Catalyst and method for preparing hydrocarbons

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing mainly C5+-hydrocarbons. Method involves contacting carbon monoxide with hydrogen at temperature 180-270°C and under increased pressure in the presence of catalytic composition comprising as measure for the total mass of catalytic composition from 5 to 30 wt.-% of cobalt, from 0.01 to 5 wt.-% of manganese and at least from 0.01 to 0.9 wt.-% of rhenium and/or ruthenium on a carried made of titanium dioxide. Invention provides reducing amount of carbon dioxide evolved in the process of hydrocarbons synthesis by Fisher-Tropsh to the level 2% vol./vol., not above, but preferably to 1% vol./vol., not above, and without reducing C5+-selectivity.

EFFECT: improved preparing method.

7 cl, 2 tbl, 4 ex

 

The technical field to which the invention relates.

The present invention relates to a catalyst and to a method for producing hydrocarbons from synthesis gas.

The level of technology

The preparation of hydrocarbons from a mixture of gases comprising carbon monoxide and hydrogen (synthesis gas)in the presence of a catalyst at elevated temperature and pressure is well known in the prior art as the Fischer-Tropsch synthesis.

Catalysts which are suitable for Fischer-Tropsch synthesis, contain, as a rule, one or more catalytically active metals from U - X group of the Periodic table of elements. In particular, iron, Nickel, cobalt and ruthenium are well-known catalytically active metals for such a catalyst, which may not necessarily be combined with one or more metal oxide and/or metals as promoters. It is established that cobalt is the best catalyst in a catalytic method for the conversion of synthesis gas mainly saturated hydrocarbons containing 5 or more carbon atoms. In other words, such a high catalyst C5+the selectivity.

There are other applications of the catalysts of similar composition, including JP-A-404122454 describes the catalyst used for purification of exhaust gases; it contains as an asset of the CSO component metal of the platinum group, such as ruthenium, rubidium, palladium or platinum, or a metal oxide, such as chromium, manganese, cobalt or Nickel, on the media, which is used as the aluminum oxide, silicon dioxide, titanium dioxide, silicon dioxide-titanium dioxide or aluminum oxide-titanium dioxide. Such catalysts suitable for use in catalytic converters intended for purification of exhaust gases, and can be used to regulate the emissions of harmful substances from the exhaust of a petrol engine.

In US-A-5134109 offered the catalyst for reforming hydrocarbons with steam, which contains at least one metal selected from rhodium and ruthenium and at least one metal selected from cobalt and manganese supported on a carrier, which is preferably a Zirconia or stabilized Zirconia.

JP-A-60064631 discloses a catalyst containing a metal of the iron group, for example, cobalt or iron, platinum group metals, such as ruthenium, rhodium, palladium, platinum or iridium, and manganese oxide supported on a carrier containing titanium dioxide. JP-A-60064631 also discloses a method of obtaining a high-calorie gas containing a hydrocarbon, C1-C4for use as fuel, low-calorie gas, representing MES hydrogen and carbon monoxide and, optional, with carbon dioxide.

JP-A-60064631 relates mainly to a method for producing methane and hydrocarbons With2-4and in no way implies an increase in the percentage With5+selectivity in the conversion of the low-calorie gas. Indeed, in example 2, which is the only example of conversion of a simple mixture of CO/H2you can ensure that when processing a mixture of 3 parts of H2and 1 part of CO in the presence of a catalytic composition containing 10% Co, 6% Mn2About3and 2% Ru on titanium media, get 74,6% CH4, 7.3% From2H6, 5,5% C3H8to 2.6% With4H10and 10.0% CO2(% by volume), i.e. With5+hydrocarbons are not installed. The conversion was carried out at 320°and, although the temperature regime presents a wider range from 150 to 400°With, as the preferred specified interval from 260 to 350°C.

Although in the patent US-A-4568663 describes promoted with cobalt rhenium catalyst on an inorganic oxide carrier, preferably titanium dioxide, which exhibits high activity and can be used to produce hydrocarbons as in the FT-synthesis, and the conversion of methanol, the catalyst is discussed in the patent US-A-4857559 in column 2, lines 19-35, where he is opposed to correspond to the second catalyst on aluminum oxide with a significantly higher activity.

Much research work has been done in the direction of the search catalysts, which are higher than the known catalysts With5+the selectivity with the same or higher activity.

The patent US-A-4857559 describes the addition of rhenium to the cobalt with the use of a number of well-known media, including oxides of aluminum, silicon, titanium, chromium, magnesium and zirconium, as well as the way the FT synthesis hydrocarbons with the use of the catalyst. However, (column 4, lines 54-59 and column 15, lines 51-55) noted that although the use of other media, in addition to aluminum oxide, Pets, catalysts based on them have a much lower activity. In the patent US-A-4 857559 determined that the yield of hydrocarbons, obtained by the addition of rhenium to the cobalt aluminum oxide as catalyst is higher than in the case of the use of an appropriate catalyst on titanium dioxide. In particular, when the FT-conversion of synthesis gas to hydrocarbons in the presence of promoted cobalt rhenium catalysts on alumina % CH4selectivity is lower, % conversion WITH higher and higher With2+selectivity than in the presence of a similar catalyst on titanium dioxide (table 1).

TABLE 1
% selectivity
Example No..CoReMedia% CO conversionC2+CH4CO2
8121Al2O33387.711.40.9
3012-TiO2*1187.611.80.6
31121TiO2*1786.512.80.7
3212-TiO2**1187.611.70.7
33121TiO2**1785.813.50.7
* media calcined at 500°C.

** media, calcined at 600°C.

Proceeding from the above description, the person skilled in the art will come to the obvious conclusion that the use of TiO2 as a carrier for the United rhenium-cobalt catalyst should be abandoned in favor of Al 2About3.

In the synthesis of hydrocarbons by the Fischer-Tropsch produced a number of byproducts, including carbon dioxide, water and gaseous hydrocarbons1-4.

Along with the increase of the % CO conversion of paramount importance to meet individual requirements, such as increased % With5+selectivity and reducing output CH4and CO2acquires the ability to adjust the list of products resulting from the reaction of the Fischer-Tropsch process.

Highly desirable, based on both economic considerations and guided by environmental considerations, is to reduce the amount of carbon dioxide emitted in the process of synthesis of hydrocarbons by the Fischer-Tropsch. In particular, it is desirable to limit the release of carbon dioxide, a byproduct of this process, up to a level of not higher than about 2./vol.%, preferably not above about 1./vol.%.

First of all it is important that the methods used to reduce CO2selectivity in the Fischer-Tropsch synthesis, would not have led to the reduction With5+the selectivity.

As can be seen from table 1, while the addition of rhenium to the cobalt catalyst on titanium dioxide leads to a slight increase of the activity: 11% conversion of carbon monoxide to 17% conversion of carbon monoxide With2+selectivity Pont is supplied, a CO2selectivity is equal to or increases in comparison with the corresponding apromotional catalyst.

WO-A-97/00231 relates to a catalyst containing cobalt and manganese and/or vanadium on the media, where the atomic ratio of cobalt: (manganese + vanadium) is at least 12:1.

This catalyst compared with catalysts containing one containing cobalt or manganese and/or vanadium in a relatively larger quantity, demonstrates higher With5+selectivity and higher activity in the synthesis of hydrocarbons by the Fischer-Tropsch. The preferred carriers are titanium dioxides, zirconium and mixtures thereof.

Highly desirable is not only a further increase With5+the selectivity of such cobalt-manganese catalysts, but also the reduction of CO2the selectivity.

Now unexpectedly discovered that the addition of small amounts of rhenium and/or ruthenium to cobalt-manganese mixed catalyst not only leads to a decrease in CO2selectivity, but allows a significant way to adjust the list of products obtained in the synthesis of hydrocarbons by the Fischer-Tropsch.

The invention

The present invention relates to a method for producing predominantly With5+the hydrocarbon is in, comprising contacting carbon monoxide and hydrogen at a temperature in the range from 180 to 270°and at an elevated pressure in the presence of a catalyst composition comprising cobalt, manganese and at least rhenium and/or ruthenium on a carrier of titanium dioxide.

According to another aspect of the present invention relates to catalytic compositions containing cobalt, manganese and rhenium on a carrier of titanium dioxide.

Detailed description of the invention

The term "predominantly" in the description of the present invention refers to the content exceeds 80 wt.%, based on the distribution of saturated hydrocarbons and carbon dioxide.

Under "range of products" in the description of the present invention refers to the full composition of the products obtained in the synthesis of hydrocarbons by Fischer-Tropsch, i.e. relative content1-4hydrocarbon, C5+hydrocarbons, water and carbon dioxide present in the resulting mixture.

The mass ratio of the rutile: anatase in the carrier of titanium dioxide is not limited to the above, and this ratio may be lower than 2:3, when the determination in accordance with ASTM D 3720-78.

The carrier of titanium dioxide can be prepared by any known from the prior art method, however, particularly preferred is the preparation, the tion of the media in the absence of sulfur-containing compounds. One example of such a method of preparation includes flame hydrolysis of titanium tetrachloride. It should be borne in mind that the powder of titanium dioxide obtained by this method may not meet the required size and shape. In this connection typically requires stage molding process for preparation of media. The molding techniques well known to the person skilled in the art and include grain size, extrusion, spray drying and passing through the dropper with hot oil as the liquid droplet.

Titanium dioxide is available as a commercial product and is well known as a material used for the preparation of catalysts or catalyst precursors.

Alternatively, or in addition to titanium dioxide, the mixture may contain a precursor of titanium dioxide. Titanium dioxide can be obtained by heating the titanium hydroxide. In the process of heating the titanium hydroxide is converted to titanium dioxide through a number of intermediate forms and sequential allocation of water molecules. The term "precursor of titanium dioxide" in the present description should be understood as a reference to the titanium hydroxide or any of the above intermediate forms.

Catalysts that can be used in the method according to the present invention preferably contain about the 5 to 30 wt.% With the calculation on the total weight of the catalytic composition, more preferably from 10 to 25 wt.% With the calculation on the total weight of catalytic composie and most preferably from 15 to 25 wt.% With the calculation on the total weight of the catalytic composition.

Catalysts that can be used in the method according to the present invention contain from 0.01 to 5 wt.% Mn calculated on the total weight of the catalytic composition, more preferably from 0.01 to 1.5 wt.% Mn calculated on the total weight of the catalytic composition.

Catalysts that can be used in the method according to the present invention preferably contain from 0.01 to 5 wt.% each:

rhenium and/or ruthenium, based on the total weight of the catalytic composition, more preferably from 0.01 to 1 wt.% each: rhenium and/or ruthenium, based on the total weight of the catalytic composition, and most preferably from 0.01 to 0.5 wt.% rhenium and/or ruthenium calculated on the total weight of the catalytic composition.

Catalysts that can be used in the method according to the present invention can optionally contain up to 20 wt.% binders, such as, for example, aluminum oxide or silicon dioxide, based on the total weight of the catalytic composition, preferably up to about 10 wt.% binders such as alumina or silicon dioxide, calculated on the total weight rolled the practical composition.

In the present invention, the size and the pore volume of the catalytic composition prior to its activation are not limited. Fit can be considered as the pore size in the range from 0.1 to 0.8 cm3/g, preferably in the range from 0.15 to 0.7 cm3/g, more preferably in the range from 0.2 to 0.5 cm3/year

A catalyst corresponding to the invention, can be prepared with well-known specialists in the field of engineering methods, such as deposition of a catalytically active compound or their predecessors on the carrier; applying by spraying, mixing and/or impregnation of the carrier catalytically active compounds or precursors; and/or extrusion of one or more catalytically active compounds or precursors together with the material of the carrier to obtain extrudates of catalyst.

For the person skilled in the art will understand that the preferred method of preparation of the catalyst may vary depending on, for example, the required size of the catalyst particles. From the experience of a specialist depends on the choice of the most appropriate method for each particular case conditions.

Extrusion can be performed using any standard, commercially available extruder. In particular, by using a screw-type extruder can jacking CME and through the holes of a suitable matrix disk to obtain extrudates of desired shape. Formed in the extrusion process of continuously cast billets can be cut to the desired length.

After the extrusion, the extrudates are dried. Drying can be accomplished at elevated temperatures, preferably at temperatures up to 500°S, more preferably up to 300°C. the drying Time is usually up to 5 hours, more preferably from 15 minutes to 3 hours.

The catalytic composition, extruded and dried, may be subjected to annealing. The calcination is carried out at elevated temperature, typically in the range from 200 to 900°C, preferably at a temperature in the range from 400 to 750°S, more preferably in the range from 500 to 650°C. the Time of calcination is usually from 5 minutes to several hours, preferably from 15 minutes to 4 hours.

The calcination is convenient to implement in an environment containing oxygen, preferably air. It should be borne in mind that, if necessary, stage drying and calcination can be combined into one.

The preferred method of preparation of the catalyst according to the present invention is the impregnation of the support of catalytically active compounds or precursors. Thus, the carrier is impregnated with, typically, a solution of compounds of cobalt, a solution of compounds of rhenium and/or ruthenium and a solution of compound Marg the NCA. It is preferable to carry out the impregnation of the carrier at the same time all the compounds of the respective metals. Thus, according to a preferred variant of the method of preparation of the catalyst for use in the method according to the present invention, includes a joint carrier impregnated with solutions of the compounds, respectively, cobalt, rhenium and/or ruthenium and manganese.

As the preferred method of preparation of the catalyst according to the present invention is the mixing of several catalytically active compounds or precursors with the carrier, followed by extrusion of the mixture and further drying and calcining the extrudate, and subsequent impregnation his other catalytically active compounds and precursors to obtain catalytic extrudates, suitable for use in the method according to the invention.

So, the media, usually mixed with a compound of cobalt with a compound of manganese and water with subsequent extrusion of the mixture obtained, after drying and calcination are impregnated with a solution of compounds of rhenium and/or ruthenium to obtain catalytic extrudates, suitable for use in the method according to the invention. It is preferable to carry out the simultaneous mixing of the carrier with soy is inanami cobalt and compounds of manganese.

Thus, according to preferred embodiment of the invention, the preparation method of catalyst for use in the method according to the present invention includes a joint extrusion of the carrier compounds cobalt and compounds of manganese, further impregnating the extrudate with a solution of compounds of rhenium and/or ruthenium.

Examples of suitable compounds of cobalt, which can be used separately or in combination in the preparation of the above catalyst include cobalt hydroxide, cobalt oxide, a carbonyl compound of cobalt halides such as cobalt chloride (uranyl or anhydrous), inorganic salts, such as cobalt sulfate, cobalt nitrate or cobalt carbonate, and organic acid salts such as cobalt acetate and cobalt formate. Preferred compounds of cobalt is cobalt hydroxide, cobalt carbonate and cobalt nitrate.

Examples of suitable rhenium compounds, which can be individually or in combination is used in the preparation of the above catalyst include oxides of rhenium chloride, rhenium carbonyl compound of rhenium, ammonium perrhenate and perriniana acid. The preferred compound of rhenium is ammonium perrhenate.

Examples of suitable compounds of ruthenium, which can be - from what eljnosti or in combination - used in the preparation of the above catalyst, include one or more halides of ruthenium such as ruthenium chloride or ruthenium iodide, halide or salt of tetravalent ruthenium such as ruthenium tetrachloride, chlorobutanol (IV) ammonium, chlorobutanol (IV) sodium, chlorobutanol (IV) potassium oxide of ruthenium, for example, dioxide or tetroxide, ruthenium salt of the acid, as, for example, routenet potassium or routenet sodium, organic compound of ruthenium, for example, a carbonyl compound of ruthenium, nitrosylated ruthenium. The preferred compound of ruthenium is nitrosylated ruthenium.

Examples of suitable salts of manganese, which may be individually or in combination is used in the preparation of the above catalyst include manganese hydroxide, manganese oxide, halides, such as chloride of manganese, inorganic salts, such as manganese sulfate, manganese nitrate or manganese carbonate, and organic acid salts such as manganese acetate and manganese formate. Preferred compounds of manganese is manganese hydroxide, manganese nitrate and manganese acetate.

Impregnation, usually accompanied by subsequent drying and calcination. Drying usually carried out at a temperature in the range 50-300°for in lot up to 24 hours, preferably from 1 to 4 hours.

Calcination generally carried out at a temperature in the range of 200-900°C, preferably in the range from 250 to 700°C. the duration of the calcination, generally ranges from 0.5 to 24 hours, preferably from 1 to 4 hours. Typically, the temperature at the stage of annealing above the average temperature during the stage of drying.

In the operation of the catalyst proposed for the method of producing hydrocarbons, in accordance with the present invention may contain at least part of the cobalt in the metallic form.

Therefore usually desirable to activate the catalyst immediately before use by its reduction with hydrogen at elevated temperature. Typically, the recovery step includes processing the catalyst at a temperature of from 100 to 450°C for from 1 to 48 hours at an elevated pressure, typically from 0.1 to 20.0 MPa (from 1 to 200 bar abs.). Recovery can be used pure hydrogen, but it is preferable to use a mixture of hydrogen and inert gas, for example nitrogen. The relative amount of hydrogen in the mixture can vary from 0 to 100% by volume.

According to one preferred embodiment variants of the invention the catalyst is placed under prescribed conditions of temperature and pressure in the atmosphere g is sobrannogo nitrogen with subsequent contacting of the catalyst with a gas mixture, containing only a small amount of gaseous hydrogen (the remainder is nitrogen gas). In the process of restoring the relative hydrogen content in the gas mixture is gradually increased up to 50% or even 100% by volume.

If possible, the activation of the catalyst, it is preferable to carry out in situ, i.e. inside the reaction apparatus. In WO-A-97/17137 describes a method of activating the catalyst in situ, which is the contacting of the catalyst in the presence of a liquid hydrocarbon with a hydrogen-containing gas at a partial pressure of hydrogen of at least 1.5 MPa (15 bar abs.), preferably with at least 2.0 MPa (20 bar abs.), more preferably, when at least 3.0 MPa (30 bar abs.). Typically, in this method, the partial pressure of hydrogen of at most 20 MPa (200 bar abs.).

It is advisable to carry out the regeneration of the exhausted catalyst, i.e. a catalyst, lost, at least partially, the initial activity of the fresh activated catalyst, exposing his deformirovaniyu hydrogen or ROR-processing. Advantageously conduct ROR-processing by successively carrying out the recovery stage hydrogen-rich recycle gas, oxidation of oxygen-containing gas and hydrogen-rich recycle gas recovery.

The method according to nastasemarian preferably carried out at a temperature, in the interval from 200 to 250°C. the Pressure generally ranges from 0.5 to 15.0 MPa (5 to 150 bar abs.), preferably from 1.0 to 8.0 MPa (from 10 to 80 bar abs.), in particular from 1.0 to 6.0 MPa (from 10 to 60 bar abs.).

Convenient to serve the hydrogen and carbon monoxide (synthesis gas) for the reaction in a molar ratio in the range from 1 to 2.5.

Volumetric hourly rate of synthesis gas (GHSV) in the method according to the present invention can vary in a wide interval and, as a rule, in the range from 400 to 10000 N1 1-1h-1for example, from 400 to 4000 N1 1-1h-1. The term GHSV is well known in chemical engineering, he refers to the volume of synthesis gas in N1, i.e. in liters at standard temperature and pressure (0°C and 1 bar abs.) (STP), which is over an hour of time in contact with one liter of catalyst particles, i.e. excluding the volume of voids between the particles in the reaction suspension. For cases when using a fixed catalyst bed, the GHSV may also be expressed per liter of catalyst layer, i.e. taking into account the volume of voids between the particles.

A method of producing hydrocarbons according to the present invention can be carried out using reactors of different types and in different modes of reaction, for example, in fixed bed mode with the suspension phase or in the fluidized bed. It is clear that the size of the catalyst particles may vary depending on, for reactions in which mode they are intended. The correct choice of the most appropriate for a given mode of reaction of the particle size of the catalyst depends entirely on the experience of the specialist.

It is clear that the specialist can choose the most optimal settings depending on the specific design of the reaction apparatus and the manner in which it will be reaction. So, in terms of the synthesis of hydrocarbons mode with a fixed layer, it is preferable to choose a volumetric hourly rate in the range from 500 to 2500 N1 1-1h-1. If you want to carry out the reaction of the hydrocarbon synthesis in slurry phase, it is preferable to choose a speed in the range from 1500 to 7500 N1 1-1h-1.

Information confirming the possibility of carrying out the invention

The following examples serve only to illustrate the present invention and in no case should not be construed as limiting the scope of the claims.

EXAMPLES

Example 1 (comparative)

Prepare a mixture consisting of to 112.5 g of a commercially available powder of titanium dioxide (P25 ex. Degussa), 49.5 g of a commercially available powder of cobalt hydroxide Co(OH)2and 8.2 g of Mn(Ac)2·4H2(Where "AC" means the acetate) and 45 g of water. The mixture is stirred for 30 min and then formed from pommosubscriber.

The extrudates are dried for 2 hours at 120°and then calcined for 2 hours at 500°C.

In the thus prepared catalyst (I) the percentage of compounds of cobalt, calculated on the cobalt metal is 22 wt.% and compounds of manganese, calculated on the metal manganese, 1.2 wt.% calculated on the total weight of the entire catalyst composition.

Example 2

Part of catalyst (I) is impregnated with an aqueous solution of ammonium perrhenate (NH4ReO4).

The extrudates are dried for 2 hours at 120°and calcined for 2 hours at 500°C.

In the thus prepared catalyst (II) the percentage of compounds of cobalt, calculated on the cobalt metal is 22 wt.%, compounds of manganese, calculated on the metal manganese, to 1.2 wt.%, compounds of rhenium, calculated on the metal rhenium (9,7×10-6mol Re/gram catalyst), is to 0.18 wt.% calculated on the total weight of the entire catalyst composition.

Example 3

Part of catalyst (I) is impregnated with an aqueous solution of nitrosylated ruthenium (Ru(NO)(NO3)×(OH)yx+y=3).

The extrudates are dried for 2 hours at 120°and calcined for 2 hours at 500°C.

In the thus prepared catalyst (III) the percentage of compounds of cobalt, in the calculations of the e on the cobalt metal is 22 wt.%, compounds of manganese, calculated on the metal manganese, to 1.2 wt.%, compounds of ruthenium, based on the metal ruthenium (9,9×10-6mol EN/gram catalyst), is 0.10 wt.% calculated on the total weight of the entire catalyst composition.

Example 4

Testing of the catalyst is carried out according to the method described in WO-A-97/00231. Catalysts I, II and III testing in the method of producing hydrocarbons. In microphotonic reactors a, b and C, containing 10 ml of catalysts I, II and III, respectively, in the form of a stationary particle layer, bring the temperature up to 260°and pump pressure up to 0.2 MPa (2 bar abs.) with a constant supply of gaseous nitrogen. Catalysts restore the in situ gaseous mixture of nitrogen and hydrogen for 24 hours. During recovery gradually increase the relative amount of hydrogen in the mixture from 0% to 100%. The humidity of the gas at the outlet support below 3000 ppmv (parts per million volume).

After restoring the pressure increase to 2.6 MPa (26 bar abs.). The reaction is carried out using a mixture of nitrogen and carbon monoxide in the ratio of N2/, Equal to 1.1:1. GHSV reaches 800 N1 1-1h-1(nl/kg/HR.). The reaction temperature is expressed as the weighted average bed temperature (WABT) With°. After 50 hours after treatment, define the following parameters for each experiment is: yield (STY), expressed in grams of hydrocarbon product per liter of catalyst particles (including the voids between particles) per hour; (C5+selectivity, expressed as a percentage of the mass of the hydrocarbon product; and CO2selectivity, marajauna as the mole percentage of converted WITH. The results are shown in Table 2.

TABLE 2
CatalystIIIIII
WABT (°)209202206
STY (g 1cat-1h-1)100100100
C5+selectivity (%)929594
CO2selectivity (%)1.21.00.8

As follows from the table, in addition to lowering CO2selectivity, activity and C5+the selectivity of both declared according to the present invention catalysts II and III, much better than the same characteristics of catalyst I.

1. The way of getting mostly C5+hydrocarbons, comprising contacting carbon monoxide with hydrogen at a temperature of 180-270°and increased pressure in the presence of catalytic to the notizie, containing calculated on the total weight of the catalytic composition is from 5 to 30 wt.% cobalt, from 0.01 to 5 wt.% manganese and at least from 0.01 to 0.9 wt.% rhenium and/or ruthenium on a carrier of titanium dioxide.

2. The method according to claim 1, where the temperature is in the range of 200-250°C.

3. The method according to any one of claims 1 and 2, which is carried out using a fixed catalyst layer.

4. Catalytic composition containing calculated on the total weight of the catalytic composition, the cobalt from 5 to 30 wt.%, manganese, from 0.01 to 5 wt.% and rhenium, at least from 0.01 to 0.9 wt.% on the media of titanium dioxide.

5. The activated catalyst for synthesis of hydrocarbons obtained by reduction with hydrogen at elevated temperature catalytic composition according to claim 4.

6. The method for the catalytic composition according to claim 4, comprising the extrusion of the carrier of titanium dioxide with compounds of cobalt and manganese with subsequent drying and, optionally, annealing and subsequent impregnation with a solution of salt of rhenium.

7. The way to obtain an activated catalyst according to claim 5 by reduction with hydrogen at elevated temperature catalytic composition according to claim 4.



 

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2 cl, 2 tbl, 2 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

The invention relates to catalysts for obtaining hydrocarbons, including liquid synthetic fuels, olefins, solid hydrocarbons and their oxygenated derivatives, such as alcohols from a mixture of CO and hydrogen

The invention relates to the production of hydrocarbons from synthesis gas

The invention relates to a method of separation of olefins from saturated hydrocarbons, and more specifically to a method of separation of olefins from saturated hydrocarbons in the stream of the Fischer-Tropsch (FT)

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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