Synthesis gas conversion process in sequentially connected reactors

FIELD: petrochemical processes.

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

EFFECT: improved process technology.

10 cl, 8 dwg, 7 ex

 

Prior art

Production of liquid fuel by means of the technology of the Fischer-Tropsch synthesis opens important perspectives for the exploitation of remote from markets. These new developments associated with the need to reduce costs and, in particular, reduce investment in order to increase the profitability of the industry.

One way to achieve this is the use of factor aliasing to reduce the investment costs related to ton obtain a liquid product.

Use for the synthesis reaction catalyst in suspension in the liquid phase ("slurry") allows the use of reactors of very large size and high performance, for example of the order of 10,000 barrels per day, with only one three-phase reactor.

Such a three-phase reactor containing the catalyst in suspension in a solvent, generally inert to the reaction. They are generally called reactors "slurry". Among the different types of reactors "slurry" is known, in particular, the reactor type autoclave with full mixing or reactors of the type of bubble columns operating in different hydrodynamic conditions, ranging from the reactor with full mixing and finishing reactor displacement without dispersion, as for the gaseous phase, the AK and the liquid phase.

Recently these types of reactors were used for the Fischer-Tropsch synthesis instead of the usual reactors with a stationary layer, the lack of which is a poor heat released by the reaction.

In patents US 5961933 and US 6060524 described method and equipment to apply reactors "slurry" type bubble column for Fischer-Tropsch synthesis. According to these patents, the reactor slurry contains a system of internal and external recirculation of fluid that allows you to achieve higher productivity for each reactor Fischer-Tropsch process.

In the patent application WO 01/00595 described method for synthesis of hydrocarbons from synthesis gas in a three-phase reactor, preferably of the type bubble column, in this way the hydrodynamic condition of the liquid phase are such that the Peclet number of the liquid phase was higher than 0 and was below 10. In addition, the superficial velocity of the gas is preferably below 35 cm·-1.

In the patent EP-B-450860 described method, providing optimal performance with three-phase-type reactor bubble column. In this patent, the purpose of which is to optimize the operation of only one reactor of this type, it is noted that characteristics mainly depend on the dispersion of the liquid phase (the Peclet number for the gaseous phase and maintain in suspension of catalyst in liquid FASEB particular, the Peclet number for the gaseous phase must not exceed 0.2. So, in this patent is not recommended to use a reactor with almost complete mixing for gaseous phase (the Peclet number close to 0 for gas), as this type of reactor does not provide enough performance.

So, this method is faced with certain limitations, in particular, with the phenomena of axial mixing. To ensure mass transfer between gas and liquid and between the liquid and the solid phase and to provide the heat necessary to resort to strong mixing present in the liquid and gaseous phases, which increases the axial mixing. In addition, the large diameters of the reactor, for example from 8 to 11 m, there is a considerable movement of the internal recirculation, leading to a strong mixing of the liquid phase. These phenomena are positive in regard to the mass transfer between gas and liquid and/or between a liquid and a solid phase, however, too strong mixing prevents the flow speed of the reaction.

The aim of the method in accordance with the present invention is to eliminate these disadvantages by combining at least two three-phase reactor, preferably at least three three-phase reactors. It was observed that the application of the sequence is part of the United reactors with strong stirring allows you to achieve the correct reaction and removes calories. This combination allows to achieve high performance in obtaining the desired products, i.e. mainly paraffins with the number of carbon atoms greater than 5, preferably greater than 10, and at the same time to limit the formation of light products (hydrocarbons C1-C4).

Description of the invention

The present invention relates to a method for the synthesis of hydrocarbons, preferably containing at least two carbon atoms in the hydrocarbon molecule, and more preferably at least 5 carbon atoms in the molecule of the hydrocarbon by contact of the gas containing mainly carbon monoxide with hydrogen in a reaction zone containing a suspension of solid particles in a liquid containing solid particles of catalyst reaction. Specified catalytic suspension is also called "slurry". The method in accordance with the present invention is carried out in a three-phase reactor. Preferably the method in accordance with the present invention is carried out in a three-phase reactor type bubble column.

The method in accordance with the present invention is a method of converting synthesis gas into liquid hydrocarbons carried out in at least two serially connected reactors, preferably in at least three series-connected reactors, containing the x, at least one catalyst in suspension in the liquid phase, distinguished by the fact that these reactors are reactors with full mixing, with the last reactor at least partially served at least part of at least one of the gas fractions collected at the outlet of at least one of these reactors, and the product mixture in the liquid phase and the catalyst leaving the last reactor at least partially separated in such a way as to obtain a liquid product with virtually no catalyst and a liquid fraction enriched in catalyst (catalytic slurry-enriched catalyst, or a concentrated catalyst slurry, which then recycle.

Each of the applied reactor is a reactor type bubble column, in which the contact between the gas and finely dispersed mixture of liquid/solid phase reactor slurry or slurry bubble column" in the Anglo-Saxon terminology).

Used catalysts can be of different nature and usually contain at least one metal, preferably selected from the metals in groups 5-11 new periodic classification of elements.

The catalyst may contain at least one activating substance (also called a promoter), preferably selected from elements of groups 1 to 7 on the new periodic rate is then. These promoters can be used separately or in combination.

As the carrier is mainly used porous material and often porous inorganic refractory oxide. For example, the carrier can be selected from the group comprising alumina, silica, titanium oxide, dvuoksid zirconium, rare earth elements, or mixtures of at least two porous mineral oxides.

Typically, the slurry may contain from 10 to 65 weight. % of catalyst. The catalyst particles have an average diameter, usually within about 10 to about 100 microns. Smaller particles can appear as a result of abrasive friction, that is, when the destruction of the original catalyst particles.

In the method according to the present invention, each reactor is almost complete mixing, and almost meets the conditions of perfect mixing. These reactors in accordance with the present invention are determined so as reactors with almost perfect mixing, and the Peclet number can preferably be used as a measure of the degree of mixing in these reactors.

Given that the reaction occurs in the liquid phase, the main factor is the control of the hydrodynamics of this phase. For each reactor can skin the th model displacement-dispersion in the liquid phase, because it is the most suitable for continuous phases. Associated with this model is the Peclet number is expressed as Pe liq=Vl*H/Dax, where Vl is the liquid velocity in the reactor, N - height expansion catalytic layer, and Dax - coefficient of axial dispersion. Preferably it should be below 10 and preferably below 8. This model is less suitable for reproducing phenomena mixing in the gas phase. However, if you still like to use it for interpreting evidence recording device when determining the Peclet number, for example, based on the variance of the concentration profile at the outlet, it turns out that you can get value, preferably lower to 0.2, preferably smaller of 0.18, more preferably less 0.15, and more preferably less 0.1 or even lower to 0.05, and in some cases less than or equal to 0.03.

All these conditions are easier to achieve in the case of a reactor with a very large diameter, for example greater than 6 m, however, these conditions may also be provided in the case of the reactor of smaller diameter, managing hydrodynamic parameters to improve the mixing and, consequently, the mass transfer gas-liquid and liquid-solid phase. Such mixing can be accomplished by any means known in the art, including, for example, generating traffic re is circulatie liquid phase using elements of the internal structure of the reactor or of external recirculation, such as recirculation paths.

The effect of mixing in the gas phase increases, if the gaseous phase is finely dispersed state, in the form of gas bubbles with a diameter not exceeding, for example, several millimeters. This condition, in addition, improves the kinetics of the reaction.

To ensure reaction in the method according to the present invention is applied serially connected reactors in the amount of at least two, preferably at least three. In addition, it is another object of the present invention, this allows to make the process of discharge synthesis gas speed. This makes it possible to optimize the configuration of series-connected reactors. In particular, if we aspire to increase the capacity of each cascade, to maximize the effect of aliasing, it is usually face the limitation of the maximum diameter of the reactor, either because of structural reasons, and taking into account the need of transportation. This diameter may, for example, be 11 m In this case, in order to obtain maximum performance, it is advisable to use reactors of the same diameter, and this can be achieved by adjusting the amount of synthesis gas fed into each of the reactors.

Cardys reactor operates at a temperature preferably in the range of 180°370°C, preferably from 180°320°and more preferably from 200°, 250°and under pressure, preferably in the range of 1 to 5 MPa (R), preferably from 1 to 3 MPa.

Thus, the method in accordance with the present invention is a method of converting synthesis gas into liquid hydrocarbons carried out in at least two serially connected reactors, containing at least one catalyst in suspension in the liquid phase, these reactors are reactors with almost complete mixing, in the last reactor at least partially served at least part of at least one of the gas fractions collected at the outlet of at least one of these reactors, and the product mixture in the liquid phase and the catalyst leaving the last reactor, at least partially sephirot thus, to obtain a liquid product with virtually no catalyst and a liquid fraction enriched in catalyst, which is then recycle. In the method according to the present invention preferably uses at least three series-connected reactor.

In the method according to the present invention, the Peclet number for fluid prepost is positive below 8, and, independently of the Peclet number for gas preferably less than 0.2 and more preferably below 0.1.

According to a preferred variant of the method in accordance with the present invention at the outlet of each reactor gaseous phase is separated from the liquid phase containing the catalyst in suspension. Preferably coming from the first reactor gas fractions are combined, processed and directed to the input of the last reactor and preferably leaving the last reactor of the gas fraction is recycled to the input of the stage production of synthesis gas.

According to a preferred variant of the method in accordance with the present invention the feed synthesis gas is distributed at the entrance of serially connected reactors so that all reactors have the same size.

The catalyst for the method in accordance with the present invention preferably contains a porous mineral carrier and at least one metal that is applied to this carrier. Preferably the catalyst is suspended in the liquid phase in the form of particles with a diameter, preferably less 200 microns.

Here is a description of several possible embodiments of the present invention. In the attached figures the same streams or items of equipment marked with the same position is s.

EXAMPLE 1

Various embodiments of the present invention, and one of them is shown in Fig. 1.

In this embodiment of the method in accordance with the present invention use three series-connected reactor. The synthesis gas flows through the pipeline 100. It is sent to the first reactor R1 in which it is dispersed within the liquid phase formed is recycled to the reaction products. The output of the first reactor R1 through line 101 remove the mixture obtained liquid product containing the catalyst in suspension (catalytic suspension), as well as not participating in the reaction gas, in the form of a dispersed phase. Through the pipeline 102 enter the second portion of the synthesis gas and the resulting mixture through a pipe 103 is sent to the second reactor R2. The output of this second reactor R2 through line 104 to remove the mixture of liquid product containing the catalyst in suspension, as well as unreacted gas as the dispersed phase. Through line 106 serves a third portion of the synthesis gas, and the resulting mixture is sent through the pipeline 107 in the third reactor R3. The output of the third reactor R3 via pipeline 108 removing a mixture of liquid product containing the catalyst in suspension, as well as unreacted gas as the dispersed phase. G is tobrasol phase is separated from the liquid phase in the separator SL. The gaseous phase is removed through line 111, process, and recycle. The liquid phase containing the catalyst in suspension (catalytic suspension), referred to separation and filtration SC. Separated from the catalyst in the liquid phase is removed through line 110, while the liquid phase with a high concentration of catalyst (concentrated catalyst slurry through the pipe 109 recycle in the first reactor R1.

EXAMPLE 2

In the method according to the present invention can perform intermediate operations of separation. In particular, the output of each reactor can be separated residual gas fraction, as shown in Fig. 2.

Residual gas fraction sephirot at the outlet of each reactor by means of separators SL1, SL2 and SL3.

This allows you not to send leaving one reactor inert gases and water contained in the residual gas fractions in the following reactor. Separators SL1, SL2 and SL3 are, for example, as sumps, it is necessary to take into account a sufficient residence time in the separating flask. We collect the pipes 111, 112 and 113 of the gas fractions are combined, process and recycle.

Collected through pipes 111, 112 and 113 of the gas fractions contain water, carbon dioxide, light hydrocarbons, and a mixture of oxide ug is erode and hydrogen. Preferably a mixture of carbon monoxide and hydrogen collected at the outlet of one reactor, refer to the following reactor (not shown in figure).

Other threads and items of equipment identical to that shown in Fig. 1.

EXAMPLE 3

In the case of the embodiment shown in Fig. 3, the gas fraction that is collected through pipes 112 and 113 at the output of the reactors R1 and R2, are combined and processed. First gas mixture is cooled in the heat exchanger-condenser C1 for condensation water. Thus obtained mixture of the three phases, which are separated in the separator S4: the aqueous phase is removed through line 114, a liquid hydrocarbon phase, which is removed through line 115, and the gaseous phase is removed through line 116. The gaseous phase is sent to the processing section T1 to at least partially separate the contained carbon dioxide. Enriched with carbon dioxide gaseous phase is separated and removed through line 117. For separation of carbon dioxide in the section processing T1 can be applied to various known methods. For example, it is possible to apply the method of leaching solvent, such as amine, or a physical solvent, such as chilled methanol, propylene carbonate or dimethyl ether tetraethyleneglycol (DMETEG). You can also use any other method based the first, for example, absorption separation or selective membrane separation. The obtained gas mixture removed from the installation of T1 through line 106, enriched with carbon monoxide and hydrogen. It still contains light hydrocarbons, in particular methane. It is directed to the input of the last reactor R3. If necessary, mix it with a spare from a mixture of carbon monoxide and hydrogen coming from the section of production of synthesis gas (not shown in the figure). Light hydrocarbons flowing through the pipeline 106 and not converted in the reactor R3, are removed through the pipeline 11 and can be recycled in the section of production of synthesis gas.

EXAMPLE 4

In Fig. 4 shows another possible variant embodiment of the invention.

The synthesis gas is fed into the first reactor R1 through line 100. At the exit of the reactor R1 gaseous phase and the liquid phase separated in separator SL1. Coming out of the separator SL1 gaseous phase is cooled in the heat exchanger C1. This cooling leads to condensation of the aqueous phase, and this condensed phase is removed through line 210, in addition, the condensed light hydrocarbon phase is removed through line 211. The resulting gaseous phase is removed through line 113 and sent to the reactor R2, while the input of the reactor R2 is mixed with the provision of the synthesis gas p. the pipeline 102. At the exit of the reactor R2 gaseous phase and the liquid phase separated in separator SL2. Coming out of the separator SL2 gaseous phase is cooled in the heat exchanger C2. This cooling leads to condensation of the aqueous phase, and this condensed aqueous phase is removed through line 212, and, in addition, for condensing light hydrocarbon phase, which is removed through line 213. The resulting gaseous phase is removed through line 112 and sent to the reactor R3 with the addition of synthesis gas by pipeline 106. At the exit of the reactor R3 gaseous phase and the liquid phase separated in separator SL3. Coming out of the separator SL3 gaseous phase is cooled in the heat exchanger C3. This cooling leads to condensation of the aqueous phase, which is removed through line 213; in addition, the condensed light hydrocarbon phase is removed through line 214.

Liquid products leaving the separators SL1, SL2 and SL3 through the pipeline 200, 201 and 202 and containing the catalyst in suspension (catalytic suspension), send in the mixture in the separator SC, which is removed through line 110 liquid products are separated from the liquid phase with a high concentration of catalyst (concentrated catalyst slurry), which recycle to the reactors R1, R2 and R3.

In the circuit of Fig. 4 separators SL1, SL2 and SL3 are shown installed separately tractorul R1, R2 and R3. Alternatively, leaving each reactor, the gas phase can be separated from the liquid phase containing the catalyst in suspension in the reactor, containing a catalyst for the liquid phase can be removed by management level.

EXAMPLE 5

This example describes the embodiment of providing circulation of catalyst between the various reactors. The corresponding diagram is shown in Fig. 5.

Since each reactor is a reactor with intensive stirring, introduced into the base of each reactor, the catalyst is uniformly distributed throughout a liquid phase in the reactor. In the example implementation shown in Fig. 5, unconverted gas fraction is separated at the head of the reactor, and the liquid phase containing the catalyst in suspension (catalytic suspension), overflowing and flows by gravity to the base of the next reactor. Transitional lines, providing passage from one reactor to the next reactor, should be as smooth slope. Collected at the outlet of the last reactor in the liquid phase at least partially separated from the contained catalyst and filtered. After that it is removed through line 110. The catalyst remaining in suspension in the residual liquid f is e (concentrated catalyst slurry), recycle together with this liquid phase in the first reactor on line, shown by the dotted line.

This embodiment can also be applied in the case where the device for separation and, in particular, for separating the gaseous phase is installed at the outlet of each reactor, as described in examples 2, 3 and 4.

The output of each of the reactors can also be separating the resulting liquid phase from the liquid phase with a high concentration of catalyst which is returned to the reactor. Instead of a single separator device SC in this case, you should set the number of separator devices corresponding to the number of reactors.

In Fig. 6 and 7 shows the schematic of the complete reactor with circulation, which can be used in the method according to the present invention. These reactors contain an internal heat exchanger, for example, consisting of cooling sections, preferably made in the form of pipes.

These reactors contain the power input and output, while water flows through the pipe 1, and the resulting steam is escaping through the pipe 2. Inside the reactor implemented system for dispersing the load 4. We can talk about the distribution plate for distributing gaseous download (synthesis gas)is fed through line 3. If necessary, the line can be fed liquid from the holding catalyst in suspension, the mixture of gas/liquid/solid phase implement at the entrance, in the case of the variant shown in Fig. 6 and 7. You can also provide separate input path of power, the system dispersion 4 receives only the gas. In Fig. 7 internal recirculation due to the design of the reactor.

EXAMPLE 6

In Fig. 8 shows another embodiment of a reactor in accordance with the present invention, with a particular variant of catalyst circulation. As in example 3, the installation includes two (first) reactor R1, R2, running in parallel to the synthesis gas, flows through the lines 100 and 102, and the reactor R3, connected and operated in series with the reactors R1 and R2, using the untransformed residual synthesis gas from the reactors R1 and R2 on lines 101 and 104. This residual synthesis gas or gas of the first stage of the process (preferably) in the setting S1 to the almost complete removal of water and possibly carbon dioxide, before directing the line 112 to power the reactor R3. Section S1 may correspond to the equipment S1 and S4 shown in Fig. 3, with the possible addition processing section T1, shown in the same figure. Special configuration, as shown in Fig. 8 and which is the difference from Fig. 3, relates to the circulation of the catalyst, i.e. the catalyst suspension at least one is solid catalyst in the liquid phase, usually consisting of the reaction products. This catalytic suspension is at least partially circulated counter-current between the different reactors, the flow catalytic suspension circulates from the last reactor R3 (the latter related to the circulation of synthetic gas) to the first reactor R2 through line 221. Another thread catalytic slurry is circulated from the reactor R2 to the reactor R1 through line 222. The third flow catalytic slurry is circulated from the reactor reactor R1 to R3 on line 223 through the separator section of the SC, then line 109, in which circulates (relatively more) concentrated catalyst slurry, and the flow of purified liquid is removed through line 110.

In an alternative embodiment, the reactor R1 is served catalytic suspension from R2, and catalytic suspension coming from R3, the first circulating line 221, and then shown by dashed line 224, the flow of catalyst slurry, removed from the reactor R2, in this alternative embodiment is directed to section SC on line 222, and then shown by the dotted line 225, then line 223.

In these two embodiments, the flow of the suspension circulates (directly, that is, not passing through the separator section) from the last or next reactor R3 to the previous or first reactor R1 or R2 (relative to the circulation syngas), and the flow is relatively concentrated suspension emerging from the separation unit SC, nourishes the last or the next reactor R3.

The advantage of these variants is that the last reactor R3 works when the concentration of the catalytic suspension that is more than the concentration of the suspension in the previous or initial(s) of the reactor(s) R1, R2. Indeed, the average concentration (catalyst) catalytic slurry reactor R3 lower concentration of the suspension flowing in R3 on line 109 due to the production of products in R3. In General, catalytic slurry leaving the reactor is less concentrated than the catalytic suspension flowing in the same reactor. The advantage of having relatively more concentrated catalyst slurry in the last reactor is that it allows you to compensate for the less favourable working conditions. With one hand behind R1 and R2 reactor R3 operates at a lower pressure than the pressure(I) reactors R1, R2. On the other hand, the synthesis gas in the reactor R1, R2 depleted reagents (H2/CO) and enriched by the reaction with an inert products, in particular methane. Therefore, due to these two phenomena, the partial pressure of the reactants (H2/CO) is significantly lower in the last (or previous) reactor R3 than in the previous or first reactor R1, R2. IP is the use of relatively high catalyst concentration in the last (or next) reactor allows to compensate the effect of lower partial pressure and makes it possible to maintain high the level of conversion in the last step. The mass content of the catalyst may be, for example, from 20 to 35 weight. %, in particular from 25 to 32 wt.%, in the first reactor R1, R2. In reactor R3 mass content of the catalyst may be a multiple of the coefficient To within from 1.03 to 1.25, in particular from 1.06 to 1.20, and, for example, from 1.08 to 1.18, compared to the value(s) percentage in one of the first (or the first) of the reactors R1, R2.

Often, in a particular variant described with reference to the previous figures, or in variants that are not represented in the present description, but obvious to a person skilled in at least one reactor (R1, R2 or R3) is fed (usually directly, i.e. without intermediate separation into fractions of the type of separation liquid/catalyst slurry) flow catalytic suspension coming from another reactor.

In General, the apparatus for implementing the method in accordance with the present invention (according to the configurations shown in the previous figures, or configurations, obvious to a person skilled in at least one reactor feed flow catalytic suspension coming directly from another reactor, and at least one flow catalytic suspension coming from the reactor, at least in part is divided in such a way as to obtain a liquid product, the PRA is almost devoid of catalyst, and catalytic slurry-enriched catalyst (concentrated), which then is recycled. Typically, each of the reactors is reported at least one other reactor through the stream of suspension sent directly to the other reactor or coming directly from the reactor.

Often enriched catalyst catalytic slurry recycle in the last reactor (e.g., R3) thus, in order to enrich the catalytic suspension in this last reactor in relation to the suspension(s) in other reactors, such as in one or more reactors (R1, R2).

How, in particular, may contain the first reaction stage is carried out in the first few reactors operating in parallel, while the gas fraction emerging from these early reactors, combined, processed and directed to the input of the last reactor. The conversion is performed in the first reactor can be defined so that all reactors have the same size.

Without leaving the scope of the present invention, it is possible to provide various modifications, obvious to the expert. In particular, in non-restrictive examples of options, the number of "first reactor" or "the last of the reactors may be different and, for example, be from 1 to 5. The above-described reactors R1, R2, R3 can be replaced reactionary the zones, which can be integrated into a smaller number of reactors, etc.

EXAMPLE 7

This example presents the material balance embodiments shown in Fig. 4.

The pipeline 100 with consumption 713 t/h enters the synthesis gas of the following composition in molar terms:

Water0,004
Hydrogen0,672
CO0,311
Methane0,013

In the used method involves three reactor R1, R2, R3 and almost complete mixing with the Peclet number from 0.02 to 0.03.

Reactor R1 operates at a temperature of 236°C. At the outlet of the reactor R1 after separation through a pipeline 200 is collected 66 t/h of liquid products containing 87% molar proportions of the components, the molecule of which contains at least 10 carbon atoms. After cooling, the gaseous phase is extracted 234 t/h of water (line 210), 67 t/h of condensed hydrocarbons (line 211) and 347 t/h of synthesis gas pressure of 2.8 MPa, which is sent to the reactor R2 through line 113 after mixing with 327 t/h of synthesis gas flowing through the pipeline 102.

At the exit of the reactor R2 after separation through the pipe 101 is collected 63 t/h of liquid products. After cooling the gaseous phase through line 212 retrieve the cabins 224 t/h of water, through the pipe 213 - 76 t/h of condensate through line 112 - 311 t/h of synthesis gas, which is sent to the reactor R3 after mixing with 293 t/h of synthesis gas by pipeline 106.

At the exit of the reactor R3 via pipeline 202 is collected 58 t/h of liquid products. After cooling, the gaseous phase is extracted 205 t/h of water, 75 t/h of condensate and 266 t/h of synthesis gas.

The overall performance of the conversion reaches 91%.

This example can be implemented with reactors of different sizes. You can also use reactors of the same size, adjusting the temperature and the conversion of liquid products used in the reactors R1, R2, R3, together with the distribution of the synthesis gas. The adjustment of conditions to increase the relative size of this reactor, providing such conditions can be realized by increasing the relative flow rate of the synthesis gas at the inlet of the reactor and/or by increasing the level of conversion in the reactor, and/or by lowering the temperature of the reactor. Preferably use only the first two parameters, the temperature remains almost the same. In the previous example, these conditions can be achieved with reactors of the same size in the management of neighboring values of pressure (which differ only by the loss of load), there is supported the bottom and the same temperature, equal to 236°C.

1. A method of converting synthesis gas into liquid hydrocarbons carried out in at least two serially connected reactors containing the catalyst suspension at least one solid catalyst in suspension in the liquid phase, according to which the specified three-phase reactors are reactors of the type of bubble columns with almost complete mixing, with the number of the scorching heat of the fluid is below 8 and the number of the scorching heat of the gas below 0.2 and a diameter of more than 6 m, with the last reactor at least partially served at least part of at least one of the gas fractions collected at the output of at least one of the other reactors at least one reactor feed flow catalytic suspension coming directly from another reactor, and at least one flow catalytic suspension coming from the reactor at least partially separated in such a way as to obtain a liquid product with virtually no catalyst and catalytic slurry-enriched catalyst, which is then recycle.

2. The method according to claim 1, wherein each of the reactors is reported at least one other reactor through the stream of suspension sent directly to the other reactor or coming directly from the reactor.

3. The method according to claim 1, in to the m specified catalytic suspension, enriched with catalyst recycle in the last reactor (R3) thus, in order to enrich the catalytic suspension of this last reactor in relation to the suspension of other reactors, for example, one or more reactors (R1, R2).

4. The method according to claim 1, containing the first reaction stage is carried out in the first few reactors operating in parallel, in which emerging from these first reactor gas fractions are combined, processed and sent to the last reactor.

5. The method according to claim 4, in which the conversion is performed in the first reactor, determine so that all reactors have the same size.

6. The method according to claim 3, in which the number of the scorching heat of the gas below 0.1.

7. The method according to claim 3, in which the output of each reactor gas phase is separated from the liquid phase containing the catalyst in suspension.

8. The method according to claim 3, in which the catalyst contains a porous mineral carrier and at least one metal deposited on the carrier, and the catalyst suspended in the liquid phase in the form of particles with a diameter less than 200 microns.

9. The method according to claim 3, in which the distribution of introducing the synthesis gas at the inlet of serially connected reactors determine thus to apply the reactors of the same size.

10. The method according to claim 3, in which a gas fraction, leaving the latter re ctor, recycle on the stage production of synthesis gas to power these reactors.

Priority items:

20.11.2001 - claims 1, 2, 4-10;

27.09.2002 - item 3.



 

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23 cl, 1 dwg

FIELD: petrochemical industry; methods of production of the polyolefin bases of the synthetic oils.

SUBSTANCE: the invention is pertaining to the method of production of the polyolefin bases of the synthetic oils by cationic oligomerization of the olefinic raw and may be used in petrochemical industry. The developed method contains: the stages of preparation of the olefinic raw, preparation and batching in the reactor of the solutions and suspensions of the components of the catalytic system Al(0)-HCl-(CH3)3CCl (TBX), isomerization of alpha-olefins and oligomerizations of the highest olefins and their mixtures under action of the catalytic system Al (0)-HCl-TBX, extractions of the dead catalyst, separation of the oligomerizate for fractions and hydrogenation of the extracted fractions under action of the catalytic agent Pd (0.2 mass %)/Al2O3+NaOH. The invention ensures improvement of the stages of the developed method. For prevention of the corrosion activity of the products the method additionally contains the stage of dechlorination of the present in the oligomerizate chlorine-containing oligoolefins by the metallic aluminum, triethylaluminum, the alcoholic solutions of KOH or using the thermal dehydrochlorination of the chlorine-containing polyolefins at the presence or absence of KOH. For improvement of the technical-and-economic indexes of the method at the expense of the increase of the output of the target fractions of polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C the method additionally contains the stage of the thermal depolymerization of the restrictedly consumable high-molecular polyolefins with the kinematic viscosity of 10-20 centistoke at 100°C into the target polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C.

EFFECT: the invention ensures improvement of all the stages of the developed method.

1 cl, 15 tbl

FIELD: petrochemical industry; methods of oil and fuels desulfurization.

SUBSTANCE: the invention is pertaining to the field of the oil and fuels desulfurization by ultrasound action on them. The method of the continuous removal of sulfides from liquid mineral fuel provides for mixing of the fuel, water medium and the dialkyl ether having the boiling point at the normal pressure of 25°C or above, and having the following formula R1OR2, in which R1 and R2 are the separate univalent alkyl groups, and the total number of carbon atoms in R1 and R2 is from 3 up to 7, with formation of the multiphase reaction medium. The multiphase reaction medium is passing through the ultrasonic chamber in the continuous running mode, in which the ultrasound acts on the multiphase reaction medium during the time sufficient to stimulate the transformation of the sulfides in the sulfides-containing mineral fuel into sulfones. The outgoing from the ultrasonic chamber multiphase reaction medium is spontaneously laminated into the water and organic phases. The organic phase is separated from the water phase in the form of the mineral fuel with the removed sulfides. The invention allows to effectively decrease the contents of sulfur in the source raw.

EFFECT: the invention ensures the effective reduction of the contents of sulfur in the source raw.

19 cl, 1 ex

FIELD: oil processing industry; petrochemical industry; methods of production of bitumen.

SUBSTANCE: the invention is pertaining to the field of reprocessing of the wastes of the oil processing industry and the petrochemical industry, in particular, to reprocessing the acid sludges and can be used for production of the bitumens applied in the road construction, in production of roofing and insulating and other materials. Substance: the acid sludge preferentially with the contents of sulfuric acid, which is not exceeding 7 % from mass of the residual acid sludge, is heated in the flowing reactor at the temperatures of the cracking and below the temperature of the coke formation. The nonvolatile hydrocarbon fraction is withdrawn from the reactor. The components with the boiling point above 200°C are extracted from the vapor hydrocarbon fraction and mixed with the non-volatile hydrocarbon fraction.

EFFECT: the invention ensures production of the bitumens applied in the road construction, in production of roofing, insulating and other materials.

2 cl, 1 dwg, 2 ex

FIELD: petroleum industry.

SUBSTANCE: invention relates to methods for processing petroleum residues in aim for preparing refined raw used in different processes in petroleum processing and to methods for isolating and concentrating heavy metals representing the industrial profit by using adsorbent adding to the reaction mass as a powdered form. For preparing liquid petroleum products a synthetic material is used as adsorbent based on hydroxyapatite of the formula Ca10(PO4)6(OH)2 adding to the reaction mass as a suspension. Demetallization of heavy petroleum raw is carried out in the presence of adsorbent, and process is carried out at temperature 200-250°C. Invention provides enhancing effectiveness, decreasing cost and expanding assortment of contact materials used in processes for adsorption demetallization of heavy petroleum raw.

EFFECT: improved preparing method.

6 tbl, 9 ex

FIELD: petrochemical processes.

SUBSTANCE: natural or associated gas and oxidizing gas are passed in continuous or pulse mode at 200-700°C and pressure 1 to 50 atm through catalyst represented by modified naturally occurring mineral schungite containing 90-95% of carbon constituent including 20 to 90% of nanocarbon forms, 70% of which have open channels, or modified schungite as carrier with metallic cocatalyst incorporated therein in amount up to 2%.

EFFECT: increased productivity of process.

6 cl, 18 ex

FIELD: crude oil treatment.

SUBSTANCE: invention relates to methods of treatment of crude oil before subsequent transportation, in particular to treatment of sulfur crude oils and gas condensates with high contents of hydrogen sulfide and mercaptans. Treatment of hydrogen sulfide-containing crude oil is carried out via multistep separation and blow-out with hydrocarbon gas either in low-pressure separation step or in additional desorption column at 25-80°C and pressure 0.1-0.5 MPa until degree of removal of hydrogen sulfide contained in crude achieves 55-90% followed by neutralization of remaining amounts of hydrogen sulfide by adding, at stirring, effective amounts of 20-40% water-alkali solution of sodium nitrite with pH at least 11 or 18-40% aqueous solution of sodium sulfite and sodium bisulfite at sulfite-to-bisulfite molar ratio 1:(0.3-0.9). In this case, sodium nitrite water-alkali solution is added on the basis of 0.9-2.0 mole (preferably 1-1.5 mole) nitrite and aqueous solution of sodium sulfite and bisulfite on the basis of 1-2 mole sulfite and bisulfite per 1 mole residual hydrogen sulfide. When treating hydrogen sulfide and mercaptan-containing crude, the latter is added with 0.9-2 mole (preferably 1-1.5 mole) nitrite per 1 mole residual hydrogen sulfide and light methyl- and ethylmercaptans. Alkali agent in above water-alkali solution of sodium nitrite is sodium hydroxide and/or water-soluble organic amine. Hydrocarbon gas used for the blow-up is preliminarily liberated from hydrogen sulfide separation gas from H2S-containing crude oil or low-sulfur petroleum gas, or natural gas preferably used on the basis of 2.5 to 10 m3/m3 oil.

EFFECT: increased efficiency of process due to elimination of pollution of commercial petroleum with nitrogen-organic compounds and use of accessible, inexpensive, and less toxic neutralizer, simultaneous neutralization of petroleum acids, reduced acidity and corrosiveness of treated commercial petroleum.

9 cl, 1 dwg, 1 tbl, 8 ex

FIELD: organic synthesis catalysts.

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

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

FIELD: organic synthesis catalysts.

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

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

33 cl, 9 dwg, 1 tbl, 10 ex

FIELD: organic chemistry, chemical technology.

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

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

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

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

EFFECT: increased efficiency of cleaning method.

23 cl, 1 dwg

FIELD: petroleum chemistry.

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

EFFECT: improved method of synthesis.

4 cl, 1 tbl, 1 dwg, 1 ex

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

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

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

8 cl, 1 tbl, 1 ex

FIELD: alternate fuel production and catalysts.

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

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

7 cl, 2 tbl, 15 ex

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

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

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

3 cl, 9 ex, 9 dwg

FIELD: organic chemistry.

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

EFFECT: improved method for production of linear olefins.

12 cl, 3 tbl, 1 dwg, 2 ex

FIELD: organic synthesis catalysts.

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

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

FIELD: petrochemical process catalysts.

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

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

7 cl, 1 tbl, 10 ex

FIELD: hydrocarbon manufacturing.

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

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

7 cl, 3 dwg, 1 tbl, 5 ex

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