Catalyst for production of hydrocarbon from synthesis gas, method for catalyst production, method of catalyst regeneration and method of hydrocarbon production from synthesis gas

FIELD: technological processes.

SUBSTANCE: present invention relates to a catalyst for hydrocarbon production from synthesis gas, to method of its production, method of such catalyst regeneration and method of hydrocarbon production with application of such catalyst. A catalyst is described to produce hydrocarbon from synthesis gas, in which metal cobalt or metal cobalt and cobalt oxides; and zirconium oxides are applied onto a catalyst substrate, which mainly consists of a silicon dioxide. This catalyst is characterised by the fact that content of admixtures in the catalyst makes less or is equal to 15 wt %. Versions of the method are described to produce such catalyst, where the catalyst is produced by simultaneous or separate application of cobalt and zirconium compounds onto a catalyst substrate by impregnation method, impregnation method by moisture capacity, by method of deposition or method of ion exchange and performance of restoration treatment or baking and restoration treatment. Versions are described to regenerate such catalyst, where the catalyst with reduced activity is treated with a regenerating gas, containing hydrogen, or regenerating gas is supplied into a reactor, or regenerating gas is supplied into any part of the outer circulation system, and the catalyst and the regenerating gas contact with each other. Versions of the method to produce hydrocarbon from synthesis gas with application of such catalyst are described, where the method is carried out with performance of reaction in a liquid phase using a reactor with a layer of suspended residue or a layer of suspended residue with an external circulation system.

EFFECT: production of catalyst having high activity, durable service life and high resistance to water without loss of strength and wear resistance.

31 cl, 3 tbl, 2 dwg, 21 ex

 

Description of related materials

Priority is claimed to patent application of Japan No. 2006-229135, filed August 25, 2006, the contents of which are incorporated here by reference.

The technical field

The present invention relates to a catalyst for producing a hydrocarbon from the so-called synthesis gas, composed primarily of carbon monoxide and hydrogen, a method for producing such a catalyst, the method of regeneration of this catalyst and method for producing hydrocarbons using such a catalyst.

The level of technology

Recent years, environmental problems such as global warming, have become much clearer. Was considered the importance of natural gas, which has a higher H/C ratio compared to other hydrocarbon fuels, coal, etc. that reduces the amount of carbon dioxide emissions. It is expected that demand for natural gas will only increase. In such circumstances, there are many small and medium-sized gas fields found in South-East Asia, Oceania and so on, which are, however, still remain undeveloped due to their location in remote areas lacking infrastructure such as pipelines and LNG, which requires huge investments in infrastructure, against the by with a stock so their development is desirable. As one of the effective measures for the development of gas fields, after the conversion of natural gas into synthesis gas, in many places, vigorously develop the technology to convert natural gas into synthesis gas and then the synthesis gas to liquid hydrocarbon fuel, such as kerosene and light oil, which is excellent transported and processed, using the reaction of the Fischer-Tropsch synthesis (f-T).

F-T synthesis reaction formula:

This reaction synthesis f-T is an exothermic reaction, which converts synthesis gas into hydrocarbons with a catalyst, so it is very important to efficiently remove heat of reaction for the stable operation of the plant. As effective responses still apply the processes of synthesis in the gas phase (reactor fixed bed, breathtaking layer, fluidized bed) and the processes of synthesis in the liquid phase (reactor with a layer of suspended sediment). Although these processes have different characteristics, recently particular attention to the process of synthesis in the liquid phase in the reactor with a layer of suspended sediment, the efficiency of discharge of the heat which is very high and which does not cause the accumulation of the received high-boiling hydrocarbon in the catalyst or the consequences of the abuser clogging of the reaction tube. This process is energetically develops.

In General, it is preferable that the catalyst activity was higher and higher. However, especially in the reactor with a layer of suspended sediment, to preserve excellent fluidized state weighted layer, there is a limit up to which you want to install the suspended sediment layer up to a certain value or below. Therefore, the increase in the activity of the catalyst becomes a very important factor in expanding the degree of freedom of the design process. The activity of various catalysts for the synthesis f-T, which is described in the present time, is at most 1 (kg-hydrocarbon/kg-catalyst/HR) with an overall performance index of the liquid hydrocarbon, the carbon number is 5 or more. It is not enough with the above point of view (R. Oukaci et al: Applied Catalysis A: General, 186 (1999) 129 - 144).

As one of the ways to improve the activity of the catalyst described method, which effectively reduces the sodium content of silicon dioxide is used as the substrate of the catalyst (J. Chen: Cuihua Xuebao, Vol. 21, 2000, pp. 169-171). However, this report provides only a single comparison between a catalyst in which the sodium content is below 0.01 wt.%, and a catalyst, in which the sodium content is about 0.3% wt., but do not include a specific description of th is effect is achieved by reducing the content of sodium up to a certain limit.

In addition, the result of a detailed study of the influence of impurities such as alkali metals and alkaline earth metals on the catalyst activity, given the example in which the activity is strongly improved compared with the conventional catalyst using a catalyst, the concentration of impurities which is within a certain interval (link to publication of unexamined patent application of Japan No. 2004-322085).

Additionally, in General, the particle size of the catalyst for the reaction of synthesis f-T, preferably smaller from the viewpoint of reducing the possibility that the diffusion of heat or chemicals will reach the level that determines the speed. However, in the reaction of synthesis f-T reactor application with a layer of suspended residue, high-boiling hydrocarbons, including produced hydrocarbons accumulate in the reaction container. So be sure to need surgery Department of the solids from the liquid conducted to the catalyst and product. Thus, if the particle size of the catalyst is too small, there arises a problem of a significant reduction of the efficiency of the operations Department. Therefore, for catalysts used in reactors with a layer of suspended residue, there is an optimal interval of particle size, which usually ranges from 20 to 250 μm. The preferred medium p is setting the log file name particles is from 40 to 150 μm. However, as shown below, the catalyst may be destroyed or crushed during the reaction, and the particle size can be small. Therefore, it is necessary to watch that.

That is, in the reaction of synthesis f-T reactor with a layer of suspended sediment surgery is often carried out at relatively high given the speed of the material-gas (0.1/second or more), and the catalyst particles strongly collide with each other during the reaction. Therefore, if the physical strength or durability (resistance to poroshkovaya) is insufficient, the particle size of the catalyst may be reduced during the reaction, and can cause problems in the above-described operations of the Department. Moreover, in the reaction of synthesis f-T produces a lot of water as a byproduct. However, if you use a catalyst which has a low resistance and can cause strength loss, destruction and poroshkovaya because of the water, the particle size of the catalyst may be reduced during the reaction. Thus, problems may occur during the operation of the Department, as described above.

In addition, typically, for optimal particle size, as described above, the catalyst for a reactor with a layer of suspended sediment is crushed to the desired particle size, and then applied in practice. Such powdered catalyst is often as a result, the camping preliminary cracking and created short-term projections. Thus, deteriorate the mechanical strength or durability of the catalyst. Therefore, when used in reactions of synthesis f-T in the layer of suspended residue, the catalyst is destroyed and crushed. As a result, the separation of high-boiling hydrocarbons from the catalyst becomes very difficult. In addition, when using porous silica as the substrate of the catalyst for the reaction of synthesis f-T, it is well known that the result is a catalyst of relatively high activity. However, when the adjustment of the particle size by grinding, for the above reasons, often, the silicon dioxide has a low resistance and is prone to destruction and shredding of water, and reduced strength. So often a problem, especially in the reactor with a layer of suspended residue.

Additionally, in the reaction atmosphere in which water that occur as a by-product in the reaction of f-T, exists in large quantities (especially in the high atmosphere maturing), reduced activity of the catalyst and the decrease is due to the formation of cobalt silicates mainly on the interface loaded cobalt, which is an active metal, and the substrate based on silicon dioxide, or loaded cobalt is oxidized or sintered. This is a problem. Additionally, since this phenomenon also leads to an increase in the rate of contamination of the catalyst with time, i.e. the reduction of the service life of the catalyst, and this becomes a factor, which increases operating costs. In General terms, the resistance of the cobalt particles, possessing activity is low, especially in the atmosphere, in which the transformation is high, the partial pressure side of the water increases and, thereby, increases the rate of pollution. As a result, the above-described decrease in the activity of the catalyst becomes noticeable. However, even in the atmosphere at which the transformation is not more than 40-60%, a decrease of catalytic activity will be held at a relatively low speed in accordance with the partial pressure side of the water. Therefore, it is important to improve the water resistance even under conditions in which the transformation is relatively low, from the point of view of the service life of the catalyst. As for suppressing the formation of cobalt silicate and improvement activity, it is believed that the addition of zirconium is effective. However, to obtain the effect of zirconium requires a large amount of Zirconia, which is about half by weight of cobalt, or even if you add more zirconium, its effect is not satisfactory (according US6740621 B2).

The factors involved in the decrease of catalytic activity may include deposition of plastics technology : turning & the Yes on the surface of the cobalt or on the surface of the separation of cobalt on the substrate and the substrate based on silicon dioxide, in addition to the above. When coating the surface of the cobalt-carbon component of the surface area of the cobalt, which may come in contact with the material gas is reduced and the catalytic activity is reduced. In addition, the poisoning of sulfur compounds, nitrogen component, etc. in the material-gas or sintering, in which the cobalt metal aglomerated, during the reaction, is normal.

When the catalyst activity is reduced, falls below the level of activity due to the factors described above, it is necessary to replace or regenerate the catalyst to maintain the efficiency of the reaction. In the reactor with a layer of suspended sediment there is a function that allows you to change the catalyst with low activity without stopping the reaction. However, if it is possible to regenerate the catalyst activity is reduced, the replacement catalyst to maintain the efficiency of the reaction is not desired, or the number of replacement can be reduced. Thus reducing operating expenses.

Description of the invention

This invention, which aims to improve the activity of the catalyst for obtaining hydrocarbons from synthesis gas and the suppression of the decrease of activity due to sintering, deposition of carbon IDN side of the water, refers to the catalyst to obtain coal the hydrogen from the synthesis gas, which can stably be used even at high conversion WITH that side the water is produced in large quantities, and has a long service life, to a method for producing such a catalyst, the method of regeneration of this catalyst and method for producing hydrocarbons using such a catalyst.

This invention relates to a catalyst for f-T synthesis, resistant to water, high activity and long life, the way of obtaining such a catalyst and method for producing hydrocarbons using such a catalyst. More specifically, the invention described in detail below.

(1) a Catalyst for obtaining hydrocarbons from synthesis gas, which contains the metal cobalt or cobalt oxides and cobalt metal; and oxides of zirconium deposited on a substrate to catalyst consisting mainly of silicon dioxide, where the concentration of impurities in the catalyst is from 0.01% wt. up to 0.15 wt.%.

(2) the Catalyst for obtaining hydrocarbons from synthesis gas described in (1), where impurities in the catalyst include simple substances and compounds of sodium, potassium, calcium, magnesium and iron.

(3) a Catalyst for obtaining hydrocarbons from synthesis gas described in (1) or (2), where the concentration of impurities in the catalyst is from 0.01% wt. up to 0.03 wt.%.

(A) a catalyst for obtaining hydrocarbons from synthesis gas, described in any of (1)to(3), where the content of cobalt metal or cobalt oxides and cobalt metal is 5 to 50% wt. in terms of metallic cobalt, and the content of oxides of zirconium is from 0.03 to 0.6 in a molar ratio of Zr/Co.

(5) a Catalyst for obtaining hydrocarbons from synthesis gas described in any of (1)to(4), where the content of alkali metals or alkaline earth metals among the impurities contained in the substrate of the catalyst that is less than or equal to 0.1% wt.

(6) a Catalyst for obtaining hydrocarbons from synthesis gas described in any of (1)to(4), where the content of each of sodium, potassium, calcium and magnesium among the impurities contained in the substrate of the catalyst that is less than or equal to 0.02 wt.%.

(7) the Catalyst for obtaining hydrocarbons from synthesis gas described in any of (1)to(6), where the substrate of the catalyst is spherical.

(8) the Catalyst for obtaining hydrocarbons from synthesis gas described in any of (1)to(7) for obtaining hydrocarbons from synthesis gas, where the catalyst was prepared by simultaneous deposition of compounds cobalt and compounds of zirconium on a substrate of a catalyst mainly composed of silicon dioxide, by impregnation, impregnation by capacity, by precipitation or ion exchange method, and then the restoration processing or annealing and vosstanovitelnoi processing.

(9) the Method of producing the catalyst described in any of (1)to(7) for obtaining hydrocarbons from synthesis gas, where the catalyst was prepared separately by applying the compounds cobalt and compounds of zirconium on a substrate of a catalyst mainly composed of silicon dioxide, by impregnation, impregnation by capacity, by precipitation or ion exchange method, and, after application of the first catalyst, drying, or drying, firing, and, after the application of the remaining components, the recovery processing or annealing and recovery processing.

(10) the Method of producing a catalyst for obtaining hydrocarbons from synthesis gas described in (9), in which the separate application of the compounds, the first of the applied compounds are zirconium compounds and the remaining damage of compounds are compounds of cobalt.

(11) the Method of producing a catalyst for obtaining hydrocarbons from synthesis gas described in any of (8)-(10), where the damage zirconium compounds and compounds of cobalt, used as raw material in the method of impregnation, impregnation method on capacity, method, deposition method or ion exchange, contain alkali metals and alkaline earth metals in an amount of from 0 to 5% wt.

(12) the Method of producing a catalyst for obtaining hydrocarbons from synthesis gas described in the yubom from (8)-(11), where the substrate of the catalyst mainly consists of silicon dioxide and receive gelatinization Zola silicic acid obtained by mixing an aqueous solution of alkali silicate and an aqueous solution of the acid, the resulting product is subjected to any one treatment with an acid or a water rinse, and then drying.

(13) the Method of producing a catalyst for obtaining hydrocarbons from synthesis gas described in (12), where the water in which the content of alkali metals or alkaline earth metals is from 0 to 0.06 wt.%, used in at least one of the processing acid and water leaching after gelatinization Zola silicic acid.

(14) the Method of producing a catalyst for obtaining hydrocarbons from synthesis gas described in (12) or (13), where the gelatinization carried out by sputtering or Sol of silicic acid in the gaseous medium or a liquid medium forming Zola silica spherical shape.

(15) the Method of producing a catalyst for obtaining hydrocarbons from synthesis gas described in any of (8)-(14), where compounds of cobalt and zirconium compounds deposited on a substrate to catalyst, consisting mainly of silicon dioxide, after reducing the concentration of impurities by purification using at least any one of water, acid or alkali.

(16) the Method of producing a catalyst for receiving the Oia hydrocarbons from synthesis gas, described in (15), where for cleaning using acid and/or ion-exchange water.

(17) a Method of producing hydrocarbons from synthesis gas using the catalyst described in any of (1)to(7), where the synthesis is performed by conducting the reaction in the liquid phase using a reactor with a layer of suspended sediment.

(18) a Method of producing hydrocarbons from synthesis gas using the catalyst described in any of (1)to(7), where the synthesis is performed by conducting the reaction in the liquid phase using a reactor with a layer of suspended sediment with external circulation system.

(19) a Method of producing hydrocarbons from synthesis gas described in (17) or (18), where the reaction in the liquid phase, the amount of catalyst, the amount of supply of the material gas, the reaction temperature and pressure reactions govern in such a way that the transformation in a single pass is from 40 to 95%.

(20) a Method of producing hydrocarbons from synthesis gas described in (17) or (18), where the reaction in the liquid phase, the amount of catalyst, the amount of supply of the material gas, the reaction temperature and pressure reactions govern in such a way that the transformation in a single pass is from 60 to 95%.

(21) a Method for regenerating catalyst activity is reduced after the process of obtaining hydrocarbons from synthesis gas using a catalyst, opisanog is in any of (1)to(7), where the catalyst with reduced activity of the regenerating process gas containing hydrogen and, thus, the catalyst and regenerating gas in contact with each other.

(22) a Method for regenerating catalyst activity is reduced after the process of obtaining hydrocarbons from synthesis gas in the reactor, which is filled with catalyst described in any of (1)to(7), where the reactor serves regenerating gas containing hydrogen, and thereby, the catalyst and regenerating gas in contact with each other.

(23) a Method for regenerating catalyst activity is reduced in the process of producing hydrocarbons from synthesis gas by the method described in (18), where in any part of the system external circulation serves regenerating gas containing hydrogen, and thereby, the catalyst and regenerating gas in contact with each other.

In accordance with this invention it is possible to obtain a highly active catalyst for f-T synthesis, with high resistance to water, a low degree of loss of strength and activity of the catalyst, very high stability and a long period of use, which is used as a catalyst having a substrate based on silicon dioxide and containing particles of cobalt, which is active even under conditions of high conversion of CO, which is formed of side water in the big if is the EU ETS, and presents a method of obtaining such a catalyst. In addition, it is possible to conduct regeneration even when reducing the activity and carry out reaction for the synthesis f-T high yield of hydrocarbon using a catalyst.

BRIEF DESCRIPTION of DRAWINGS

In FIG. 1 shows the ratio of sodium in the substrate on the basis dioxide flint and maturing in the reaction of synthesis f-T catalyst, in which the oxides of zirconium and cobalt deposited on a substrate of silicon dioxide and the catalyst in which cobalt deposited on a substrate of silicon dioxide.

Figure 2 shows the ratio of the content of alkali metals or alkaline earth metals in the substrate on the basis dioxide flint and maturing in the reaction of synthesis f-T catalyst in which cobalt deposited on a substrate of silicon dioxide.

The BEST WAY of carrying out the INVENTION

Hereinafter the invention is described in more detail.

The authors of this invention have found that when comparing catalyst with minor impurities, in which the cobalt metal or cobalt oxides and cobalt metal; and oxides of zirconium deposited on a substrate, consisting mainly of silicon dioxide, with a catalyst with minor impurities, in which the cobalt metal or cobalt oxides and metal is the second cobalt deposited on a substrate of the catalyst, and oxides of zirconium is not applied on the substrate of the catalyst, the resistance to water is significantly improved, especially in conditions of high maturing; the service life of the catalyst also increases under conditions of relatively low maturing; also improves the activity; and the regeneration of the catalyst becomes easy. And they developed this invention. In addition, it is possible to receive and to produce a catalyst having high wear resistance and high strength without reducing activity, when using a spherical substrate of the catalyst having certain physical properties. In addition, the term "impurities in the catalyst in this invention also includes an impurity in the substrate of the catalyst, composed primarily of silicon dioxide.

The catalyst in accordance with this invention is a catalyst based on cobalt, active in the reaction of synthesis of f-T and the substrate which is chosen such that mainly consists of silicon dioxide. The term "substrate catalyst mainly composed of silicon dioxide, includes the substrate of the catalyst containing a minor amount of unavoidable impurities arising in the process of obtaining a substrate of silicon dioxide is other than silicon dioxide, or one that contains alumina and/or zeolite in the substrate, e.g. the R, if you enter an acid center. (Hereinafter, the substrate of the catalyst, mainly consisting of silicon dioxide, called simply "substrate of silicon dioxide".) In addition, the term "inevitable impurities" includes impurities (metals and metal compounds containing metal, which affects the efficiency of the catalyst, and such impurities are contained in the cleaning water used in the process of obtaining a substrate of silicon dioxide, impurities contained in the source material, and additives that are added from the apparatus for the production of catalyst. When using the apparatus, the source of raw materials and purifying water used for obtaining the primary catalyst for the reaction of synthesis f-T, metal elements impurities include sodium, potassium, calcium, magnesium, iron and aluminum. However, the aluminum, which is an impurity element, not an inevitable impurity, which affects the efficiency of the catalyst in accordance with this invention, since a large part of aluminum oxide contained in the source of silicon dioxide to the substrate of the silicon dioxide exists in the form of aluminum oxide or zeolite in a substrate of silicon dioxide. Therefore, impurities in the catalyst in accordance with this invention include sodium, potassium, calcium, magnesium and iron, while using the device, raw materials and ochimusha the water, used to obtain the primary catalyst for the reaction of synthesis of f-I. in Addition, sodium and potassium are added mainly from sodium silicate, is used as the raw material for a substrate of silicon dioxide, calcium and magnesium are added mainly of purifying water, and iron mixed with mainly of silicon dioxide, which is the raw material, purifying water or industrial apparatus. In addition, you should also consider other impurities, depending on the equipment or working conditions in the production of the catalyst, which may appear impurities.

It is sufficient if the coating method is a conventional method of impregnation, impregnation method on capacity, deposition method or the method of ion exchange or the like. For compounds of zirconium or compounds of cobalt, which are the raw material (precursor), is used for applying compounds, there are no restrictions, provided that their counterions ((CH3COO)-Co(CH3COO)2for example, in the case of acetate) evaporate or decompose during the reduction processing or roasting and recovery processing, which is carried out after application, and they dissolve in the solvent. Although there may be acetates, nitrates, carbonates, chlorides, etc., it is preferable to use a water-soluble compound suitable for when is teniu in aqueous solution when applied, to reduce production costs or providing a safe environment for production. Specifically, as the zirconium acetates, nitrates of zirconium, oxides of zirconium nitrate or cobalt acetates, nitrates of cobalt, etc. easily changed to oxides of zirconium or cobalt oxides during annealing and further restorative treatment of the oxides of cobalt is also simple, they are considered to be preferred.

Rather, if an appropriate number of deposited cobalt is greater than or equal to the lowest number, with activity, and less than or equal to the number of deposited cobalt, in which the degree of dispersion of cobalt on the substrate is significantly reduced, and as a result increases the proportion of cobalt, which may not contribute to the reaction. More specifically, the amount of deposited cobalt is from 5 to 50% wt. and, preferably, from 10 to 40% wt. If the amount of deposited cobalt below this interval, the activity may not be satisfactory, and if the amount of deposited cobalt exceeds this interval, the degree of dispersion is reduced, and this reduces the efficiency of cobalt on the substrate, and it becomes uneconomical, which is undesirable. The term "amount of deposited cobalt" refers to the ratio of the mass of cobalt metal to total weight of catalyst based on the assumption that Koba is before the substrate was recovered 100%, as the cobalt on the substrate is not limited to the final regeneration to 100%.

Rather, if an appropriate number of deposited Zirconia added with cobalt, greater than or equal to the smallest number necessary to improve stability, extend service life, improve activity and facilitate regeneration, and less than or equal to the number of deposited zirconium, in which the degree of dispersion of zirconium on the substrate is significantly reduced and, as a result, an increasing proportion of zirconium, which may not facilitate the desired effect, and adding zirconium becomes significant and uneconomical. More specifically, the molar ratio of cobalt to zirconium is Zr/Co=0.03 to 0.6 and preferably from 0.05 to 0.3. If the number of deposited zirconium below this interval, the effect of improving the stability, the effect of increasing the service life, the effect of improving the activity and the effect of promoting regeneration may not be satisfactory, and if the number of deposited zirconium exceeds this interval, the effectiveness of zirconium on the substrate is reduced, and it becomes uneconomical, which is undesirable.

To demonstrate the above procedure, it was determined that the preferred structure of the catalyst is one in which the oxides of zirconium are located on the substrate and the silicon dioxide, and particles of cobalt, demonstrating the activity, are the oxides of zirconium. Possessing activity of cobalt particles may be particles of cobalt, all of which are metallized restorative treatment, or particles of cobalt, most of which are metallized, but the part which remains in the form of cobalt oxide. It is believed that the improvement in water resistance occurs when the suppression of oxidation with the activity of the cobalt particles, due to the fact that is simply to support restoring the atmosphere in the reaction field, which has a side water, due to the ability of zirconium oxides to absorb oxygen, in addition to the suppression of the formation of cobalt silicates, which increases side water by reducing the surface contact of particles of cobalt, with activity, and a substrate of silicon dioxide, as the oxides of zirconium exist in a substrate of silicon dioxide. In addition, it is believed that the interaction between oxides of zirconium and cobalt particles having activity greater than the interaction between a substrate of silicon dioxide and particles of cobalt with activity. So, I think that is difficult for the sintering of particles of cobalt, with activity in the catalyst, in which compounds of cobalt and zirconium compounds nanesenia substrate, hence improves resistance to water, even in an atmosphere where water side, which has a tendency to sintering. In addition, since the oxides of zirconium easily keep restoring the atmosphere, as described above, the deposition of carbon on the particles of cobalt, with activity also decreases. I think that the effect of increasing the service life due to the fact that the structure of the catalyst has activity may persist for longer periods of time due to the aforementioned improvement in water resistance, suppression of sintering and to suppress deposition of carbon.

Additionally, assume that, since the interaction between oxides of zirconium and compounds of cobalt is greater than the interaction between a substrate of silicon dioxide and compounds of cobalt, improves the activity effect is based on the fact that when the catalyst in which compounds of cobalt and zirconium compounds deposited on a substrate, compared with the catalyst, in which connection without cobalt compounds of zirconium deposited on a substrate, the degree of dispersion of cobalt above and the active surface area more. In addition, I believe that promoting regeneration effect of adding zirconium based on the fact that the oxides of zirconium easily keep restoring the th atmosphere, as explained above.

Although the application of the compounds cobalt and compounds of zirconium on a substrate of a catalyst mainly composed of silicon dioxide can be carried out by the above methods of application, application may be performed separately or simultaneously.

If the application is conducted separately, get the solution of compounds of cobalt and the solution of zirconium compounds, and then the substrate of the catalyst, consisting mainly of silicon dioxide, are first applied one solution and, after drying, or drying, roasting, on the substrate of the catalyst is then applied another solution. After applying, if necessary, conduct drying and subsequent reduction or spend the firing and subsequent recovery. When carrying out such treatments all particles of cobalt metallizers, or part of the compounds of cobalt is oxidized, while the remaining compounds of cobalt metallservisa and oxidized zirconium compounds.

In addition, as a result of intensive studies applying compounds cobalt and compounds of zirconium on a substrate of silicon dioxide in cases where the application is carried out separately, it becomes apparent that it is preferable in obtaining a catalyst to cause the zirconium compounds and compounds of cobalt sequentially and in the order specified, and Vice versa, in the catalyst, in which first UNOSAT compounds of cobalt, and then zirconium compounds, reduces the effect of improving the activity, the effect of increasing the lifetime and the effect of improving the resistance to water compared with the first catalyst. As stated above, I believe that this is caused by the improvement of the activity of zirconium oxides due to the strong dispersion of cobalt and function of suppressing the formation of cobalt silicates in the presence of water on the side surface of contact between particles of cobalt, with activity, and a substrate of silicon dioxide, and believe that high efficiency is achieved due to the presence of oxides of zirconium between particles of cobalt, with activity, and a substrate made of silicon dioxide.

On the other hand, if the deposition is conducted at the same time, compounds of cobalt and zirconium compounds simultaneously applied in a single operation in the form of prepared mixed solution of compounds cobalt and compounds of zirconium. After coating are dried, if necessary, and then reductive treatment or calcination and restorative treatment. When carrying out such processing all connections cobalt metallizers, or part of the compounds of cobalt metallservisa, while the remaining compounds of cobalt is oxidized, and then oxidized zirconium compounds.

However, when conducting simultaneous application becomes caviano, the resistance to water can be reduced as compared with the catalyst, in which the zirconium compounds are absent. I believe that this is because the catalyst with the simultaneous application of particles of cobalt, with activity, and the oxides of zirconium accept such an unstable form that the surface of the particles of cobalt, with activity decreasing due to contact with a side of water.

The additional amount of zirconium required to obtain a satisfactory action is greatly increased if the catalyst contains many impurities and is therefore inefficient and insufficient to achieve a satisfactory action of zirconium. However, for catalysts in accordance with this invention proved satisfactory and improved action receive only adding small amounts of zirconium, as described above. Especially the above-described effect is noticeable when applied, the substrate of the catalyst with a small amount of impurities, presumably, this is due to the fact that can be easily obtained homogeneous composite connection substrate of silicon dioxide and zirconium, as the content of impurities is negligible, and the surface properties of a substrate of silicon dioxide can be effectively changed neznacit is determined as being the amount of Zirconia.

In addition, the catalyst in which zirconium compounds and compounds of cobalt deposited sequentially improved activity compared to catalyst, in which the applied compounds of cobalt and no zirconium compounds. When the authors of the present invention studied the changes in the degree of dispersion of cobalt adding zirconium, it became obvious that the degree of dispersion of the cobalt tends to increase with increasing number of deposited zirconium. I believe that improving the activity of adding zirconium is due to the fact that the degree of dispersion of cobalt increases, as described above, and the formation of cobalt silicates suppressed. In addition, if you use a substrate made of silicon dioxide with a small amount of impurities, the above effect is enhanced further. Also believe that this increase is due to the fact that the properties of the substrate surface of the silicon dioxide can be homogeneous modified by adding small amounts of zirconium at a low content of impurities.

Below is the method of obtaining the above-described catalyst. First, an aqueous solution of a precursor comprising compounds of zirconium, impregnate the substrate of the catalyst containing a small amount of impurities consisting mainly of the C of silicon dioxide, then applied an aqueous solution of a precursor containing compounds of cobalt, and then dried, calcined and restore, if necessary, to obtain the catalyst for f-T synthesis. After application of the compounds of zirconium can be consistently carried drying (for example, at 100°C for one hour in air) and firing (for example, at 450°C for five hours), or may be performed only drying; and then at the next stage, carry out the impregnation and coating of cobalt. To protect the effectiveness of the addition of zirconium from decreasing due to the fact that zirconium compounds are mixed with compounds of cobalt during the impregnation and coating of cobalt, zirconium compounds can be converted into oxides of zirconium firing. The catalyst for f-T synthesis is produced by drying, if necessary, carried out after impregnation and coating compounds of cobalt, followed by reduction of compounds of cobalt on the surface of the substrate of the catalyst to cobalt metal (for example, at 450°C for 15 hours in a stream of hydrogen at normal pressure). However, recovery may be performed after conversion into the oxide in the kiln, or recovery can be carried out immediately, without firing. In addition, this recovery is still some compounds of cobalt, as they are not recoverable. About the however, to obtain excellent activity, preferably, to compounds of cobalt, which is restored to cobalt metal, accounted for the majority of in comparison with compounds of cobalt, which is not restored. This can be confirmed by the method of chemical adsorption. You need to immediately process the catalyst after recovery so as to protect the catalyst from contact with the atmosphere and oxidation and deactivation. However, stabilization, which protects the surface of the cobalt metal substrate catalyst from atmospheric effects, the treatment of the catalyst at atmospheric conditions becomes possible. As such stabilizing processing method used so-called passivation (passivating) treatment of the catalyst with nitrogen, carbon dioxide and inert gas, which contains a low concentration of oxygen, thereby oxidizing only the top layer of cobalt metal substrate catalyst, or a method of immersing in the reaction solvent, a molten paraffin CFT, etc. when carrying out the reaction of synthesis f-T in the liquid phase, thereby preventing the catalyst from the weather. Suitable stabilizing processing may be carried out according to the situation.

In addition, to improve activity, durability and water resistance, it is effective to reduce impurities in the catalyst is, non-active metals and the constituent elements of the substrate of the catalyst to control them to some extent. In the case when the silicon dioxide in accordance with this invention is used as the substrate of the catalyst, as described above, alkali metals such as Na and K, alkaline earth metals such as Ca and Mg, and Fe are often contained as impurities in a substrate of silicon dioxide. When the authors of this invention have studied in detail the effect of such impurities with the use of cobalt as the active metal, it was found that the activity of the fusion reaction f-T is significantly reduced if the alkaline metal or alkaline earth metal is present in large quantities. Particularly strong is the impact of the presence of sodium.

Although sodium, potassium, calcium, magnesium and iron, which are impurities in accordance with this invention, there are mainly in the form of compounds, especially in the form of oxides, they can exist in small quantities in the form of simple metals or non-oxide forms. To obtain the excellent activity of the catalyst service life and high resistance to water of the catalyst in accordance with this invention, it is necessary to reduce the total amount of impurities in the catalyst to 0.15 wt.%. or less in terms of metal. If the total amount exceeds this value, the activity is strongly reduced. Therefore, the disadvantages become significant. In particular, the total number of, preferably, less than or equal to 0.03 wt.%. in terms of metal. However, if the amount of impurities is reduced excessively, improving the cleanliness costs and becomes uneconomical. Therefore, the amount of impurities in the catalyst is preferably greater than or equal to 0.01% wt. in terms of metal. As the number of impurities also depends on the amount of damage or predecessor, it is difficult to limit the amount of impurities in the precursor. However, to reduce the amount of impurities in the catalyst effectively reduce the amount of impurities in the precursor compounds of cobalt and oxides of zirconium, as described above, but also effectively reduce the amount of each element of the alkali metal or alkaline earth metal up to 5% wt. or less in terms of metal.

Elements that have the worst effect on the catalyst activity, among impurities in the catalyst include alkali metals and alkaline earth metals. These metals are of purifying water or the source material, which is mainly used at the stage of obtaining a substrate of silicon dioxide, and therefore, sodium, potassium, magnesium and calcium often cause problems. In Fig. 1 shows the results obtained in the study of Taimazov the dependence between the concentration of sodium in the substrate of silicon dioxide and the transformation in the synthesis reaction of the f-T, in the form factor of catalytic activity, for the case in which the catalyst contains oxides of zirconium in accordance with this invention, and for the variant in which the catalyst does not contain zirconium, as a comparative example. The catalyst contains oxides of zirconium, is a catalyst in which zirconium compounds applied on a substrate of silicon dioxide is first and compounds cobalt and put cooked after. As evident from this figure, for a catalyst containing the oxides of zirconium, the decrease in conversion WITH a lower concentration of sodium is relatively small, but the trend of changes caused by the sodium concentration was not affected by the presence/absence of zirconium oxides. Additionally, in Fig. 2 shows the results obtained in the study of interdependence between the concentration of each of sodium and potassium, which are the alkali metals, calcium and magnesium, which are alkaline earth metals, in a substrate of silicon dioxide and the transformation in the synthesis reaction of the f-T, as the ratio of catalytic activity for the variant in which the catalyst contains oxides of zirconium (for catalyst in which cobalt is applied on a substrate of silicon dioxide). Within the interval in which the content of this metal is found in the substrate of the catalyst is below 0.01 wt.%. in terms of the metal, the influence of alkali metals and alkaline earth metals is barely noticeable. However, if the content exceeds 0.1% by weight. in terms of metal, it is possible to say that the activity gradually decreases. It Is Evident From Fig. 1 shows that the tendency to change transformation WITH change of concentration of alkali metals and alkaline earth metals also does not depend on the presence/absence of zirconium oxides. Therefore, even in the catalyst in accordance with this invention the metal content is also determined to some extent. Therefore, the content of each of the alkali metals and alkaline earth metals in the substrate of the catalyst is preferably less than or equal to 0.1% wt. in terms of metal, more preferably, less than or equal to 0.07 wt.%. in terms of metal, even more preferably less than or equal to 0.04% by weight. in terms of metal, and particularly preferably less than or equal to 0.02 wt.%. in terms of metal. Therefore, under normal manufacturing a substrate of silicon dioxide, the content of each of sodium, potassium, magnesium and calcium, preferably less than or equal to 0.1% wt. in terms of metal, more preferably, less than or equal to 0.07 wt.%. in terms of metal, even more preferably less than or equal to 0.04% by weight. in terms of metal, and particularly preferably less than or equal to 0.02 wt.%. the conversion to the metal.

As described above, if the total amount of impurities in the catalyst exceeds 0.15 wt.%. in terms of the metal, the catalyst activity is greatly reduced in the same way as above, it is extremely uneconomical decrease in the content of each of the alkali metals and alkaline earth metals in the catalyst substrate. If the content of alkali metals and alkaline earth metals in the substrate of the catalyst is reduced to about 0.01% wt. in terms of the metal, as described above, it is possible to obtain a satisfactory effect. Therefore, from a cost perspective it is preferable that the content of each element of alkali metals and alkaline earth metals in the catalyst substrate was greater than or equal to 0.01% wt. in terms of metal.

In addition, the method of flameless atomic absorption analysis of the substrate-catalyst and catalyst dissolved with the use of hydrochloric acid can be used as a method of measuring the concentration of impurities. In addition, impurities contained in the substrate of silicon dioxide, and other impurities can be separated from each other by analyzing impurities only in the substrate of the catalyst and a separate analysis of the impurities in the entire catalyst. For example, as aluminum, it is possible to separate the aluminum, which exists in the form of aluminum oxide or C is the Olite in a substrate of silicon dioxide, and aluminum contained in the portions other than the substrate of silicon dioxide. In addition, when measuring impurities in a substrate of silicon dioxide, impurities can also be analyzed using the ICP emission spectral analysis instead of flameless atomic absorption analysis.

If you use a substrate of the catalyst, which can be preserved from contamination by impurities in the production process, it is preferable to take measures so that impurities are not mixed during retrieval. Usually the method of obtaining silicon dioxide is conventionally classified into a dry method and wet method. The dry method includes a method of burning arc method, etc. Wet method involves deposition method, gel method, etc. Although it is possible to obtain the substrate of the catalyst by any method of obtaining, technically or economically difficult to mold the substrate of the catalyst in a spherical shape above methods, excluding gel method. Therefore, the preferred gel method, in which you can spray colloidal solution of silicic acid in a gaseous medium or a liquid medium for simple molding it into a spherical shape.

For example, if a substrate made of silicon dioxide receive the above gel method, usually used a lot of cleansing water. In this case, if you use water containing large amounts of impurities, such the AK technical water, many of the impurities remains in the substrate of the catalyst, and the catalyst activity is greatly reduced, which is undesirable. However, it becomes possible to obtain excellent substrate of silicon dioxide with a low content of impurities in the application of cleansing water with low content of impurities or purifying water which does not contain impurities, such as ion-exchange water. In this case, the content of each element of alkali metals or alkaline earth metals in purifying water, preferably less than or equal to 0.06 wt.%. in terms of metal. If the content is higher, the content of impurities in a substrate of silicon dioxide increases, and the catalyst activity after deposition is significantly reduced. This is undesirable. Ideally, it is preferable application of ion-exchange resin. To obtain ion-exchange water, it can be obtained by the use of ion-exchange resin, etc. However, it is also possible to obtain the ion-exchange water by carrying out ion exchange using silica gel formed as postandartnee products on the production line for silicon dioxide. Theoretically, the trapping of impurities in purifying water using silica carry out ion exchange between hydrogen silanol on the surface of silicon dioxide and ions of impurities such as ions, alkaline what's metal and alkaline earth metal ions. Therefore, even in purifying water that contains small amounts of impurities, it is possible to some extent to prevent the trapping of impurities bringing the pH of the cleansing water to low values. Additionally, since the number of ion exchange (impurities) is proportional to the number of used cleaning water, it becomes possible to reduce the amount of impurities in a substrate of silicon dioxide by reducing the amount of cleansing water, in other words, improving the efficiency of use of water at all stages of the washing water.

If an impurity in a substrate of silicon dioxide can be reduced by conducting pre-processing such as cleaning water, cleaning with acid, alkali cleaning, etc. without significant change in the physical or chemical properties of the substrate of the catalyst, such pre-treatment is very effective to improve the activity of the catalyst.

For example, when cleaning a substrate of silicon dioxide is particularly effective to clean a substrate of silicon dioxide is acidic aqueous solutions, such as nitric acid, hydrochloric acid and acetic acid, or clean a substrate of silicon dioxide ion-exchange water. After cleaning these acids effectively to further clean the substrate of silicon dioxide clean water, so the th as ion exchange water, if some amount of acid remaining in the substrate of the catalyst becomes a hindrance.

In addition, in the production of silicon dioxide, is also the firing order to improve the strength of the particles, improving the activity of surface silanol groups, etc. However, if the firing is carried out in the condition in which the amount of impurities is relatively high, it is difficult to decrease the content of impurities cleaning a substrate of silicon dioxide as an impurity elements included in the skeletal structure of silicon dioxide. Therefore, to reduce the concentration of impurities cleaning a substrate of silicon dioxide, it is preferable to apply the unfired silica gel.

When applying the catalyst and the substrate of the catalyst, as described above, it is possible to obtain a catalyst with significantly increased activity, service life and high resistance to water in the reaction of synthesis of f-T.

To maintain a high degree of dispersion of the metal and improve efficiency, which promote reactions deposited on a substrate of the active metal, it is preferable to use a substrate of the catalyst with high specific surface area. However, to increase the specific surface area is necessary to reduce the diameter of pores and increase the pore volume. However, if these two factors increase the durability or strength decrease is are stated, what is undesirable. From the point of view of the physical properties of the substrate of the catalyst is greatly preferred substrate of the catalyst, which has a pore diameter of from 8 to 50 nm, the specific surface area of from 80 to 550 m2/g and a pore volume of 0.5 to 2.0 ml/g at the same time. More preferred is a substrate of the catalyst having a pore diameter of from 8 to 30 nm, specific surface area of from 150 to 450 m2/g and a pore volume of 0.6 to 1.5 ml/g at the same time, and even more preferred is a substrate of the catalyst having a pore diameter of from 8 to 20 nm, the specific surface area of from 200 to 400 m2/g and a pore volume of 0.7 to 1.2 ml/g at the same time. The above specific surface area can be measured using the BET method and the pore volume can be measured by the method of introducing mercury or titration method in water. In addition, although the diameter of pores can be measured by the method of getpagesize, a method of introducing mercury or mercury porosimetry etc., it can be calculated from the specific surface area and pore volume.

To obtain a catalyst which has a satisfactory activity for the reaction of synthesis f-T requires a specific surface area greater than or equal to 80 m2/, If the specific surface area is lower, the degree of dispersion of the material on the substrate is reduced, and the efficiency of active participation the x metals in the reaction is reduced, what is undesirable. In addition, if the specific surface area greater than 550 m2/g, it becomes impossible to pore volume and pore diameter of simultaneously meet the above limits, which may be undesirable.

When reducing the diameter of the pores becomes possible to increase the specific surface area. If the pore diameter of less than 8 nm, the diffusion rate of the gas in the pores is different for hydrogen and carbon monoxide. Therefore, the partial pressure of hydrogen is high inside the pores, and light hydrocarbon such as methane, which can be a side product of the reaction of synthesis f-T, accumulates in large quantities. This is undesirable. In addition, because the diffusion rate of the accumulated hydrocarbons in the pores are also reduced, resulting in increases in the observed reaction rate, which is undesirable. In addition, when compared with fixed pore volume, specific surface area decreases with increasing diameter of the pores. Therefore, if the pore diameter exceeds 50 nm, it becomes difficult to increase the specific surface area, and decreases the degree of dispersion of the active metals, which may be undesirable.

The pore volume is preferably from 0.5 to 2.0 ml/year If the pore volume less than 0.5 ml/g, it becomes impossible to match the pore size and specific surface area indicated above in which arvalem, what is undesirable. If the pore volume has a value greater than 2.0 mg/g, significantly reduced strength, which is undesirable.

As described above, the catalyst synthesis f-T reaction in the reactor with a layer of suspended sediment requires stability, wear resistance and toughness. In addition, because a large amount of water formed as a by-product in the reaction of synthesis f-T, when applying the catalyst or catalyst substrate are destroyed and pulverized in the presence of water, there are the above-described inconveniences, which require careful attention. Therefore, it is preferable to use a spherical substrate of the catalyst instead of the crushed catalyst substrate, which has a high probability of premature cracking and sharp corners which are susceptible to damage and delamination. Upon receipt of a spherical substrate of the catalyst can be used a method of dispersion, such as a common method of drying by atomization. Especially sputtering method is suitable for obtaining a spherical substrate of silicon dioxide with a particle size of from about 20 to 250 microns and allows to obtain a spherical substrate of silicon dioxide having excellent wear resistance, toughness and resistance to water.

A method of producing a substrate of silicon dioxide is illustrated below. The Sol of silicic acid, the floor is built in terms in which an aqueous solution of alkali metal silicate and an aqueous solution of acid is mixed at pH from 2 to 10.5, gelatinizing by sputtering in a gas medium, such as air, or in an organic solvent, in which the Sol is not soluble, and then subjected to acid treatment, washed with water and dried. An aqueous solution of sodium silicate, is suitable as the alkali metal silicate has a molar ratio of Na2O:SiO2preferably from 1:1 to 1:5, and the concentration of silicon dioxide is preferably from 5 to 30% wt. The acid can be applied nitric acid, hydrochloric acid, sulfuric acid, organic acid, etc. where sulfuric acid is preferred from the point of view of the fact that the production does not result in corrosion of the container and remains of organic matter. The concentration of the acid is preferably from 1 to 10 mol/l If the concentration is lower, the development of gelatinization is much slower. If the concentration is higher, the rate of gelatinization becomes too large and its control is difficult. In result, it becomes difficult to obtain desired properties, which is undesirable. In addition, the method of spraying or Sol of silicic acid in an organic solvent as the organic solvent can be used kerosene, paraffin, to ilol, toluene, etc.

If you apply the above-described composition or method of production, it becomes possible to obtain a catalyst for the synthesis of f-T, which has a high activity without loss of strength or durability.

In addition, with the use of catalyst for the synthesis of f-T in accordance with this invention, it becomes possible to conduct the reaction for the synthesis f-T with high efficiency at low cost and to obtain a suitable product. That is, the reaction of synthesis f-T carry out the reaction in the liquid phase with the use of a reactor with a layer of suspended sediment with the use of the catalyst obtained in accordance with this invention, high selectivity to liquid products, the carbon number of which is greater than or equal to five, which represent the majority of products, as well as a very high rate of production of liquid products per unit mass of catalyst (performance hydrocarbon). Moreover, since the crushing of the catalyst during use, and reduction in activity caused adverse water is negligible, the invention has the advantage that in the long life of the catalyst. Given these characteristics, it becomes possible to carry out reaction for the synthesis f-T at low cost and with high efficiency.

If you use the catalyst in the accordance with this invention, the decrease in activity caused by-water, etc. is negligible. So excellent reaction synthesis f-T can be carried out even in conditions in which a single-stage transformation, in which the partial pressure side of the water becomes very high, ranging from 60 to 95%. The term "single-stage transformation" includes the transformation in a single pass of the material gas through the reactor, which differs from the variant in which the gas containing unreacted material-gas, discharged from the reactor and re-fed into the reactor. Even if single-stage transformation is relatively low, ranging from 40 to 60%, the decrease in activity caused adverse water remains very low. Therefore, the service life of the catalyst is increased, thereby reducing the cost of the catalyst. If single-stage transformation is reduced to 40% or less, the cost of the device for recirculation of residual gas increases. So usually this operation is carried out at 40% or more.

In addition, if the decrease in activity is due to too high of transformation or too long reaction time, the catalyst may be regenerated gas containing hydrogen instead of synthesis gas. As a method of regeneration of the catalyst used method of regeneration within the reactor, wherein the reactor is udaetsya regenerating gas instead of the synthesis gas, thereby providing contact regenerating gas and catalyst with each other, or a method of regeneration outside of the reactor, which removes the catalyst or the suspension containing the catalyst, and then fill in a separate container, called the regeneration column, the catalyst or suspension, then served regeneration gas. In addition, when using an external circulation system, in which the reactor for the synthesis of f-T works so that the suspension containing the catalyst circulates outside the reaction container, can be used a method of regeneration in situ, in which the regeneration gas and the suspension containing the catalyst in contact with each other in any part of the external circulation system, while the reaction proceeds. However, even in such an operating system can be used method of regeneration within the reactor and method of regeneration outside of the reactor. Although the method of regeneration within the reactor has the advantage that there is no need for regeneration column or device regeneration in situ, its disadvantage is that the production is completely stopped during the operation of regeneration. Therefore, you must choose a method of regeneration taking into account the cost of the regeneration column or device regeneration in-situ and time required for regeneration (time stop production), etc. In addition, if the method of regeneration in situ, there is an advantage that the regeneration of the catalyst can be carried out without interrupting production. But the method of regeneration in situ has the disadvantage that the contact time of the regeneration gas and catalyst can be prolonged, or the degree of freedom in the conditions of regeneration is slightly reduced, since it is preferable that the pressure, temperature and other parameters of regeneration were the same as the reaction conditions of the synthesis f-T, as indicated below. However, this method of regeneration in situ is preferred in the case of the reaction process with the use of an external circulation system that uses the catalyst lifetime can be increased in conditions of regeneration that can be implemented in this process.

The hydrogen content in the regeneration gas is preferably greater than or equal to 5% and can be 100%. Otherwise, the regeneration gas may contain an inert gas, such as nitrogen or argon. Conditions of regeneration is not particularly limited, as long as they are conditions in which regeneration of the catalyst. As a mechanism of regeneration of the catalyst offered contact a regeneration gas containing hydrogen, and a catalyst, the repeated recovery of cobalt, oxidized side water, and UD is of deposited carbon with hydrogen.

In the method of regeneration within the reactor in the reactor with a layer of suspended sediment, in which the catalyst is dispersed in a liquid hydrocarbon solvent, it is preferable to apply the regeneration conditions (temperature, pressure, time, speed, gas flow etc) such that the solvent is not lost due to the transformation of liquid hydrocarbon components in the gas hydrocracking or by evaporation of liquid hydrocarbon, from the point of view of re-operation after regeneration. However, when the regeneration is carried out in such conditions, when the volume of solvent is reduced, the regeneration can be carried out using a solvent which has a high boiling point and has no adverse effect on the reaction of synthesis f-T, such as poly alpha olefin. If the regeneration is carried out by means of the regeneration inside the reactor, preferably, the regeneration temperature is from 100 to 400°C., pressure of regeneration is from normal pressure to the reaction pressure, the regeneration time is from 5 minutes to 50 hours and the flow rate of the gas for regeneration is such that the flow rate of hydrogen in the regeneration gas was almost the same as the flow rate of hydrogen in the synthesis gas by the reaction. In the method of regeneration within the reactor, if the pressure of regeneration is lower reaction Yes the population, it is possible to apply a compressor to increase the reaction pressure in the reaction, and there is no need to re-establish the compressor for regeneration. It is preferable from the viewpoint of the cost of the device.

In the way of regeneration in situ, in which the catalyst in the regeneration gas and the suspension in contact with each other in any external part of the circulation system when the continuation of the reaction, if the temperature and pressure of the regeneration differs from the reaction conditions of the synthesis f-T, you need a device for changing the temperature or pressure. Therefore, the cost of the device increases. Therefore, it is preferable to apply such conditions regeneration, so that the pressure and temperature were the same as the reaction conditions of the synthesis of f-So the Regeneration gas may be introduced into any part of the external circulation system to perform the regeneration. Container for regeneration can be installed so that the container was on the outside line circulation and regeneration gas was supplied from the bottom of the container. However, when installing a container such as a tank for separation of the catalyst, on an outside line circulation it is possible to enter a regeneration gas in the container to conduct regeneration.

In the way of regeneration outside the reactor, in which the regeneration column is filled extracted the first catalyst and then it serves the regeneration gas, it is possible to choose a reactor with a fluidized bed reactor with a fixed layer, in addition to the reactor with a layer of particulate residue. However, as there is no need to consider the hydrocracking of the solvent in the reaction gas and solids in the reactor with a fluidized bed, a reactor with a fixed layer, etc., regeneration temperature may be determined taking into account the speed of regeneration and sintering of cobalt. In addition, the pressure of the regeneration can be selected independently of the pressure of the reactor, but taking into account the capacity of the compressor regeneration device. However, as the cost of the compressor increases with increasing opportunities to increase pressure, you must take into account and to determine the dependence of the pressure on the time of regeneration.

When applying the catalyst with a small amount of impurities in accordance with this invention it is possible to carry out the regeneration of the above method, even without the addition of zirconium. However, regeneration becomes easier with the addition of zirconium. In the same conditions for regeneration of the catalyst, which is added to the zirconium, the regeneration effect may be more noticeable, and the regeneration conditions can be set more gently. That is, it becomes possible to set a lower temperature regeneration, and it is possible to avoid relative to you is okeh temperature, where is the hydrocracking of the solvent in the restoration of the layer of suspended residue, for example, during regeneration in situ.

In addition, as the synthesis gas used for the reaction of synthesis f-T in accordance with this invention, the gas in which the amount of hydrogen and carbon monoxide is greater than or equal to 50% vol. in relation to the total volume, is preferred from the standpoint of performance, and particularly preferably, the molar ratio (hydrogen/carbon monoxide) of hydrogen to carbon monoxide ranged from 0.5 to 4.0. The reason is as follows. That is, if the molar ratio of hydrogen to carbon monoxide of less than 0.5, because the amount of hydrogen in the material gas is too low, the reaction of hydrogenation (reaction synthesis f-T) carbon monoxide is very difficult, and the performance of liquid hydrocarbons is low. On the other hand, if the molar ratio of hydrogen to carbon monoxide exceed 4.0, due to the fact that the amount of carbon monoxide in the material gas is too low, the performance of liquid hydrocarbon is small regardless of the activity of the catalyst.

Examples

Although this invention is described in more detail in the following examples, the invention is not limited to these examples.

1 g of Co/Zr/SiO2the catalyst was prepared as follows: first cause Zr method is m impregnation on capacity with subsequent drying and calcination, then put Co with subsequent drying, calcination, restoration and passivation (a substrate of silicon dioxide produced by Fuji Silysia Chem. Ltd. and has a spherical shape with an average particle size of 100 μm, the amount of the applied Co from 20 to 30% wt. and Zr/Co=0 to 0.3) and 50 ml of n16(n-hexadecane) are loaded into an autoclave with an inner volume of 300 ml Then F (flow rate of synthesis gas (H2/CO=2)) adjusted so as to obtain W (weight of catalyst)/F (flow rate of synthesis gas)=3 (g·h/mol), while rotating the stirrer at 800 rpm-1in the conditions of 230°C and 2.0 MPa-G. Then the composition of the injected gas and gas from the autoclave determined using gas chromatography. Get the values of conversion, selectivity CH4the selectivity of CO2and performance of hydrocarbon.

Additionally, the following experiments are conducted to assess the stability of the catalyst to water.

1 g of Co/Zr/SiO2the catalyst was prepared as described above and 50 ml of n16loaded into an autoclave with an inner volume of 300 ml Then F (flow rate of synthesis gas (H2/CO=2)) from W/F govern in such a way that the transformation FROM first becomes 60%, while the agitator rotates at 800 rpm-1in the conditions of 230°C and 2.0 MPa-G. Then, after a few hours of steady work, in the reaction system type H2About using micronesica is receiving the equivalent partial pressure of H 2About 90% of the transformation. Appendix H2About stop after 24 hours and within a few hours continue stable operation.

The conversion, selectivity CH4the selectivity of CO2and time saving activity, described in the following examples, calculated by the formulas shown below, respectively.

The conversion of CO (%)={[(amount (mol))-(amount of CO in the effluent from the reactor gas (mol)]/(amount (mol))}×100

The selectivity of CH4(%)=[(number of educated CH4(mol))/(number reacted WITH (mol)]×100

The selectivity of CO2(%)=[(amount of formed CO2(mol))/(number reacted WITH (mol)]×100

Time saving activity (%)=[(transformation after stopping the addition of N2On (%))/(conversion before adding the H2On (%))]×100

The effectiveness of this invention are shown below in the examples and comparative examples.

In addition, the total amount of alkali metals and alkaline earth metals in the catalysts from tables 1-3 includes a number of simple substances and compounds of sodium, potassium, calcium and magnesium in terms of metal. It should be noted that as the amount of potassium is very small compared to the rest, the concentration of potassium is not described as an independent who I concentration of component in the substrate of the catalyst in the tables. Furthermore, the total amounts of impurities in the catalyst shows the total number of simple substances and compounds of sodium, potassium, calcium, magnesium and iron in terms of metal. In addition, the number of compounds of aluminum, calculated on the metal substrate of silicon dioxide is also shown as a reference.

Example 1

When conducting the FT synthesis reaction using the catalyst indicated in table 1, the transformation is 85,4%, the selectivity of CH4is 4.3%, the selectivity of CO2is 2.0%, the performance of the hydrocarbon with the carbon number of five or more is 1,32 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is 80.2 per cent.

Example 2

When conducting the FT synthesis reaction using the catalyst indicated In table 1, the transformation amounted to 83.1%, the selectivity of CH4is 4.1%, the selectivity of CO21.7%, the performance of the hydrocarbon with the carbon number of five or more is 1,29 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity amounted to 83.1%.

Example 3

When conducting the FT synthesis reaction using the catalyst indicated in table 1, the transformation is 82,2%, the selectivity of CH4is 4.5%, the selectivity of CO2for example the t of 1.7%, the performance of the hydrocarbon with the carbon number of five or more is 1.27mm (kg-hydrocarbon/kg-catalyst/HR) and time saving activity was 85.1%.

Example 4

When conducting the FT synthesis reaction using the catalyst, denoted by D in table 1, the transformation is 81,2%, the selectivity of CH4is 4.6%, the selectivity of CO2is 1.4%, the performance of the hydrocarbon with the carbon number of five or more are 1.23 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is to 87.6%.

Example 5

When conducting the FT synthesis reaction using the catalyst indicated in table 1, the transformation is 67,4%, the selectivity of CH4is 5.8%, the selectivity of CO2is 0.9%, the performance of the hydrocarbon with the carbon number of five or more is 1.05 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is of 80.3%.

Example 6

When conducting the FT synthesis reaction using the catalyst, denoted by F in table 1, the transformation is 77,6%, the selectivity of CH44.9%, the selectivity of CO21.1%, the performance of the hydrocarbon with the carbon number of five or more is between 1.19 (kg-hydrocarbon/kg-catalyst/HR) and the sector of activity is 88.5%.

Example 7

When conducting the FT synthesis reaction using the catalyst, denoted by G in table 2, the transformation is 82,0%, the selectivity of CH4is 4.5%, the selectivity of CO2is 1.6%, the performance of the hydrocarbon with the carbon number of five or more is 1.27mm (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is 93.2%.

Example 8

When conducting the FT synthesis reaction using the catalyst, denoted by N in table 2, the transformation is 79,1%, the selectivity of CH4is 4.1%, the selectivity of CO21.1%, the performance of the hydrocarbon with the carbon number of five or more is 1,22 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is 93,8%.

Example 9

When conducting the FT synthesis reaction using the catalyst, designated I in table 2, which is obtained by the simultaneous addition of Co and Zr and conduct recovery and the passivation after drying and firing, the transformation is 80,7%, the selectivity of CH44.9%, the selectivity of CO2is 1.5%, the performance of the hydrocarbon with the carbon number of five or more $ 1.25 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is 31.1 per cent. Time maintain the surveillance activity is significantly reduced when adding Co and Zr.

Example 10

When conducting the FT synthesis reaction using the catalyst, denoted by J in table 2, which is obtained by the simultaneous addition of Co and Zr and conduct recovery and the passivation after drying and firing, the transformation is 76,5%, the selectivity of CH4is 4.3%, the selectivity of CO2is 1.0%, the performance of the hydrocarbon with the carbon number of five or more is 1.21 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity was 25.0%. Time saving activity is significantly reduced when adding Co and Zr.

Example 11

When conducting the FT synthesis reaction using the catalyst, denoted by N in table 2, which is obtained from the reverse order of addition of Co and Zr, i.e. first load Co and conduct drying and firing and then uploading Zr, and conducting drying, calcination, recovery and passivation, the transformation is 74,1%, the selectivity of CH44.9%, the selectivity of CO2is 1.0%, the performance of the hydrocarbon with the carbon number of five or more is 1.16 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is of 89.1%. When this example is compared with the catalyst described in example 7, which is obtained first by adding Zr and subsequent drying and firing the m and then the addition of Co, followed by drying, firing, the restoration and passivation, the composition of the catalyst are the same. However, the retention of activity when the activity analysis, reaction and resistance to water decreases. That is, for catalyst, which is obtained first by adding Zr and then adding Co, oxides of zirconium are on the contact surface of particles of cobalt, with activity, and a substrate of silicon dioxide. Therefore, the degree of dispersion of cobalt improves, and the suppression of the formation of cobalt silicate occurs when water side. When compared with the catalyst of comparative example 2 in which no added Zr, even for a catalyst, in which first add Co, and then add Zr, activity improved slightly, resistance to water also improves, it is believed that this is due to the preservation of reducing atmospheric oxides of zirconium.

Example 12

When conducting the FT synthesis reaction using the catalyst indicated In table 1, under conditions in which the W/F is 1.5 g·h/mol, the transformation is 72.9%, the selectivity of CH4is 4.2%, the selectivity of CO2is 0.6%, the performance of the hydrocarbon with the carbon number of five or more 2.25 (kg-hydrocarbon/kg-catalyst/HR).

Example 13

1 g of catalyst and 50 ml of n 16loaded into an autoclave with an inner volume of 300 ml Then F (flow rate of synthesis gas (H2/CO=2)) from W/F adjusted so that the transformation FROM first becomes about 60% at 800 min-1in the conditions of 230°C and 2.0 MPa-G. Then, after 24 hours of stable operation, W/F increase decrease F W/F so that the transformation exceeded 90%. Then the catalyst is kept in the condition in which the activity is subject to reduction. After 24 hours in this condition, return the original W/F and confirm the decrease of activity. This is followed by a regeneration of the catalyst in-situ while maintaining the pressure and the temperature drops to 150°C and the supply of hydrogen at 50 ml/min After maintaining this state for 30 hours the reaction of synthesis f-T is carried out at a feed synthesis gas thereby to obtain the first value of W/F and the temperature is raised to 230°C.

When analysis of the catalyst described above is carried out with the use of catalyst indicated In table 1, the first transformation is 63,0%, the transformation FROM the first W/F after reduction activity at high W/F makes 44.3%, and the transformation after regeneration with hydrogen is 51,0%. Although the activity is reduced and the transformation is reduced by 18.7% after work catalyst under conditions of high W/F, the transformation is restored to ,7% after regeneration with hydrogen.

Comparative example 1

When conducting the FT synthesis reaction using the catalyst, designated L in table 3, the transformation is 81,6%, the selectivity of CH4is 4.6%, the selectivity of CO2is 1.5%, the performance of the hydrocarbon with the carbon number of five or more is 1,22 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is to 77.7%.

Comparative example 2

When conducting the FT synthesis reaction using the catalyst, labeled M in table 3, the transformation is 69,5%, the selectivity of CH4is 5.3%, the selectivity of CO2is 0.9%, the performance of the hydrocarbon with the carbon number of five or more is 1.07 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity 75.6%.

Comparative example 3

When conducting the FT synthesis reaction using the catalyst, denoted by N in table 3, the transformation is only 55.2%, the selectivity of CH4is 6.2%, the selectivity of CO2is 1.4%, the performance of the hydrocarbon with the carbon number of five or more is 0.81 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is of 80.9%.

Comparative example 4

When conducting the synthesis reaction CFT applied with the eating of the catalyst, indicated in table 3, the transformation is 32.3%, selectivity of CH4is 8.0%, the selectivity of CO21.1%, the performance of the hydrocarbon with the carbon number of five or more is 0.46 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is to 85.8%.

Comparative example 5

When conducting the FT synthesis reaction using the catalyst, denoted by R in table 3, the transformation is 24,1%, the selectivity of CH4is 7.3%, the selectivity of CO2is 1.5%, the performance of the hydrocarbon with the carbon number of five or more is about 0.34 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity of 82.9%.

Comparative example 6

When conducting the FT synthesis reaction using the catalyst, denoted by Q in table 3, the transformation is 8.3%, the selectivity of CH49.0%, the selectivity of CO2is 1.5%, the performance of the hydrocarbon with the carbon number of five or more is 0.12 (kg-hydrocarbon/kg-catalyst/HR) and time saving activity is 81,1%.

Comparative example 7

When the experiment with regeneration of the catalyst shown in example 13, a catalyst, designated L in table 3, the first paragraph is avramania WITH was 62.4 per cent, the transformation after decreasing the activity at high W/F was 36.3 percent, and the transformation after regeneration with hydrogen was 41.1%. Although the activity is reduced and the transformation is reduced by 26.1% after work catalyst under conditions of high W/F, the transformation is recovered by 5.1% after regeneration with hydrogen.

Comparative example 8

When the experiment with regeneration of the catalyst shown in example 13, a catalyst, denoted by N in table 3, the first transformation was 60.2%, the transformation after returning to the first W/F after reduction activity at high W/F was equal to 37.5%, and the transformation after regeneration with hydrogen was 42.7 percent. Although the activity is reduced and the transformation is reduced by 22.7% after work catalyst under conditions of high W/F, the transformation is recovered by 5.2% after regeneration with hydrogen.

Table 1
Example123456
CatalystABC DEF
Na concentration in the substrate
catalyst (h/m)
110110110110110110
Ca concentration in the substrate of the catalyst (h/m)707070707070
Mg concentration in the substrate of the catalyst (h/m)171717171717
Fe concentration in the substrate of the catalyst (h/m)272727272727
Al concentration in the substrate of the catalyst (h/m)8383838383 83
The total amount of alkali metals and alkaline earth metals in the catalyst (h/m)134126113101157155
The total number of impurities in the catalyst (h/m)153143129115178176
The amount of damage (%)303030302020
The molar ratio of Zr/Co0,030,10,20,30,010,03
W/F (g·h/mol)3,03,03,03,03,03,0
CO conversion (%) 85,483,182,281,267,477,6
CH4selectivity (%)4,34,14,54,65,8a 4.9
CO2selectivity (%)2,01,71,71,40,91,1
The performance of the C5+ hydrocarbon (kg-hydrocarbon/kg-catalyst)1,321,291,271,231,051,19
Time saving activity (%)an 80.283,185,187,680,388,5
1) the performance of the hydrocarbon with the carbon number of 5 or higher

Table 2
Example123456
CatalystGHIJKB
Na concentration in the substrate
catalyst (h/m)
110110110110110110
Ca concentration in the substrate of the catalyst (h/m)707070707070
Mg concentration in the substrate of the catalyst (h/m)171717171717
Fe concentration in the substrate of the catalyst (the./million) 272727272727
Al concentration in the substrate of the catalyst (h/m)838383838383
The total amount of alkali metals and alkaline earth metals in the catalyst (h/m)149133126149149126
The total number of impurities in the catalyst (h/m)170151143170170143
The amount of damage (%)202030202030
The molar ratio of Zr/Co0,1 0,30,10,10,10,1
W/F (g·h/mol)3,03,03,03,03,01,5
CO conversion (%)82,079,180,776,574,172,9
CH4selectivity (%)4,54,1a 4.94,3a 4.94,2
CO2selectivity (%)1,61,11,51,01,00,6
The performance of the C5+ hydrocarbon (kg-hydrocarbon/kg-catalyst)1,271,221,251,211,16 2,25
Time saving activity (%)93,293,831,125,0of 89.183,1
1) the performance of the hydrocarbon with the carbon number of 5 or higher

Table 3
Comparative example123456
CatalystLMNOPQ
Na concentration in the substrate
catalyst (h/m)
1101102100210021002100
Ca concentration in the substrate of the catalyst (h/m)7070 250250250250
Mg concentration in the substrate of the catalyst (h/m)1717100100100100
Fe concentration in the substrate of the catalyst (h/m)272727272727
Al concentration in the substrate of the catalyst (h/m)838383838383
The total amount of alkali metals and alkaline earth metals in the catalyst (h/m)1381581561185817151960
The total number of impurities in the catalyst (h/m)157179 1579187817341982
The amount of damage (%)302030203020
The molar ratio of Zr/Co000,10,100
W/F (g·h/mol)3,03,03,03,03,03,0
CO conversion (%)81,669,555,232,324,18,3
CH4selectivity (%)4,65,36,28,07,39,0
CO2selectivity (%) 1,50,91,41,11,51,5
The performance of the C5+ hydrocarbon (kg-hydrocarbon/kg-catalyst)1,221,070,810,460,340,12
Time saving activity (%)77,775,680,985,882,981,1
1) the performance of the hydrocarbon with the carbon number of 5 or higher

INDUSTRIAL APPLICABILITY

In accordance with this invention presents a catalyst which has an improved catalyst for the production of hydrocarbons from synthesis gas, which reduced the decrease in activity due to sintering, deposition of carbon or side of the water; which is suitable for stable use in high-maturing, in which large quantities of produced water side; and has a long service life, also shows how received what I such a catalyst method of regeneration of this catalyst and method for producing hydrocarbons using such a catalyst. In this aspect of the industrial applicability of the present invention is obvious.

1. The catalyst for obtaining hydrocarbons from synthesis gas, which contains the metal cobalt or the cobalt metal and cobalt oxides; oxides of zirconium deposited on the substrate of the catalyst, consisting mainly of silicon dioxide, where the concentration of impurities in the catalyst is less than or equal to 0.15 wt.%.

2. The catalyst for obtaining hydrocarbons from synthesis gas according to claim 1, where the admixture of catalyst are simple substances and compounds of sodium, potassium, calcium, magnesium and iron.

3. The catalyst for obtaining hydrocarbons from synthesis gas according to claim 1, where the concentration of impurities in the catalyst is less than or equal to 0.03 wt.%.

4. The catalyst for obtaining hydrocarbons from synthesis gas according to claim 1, where the content of cobalt metal or cobalt oxides and cobalt metal is 5 to 50 wt.% in terms of metallic cobalt and the content of oxides of zirconium is from 0.03 to 0.6 molar ratio of Zr/Co.

5. The catalyst for obtaining hydrocarbons from synthesis gas according to claim 1, where the content of alkali metals or alkaline earth metals among the impurities contained in the substrate of the catalyst, costal is no less than or equal to 0.1 wt.%.

6. The catalyst for obtaining hydrocarbons from synthesis gas according to claim 1, where the content of each of sodium, potassium, calcium and magnesium among the impurities contained in the substrate of the catalyst that is less than or equal to 0.02 wt.%.

7. The catalyst for obtaining hydrocarbons from synthesis gas according to claim 1, where the substrate of the catalyst is spherical.

8. Method for the preparation of the catalyst according to any one of claims 1 to 7 to obtain hydrocarbons from synthesis gas, where the catalyst was prepared by simultaneous deposition of compounds cobalt and compounds of zirconium on a substrate of a catalyst mainly composed of silicon dioxide, by impregnation, impregnation by capacity, by precipitation or ion exchange method, and then the restoration processing or annealing and recovery processing.

9. The method of producing catalyst according to any one of claims 1 to 7 to obtain hydrocarbons from synthesis gas, where the catalyst was prepared separately by applying the compounds cobalt and compounds of zirconium on a substrate of a catalyst mainly composed of silica by impregnation, impregnation by capacity, by precipitation or ion exchange method, and after application of the first catalyst, drying, or drying, firing, and after the application of the remaining components, the recovery processing or annealing in stravitelne processing.

10. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to claim 9, in which the separate application of the compounds, the first of the applied compounds are zirconium compounds, and the remaining damage of compounds are compounds of cobalt.

11. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to claim 8, where the damage zirconium compounds and compounds of cobalt, used as raw material in the method of impregnation, impregnation method on capacity, method, deposition method or ion exchange, contain alkali metals and alkaline earth metals in an amount of 5 wt.% or less, and, if necessary, the method comprises a stage of reducing the concentration of impurities.

12. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to claim 8, where the substrate of the catalyst, mainly consisting of silicon dioxide, is produced by gelatinization Zola silicic acid obtained by mixing an aqueous solution of alkali silicate and an aqueous solution of the acid, the resulting product is subjected to any one, at least, treatment with acid or by washing with water, and then drying.

13. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to item 12, where the water in which the content of alkali metals or alkaline earth metals is less than or equal to 0.06 wt.%, the use of the comfort, at least any one of the processing acid and water leaching after gelatinization Zola silicic acid.

14. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to item 12, where the gelatinization carried out by sputtering or Sol of silicic acid in the gaseous medium or a liquid medium forming Zola silica spherical shape.

15. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to claim 8, where the compounds of cobalt and zirconium compounds deposited on a substrate to catalyst, consisting mainly of silicon dioxide, after reducing the concentration of impurities by purification with the use of at least any one of water, acid or alkali.

16. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to item 15, where cleaning is used acid and/or ion-exchange water.

17. A method of producing hydrocarbons from synthesis gas using the catalyst according to any one of claims 1 to 7, where the synthesis is carried out by conducting the reaction in the liquid phase using a reactor with a layer of suspended sediment.

18. A method of producing hydrocarbons from synthesis gas using the catalyst according to any one of claims 1 to 7, where the synthesis is carried out by conducting the reaction in the liquid phase using a reactor with a layer of suspended sediment with external circulation system.

19. SP is a way to obtain hydrocarbons from synthesis gas by 17, where in the reaction in the liquid phase, the amount of catalyst, the amount of supply of the material gas, the reaction temperature and pressure reactions govern in such a way that the transformation in a single pass is from 40 to 95%.

20. A method of producing hydrocarbons from synthesis gas through 17, where in the reaction in the liquid phase, adjusting the amount of catalyst, the amount of supply of the material gas, the reaction temperature and pressure reactions govern in such a way that the transformation in a single pass is from 60 to 95%.

21. Method for regenerating catalyst activity is reduced after the process of obtaining hydrocarbons from synthesis gas using the catalyst according to any one of claims 1 to 7, where the catalyst with reduced activity of the regenerating process gas containing hydrogen and, thus, the catalyst and regenerating gas in contact with each other.

22. Method for regenerating catalyst activity is reduced after the process of obtaining hydrocarbons from synthesis gas in the reactor, which is filled with a catalyst according to any one of claims 1 to 7, where in the reactor serves regenerating gas containing hydrogen and, thus, the catalyst and regenerating gas in contact with each other.

23. Method for regenerating catalyst activity is reduced after the process of obtaining hydrocarbons from synthesis gas the way the m p, where any part of the system external circulation serves regenerating gas containing hydrogen and, thus, the catalyst and regenerating gas in contact with each other.

24. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to claim 9, where the damage zirconium compounds and compounds of cobalt, used as raw material in the method of impregnation, impregnation method on capacity, method, deposition method or ion exchange, contain alkali metals and alkaline earth metals in an amount of 5 wt.% or less, and, if necessary, the method comprises a stage of reducing the concentration of impurities.

25. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to claim 9, where the substrate of the catalyst, mainly consisting of silicon dioxide, is produced by gelatinization Zola silicic acid obtained by mixing an aqueous solution of alkali silicate and an aqueous solution of the acid, the resulting product is subjected to any one, at least, treatment with acid or by washing with water, and then drying.

26. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas A.25, where the water in which the content of alkali metals or alkaline earth metals is less than or equal to 0.06 wt.%, use in at least any one of the processing acid and water leaching after gelatinization AOR what I silicic acid.

27. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas A.25, where the gelatinization carried out by sputtering or Sol of silicic acid in the gaseous medium or a liquid medium forming Zola silica spherical shape.

28. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas according to claim 9, where the compounds of cobalt and zirconium compounds deposited on a substrate to catalyst, consisting mainly of silicon dioxide, after reducing the concentration of impurities by purification with the use of at least any one of water, acid or alkali.

29. A method of producing a catalyst for obtaining hydrocarbons from synthesis gas by p, where cleaning is used acid and/or ion-exchange water.

30. A method of producing hydrocarbons from synthesis gas by p, where in the reaction in the liquid phase, the amount of catalyst, the amount of supply of the material gas, the reaction temperature and pressure reactions govern in such a way that the transformation in a single pass is from 40 to 95%.

31. A method of producing hydrocarbons from synthesis gas by p, where in the reaction in the liquid phase, adjusting the amount of catalyst, the amount of supply of the material gas, the reaction temperature and pressure reactions govern in such a way that the transformation in a single pass is from 60 to 95%.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of removing oxygenate from a stream containing 50-99.99 wt % paraffins and 0-50 wt % olefins, which involves the following steps: a) passing a supply stream containing 50-99.99 wt % of one or more starting C10-C15-paraffins, 0-50 wt % olefins and one or more oxygenates through an adsorbent layer which is an exchange alkali or alkali-earth cation of zeolite X in order to remove virtually all said oxygenates; and b) removing paraffin(s) from the adsorbent layer to obtain a clean stream.

EFFECT: use of present method enables to remove a wide range of oxygenates from raw materials, a large portion of which contains C10-C15-paraffins.

4 cl, 2 tbl, 1 ex, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to two versions of a method for selective production of hydrocarbons which are suitable for making diesel fuel, one of which is characterised by that it includes a step where a decarboxylation/decarbonylation reaction is carried out by reacting material from renewable sources containing C8-C24 fatty acids, esters of C8-C24 fatty acids, triglycerides of C8-C24 fatty acids or metal salts of C8-C24 fatty acids or their combination, and a solvent or mixture of solvents if desired, with a heterogeneous catalyst which, if necessary, is pre-treated with hydrogen at 100-500 °C before brought into contact with the raw material, which contains 0.5-20 % one or more group VIII metals selected from platinum, palladium, iridium, ruthenium and rhodium or 2-55% nickel on a carrier selected from oxides, mesoporous substances, carbonaceous carriers and catalyst structural carriers, at temperature of 200-400°C and pressure between 0.1 and 15 MPa, to obtain a mixture of hydrocarbons as the product.

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29 cl, 3 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining synthetic liquid hydrocarbons from hydrocarbon gases involves catalytic vapour-carbon dioxide conversion of the starting material and recycled products with supply of high-grade heat and obtaining synthetic gas, catalytic processing of the synthetic gas using a Fischer-Tropsch method while tapping low-grade heat through evaporation cooling, division of products obtained from processing synthetic gas into three streams: a mixture of liquid hydrocarbons, water and exhaust gases, and subsequent division of the obtained mixture of liquid hydrocarbons into a fraction of commercial grade hydrocarbons (petrol, kerosene, diesel fuel) and C21+ hydrocarbons, distinguished by that starting gaseous material fed at constant pressure of 0.8-3.0 MPa after purification from sulphur compounds is divided into two streams, one of which together with a portion of waste gases from the Fischer-Tropsch synthesis reactor, carbon dioxide, extracted from exhaust flue gases, and water vapour, are fed into a radial-spiral catalytic reactor for vapour-carbon dioxide conversion, which is carried out at temperature 950-1050°C; the obtained synthetic gas is fed into a steam boiler as heating medium, after partial cooling in which the synthetic gas is further cooled to 20-40°C by an external coolant for moisture removal and is separated from moisture in a surface cooler - drier for synthetic gas, after which it is fed into a Fischer-Tropsch synthesis reactor, and the second stream of starting gaseous material is mixed with another portion of exhaust gases from the Fischer-Tropsch synthesis reactor and fed into the burner of the catalytic reactor as fuel, where before feeding into the burner, the said mixture and air necessary for combustion are heated in a heat recovery unit through partial cooling of flue gases coming out of the catalytic reactor, after which the flue gases are further cooled by an external coolant for moisture removal in the surface cooler-drier for flue gases, further carbon dioxide is removed from the flue gases and fed into the catalytic reactor for vapour-carbon dioxide conversion, flue gases cooled and purified from carbon dioxide are removed from the installation, and the condensate extracted in cooler-driers for synthetic gas and flue gases, and water obtained after separation of Fischer-Tropsch reaction products are purified in a water treatment unit and taken for steam generation, necessary for vapour-carbon dioxide conversion of the starting gaseous material, into a boiler in which the condensate is heated and evaporated using heat of the synthetic gas.

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FIELD: chemistry.

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12 cl, 2 dwg

FIELD: chemistry.

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EFFECT: use of the proposed invention provides for economisation by reducing the number of units of the equipment used and equipment expenses, and also reduces amount of hydrogen required for carrying the process.

9 cl, 1 tbl, 1 dwg

FIELD: chemistry.

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10 cl, 1 ex, 1 dwg

The invention relates to analytical chemistry of organic compounds and can be applied for detection of nonane in the air of working zone of petroleum, tire and paint industry

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FIELD: process engineering.

SUBSTANCE: invention relates to chemistry and metallurgy and may be used in producing valuable products from red sludge. Sludge processing comprises the following stages: a) reducing at least a portion of iron oxide (III) and/or iron hydroxide (III) contained in red sludge by at least one-type reducer that contains at least one-type hydrocarbon; b) separating at least one solid phase of reaction mix from at least one liquid and/or gas phase. Note here that said one solid phase, and/or liquid phase, and/or gas phase contains one valuable products containing at least magnetite. Methane and/or natural gas and/or ethanol may be used as said reducer. Separated solid phase is separated into one first magnetising produc and one second non-magnetising product. The latter is use as at least additive to cement. At least one component produced from gas phase separated at stage b) is used as initial product for synthesis of hydrocarbons. In said synthesis, at least one component of red sludge is used to make a surfactant.

EFFECT: expanded applications.

16 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemisry, gas chemistry, coal chemistry and a catalyst for synthesis of hydrocarbons containing 5 or more carbon atoms from CO and H2 (Fischer-Tropsch synthesis), a method for synthesis of C5+ hydrocarbons using said catalyst and a method of producing said catalyst. Described is a catalyst for synthesis of C5+ hydrocarbons containing a support in form of fluorinated γ-aluminium oxide, 30 wt % cobalt and 0.5 wt % rhenium. Described is a method of producing said catalyst, involving preliminary thermal treatment of the γ-aluminium oxide-based support and then adding cobalt and rhenium via step-by-step saturation with aqueous solutions of cobalt nitrate and ammonium perrhenate and step-by-step thermal treatment, wherein the support used is fluorinated γ-aluminium oxide. The invention also describes a method of producing C5+ hydrocarbons via catalytic conversion of CO and H2 using said catalyst.

EFFECT: high selectivity with respect to formation of desired hydrocarbon products (over 90%) and low selectivity with respect to formation of by-product - methane (less than 4%), wherein the relationship between the output of the desired products and the conversion of carbon oxide (output C5+-Kco) is linear in the conversion interval from 0 to 80-90%.

4 cl, 4 ex, 1 tbl, 6 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to production of zeolite catalysts, catalysts thus produced and method of producing synthetic fuel using produced catalyst. Proposed methods comprises zeolite two-step loading, impregnating zeolite with cobalt compound in solution and drying in air flow after every loading. Invention covers also catalysts produced by said methods. It covers also the method of producing synthetic fuel using produced catalyst, its activation and synthesis of hydrocarbons, particular, aliphatic hydrocarbons C5-C10 from synthesis gas that represents CO and H2.

EFFECT: higher activity and isomeric selectivity.

36 cl, 2 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to Fishcher-Tropsch synthesis catalysts. Described is a transition metal-based nanocatalyst for Fischer-Tropsch synthesis, which contains nanoparticles of a transition metal and polymer stabilisers, wherein the transition metal is selected from a group comprising ruthenium, cobalt, nickel, iron and rhodium, or any combination thereof, in which nanoparticles of the transition metal are dispersed in a liquid and the size of the nanoparticles of the transition metal is equal to 1-10 nm. Described is a method of preparing the described nanocatalyst, said method comprising the following steps: mixing and dispersing transition metal salts and polymer stabilisers in liquids, and reducing the transition metal salts with hydrogen in order to obtain a transition metal-based nanocatalyst, where temperature is equal to 100-200°C and concentration of the transition metal salts dissolved in the liquids is equal to 0.0014-0.014 mol/l. Described is a Fischer-Tropsch synthesis process which is carried out using the described nanocatalyst for converting carbon oxide and hydrogen to hydrocarbons.

EFFECT: obtaining an active nanocatalyst for the Fischer-Tropsch synthesis process.

17 cl, 1 tbl, 1 dwg, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining a Fischer-Tropsch synthesis product from a gaseous mixture of hydrocarbons containing methane, ethane and, optionally, hydrocarbons with a large number of carbon atoms, in which content of methane is approximately 60 vol. %, via the following steps: (a) adiabatic preliminary reforming of the hydrocarbon mixture in the presence of a reforming catalyst containing oxide carrier material and a metal which is selected from a group comprising Pt, Ni, Ru, Ir, Pd and Co, in order to convert ethane and optional hydrocarbons with a large number of carbon atoms into methane, carbon dioxide and hydrogen, (b) heating the gaseous mixture obtained at step (a) to temperature higher than 650°C, (c) performing non-catalytic incomplete oxidation by bringing the hot mixture from step (b) into contact with an oxygen source in a reactor burner to form a stream coming from the reactor at temperature between 1100 and 1500°C, (d) performing Fischer-Tropsch synthesis using arterial in form of a gas containing hydrogen and carbon monoxide, which is obtained at step (c) and (e) where the synthesis product obtained at step (d) is split into a relatively light stream and a relatively heavy stream. The relatively heavy stream contains a Fischer-Tropsch synthesis product and the relatively light stream contains unconverted synthetic gas, inert substances, carbon dioxide and C1-C3 hydrocarbons, and where a first portion of the light stream is recycled to step (a) in order to subject it to preliminary reforming, and where a second portion of the light stream is recycled to the reactor burner at step (c) in order to subject it to incomplete oxidation, and where temperature at step (a) is controlled to provide the amount of the light stream which is recycled to step (a).

EFFECT: method is an improved process of obtaining a Fischer-Tropsch synthesis product where oxygen consumption is low.

10 cl, 1 tbl, 1 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to versions of a method of converting oxygenated organic compounds to hydrocarbons, one of which involves the following steps: (a) directing a feed stream of synthesis gas into a synthesis section in order to obtain easily convertible oxygenates, (b) feeding the stream from the said synthesis section containing easily convertible oxygenates into a gasoline synthesis section, (c) feeding the stream from the gasoline synthesis section into a separator and extracting from the said separator hydrocarbons which boil in the boiling point interval of the gasoline fractions, (d) mixing the stream recycled from the separator, which contains unreacted synthesis gas and volatile hydrocarbons, with the feed stream of synthesis gas from step (a), (e) feeding crude material which contains hard-to-convert oxygenates into the synthesis section at step (a), in which easily convertible oxygenates include compounds selected from a group comprising methanol, ethanol, dimethyl ether, acetone, propanol, diethyl ether, isobutanol, propionaldehyde or mixtures thereof, and in which the material containing hard-to-convert oxygenates includes compounds selected from a group comprising formaldehyde, acetaldehyde, hydroxyaldehyde, glyoxal, acetone, acetic acid, MeOAc, EtOAc, furfurol, furfuryl alcohol, phenol, anisole, pyrocatechol, guaiacol, cresol, cresolol, eugenol, naphthol or mixtures thereof.

EFFECT: longer catalyst activity cycle when producing gasoline.

8 cl, 4 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to Fisher-Tropsh synthesis catalysts. Fisher-Tropsh catalyst comprise carrier and active cobalt-containing component Note here that said component represents cobalt oxide structures immobilised on catalyst surface that feature maximum hydrogen consumption at 500-800°C on graph of thermally programmed reduction. Note also that amount of cobalt oxide structures on catalyst surface should be sufficient for use of 0.3 mmol of H2/g catalyst. Invention covers also method of producing above describe catalyst comprising adding cobalt on liquid or solid phase carrier to perform catalyst activation to form active cobalt-containing component in the form of immobilised surface cobalt oxide structures. It covers also method of producing hydrocarbons on above described Fisher-Tropsh synthesis catalyst via conversion of CO and H2 at 180 to 300°C and 0.1 to 3 MPa.

EFFECT: highly active and selective Fisher-Tropsh catalyst.

11 cl, 2 tbl, 2 dwg, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to gas- and coal chemistry. Described is a catalyst for synthesis of hydrocarbons from CO and H2, containing a catalytically active component selected from group VIII metals, a porous support which has an oxide component and high heat-conductivity carbon material, characterised by that the carbon material has a nanostructure and lies on the surface of the support, and content of components in the catalyst is as follows (in wt %): catalytically active component 10-45; porous support 40-80; carbon material 5-35. Described also is a method of producing said catalyst, involving deposition of the catalytically active component selected from group VIII metals onto the surface of the pores of the support followed by formation of nanostructures of the high heat-conductivity carbon material, and then further deposition of the catalytically active component onto the surface of the nanostructures of the carbon material.

EFFECT: method enables to obtain a catalyst with high heat-conductivity and selectivity towards the end product.

8 cl, 1 tbl, 19 ex

FIELD: oil and gas production.

SUBSTANCE: system of liquid fuel synthesis consists of reforming unit converting stock hydrocarbon material for production of synthetic gas containing gaseous monoxide of carbon and gaseous hydrogen as basic components. Further, the system consists of a reactor synthesising liquid hydrocarbons out of gaseous monoxide of carbon and gaseous hydrogen contained in synthetic gas by means of reaction of Fischer- Tropsch synthesis. The system also includes a refinement processing unit treating liquid hydrocarbons synthesised in the reactor, and a unit heating liquid hydrocarbons introduced into the refinement processing unit with utilisation of spent gas. This gas is produced by combustion of gaseous fuel in a burner of the reforming unit and is withdrawn from the reforming unit as heat carrier. Spent gas is supplied into the refinement processing unit directly. The latter corresponds either to a rectifying column performing fraction distillation of liquid hydrocarbons into multitude of types of liquid fuel with different boiling temperature and/or to a reactor for hydrogenation of liquid hydrocarbons.

EFFECT: increased heat efficiency of whole system of liquid fuel synthesis.

2 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to methods for synthesis of aromatic hydrocarbons from methane, particularly from natural gas. Described is a method of converting methane from a stream of natural gas into higher molecular weight hydrocarbons, including aromatic hydrocarbons, involving: (a) bringing starting material containing methane into contact with a dehydrocyclisation catalyst in conditions which are efficient for conversion of said methane into aromatic hydrocarbons and obtaining a first output stream containing aromatic hydrocarbons and hydrogen, where the said first output stream contains at least 5 wt % aromatic rings more than the said starting material; and (b) reacting at least a portion of hydrogen from the said first output stream with carbon dioxide, fed into the process in form of a portion of a stream of natural gas in conditions which are efficient for obtaining a second output stream, having low content of hydrogen compared to the said first output stream; where the reaction (b) involves: (I) (1) reaction of hydrogen with the obtained hydrocarbons and water (2) removal of at least a portion of water from the said second output stream and (3) returning at least a portion of hydrocarbons from the said second output stream into the said contact (a).

EFFECT: converting methane into aromatic hydrocarbons, the methane being contained in a stream of natural gas which contains a large amount of carbon dioxide.

21 cl, 2 ex, 3 dwg

FIELD: oil and gas industry.

SUBSTANCE: paraffin hydrotreating method involves the first stage at which paraffin with content C21 or higher of normal paraffins 70% wt or higher is used as basic material, and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking, catalyst consisting of metal of group VIII of the Periodic Table, which is put on carrier containing amorphous solid acid; the second stage at which raw material from paraffin is replaced for some time with light paraffin with content C9-20 of paraffins 60% wt or higher, and light paraffin contacts with catalyst at reaction temperature of 120-335 °C in presence of hydrogen for hydrocracking; and the third stage at which raw material of light paraffin is replaced with paraffin and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking. Also, invention refers to method for obtaining material of fuel system, which involves the above method.

EFFECT: use of this invention allows improving activity of hydrocracking catalyst, which deteriorates with time.

6 cl, 1 tbl, 4 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to processes of generating catalysts for hydrogenation of plant oil and fat. The invention describes a method of regenerating a spent palladium-containing catalyst for hydrogenating plant oil and fat through treatment with sodium hydroxide solution and washing with a condensate, where the catalyst is pre-washed with steam condensate until there are no traces of fat while simultaneously bubbling with hydrogen. Treatment is carried out with 10% solution of sodium hydroxide while blowing with hydrogen at the same time. Washing is carried out with steam condensate until there are completely no traces of alkali and soap and drying is carried out in a hydrogen stream at 145-150°C for 8-9 hours.

EFFECT: attaining high degree of purification and regeneration of the catalyst.

2 ex

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