Catalyst for producing hydrocarbon from synthesis gas and a method for preparing catalyst

FIELD: synthesis gas reaction catalysts.

SUBSTANCE: invention relates to catalyst for producing hydrocarbon from synthesis gas, which is suitable for hydrogenating carbon monoxide and obtaining hydrocarbon from carbon monoxide. Catalyst is composed of carrier, on which metal compound is deposited, catalyst containing impurities within a range from 0.02 to 0.15 wt %. Preparation of catalyst comprises preliminarily treating catalyst support to reduce concentration of impurities followed by depositing metal on support. Catalytic production of hydrocarbon from synthesis gas is also described.

EFFECT: increased activity, strength, and abrasion resistance of catalyst.

59 cl, 1 dwg, 1 tbl, 7 ex

 

The technical field to which the invention relates.

The present invention relates to a catalyst for obtaining hydrocarbons from synthesis gas, which is suitable for the hydrogenation of carbon monoxide and receive hydrocarbons from carbon monoxide, the method of production of the catalyst and to a method for producing hydrocarbons using the catalyst.

The level of technology

In recent years, due to General environmental problems such as global warming, natural gas again becomes appreciate, because natural gas has a higher ratio of hydrogen/carbon, compared to other hydrocarbon fuels, coal and the like, and thereby can reduce carbon dioxide emissions, representing the agent that causes global warming, and because there are large reserves of natural gas, the demand for natural gas is expected, will grow even stronger in the future. Under such circumstances, there are many small and medium-sized gas fields, located in the South-East Asia, Oceania and the like, which, however, remain undeveloped due to their location in remote locations with no infrastructure such as pipelines and LNG installation requiring large investments in infrastructure, which is incompatible with their small reserves, so that chelation is correctly their development. As one of the most effective means for their development in different areas are actively developing research and development of technology in which natural gas is converted to synthesis gas, and then the synthesis gas is converted into liquid hydrocarbon fuel, such as kerosene and gasoil, convenient in transportation and handling, through the use of the reaction of the Fischer-Tropsch synthesis.

The reaction of the Fischer-Tropsch synthesis, which converts synthesis gas into hydrocarbons using a catalyst is an exothermic reaction, where stable operation is essential to effectively remove the heat of reaction. As time-tested methods of reaction there are ways of gas-phase synthesis in a fixed bed, seized layer or fluidized bed) and a method of liquid-phase synthesis (in the layer of suspension), with its own characteristics. In recent years, the method of liquid-phase synthesis carried out in the layer of suspension, attracts attention, is studied and intensively developed for the reason that it shows higher removal efficiency of the heat, but eliminates the accumulation of the generated high-boiling hydrocarbon on the catalyst, and the resulting clogging of the pipe reactor.

As a rule, it is obvious that the higher catalytic activity is preferred,in particular, in the case of the layer of suspension, there is a restriction that the concentration of the suspension must have a specified value or to be below it in order to maintain a favorable state of suspension, therefore, the increase of catalytic activity is a crucial factor in increasing the design flexibility of the method. Known catalytic activity of various types of catalysts for Fischer-Tropsch synthesis are at most, from the point of view of the speed of the liquid hydrocarbon with the number of carbon atoms equal to five or higher, approximately 1 kg of hydrocarbon/kg-catalyst · hour, which is not always sufficient in light of the above considerations (see non-patent document 1).

As a way to increase catalytic activity information is available about what the effect of reducing the sodium content in the silicon oxide used as the carrier of the catalyst (see non-patent document 2), however, the comparison is made only between the silicon oxide with a sodium content below 0.01 wt.% and silicon oxide with a sodium content of about 0.3 wt.%, and there is no specific description regarding the highest level of sodium that you should pay attention to.

In addition, as a rule, the diameter of the catalyst particles to the reaction of the Fischer-Tropsch synthesis is preferably so is scarlet, almost to the extent possible in the sense of decreasing opportunities for diffusion of heat and matter to rise to the level that determines the speed. However, in the case of the reaction of the Fischer-Tropsch synthesis in a layer of the suspension, except the generated hydrocarbons in the reactor accumulates high-boiling hydrocarbon, inevitably requiring the operation of separation of solids and liquids to separate the product from the catalyst, so that raises another problem, namely the catalyst with too small diameter particles greatly reduces the efficiency of the operations division. For this reason, the catalyst layer slurry must exist an optimum range of particle diameters, and, as a rule, is regarded as the preferred range of average particle diameter from about 20 to about 250 microns, or from about 40 to about 150 microns; however, as shown below, in some cases called cracking and conversion of the catalyst powder with obtaining particles of a smaller diameter during the reaction and requires caution.

In particular, in the reaction of the Fischer-Tropsch synthesis in the layer of suspension work is often performed at an exceptionally high linear velocity of the material gas above the liquid (>0.1 m/sec), so that the catalyst particles vigorously collide with each other during the reaction is possible by reducing the diameter of the particles during the reaction, when the physical strength and abrasion resistance (resistance to turning into powder) are insufficient, which sometimes causes inconvenience when the split operation. In addition, in the reaction of the Fischer-Tropsch synthesis as a by-product generated volumes of water, however, in the case of using a catalyst with a low resistance to water, which affects its strength, causing a slight cracking and turning into powder during the reaction, the diameter of the catalyst particles can be reduced to fine powder, sometimes causing discomfort when the split operation, in the same way as described above.

As already mentioned, modern catalytic activity is not sufficient and requires a catalyst with a higher catalytic activity, including from the point of view of convenience in controlling the installation.

In addition, typically, the catalyst layer slurry often is put into practical use, being obtained with the control size by grinding, in order to obtain such appropriate particle diameter, as described above. However, this catalyst is ground type often has cracks or sharp edges that occur initially and has a lower mechanical strength and abrasion resistance, without solving the problem related to the propensity cat who lyst to cracking with the generation of fine powders, which makes difficult the separation of the generated high-boiling hydrocarbon from the catalyst when used in the reaction of the Fischer-Tropsch synthesis in a layer of the suspension. Similarly, it is widely known that can be the catalyst of relatively high activity as the catalyst carrier for the reaction of the Fischer-Tropsch synthesis using porous silicon oxide, however, the control of size during grinding also causes a reduction in strength for the reason described above and, in addition, the silicon oxide has a lower resistance to water and often cracks in the powder, when water is present, easily causing problems, especially in the case of the layer of suspension.

(Non-patent document 1) R. Oukaci et al., Applied Catalysis A: General 186 (1999), p.129-144.

(Non-patent document 2) J. Chen et al., Cuihua Xuebao, Vol.21 (2000), p.169-171.

The invention

The aim of the present invention is to provide a catalyst for Fischer-Tropsch synthesis, which solves the problems described above and has a high activity without affecting its catalytic strength and abrasion resistance; a method of producing catalyst and method for producing hydrocarbons using the catalyst.

The present invention relates to a catalyst for Fischer-Tropsch synthesis, with high strength and activity, to a method for producing the catalyst and a method for producing hydrocarbons using the catalyst. A more detailed description will be presented next.

(1) a Catalyst for obtaining hydrocarbons from synthesis gas containing catalyst carrier, which caused a compound of the metal, in which the content of impurities in the catalyst is in the range from 0.01 to 0.15 wt.%.

(2) the Catalyst according to item (1), in which the content of the alkali metal or alkaline earth metal in the catalyst carrier is in the range from 0.01 to 0.1 wt.%.

(3) the Catalyst according to item (1) or (2), in which the catalyst carrier at the same time has a pore size in the range from 8 to 50 nm, a surface area ranging from 80 to 550 m2/g and a pore volume ranging from 0.5 to 2.0 ml/year

(4) the Catalyst according to any one of items (1)to(3), in which used catalyst carrier is a carrier that allows the specified catalyst having a ratio of the cracking or conversion into powder 10% or below, when the ultrasonic wave is emitted for four hours at room temperature on the catalyst dispersed in the water.

(5) the Catalyst according to any one of items (1)to(4), in which the catalyst carrier is a silicon oxide spherical shape.

(6) the Catalyst according to any one of items (1)to(5), in which the specified connection metal contains at least one kind selected from the group consisting of iron, Koba is it, Nickel and ruthenium.

(7) the Catalyst according to item (6), in which the compound of the metal derived from the precursor compound of the metal with the content of the alkali metal or alkaline earth metal 5 wt.% or less.

(8) the Method of producing catalyst according to any one of items (1)to(7), in which the compound of the metal is applied to the catalyst carrier after pre-treatment of the carrier of the catalyst to reduce the concentration of impurities in the catalyst carrier.

(9) the Method of producing catalyst according to item (8), in which pre-processing is a washing with acid and/or water after ion exchange.

(10) the Method of producing catalyst according to item (8) or (9), in which the catalyst was prepared using the catalyst carrier obtained with the use of flush water to the content of the alkali metal or alkaline earth metal to 0.06 wt.% or below, at the stage of receiving the catalyst carrier.

(11) the Method of producing the catalyst according to any one of items (8)to(10), in which the catalyst carrier has a spherical shape obtained by atomization method.

(12) the Method of producing the catalyst according to any one of items (8)to(11), in which the catalyst carrier is a silicon oxide.

(13) a Method of producing hydrocarbons in which the hydrocarbons p is to obtain from synthesis gas using a catalyst, on any of the items(1)-(7).

In accordance with the present invention it is obvious that it is possible to obtain catalyst for Fischer-Tropsch synthesis with exceptionally high activity without compromising strength and abrasion resistance of the catalyst and the reaction of the Fischer-Tropsch synthesis with a high rate of receipt of hydrocarbon using a catalyst.

A brief description of the drawing which is a graph showing the relationship between the metal content in the catalyst carrier of silicon oxide and CO conversion.

A detailed description of the preferred embodiments

Next, you will see a more detailed description of the present invention.

Close considering the impurities contained in the catalyst, the authors of the present invention found that a significant increase of catalytic activity can be achieved by reducing impurities and that the catalyst with high strength and abrasion resistance can be obtained without reducing the activity of using a specific catalyst carrier of the present invention.

The catalyst in accordance with the present invention is not specifically limited to any one of them, since the catalyst contains a metal having activity towards the reaction Shin is ESA Fischer-Tropsch, these catalysts, which contain iron, cobalt, Nickel, ruthenium, etc. are acceptable, and as a catalyst carrier preferably choose porous oxides and the like, comprising silicon oxide, aluminum oxide, titanium oxide, etc. in accordance with your choice of catalyst carrier. As a method of producing catalyst can be used the usual way impregnation, the impregnation method with the pores are filled, the precipitation method, the method of ion exchange and the like, the load Value is difficult to define, because the value varies depending on the particular compounds used metal, but the acceptable range between the minimum amount at which activity is observed or above and marked by an amount which causes a drop in efficiency to the response due to a sharp reduction in the dispersion of the compound of the metal on the catalyst carrier, or below. For example, when using a cobalt, the number range is from 5 to 50 wt.%, preferably from 10 to 40 wt.%. If the number is below the limits, the desired activity cannot be achieved, and in the case of amounts in excess of these limits, the dispersion uneconomical reduces the efficiency of the use of cobalt deposited on a catalyst carrier, to lower that undesired hair is O.

After application of the precursor compounds of the metal catalyst carrier of the calcination and/or repair carried out accordingly, so that the catalyst for Fischer-Tropsch synthesis can be obtained.

As a result of much research, the authors present invention for the first time found that reduced amounts of impurities other than the compound of the metal, and the element constituting the catalyst carrier in the catalyst control impurities, which must be within certain limits, can significantly increase the activity. For example, in the case of using silicon oxide as catalyst carrier, typically a silicon oxide often contains alkaline metal such as Na, alkaline earth metal such as Ca and Mg, and Fe, Al, etc. as impurities. The influence of these impurities was studied in detail using cobalt as a metal link, and found that a large amount of alkali metal and/or alkaline earth metal causes a significant reduction in activity in the reaction of the Fischer-Tropsch synthesis. In addition, we discovered that most heavily influenced by the sodium.

In order to achieve the desired catalytic activity, the amount of impurities in the catalyst must be reduced to 0.15 wt.% or below. If the impurities are above these limits, activity pain is her part is reduced, that is a serious fault. However, excessive reduction in the number of impurities leads to higher costs, therefore, the preferred amount of impurities in the catalyst is 0.01 wt.% or higher. The amount of impurities in the precursor compound of the metal it is difficult to determine, because it depends on the applied amount and type of precursor, however, to reduce the amount of impurities in the catalyst useful for limiting the number of impurities in the precursor compound of the metal, in particular the content of the alkali metal or alkaline earth metal up to 5 wt.% or less.

In addition, as a result of thorough research carried out by the authors of the present invention, it was found that the addition of impurities in the catalyst, the most negative influence on the activity of the catalyst have alkali metals and alkaline earth metals. Therefore explored the relationship between the concentrations of these metals in the catalyst carrier of the silicon oxide and the conversion of CO used in the reaction of the Fischer-Tropsch synthesis, which is an indicator of the activity of the catalyst, and the result is shown in the drawing. From the drawing it is obvious that, when the content of these metals is in the range of 0.01 wt.% or below, alkali metal and alkaline earth metal influence is weak, however, when it is within the Ah more than 0.01 wt.%, the activity gradually decreases. From the above review, the content of the alkali metal or the content of alkaline earth metal in the catalyst carrier is preferably 0.1 wt.% or below, more preferably, it consists of 0.07 wt.% or below and most preferably, it consists of 0.04 wt.% or below. When the content of impurities in the carrier of the catalyst becomes to 0.15 wt.% or higher, the catalyst activity drops significantly. In this case, therefore, an excessive decrease in the content of the alkali metal and the content of alkaline earth metal in the catalyst carrier leads to additional costs, alkali metal and alkaline earth metal may be present in the catalyst in amounts that do not influence negatively on the catalytic activity. As described above, when the content of the alkali metal and the content of alkaline earth metal in the catalyst carrier is reduced to 0.01 wt.% or below, it is possible to achieve a sufficient effect, therefore, from the point of view of economic efficiency, the content of the alkali metal and the content of alkaline earth metal preferably be 0.01 wt.% or higher.

In the case of a catalyst carrier, which can be obtained without contamination by the admixture of getting on the basis of the workpiece, it is preferable to include in the way gender is ing such a workpiece, not containing impurities.

For example, typically, a large amount of flush water used when receiving the catalyst carrier made of silicon oxide, however, when used wash water containing impurities, such as water, a large number of impurities remains in the catalyst carrier, causing a significant loss of catalytic activity, which is undesirable. However, when using the washing of water with low content of impurities or without impurities can be obtained the desired catalyst carrier made of silicon oxide with a lower content of impurities. In this case, the content of the alkali metal or the content of alkaline earth metal in the wash water is preferably 0.06 wt.% or lower, and the content exceeding 0.06 wt.% leads to an increase in the content of impurities in the catalyst carrier of silicon oxide, which causes a significant reduction in catalytic activity after receiving that undesirable. Ideally, it is preferable to use water after ion exchange, and water subjected to ion exchange, can be obtained using ion-exchange resins and the like, as well as using silica gel, for example, when the catalyst carrier using silica as the silica gel is formed in a line retrieve of silicon oxide as the side product. In theory, the silicon oxide captures impurities in the wash water through ion exchange between hydrogen silanol on the surface of silicon oxide and ion impurities. Therefore, even if the washing water containing impurities in small amounts, the capture of impurities can be prevented to some extent by setting the pH of the wash water to a lower level. In addition, the amount of ion exchanged (number of contamination by impurity) is proportional to the number of used wash water, thus reducing the amount of impurities in the silicon oxide can be achieved by reducing the amount of wash water, in other words, by increasing the efficiency of water use until the end of the water washing.

We can reduce the number of impurities in the catalyst carrier through pre-treatment without significant changes in physical and chemical properties of the catalyst carrier, such pre-processing is extremely effective to improve the activity of the catalyst. Such pre-processing may be a processing, respectively using water washing, acid washing, alkali washing, etc. and, for example, when washing the catalyst carrier of the silicon oxide efficient rinsing solution is m acid, for example, a solution of nitric acid, hydrochloric acid, dilute acetic acid, and the like, and washing water, which undergoes ion exchange. After washing these acids, when a part of the acid remaining in the catalyst carrier, becomes an obstacle for effective backwashing with clean water, for example water, which undergoes ion exchange.

In addition, upon receipt of the silicon oxide often spend calcining the purpose of increasing the strength of the particles, the activity of surface silanol groups, etc. However, when the calcination is carried out in conditions of relatively large impurities, the impurity elements are captured in the skeletal structure of silicon oxide. Thus, even if to reduce the content of impurities rinse catalyst carrier made of silicon oxide, reducing the content of impurities is hard to achieve. Therefore, when you want to reduce the content of impurities by washing the catalyst carrier made of silicon oxide, the use of silica gel without calcination is preferred.

When using the catalyst described above, it is possible to obtain a catalyst exhibiting exceptionally high activity in the reaction of the Fischer-Tropsch synthesis. That is, the effect is noticeable when using cobalt as a compound of metal and silicon oxide as but is of Italia catalyst.

To maintain a higher degree of dispersion of the metal to improve the effectiveness of the contribution to the reaction caused by the connection of metal, it is preferable to use a catalyst carrier having a large specific surface area. However, to increase the specific surface area is required to reduce the diameter of pores and increase the pore volume, because the increase of these two factors leads to a decrease in abrasion resistance and strength, which is undesirable. Through careful research, the authors of the present invention have found that, as a catalyst carrier, which is the aim of the present invention, particularly preferred catalyst having at the same time the diameter of pores in the range from 8 to 50 nm, specific surface area in the range from 80 to 550 m2/g and a pore volume ranging from 0.5 to 2.0 ml/g, as its physical properties. More preferably, it had at the same time the diameter of pores in the range from 8 to 30 nm, specific surface area ranging from 150 to 450 m2/g and a pore volume in the range from 0.6 to 1.5 ml/g and most preferably, it had at the same time the diameter of pores in the range from 8 to 20 nm, specific surface area ranging from 200 to 400 m2/g and a pore volume in the range from 0.8 to 1.2 ml/year

To obtain a catalyst having sufficient activity in the reaction is the AI of the Fischer-Tropsch synthesis, the specific surface area should be 80 m2/g or more. When such a specific surface area of the dispersion of the deposited metal joints decreases with decrease in the efficiency of the contribution to the reaction of the compound of the metal, which is undesirable. When the specific surface area of more than 550 m2/g is difficult to achieve pore volume and pore diameter of simultaneously satisfy the above-described parameters, and this is a flaw.

The increase in specific surface area, when the diameter of pores is reduced, it is possible, however, when the diameter of pores becomes lower than 8 nm, produce large quantities of light hydrocarbon, such as methane, which can be called a by-product in the reaction of the Fischer-Tropsch synthesis, because the hydrogen and carbon monoxide have different speed of the gas diffusion in the pores, and as a result, the hydrogen has a higher partial pressure in the inner part of the pore, which is undesirable. In addition, the diffusion rate of the generated hydrocarbons in the pores is reduced, and the high reaction rate also decreases, which is undesirable. In addition, when the pore diameter of more than 50 nm, it is difficult to increase the specific surface area, therefore, the dispersion of the compound of the metal is reduced, which is undesirable.

Preferably the pore volume is in the range from 0.5 to 2.0 ml/g When the amount is less than 0.5 ml/g, it becomes difficult to hold both the pore size and specific surface area in the above-described range, and if more than 2.0 ml/g, the strength is significantly reduced, which is undesirable.

As described above, the catalyst for Fischer-Tropsch synthesis, which is intended for the layer of suspension, must have resistance to abrasion and to be strong. In addition, in the reaction of the Fischer-Tropsch synthesis a large amount of water formed as a by-product, therefore, the use of a catalyst which crack to powder in the presence of water causes inconvenience as described above, and requires caution. Thus, preferably using a catalyst carrier having a spherical shape than the catalyst carrier structure having a high probability of cracks, sharp corners which may be damaged and to lengthen. When receiving a spherical catalyst carrier, we will apply the method of granulating or spray, when receiving a spherical catalyst carrier made of silicon oxide having a particle diameter of from about 20 to 250 microns, for use suitable method of atomization, whereby can be obtained spherical catalyst carrier made of silicon oxide having a high abrasion resistance and resistance to water.

The method of obtaining such a catalyst carrier made of silicon oxide will be described below. The Sol of silicon oxide is generated through mix the solution of alkali metal silicate and acid solution under conditions of pH from 2 to 10.5: Sol of silica dispersed in a gaseous medium or in an organic solvent, in which the Sol is insoluble, so the Sol becomes a gel, and silica gel passes through the acid treatment, the treatment water rinse and dry processing. In this case, as a solution of silicate of an alkali metal is preferred sodium silicate in which the molar ratio of Na2O:SiO2is preferably from 1:1 to 1:5, and the concentration of silicon oxide is from 5 to 30 wt.%. As the acid to be used, suitable are nitric acid, hydrochloric acid, sulfuric acid, organic acid, etc. while sulfuric acid is preferred because it dekorativni for a container used in the method of production, and not leaving organic material. The concentration of the acid is preferably in the range from 1 to 10 mol/L. Below these limits the progress of gelation slows significantly, and beyond gelation occurs too quickly, so that it becomes difficult to control and, thus, it is difficult to achieve the required values of the physical properties, which is undesirable. In addition, when carrying out sputtering method in an organic solvent as the organic solvent can be used kerosene, paraffin, xylene, toluene, etc.

Spherical wear the spruce catalyst, obtained through the above-described way, a little damaged in the collision between the catalysts, when cracking under the action of water and spraying. There are different methods for the quantitative determination of bursting and spraying on the basis of which the authors of the present invention were tested resistance to abrasion when espousals ultrasonic wave, at a temperature ranging from room temperature to 400°C, while the dispersion of the catalyst in water. As a generator of ultrasound use the device with a frequency of 47 kHz and output power of 125 watts (manufacturer: Branson Ultrasonics Corp., product name: BRANSONIC Model 2210J) and 1 g of catalyst, not containing particles smaller than 20 microns, dispersed in 3 ml of pure water, emit ultrasound at room temperature for four hours, and the mass % of particles less than 20 microns in the sample as a whole is determined by the number of cracked or powdered catalyst. This assessment, based on the method, it is confirmed that when the number of cracked or powdered catalyst is 10 wt.% or below, the actual use of the layer of suspension does not cause problems from the standpoint of separation of the generated high-boiling hydrocarbons from the catalyst. In the case of the catalyst, in which RA is treskavica or powdered catalyst exceeds 10 wt.%, the separation efficiency drops significantly, which is undesirable.

Using the composition, structure and the production method, described above, can be the catalyst for Fischer-Tropsch synthesis, which has a higher activity without compromising strength and abrasion resistance of the catalyst.

In addition, when using the catalyst for Fischer-Tropsch synthesis in accordance with the present invention it becomes possible to obtain the product through reaction of the Fischer-Tropsch synthesis with higher efficiency and lower costs. In particular, when the reaction of the Fischer-Tropsch synthesis is performed with the use of a catalyst obtained by using the present invention, the selectivity of liquid product having the number of carbon atoms equal to five or higher as the main product is high, and the speed of delivery of liquid product per unit mass of catalyst (receive rate of the hydrocarbon) is very high. In addition, the catalyst sprayed a little, and decrease the activity of the catalyst when it is used very little, therefore, the catalyst has a longer lifetime, which is one of the features. When these features of the reaction of the Fischer-Tropsch synthesis can be performed with higher efficiency at lower cost is.

Examples

Next will be given more detailed description of the present invention based on examples, but the present invention is not limited to these examples.

Using an autoclave with an inner volume of 300 ml, load 2 g of catalyst Co/SiO2(catalyst carrier of silica, get a Fuji Silysia Chemical Ltd., has a spherical shape with an average particle diameter of 100 μm, and the load Co from 16 to 30 wt.%) and 50 ml of n-C16(n-hexadecane) and then the reaction of the Fischer-Tropsch synthesis is carried out in conditions 230°C and 2.0 MPa-G, under stirring with a stirrer at 800 rpm, through the introduction of synthesis gas (H2/CO=2) at a flow rate of W (weight of catalyst)/F (flow rate of synthesis gas)=5 (g·h/mol), unless specifically indicated otherwise. The CO conversion, selectivity CH4and selectivity of CO2calculated by the formulas below.

Next, the effect of the present invention will be described with discussion of the results of examples and comparative example.

Example 1

20 wt.% Co put on a catalyst carrier made of silicon oxide, having the characteristics as shown in column A in the table, and carry out the reaction of the Fischer-Tropsch synthesis. The result of the conversion is the CO is 75,9%, selectivity CH4is 5.3% and the selectivity of CO2is 1.4%.

Example 2

20 wt.% Co put on a catalyst carrier made of silicon oxide, having the characteristics as shown in column B in the table, and carry out the reaction of the Fischer-Tropsch synthesis. As a result, the conversion of CO is to 75.8%, selectivity CH4is 4.6% and the selectivity of CO2is 1.0%.

Example 3

Catalyst carrier made of silicon oxide, having the characteristics as shown in column G of the table, washed with hydrochloric acid and water, which undergoes ion exchange with obtaining a catalyst carrier made of silicon oxide, as shown in column C in the table. 20 wt.% Co put on a catalyst carrier made of silicon oxide, carry out the reaction of the Fischer-Tropsch synthesis, and as a result, the conversion of CO is 74,1%, selectivity CH4is 4.8% and the selectivity of CO2is 1.0%. In addition, the tests on the abrasion resistance of emitting ultrasonic waves at room temperature, as described above, and the result is measured against a cracked or powdered catalyst, the mass ratio of particles of 20 μm or less is 0.00%. After that, collect the catalyst was subjected to exposure for 1000 hours, and spend the measurement location is adelene particle sizes. The mass ratio of particles of 20 μm or less is 0.00%.

Example 4

20 wt.% Co put on a catalyst carrier made of silicon oxide with a pore diameter of 30 nm, as shown in column D in the table, and carry out the reaction of the Fischer-Tropsch synthesis. As a result, the conversion of CO 46.4%, selectivity CH4is 7.8% and the selectivity of CO2is 1.0%.

Example 5

The same reaction as in example 3 is carried out, allowing the application to the media only 30 wt.% Co and bringing W/F 1.5 (g·h/mol). As a result, the conversion of CO accounts for 74.7%, selectivity CH4is 3.7% and the selectivity of CO2is 0.6%,and receive rate of the hydrocarbon having the number of carbon atoms of 5 or above is 2.1 kg-hydrocarbon/kg-catalyst·h.

Example 6

30 wt.% Co put on a catalyst carrier made of silicon oxide having physical properties as shown in column E in the table, and carry out the reaction of the Fischer-Tropsch synthesis, bringing W/F to 1.5. As a result, the conversion of CO is 71,7%, selectivity CH4is 4.4% and the selectivity of CO20.7%, and the rate of receipt of hydrocarbons having a number of carbon atoms of 5 or higher is 1.9 kg-hydrocarbon/kg-catalyst·h.

Example 7

16 wt.% Co cause wear on the ü catalyst from silicon oxide, having physical properties as shown in column F in the table, and carry out the reaction of the Fischer-Tropsch synthesis, bringing W/F to 2. As a result, the conversion of CO is 74.8%, selectivity CH4is 4.9% and the selectivity of CO2is 1.1%, and the rate of receipt of hydrocarbons having a number of carbon atoms is 5 or higher, 1.4 kg of hydrocarbon/kg-catalyst·h.

Comparative example 1

20 wt.% Co put on a catalyst carrier made of silicon oxide having a large number of impurities, as shown in column G of the table, and carry out the reaction of the Fischer-Tropsch synthesis. As a result, the conversion of CO is 24.0%, selectivity CH4is 8.3% and the selectivity of CO2is 0,84%.

Industrial application

As discussed in detail above, in accordance with the present invention the catalyst for Fischer-Tropsch synthesis, which has a very high activity can be obtained without reducing the strength and abrasion resistance of the catalyst, and the reaction of the Fischer-Tropsch synthesis with a higher rate of receipt of hydrocarbons can be carried out using a catalyst.

MarkABCDEF
The pore size (nm)1010103010810
Surface area

(m2/g)
250235330110346430341
Pore volume (ml/g)0,810,811,131,001,160,821,20
The Na concentration in the media (h/million Mac)1201051101801763161480
The Ca concentration in the media (h/million Mac)75325111011118741
The concentration of Mg in the media (h/million Mac)1381015162722
The concentration of Fe in the media (h/million Mac)25201320293315
The Al concentration in the media (h/million Mac)946242349210350

1. Catalyst d is I receive hydrocarbons from synthesis gas, contains:

the catalyst carrier, which caused a compound of the metal, in which the content of impurities in the catalyst is from about 0.01 to 0.15 wt.%.

2. The catalyst according to claim 1, in which the content of the alkali metal or alkaline earth metal in the catalyst carrier is from about 0.01 to 0.1 wt.%.

3. The catalyst according to claim 2, in which the catalyst carrier at the same time has a pore diameter of from about 8 to 50 nm, the surface area of from 80 to 550 m2/g and a pore volume of 0.5 to 2.0 ml/year

4. The catalyst according to claim 1, in which the catalyst carrier at the same time has a pore diameter of from about 8 to 50 nm, the surface area of from 80 to 550 m2/g and a pore volume of 0.5 to 2.0 ml/year

5. The catalyst according to claim 1, in which the catalyst carrier allows the catalyst to have the degree of cracking or spray no more than 10%, when the emitted ultrasonic wave within a predetermined period of time at room temperature on the catalyst dispersed in the water.

6. The catalyst according to claim 2, in which the catalyst carrier allows the catalyst to have the degree of cracking or spray no more than 10%, when the emitted ultrasonic wave within a predetermined period of time at room temperature on the catalyst dispersed in the water.

7. Catalysate is R. according to claim 3, in which the carrier of the catalyst allows the catalyst to have the degree of cracking or spray no more than 10%, when the emitted ultrasonic wave within a predetermined period of time at room temperature on the catalyst dispersed in the water.

8. The catalyst according to claim 1, in which the catalyst carrier is a silicon oxide spherical shape.

9. The catalyst according to claim 2, in which the catalyst carrier is a silicon oxide spherical shape.

10. The catalyst according to claim 3, in which the catalyst carrier is a silicon oxide spherical shape.

11. The catalyst according to claim 4, in which the catalyst carrier is a silicon oxide spherical shape.

12. The catalyst according to claim 5, in which the catalyst carrier is a silicon oxide spherical shape.

13. The catalyst according to claim 6, in which the catalyst carrier is a silicon oxide spherical shape.

14. The catalyst according to claim 7, in which the catalyst carrier is a silicon oxide spherical shape.

15. The catalyst according to claim 1 in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

16. The catalyst according to claim 2, in which the compound of the metal contains at least one member of the series, including iron, obalt, Nickel and ruthenium.

17. The catalyst according to claim 3, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

18. The catalyst according to claim 4, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

19. The catalyst according to claim 5, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

20. The catalyst according to claim 6, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

21. The catalyst according to claim 7, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

22. The catalyst according to claim 8, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

23. The catalyst according to claim 9, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

24. The catalyst according to claim 10, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

25. The catalyst according to claim 11, in which the compound of the metal contains at least one member of the series, including iron, cobalt, neither the spruce and ruthenium.

26. The catalyst according to item 12, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

27. The catalyst according to item 13, in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

28. The catalyst 14 in which the compound of the metal contains at least one member of the series, including iron, cobalt, Nickel and ruthenium.

29. The catalyst according to item 15, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

30. The catalyst according to item 16, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

31. The catalyst 17 in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

32. The catalyst b, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and Melo notemily metal, not more than 5 wt.%.

33. The catalyst according to claim 19 in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

34. The catalyst according to claim 20, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

35. The catalyst according to item 21, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

36. The catalyst according to item 22, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

37. The catalyst according to item 23, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

38. The catalyst according to paragraph 24, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, localseo alkali metal and alkaline earth metal, not more than 5 wt.%.

39. The catalyst A.25, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

40. The catalyst b, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

41. The catalyst according to item 27 in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

42. The catalyst b, in which the compound of the metal derived from the precursor compound of the metal content of at least one member of the series, including alkali metal and alkaline earth metal, not more than 5 wt.%.

43. A method of producing a catalyst containing a catalyst carrier, which caused a compound of the metal, in which the content of impurities in the catalyst ranges from about 0.01 to 0.15 wt.%, including:

pre-treatment of the carrier of the catalyst to reduce the concentration of impurities in the catalyst carrier and

application connection meta the La on the catalyst carrier after pre-processing.

44. The method according to item 43, in which the stage of pre-processing includes washing of the catalyst carrier using acid and/or water after ion exchange.

45. The method according to item 43, further comprising obtaining a catalyst using the catalyst carrier obtained with the use of wash water containing alkali metal or alkaline earth metal is not more than 0.06 wt.% at the stage of receiving the catalyst carrier.

46. The method according to item 44, further comprising obtaining a catalyst using the catalyst carrier obtained with the use of wash water containing alkali metal or alkaline earth metal is not more than 0.06 wt.% at the stage of receiving the catalyst carrier.

47. The method according to item 43, further comprising receiving the catalyst carrier in a spherical form by atomization method.

48. The method according to item 44, further comprising receiving the catalyst carrier in a spherical form by atomization method.

49. The method according to item 45, further comprising receiving the catalyst carrier in a spherical form by atomization method.

50. The method according to item 46, further comprising receiving the catalyst carrier in a spherical form by atomization method.

51. The method according to item 43, in which the media can produce the RA is a silicon oxide.

52. The method according to item 44, in which the catalyst carrier is a silicon oxide.

53. The method according to item 45, in which the catalyst carrier is a silicon oxide.

54. The method according to item 46, in which the catalyst carrier is a silicon oxide.

55. The method according to p, in which the catalyst carrier is a silicon oxide.

56. The method according to p, in which the catalyst carrier is a silicon oxide.

57. The method according to § 49, in which the catalyst carrier is a silicon oxide.

58. The method according to item 50, in which the catalyst carrier is a silicon oxide.

59. A method of producing hydrocarbons, including the production of hydrocarbons from synthesis gas using a catalyst in which the content of impurities is in the range from about 0.01 to 0.15 wt.%.



 

Same patents:

FIELD: petroleum processing.

SUBSTANCE: catalytic removal of sulfur compounds, including mercaptans, hydrogen sulfide, sulfides, and the like, from light petroleum product, in particular gasolines, kerosene, diesels, and others, is accomplished by passing crude material at 20-30°C and volumetric flow rate 0.1 h-1 through catalytic system, said catalytic system being consisted of manganese and iron-containing cluster compound of general formula C18H15MnFeOCl2 deposited on anhydrous clinoptilolite at weight ratio 1:1.

EFFECT: enabled production of high-quality product from which up to 99 wt % sulfur is removed at ambient temperature.

5 tbl, 4 ex

FIELD: chemical engineering.

SUBSTANCE: invention relates to chemical process and catalytic reactors suitable for carrying out the process. In particular, Fischer-Tropsch synthesis is described involving compact block of catalytic reactor (10) forming passages wherein gas-permeable catalyst structure (16) is present, said passages extending between manifolds (18). Synthesis is performed in at least two steps since reactor block provides at least two consecutive passages (14, 14a) for Fischer-Tropsch synthesis process interconnected through manifold wherein gas flow velocity in the first passages is high enough to limit conversion of carbon monoxide to 65%. Gases are cooled in manifold between two steps so as to condense water steam and then passes through the second passage at flow velocity high enough to limit conversion of the rest of carbon monoxide to 65%.

EFFECT: reduced partial pressure of water steam and suppressed oxidation of catalyst.

17 cl, 3 dwg

FIELD: crude oil treatment.

SUBSTANCE: treatment of hydrogen sulfide-containing crude oil before transportation and separation comprises multistep separation of original crude oil followed by dehydration and desalting, flushing with hydrocarbon gas in desorption column, and addition of monomethanolethanolamine (obtained by reaction of monomethanolamine with formaldehyde), and stirring. Flushing is accomplished with hydrogen sulfide-containing gas ensuring weight percentage of hydrogen sulfide in post-flushing oil no higher than 200 ppm. After addition of monomethanolethanolamine, according to invention, up to 10% of fresh washing water is additionally charged. All aforesaid operations are carried out before desalting step.

EFFECT: reduced contents of hydrogen sulfide and water in commercial oil.

1 dwg, 3 tbl

FIELD: oil production, oil refinery and petrochemical industries, particularly for hydrogen sulfide and mercaptan neutralization in hydrocarbon medium with the use of chemical neutralization agents.

SUBSTANCE: hydrogen sulfide and mercaptan neutralizing agent comprises 30-58% by weight of formalin, alkali metal, preferably sodium, hydroxide or carbonate in amount of 0.1-3% by weight, hexamethylenetetramine in amount of 15-25% by weight, remainder is tertiary alkamine, preferably triethanolamine and/or methyldethanolamine. Neutralizing agent in accordance with the second embodiment additionally includes bactericide composition.

EFFECT: increased neutralizing agent efficiency, enhanced manufacturability (low solidification temperature) and reactivity, provision of high hydrocarbon medium (oil, oil product and gaseous hydrocarbon) cleaning of hydrogen sulfide and light-weight mercaptans at room and increased temperatures (of 10-90°C and higher), improved bactericidal activity and corrosion inhibiting effect in hydrogen sulfide mediums, possibility of neutralizing agent usage as bactericide and corrosion inhibitor in oil-field media.

7 cl, 15 ex, 1 tbl

FIELD: petrochemical process catalyst.

SUBSTANCE: invention, in particular, relates to precursors of catalysts used in production of hydrocarbons from synthesis gas. Preparation of catalyst precursor involves contacting crude catalyst carrier, which is partly soluble in aqueous acid solution and/or in neutral aqueous solution, with modifying component of general formula Me(OR)x, wherein Me is selected from Si, Zr, Ti, Cu, Zn, Mn, Ba, Co, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Ti, Mg, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, Ta, and W; R represents alkyl or alkoxy group; and x is integer from 1 to 5. Therefore, modifying component is introduced into catalyst carrier or deposited onto surface thereof to form protected modified catalyst carrier, which is less soluble and more inert in aqueous acid solution and/or in neutral aqueous solution than crude carrier. Resulting catalyst carrier is then subjected to heat treatment at temperature lower than 100° C so that calcination of the carrier does not take place. Non-calcined protected modified catalyst carrier is mixed with aqueous solution of cobalt, which is active component of catalyst or its precursor, to form slurry. Which is exposed to subatmospheric pressure to facilitate impregnation of the catalyst carrier with cobalt or its precursor. Impregnated carrier is then dried at subatmospheric pressure and finally calcined.

EFFECT: enhanced selectivity and activity of catalyst in Fischer-Tropsch synthesis and eliminated need to perform calcination step after contact of crude Carrier with modifying component and drying.

16 cl, 5 dwg, 1 tbl, 6 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: lube fractions are brought into contact with N-methylpyrrolidone in extraction tower according to three-step countercurrent purification scheme to form raffinate and extract solutions. When distillate fraction II (300-400°C) is purified, of sulfoxide is preliminarily added in amount of 0.1-0.5% based on the weight of solvent. Distillate fraction III (350-420°C) is then purified after addition to solvent of 0.5-1.5% of extract obtained from purification of distillate fraction II.

EFFECT: deepened purification of raffinate, increased yield of raffinate as commercial product, and enabled qualified application of extract by-product.

11 tbl, 6 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: lube fractions are brought into contact with N-methylpyrrolidone in extraction tower according to three-step countercurrent purification scheme to form raffinate and extract solutions. When distillate fraction II (300-400°C) is purified, of sulfoxide is preliminarily added in amount of 0.1-0.5% based on the weight of solvent. Distillate fraction III (350-420°C) is then purified after addition to solvent of 0.5-1.5% of extract obtained from purification of distillate fraction II.

EFFECT: deepened purification of raffinate, increased yield of raffinate as commercial product, and enabled qualified application of extract by-product.

11 tbl, 6 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: petroleum processing and petrochemistry.

SUBSTANCE: oxidation is performed at 20-60°C with hydrogen peroxide aqueous solution in presence of molybdenum-containing catalyst, in particular molybdenum bis-alkylsulfoxide peroxo complexes.

EFFECT: increased yield of sulfoxides, oxidation selectivity, and oxidation rate.

2 tbl, 6 ex

FIELD: chemical industry; petrochemical industry; gaseous industry; oil-producing industry; oil-processing industry; installation for purification of the hydrocarbon raw from methanol.

SUBSTANCE: the invention is pertaining to the technology of purification of the hydrocarbon raw from methanol and may be used in gaseous, petroleum, petrochemical and chemical industries. The installation includes the assembly of the preliminary separation of the raw connected with the block of the adsorbing purification, the pipeline links and the shut-off-adjusting fittings. The assembly of the preliminary separation includes: the block of the preheating of the raw consisting of the heat exchangers (1) and (2), the rectifying column (3) with the connecting pipes for feeding of the liquid hydrocarbon raw (4), withdrawal of the methanol with the light fraction of hydrocarbons (5) and the withdrawal of the hydrocarbon tailings (6) with the bottom heating, the cooler (10) and container(11). The block of the raw preheating is connected to the connecting pipe (4) of the raw feeding into the rectifying column (3), and the connecting pipe (5) for the raw withdrawal in series through the raw preheating block, the cooler (10) and the container (11) directly connected with the block of adsorbing purification. In the other version the block of the raw preheating is connected to the connecting pipe (4) of feeding of the liquid hydrocarbon raw into the rectifying column (3), and the connecting pipe (5) of withdrawal through the heat exchanger (1) and the cooler (10) is connected to the connecting pipe (23) of the inlet into the extraction column. The connecting pipe (25) of withdrawal of the methanol with the light fraction of hydrocarbons out of the extraction column (20) is connected to the inlet connection pipe (28) of the separator (21), and the connecting pipe (26) of withdrawal of the water-methanol mixture is connected with the intermediate container (22). The connecting pipe (29) of withdrawal of the methanol with the light hydrocarbons from the separator (21) is connected to the block of the adsorbing purification. The connecting pipe (29) of withdrawal of the water-methanol mixture of the separator (21) is connected to the intermediate vessel (22), which outlet is connected to the feeding line of the extracting liquid into the extraction column (20). The invention reduces the operational costs, increases the lifetime of zeolite.

EFFECT: the invention ensures reduction of the operational costs, the increased lifetime of zeolite.

2 cl, 2 dwg, 2 ex

FIELD: chemical engineering.

SUBSTANCE: invention relates to chemical process and catalytic reactors suitable for carrying out the process. In particular, Fischer-Tropsch synthesis is described involving compact block of catalytic reactor (10) forming passages wherein gas-permeable catalyst structure (16) is present, said passages extending between manifolds (18). Synthesis is performed in at least two steps since reactor block provides at least two consecutive passages (14, 14a) for Fischer-Tropsch synthesis process interconnected through manifold wherein gas flow velocity in the first passages is high enough to limit conversion of carbon monoxide to 65%. Gases are cooled in manifold between two steps so as to condense water steam and then passes through the second passage at flow velocity high enough to limit conversion of the rest of carbon monoxide to 65%.

EFFECT: reduced partial pressure of water steam and suppressed oxidation of catalyst.

17 cl, 3 dwg

FIELD: disproportionation reaction catalysts.

SUBSTANCE: invention relates to Fischer-Tropsch catalyst containing cobalt and zinc, to a method for preparation thereof, and to Fischer-Tropsch process. Catalyst according to invention containing co-precipitated cobalt and zinc particles, which are characterized by volume-average size below 150 μm and particle size distribution wherein at least 90% of the catalyst particle volume is occupied by particles having size between 0.4 and 2.5 times that of the average particle size and wherein zinc/cobalt atomic ratio within a range of 40 to 0.1. Catalyst is prepared by introducing acid solution containing zinc and cobalt ions at summary concentration 0.1 to 5 mole/L and alkali solution to reactor containing aqueous medium wherein acid solution and alkali solution come into contact with each other in aqueous medium at pH 4-9 (deviating by at most 0.2 pH units) at stirring with a speed determined by supplied power between 1 and 300 kW/L aqueous medium and temperature from 15 to 75°C. Resulting cobalt and zinc-including precipitate separated from aqueous medium, dried, and further treated to produce desired catalyst. Employment of catalyst in Fischer-Tropsch process is likewise described.

EFFECT: enhanced strength and separation properties suitable for Fischer-Tropsch process.

13 cl, 2 dwg, 1 tbl, 5 ex

FIELD: production of pigments and catalysts based on titanium dioxide, in particular, process for treatment of titanium dioxide for removal of sulfur, in particular sulfates.

SUBSTANCE: method involves treating calcined titanium dioxide at elevated temperatures using aqueous solution containing one or more ammonium compounds; separating titanium dioxide from aqueous solution and drying titanium dioxide. Ammonium compounds preferably used in treatment process are ammonium acetate or ammonium chloride.

EFFECT: increased efficiency in cleaning of titanium dioxide from sulfur, in particular sulfates.

9 cl, 5 tbl, 5 ex

FIELD: petrochemical process catalyst.

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

EFFECT: optimized catalyst preparation procedure.

23 cl, 2 dwg, 1 tbl, 12 ex

FIELD: 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: gas treatment.

SUBSTANCE: invention relates to novel catalysts, which can be, in particular, used in automobile engine exhaust treatment, in processes of deep oxidation of toxic organic impurities in industrial emission gases, and in other applications. Adsorption-catalytic system, including granules of sorbent capable of sorbing at least one of reagents and catalyst, represents geometrically structured system wherein catalyst is made in the form of microfibers 5-20 μm in diameter, sorbent granules are disposed inside catalyst, and size ratio of sorbent granules to catalyst microfibers is at least 10:1. Catalyst microfibers are structured in the form of woven, knitted, or pressed material. Gas treatment process involving use of such system is based on that gaseous reaction mixture to be treated is passed through above-defined system while periodically varying temperature of mixture, in particular raising it, to accomplish or regeneration of sorbent.

EFFECT: enhanced process simplicity and reliability (simple process government system, absence of mechanical stream switching devices, reduced power consumption, and enabled continuous gas treatment.

2 cl, 2 ex

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