.01-0.2; sodium, 0.01-0.3; the remainder being silicon. Catalyst has mechanic crushing strength of 22-40 kg/ball, wear resistance 900-1400 s, bulk density, 720-11000 kg/m3 and catalytic activity by gasoline yield, mass-%: 62.0-64.9 in cracking of kerosene-gas oil fraction and 41.5-45.7 in cracking of vacuum gas oil.

EFFECT: enhanced efficiency.

FIELD: chemical industry; petrochemical industry; methods of production of the catalysts and hydrocarbons with their use.

SUBSTANCE: the invention is pertaining to the method of production of the catalyst for production of hydrocarbons and to the method for production of hydrocarbons at the presence of the catalyst on the basis of the metal of VIII group on the carrier - the refractory oxide. The presented method of production of the catalyst for production of hydrocarbons on the basis of the metal of VIII group on the carrier - the refractory oxide provides for mixing of the refractory oxide with the surface area of no less than 0.5 m2 /g with the solution of the precursor of this refractory oxide and with the metal or with the precursor of this metal till production of the suspension, drying of the suspension and its calcination. The invention also presents the method of production of the hydrocarbons providing for contacting of the mixture of the hydrocarbon monoxide with hydrogen at the heightened temperature and pressure at presence of the catalyst produced by the method described above. The technical result is production of the catalyst with higher activity in the synthesis of the hydrocarbons at conservation of high selectivity.

EFFECT: the invention ensures production of the catalyst with the higher activity in the synthesis of the hydrocarbons at conservation of the high selectivity.

8 cl, 1 tbl, 1 ex

FIELD: petrochemical industry; methods of production of the cracking bead catalyst.

SUBSTANCE: the invention is pertaining to the field of petrochemical industry, in particular, to the method of production of the cracking zeolite-containing catalysts (ZCCs). The bead catalyst is produced by mixing of the water solutions of the sodium silicate, aluminum sulfate and suspensions of NaY-type zeolite and alumina, molding of the hydrogel granules in the oil column, treatment with the solution of sodium sulfate and the following activation by the solution of ammonium sulfate or ammonium nitrate with the mixture of the rare-earth elements (REE), by the solution of the platonic-chloro-hydrogen acid, the drying and calcination in the steam aerosphere. At that the aluminum sulfate solution has the concentration of 0.5-7.0 kg/m3, and the calcinations is conducted at the steam concentration above 40 vol.%. The technical result of the invention is the controlled raise of the loose mass in the range of 650-850 kg/m3, the increase of activity and improvement of the mechanical properties of the bead catalyst.

EFFECT: the invention ensures the controlled raise of the loose mass in the given above range, the increase of activity and improvement of the mechanical properties of the bead catalyst.

6 ex, 1 tbl, 1 dwg

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to improved method for preparing double metal cyanide catalysts effective to catalyze synthesis of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms. Method is characterized by that aqueous solutions of metal salt and metal cyanide salt are first brought to react in presence of organic complex ligands and, if necessary, one or several other complexing components to form dispersion of double metal cyanide catalyst, which is filtered to give filtration precipitates. The latter are washed with one or several aqueous or nonaqueous solution of organic complex ligands in flowing washing mode and, if necessary, one or several other complexing components, after which washed filtration precipitates are dried after optional squeezing and mechanical removal of moisture. Washing and drying stages are performed on the same filter.

EFFECT: significantly simplified process due to avoided repetitive redispersing of catalyst followed by transferring filtration precipitate to another equipment.

9 cl, 13 ex

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