Method of production of the hydrocarbons out of the gaseous hydrocarbon raw materials

FIELD: chemical industry; natural gas industry; methods of production of the hydrocarbons out of the gaseous hydrocarbon raw materials.

SUBSTANCE: the invention presents the method of production of the hydrocarbons out of the gaseous hydrocarbon raw with usage of Fischer-Tropsch catalyst including the following phases: i) transformation by means of the partial oxidization of the gaseous hydrocarbon raw material and the oxygen-containing gas into the synthesis gas at the heightened temperature and pressure; ii) the catalytic conversion of the synthesis gas of the phase (i) with usage of Fischer-Tropsch catalyst on the basis of cobalt on zirconium oxide into the stream containing the hydrocarbon; iii) division of the hydrocarbons-containing stream of the phase (ii) into the stream the hydrocarbon product and the recycling stream; and iv) withdrawal of the carbon dioxide from the recycling stream and return of the carbon dioxide depleted recycling stream into the phase (i).

EFFECT: the invention ensures effective production of the hydrocarbons out of the gaseous hydrocarbon raw materials.

6 cl, l tbl, 1 ex

 

The technical field to which the invention relates.

The present invention relates to a method of producing hydrocarbons from a gaseous hydrocarbon.

This method first involves the conversion of hydrocarbons into synthesis gas by partial oxidation using oxygen-containing gas. After that, the synthesis gas is catalytically converted into hydrocarbons using a catalyst Fischer-Tropsch process.

Prior art

In the patent US-A-4046829 disclosed a method of producing hydrocarbons from coal using catalyst Fischer-Tropsch iron-based. The coal is gasified and the resulting synthesis gas is subjected to wet cleaning and then to partial oxidation with oxygen. After the conversion of synthesis gas by the Fischer-Tropsch separate light hydrocarbons, which recycle and after the removal of carbon dioxide they are mixed with the synthesis gas and then subjected to partial oxidation.

In the patent US-A-4433065 disclosed a method of producing hydrocarbons from coal using catalyst Fischer-Tropsch cobalt-based. After removal of liquid hydrocarbons from the gas phase to remove the carbon dioxide. After separation of the hydrogen-rich stream is returned to the partial oxidation process, a stream containing light hydrocarbons, return to the process gas in the classification of coal, and a stream containing carbon monoxide, is subjected to combustion to generate electricity.

In the patent US-A-5324335 disclosed a method of producing hydrocarbons from coal using catalyst Fischer-Tropsch iron-based, where the hydrocarbon gas is subjected to steam reforming with the aim of obtaining synthesis gas. After removal of carbon dioxide, synthesis gas is subjected to transformation by Fischer-Tropsch. Light hydrocarbons are separated, recycled and mixed with the synthesis gas.

Disclosure of the invention

The aim of the present invention is to develop a method for the production of relatively heavy hydrocarbons using a cobalt catalyst for Fischer-Tropsch. More specifically, the invention relates to a cobalt catalyst, in particular cobalt-zirconium catalyst, which facilitates production of relatively large quantities of hydrocarbon fractions With10-C14along with the lighter and heavier fractions. However, this favoring the formation of C10-C14-hydrocarbons, particularly unsaturated hydrocarbons, is a consequence of the formation of large quantities of exhaust gases in comparison with the process, which is optimal for the formation of most heavy paraffinic products. In projects of installations on the basis of modern concepts of these is Rhodesia gases may not be directed to flaring, but should be used or subjected to recycling.

The present invention offers a solution to the problem in the method of producing hydrocarbons from a gaseous hydrocarbon feedstock, comprising the following stages:

i) conversion by partial oxidation of a gaseous hydrocarbon and oxygen-containing gas in the synthesis gas at elevated temperature and pressure;

ii) catalytic conversion of synthesis gas stage (i) using a catalyst Fischer-Tropsch-based cobalt-containing hydrocarbon stream;

iii) separation containing hydrocarbon stream stage (ii) on the stream of hydrocarbon product and a recycle stream; and

iv) removing carbon dioxide from re-circulating flow and return depleted carbon dioxide recycle stream to the step (i).

According to the method of the invention containing hydrocarbon stream is separated into a stream of hydrocarbon product and recirculating flow. From the recirculating stream to remove carbon dioxide and depleted in carbon dioxide recycle stream is used as a raw material for transformation using partial oxidation. Remove predominantly of at least 70 vol.% carbon dioxide, preferably at least 80 vol.% and, even more preferably at least 90 vol.%. R the recirculating flow mainly includes hydrogen, carbon monoxide, C1-C3-hydrocarbons, in some cases With4and a small number With5+-hydrocarbons and inert substances such as nitrogen and inert gases.

Recycling recycle stream without first removing carbon dioxide has led to the synthesis gas with a low ratio of N2/WITH that is unacceptable for use in the process of converting synthesis gas according to the method of Fischer-Tropsch in the target hydrocarbons. Direct use of re-circulating flow for the conversion by partial oxidation would lead to the synthesis gas with an excessively high content of inert substances. Remove the carbon dioxide before it is used for the conversion by partial oxidation should reduce the amount of inert substances in the resulting synthesis gas. In turn, the use of depleted carbon dioxide recirculating flow leads to a lower consumption of oxygen for the conversion by partial oxidation. The recirculated flow optimizes the performance of the process on carbon. This, in turn, increases thermal efficiency of the process. Finally, the carbon dioxide removal costs less than the transformation of carbon dioxide to carbon monoxide.

According to the invention, the method allows the use of CA is Aligator Fischer-Tropsch cobalt-based, in particular, the catalyst containing cobalt, zirconium oxide, which contributes to obtaining10-C14-hydrocarbons, while the exhaust gases do not cause a significant increase in expenses and the amount of carbon dioxide that must be removed is minimal due to the use of hydrocarbons, which produces less carbon dioxide.

The recycling process is depleted in carbon dioxide recirculating flow is simplified when this depleted carbon dioxide recycle stream first komprimiert, mixed with gaseous hydrocarbons and then subjected to conversion by partial oxidation using oxygen-containing gas.

To avoid accumulation in the process of inert substances it is advisable that part of the recycle stream from step (iii), for example from 5 to 50 vol.%, preferably from 10 to 40 vol.%, all flow was used as a fuel reforming with water vapor gaseous hydrocarbon feedstocks to hydrogen addition to the synthesis gas production stage (i).

Accordingly, inert materials, such as carbon dioxide and nitrogen, is removed from the process after combustion as the combustion gas, while hydrogen or enriched in hydrogen synthesis gas, abrazos is the action scene in the process of reforming of methane with water vapor, can be used to adjust the relationship of H2/CO in the synthesis gas.

According to another preferred variant, the portion of the recirculating gas stage iii or stage (iv) is used as fuel to generate electricity.

Finally, it is preferable that the flow of the hydrocarbon product was subjected to catalytic hydrocracking. When this molecular weight distribution of the produced hydrocarbons can be adjusted.

Suitable hydrocarbons include methane, natural gas, associated gas or a mixture With1-C4-hydrocarbons. The raw material contains mainly, i.e. more than 90 vol.%, mostly more than 94%, With1-C4-hydrocarbons and preferably contains at least 60 vol.% methane, preferably at least 75%, more preferably 90%. Very appropriate use of natural gas or associated gas. In the case of raw materials suitable sulfur removal.

Generated in the process and referred to in the present description hydrocarbons (usually liquid or solid) are mainly3-C100-hydrocarbons, preferably4-C60-hydrocarbons, in particular With5-C40-hydrocarbons and, more preferably, From6-C20-hydrocarbons or their mixtures which. These hydrocarbons or mixtures thereof are liquid or solid at temperatures from 5 to 30°C (1 bar), in particular at 20°C (1 bar), and usually have a paraffinic nature, while perhaps the content up to 30 wt.%, preferably up to 15 wt.%, either olefins or oxygenated compounds.

Partial oxidation of gaseous raw materials, giving a mixture of mainly carbon monoxide and hydrogen, is carried out on the installation of oxidation in accordance with various developed methods. Can be used as catalytic and non-catalytic methods. Among these methods is the Process of Gasification company Shell. A detailed description of this process can be found in the Oil and Gas Journal, September 7, 1971, p.86-90. The partial oxidation process can be carried out in conjunction with the process of reforming, such as autothermal reforming process.

Oxygen-containing gas is air (containing about 21% oxygen) or oxygen-enriched air, mainly containing up to 100% oxygen, preferably at least 60 vol.% oxygen, more preferably at least 80 vol.% oxygen, more preferably at least 98 vol.% the oxygen. Oxygen-enriched air can be obtained by using cryogenic methods, but mainly it is derived membrane manner, for example by the method described in WO93/06041.

For an attitude adjustment H2/CO in the synthesis gas in a partial oxidation process can be carbon dioxide and/or water vapor. To add raw or carbon dioxide, or water vapor in quantities mainly up to 15% vol. in the calculation of the synthesis gas, preferably up to 8% vol. and, more preferably, up to 4 vol.%. As a suitable source of water vapor can be used water formed in the synthesis of hydrocarbons. As a suitable source of carbon dioxide may be used carbon dioxide from waste gases in the expansion stage of combustion. The relation of H2/CO in the synthesis gas is mainly in the range from 1.5 to 2.3, preferably from 1.8 to 2.1. If desired (small) additional quantity of hydrogen can be obtained by reforming of methane, preferably in combination with the reaction of the water transfer. As carbon monoxide and carbon dioxide generated together with hydrogen, can be used in the reaction for the synthesis of hydrocarbons or recycling with the aim of increasing the efficiency of the carbon.

The share of processed hydrocarbons, which turns into the first stage of the process of the invention is mainly 50-99 wt.%, preferably about 80 to 98 wt.% and, more preferably, 85-96 wt.%.

A gaseous mixture comprising mainly hydrogen, is KIS carbon and possibly nitrogen, enter into contact with a suitable catalyst at a stage catalytic conversion, which usually produces liquid hydrocarbons. With the catalyst comes into contact, at least 70 vol.% synthesis gas, preferably at least 80%, more preferably at least 90%, even more preferably, the whole amount of the synthesis gas.

The catalysts used for the catalytic conversion of a mixture comprising hydrogen and carbon monoxide, hydrocarbons, in the technique known and generally referred to as catalysts for Fischer-Tropsch. Catalysts for use in the synthesis of hydrocarbons by the Fischer-Tropsch include as catalytically active component, a cobalt.

The catalytically active cobalt is mainly applied to porous media. The porous carrier may be selected from suitable refractory oxides or silicates of metals, or their known in the art of combinations. Among the specific examples of preferred porous media composed of oxides of silicon, aluminum, titanium, zirconium, cerium, gallium and mixtures thereof, first and foremost, the oxides of silicon and titanium.

The amount of catalytically active cobalt on the media lies mainly in the range from 3 to 300 weight. parts per 100 weight. parts of the material of the carrier, preferably from 10 to 80 weight. parts and, most preferably, from 20 to 60 weight parts.

If desired, the catalyst for the Fischer-Tropsch cobalt-based may also contain one or more metals or metal oxides as promoters. Suitable metal oxide promoters can be selected from groups IIA, IIIB, IVB, VB and VIB of the Periodic table of the elements or from actinides and lanthanides. In particular, the oxides of magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, titanium, zirconium, hafnium, thorium, uranium, vanadium, chromium and manganese are the most suitable promoters. Particularly suitable metal oxide promoters for the catalyst used to obtain waxes, for use in the present invention are the oxides of manganese and zirconium. Suitable metal promoters can be selected from groups VIIB and VIII of the Periodic table. Especially suitable are the rhenium and the noble metals of group VIII, particularly preferred of them are platinum and palladium. The number present in the catalyst promoter is mainly in the range from 0.01 to 100 weight. parts, preferably from 0.1 to 40, more preferably from 1 to 20 weight. parts per 100 weight. parts of the media.

The catalytically active cobalt and promoter (in case of its presence) can be applied on a material carrier using any suitable process, such as impregnation, mixing or extras is her. After application of cobalt and optionally promoter on material media last coated components are usually subjected to calcination at a temperature of generally from 350 to 750°With, mainly at temperatures ranging from 450 to 550°C. the Aim of the operation of annealing is to remove water of crystallization, decomposition of volatile products of decomposition and transformation of organic and inorganic compounds to the corresponding oxides. Formed after calcination the catalyst may be activated by the performance of its contact with hydrogen or a hydrogen-containing gas, usually at temperatures of from about 200 to 350°C.

The process of catalytic conversion can be carried out on the conversion setting in a traditional, well-known in the technique of synthesis conditions. Typically, the catalytic conversion can be effected at a temperature in the range from 150 to 350°C, preferably from 180 to 270°C. Usually applied full pressure for catalytic conversion is in the range from 1 to 200 abs. bar, more preferably from 10 to 70 abs. bar. In the catalytic conversion are mainly formed With5-C20-hydrocarbons (at least 50 wt.% C5+, preferably 70 wt.%).

Number10-C14that directly formed on the adiya's (ii) of the process, is mainly from 12 to 27 wt.% for flow of the product5+preferably from 17 to 27 wt.% and, more preferably, from 22 to 27 wt.%. Preferred large number as a fraction With10-C14is a valuable raw material for long continuous fibers.

The average value of the ASF (signs of the elementary properties) for the flow of product5+stage (ii) of the method according to the present invention is acceptable in the range from 0.95 to 0.80, preferably from 0.92 to 0.82, preferably from 0.90 to 0.85. Higher values will result in a relatively small number of fractions With10-C14and lower values to too many1-C4products with low value. The value of the ASF can be optimized by changing the reaction conditions, especially the relationship of H2/CO and temperature, but in addition flow rate of the hydrogen gas and pressure, and the appropriate selection of catalyst. The most preferred cobalt oxide of zirconium. The relative low value of the ASF (when compared with the process of the Fischer-Tropsch focused on the production of wax) leads to a large gas fraction that is sent for recycling. In these circumstances it is particularly important destruction of CO2.

The method according to the present invention is particularly suitable for installations Fisher-the Ropsha, with a two - or three-stage process of Fischer-Tropsch. Relatively low values ASF not only directly lead to a large number of1-C4products, but these large quantities of gas will be (while keeping other variables constant) to mediated increase in the fraction of C1-C4on the second and third stages (N2/CO and flow rate of hydrogen).

Used catalyst Fischer-Tropsch cobalt-based results in the release of large quantities of paraffins and, more preferably, mostly unbranched paraffins. Some of them may boil above the boiling within the so-called middle distillates. Used herein, the term "middle distillate" refers to hydrocarbon mixtures boiling within which largely correspond to boiling within the kerosene and gas oil fractions obtained using a conventional atmospheric distillation of crude oil. Limits boiling point of middle distillates usually correspond to from about 150 to about 360°C.

Paraffin hydrocarbons with higher boiling within (if present) can be isolated and subjected to additional hydrocracking unit known in the art catalytic hydrocracking of obtaining the target medium distillate is. Catalytic hydrocracking is carried out by contacting the paraffin hydrocarbons at elevated temperature and pressure in the presence of hydrogen with a catalyst containing one or more metals having hydrogenation activity and supported on a carrier. In a number of suitable hydrocracking catalysts include catalysts comprising metals selected from groups VIB and VIII of the Periodic table of elements. Preferably, the hydrocracking catalysts contain one or more noble metals from group VIII. Preferred noble metals are platinum, palladium, rhodium, ruthenium, iridium and osmium. The most preferred catalysts for use at the stage of hydrocracking catalysts, including platinum.

The amount of catalytically active metal present in the hydrocracking catalyst may vary within wide limits and generally ranges from about 0.05 to about 5 weight. parts per 100 weight. parts of the material medium.

In the technique known suitable conditions for optimal catalytic hydrocracking in a hydrocracking unit. Typically, the hydrocracking is carried out at a temperature ranging from about 175 to 400°C. Typical values of partial pressure of hydrogen used in the process of hydrocracking, Les is at in the range from 10 to 250 bar.

The process can be conveniently and profitably implemented in recirculation mode or in the mode of single pass (one pass), in which no recirculation flows. This mode is a single pass makes the process relatively simple and relatively cheap.

Recycle stream obtained after the separation of the hydrocarbons may contain gaseous under normal conditions, the hydrocarbons formed in the process of synthesis, nitrogen, unconverted methane and other hydrocarbon raw materials, carbon dioxide, hydrogen and water. Suitable gaseous under normal conditions, the hydrocarbons are1-C5-hydrocarbons, mainly With1-C4-hydrocarbons and preferably C1-C3-hydrocarbons. These hydrocarbons or mixtures thereof are gaseous at temperatures of 5-30°C (1 bar), in particular at 20°C (1 bar). Further, there may be oxygendemand compounds, such as methanol and dimethyl ether. Removal of carbon dioxide can be used in any suitable way, such as adsorption processes using amines, in particular in combination with a physical solvent, such as ADIP process or SULFINOL process, described in particular in GB 1444936, GB 1131989, GB 965358, GB 957260 and GB 972140. Sufficient removal of the re-circulating item is current, at least 70 vol.% present carbon dioxide, preferably 80% vol. and, more preferably 90 vol.%. With the aim of obtaining an optimal balance between optimal use of carbon efficiency of the process and removing the inert substance acceptable to from 50 to 90 vol.% and preferably from 60 to 80 vol.% re-circulating flow is returned to the step (i) of the process.

Example 1

563,8 l/h of a gaseous stream of hydrocarbons with the composition presented in the following table 1, and 100.3 l/h-depleted carbon dioxide recycle stream (composition shown in table 1) catalytic process Fischer-Tropsch served in together with the substantially purified oxygen from the air separator to the partial oxidation reactor and converted into synthesis gas. The resulting synthesis gas contains H2and WITH respect 1,58 and fed to the fixed catalyst bed located in megatropolis reactor Fischer-Tropsch process. The catalyst contained in the reactor is a catalyst for Fischer-Tropsch cobalt-based on zirconium oxide. In the reactor, the synthesis gas is converted into a hydrocarbon containing stream with C5+/C1the selectivity of 85%. A stream containing hydrocarbons, is separated into two streams - a stream of hydrocarbon product and the gas flow. 50% of the gas stream is otpravlyaut in the plant to remove carbon dioxide, to get the recirculated stream depleted in carbon dioxide. Thus obtained recirculating stream of carbon dioxide is subjected to compression and fed into the reactor for partial oxidation (see table).

Table 1.
The amount and composition of natural gas hydrocarbons and depleted in carbon dioxide recycle stream fed to the reactor for partial oxidation
ConnectionSpeed is fed to the reactor for partial oxidation of flow in l/h
Supplied natural gasReturn stream
Methane499,218,2
Ethan21,72,5
Propane13,91,8
n-butane8,71,0
n-pentane2,00,4
n-hexane1,30,1
CO216,12,0
H2021,7
CO043,7
With7and other 0,98,9
The total number of563,8100,3

1. A method of producing hydrocarbons from a gaseous hydrocarbon feedstock using a catalyst Fischer-Tropsch process, which includes stages:

i) conversion by partial oxidation of a gaseous hydrocarbon and oxygen-containing gas in the synthesis gas at elevated temperature and pressure;

ii) catalytic conversion of synthesis gas stage (i) using a catalyst Fischer-Tropsch cobalt-based oxide containing zirconium in the hydrocarbon stream;

iii) separation containing hydrocarbon stream stage (ii) on the stream of hydrocarbon product and a recycle stream; and

iv) removing carbon dioxide from re-circulating flow and return depleted carbon dioxide recycle stream to the step (i).

2. The method according to claim 1, which is depleted in carbon dioxide recycle stream admixed gaseous hydrocarbons.

3. The method according to claim 1 or 2, wherein a portion of the recirculating stream from step (iii) use as a fuel reforming with water vapor gaseous hydrocarbon feedstocks to hydrogen addition to the synthesis gas production stage (i).

4. The method according to claim 1 or 2, wherein a portion of the recirculating in the eye with stage iii or stage (iv) is used as fuel to generate electricity.

5. The method according to claim 1 or 2, in which the flow of the hydrocarbon product is subjected to catalytic hydrocracking.

6. The method according to claim 1 or 2, in which the flow of the hydrocarbon product contains from 17 to 27 wt.% and preferably from 22 to 27 wt.% C10-C14.



 

Same patents:

FIELD: chemical technology.

SUBSTANCE: method involves filtration of depleted mineral oils through a mixture of Fe3+ oxide and sand taken in the weight ratio sand : Fe3+ oxide = 1:(0.5-1.0). Method provides enhancing degree of purification of depleted mineral oils.

EFFECT: improved method of treatment.

1 tbl, 8 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: in particular, invention aims at producing extraction dearomatized component from reformat of gasoline fraction, which component may be used in production of petroleum solvents such as hexane solvents. Process comprising countercurrent extraction of aromatic hydrocarbons with liquid selective extractant to separate dearomatized component (raffinate) and subsequent extractive rectification of resulting extract phase by distilling off aromatic hydrocarbons is characterized by that liquid selective extractant is diethylene glycol or triethylene glycol, countercurrent extraction is carried out at 125-140°C, extractive rectification is carried out using process steam in presence of saturated selective extractant wherein evaporation of water is performed with the aid of energetic steam, unsaturated selective extractant after extractive rectification and recycled gasoline are sent to extraction stage preliminarily using unsaturated selective extractant as heat carrier to generate process steam, and energetic steam condensate is used to heat recycled gasoline to 80-130°C.

EFFECT: enhanced process efficiency.

3 cl, 1 dwg, 1 tbl, 3 ex

FIELD: chemical industry; other industries; production of the catalyst used for production of the hydrocarbons from the synthesis gas.

SUBSTANCE: the group of inventions is pertaining to production of the catalyst used for production of the hydrocarbons from the synthesis gas and also to the method of production of such catalyst. The catalyst suitable for the synthesis of the hydrocarbons from the synthesis gas contains: from 2% up to 50 % of cobalt and from 0.1% up to 15% of magnesium or the mixture of magnesium and zirconium located on the substrate made out of titanium dioxide. The method of production of the catalyst provides for addition of magnesium nitrate and cobalt nitrate within the range from 1:1.5 up to 1:3.0 (mass./mass.) to the distilled) water in amount from 1.5 up to 3.5 liters with production of 8-15 mass % solution; heating up of the solution at the temperature within the range of from 60 up to 90°С at continuous stirring; the dropwise addition of 8-15 mass % of the sodium bicarbonate solution to the heated up solution in the conditions of the stirring up to the solution рН being within the limits from 7.5 up to 8.5, maintaining of the temperature of solution within the limits from 60 up to 90°С; addition of zirconium oxide and the ground titanium dioxide in the ratio within the range from 1:4 up to 1:6 (mas./mass.) at stirring during the time span being within the limits from 20 up to 50 minutes; filtration of the produced as the result of it solution in the vacuum; flashing of the residue for withdrawal of the nitrates; drying of the filtrate at the temperature being within the range from 65 up to 80°C during the time span being within the limits from 6 up to 15 hours; cooling of the dry filtrate. The group of inventions allows to achieve the increased activity and efficiency of the catalyst, and also the throughput efficiency of the catalytic process.

EFFECT: the group of the inventions ensures the increased activity and efficiency of the catalyst and the increased throughput efficiency of the catalytic process.

7 cl, 3 ex

FIELD: oil-producing industry; petrochemical industry; other industries; equipment for purification of the petroleum from hydrogen sulfide and mercaptans.

SUBSTANCE: the invention may be used for the field purification of the sulfur-bearing oils from hydrogen sulfide and the light methyl mercaptans and ethyl mercaptans. The prepared petroleum through the pipeline (1) is fed into the upper part of the blowing column (3) (Fig.1), and the hydrocarbon gas through the pipeline (2) is fed into the lower part of the blowing column. The partially purified petroleum from the vat of the column (3)is fed into the separator (4), which through the by-pass pipelines is connected to inlet pipelines of the sulfur-bearing oil and the hydrocarbon gas. Further the petroleum from the vat of the separator (4) and the reactant-neutralizing agent from the vat of the tank (5) by means of the mixer (10), in the capacity of which predominantly use the centrifugal pump, is fed into the tubular reactor (11), which is supplied with the quiescent mixer of the reaction mixture. The reaction mixture from the tubular reactor (11) comes in the buffering tank (13). In other version of the installation (Fig.2) the prepared petroleum goes through the pipeline (1) into the nozzle of the liquid-gas ejector (14), which gaseous fitting pipe is connected to the feeding pipeline (2), and the liquid fitting pipe is connected to the sulfur-bearing petroleum feeding pipeline. The gas-petroleum mixture from the liquid-gas ejector (14) comes into the separator (15), which upper part is connected to the suction fitting pipe of the liquid-gas ejector (16) of the pump -ejector installation. The invention allows to reduce the share of the total sulfur, the water, the light mercaptans and the products of the hydrogen sulfide neutralization by the reactant in the separator oil, to reduce the material inputs at operation of the installation.

EFFECT: the invention allows to reduce the share of the total sulfur, the water, the light mercaptans and the products of the hydrogen sulfide neutralization by the reactant in the separator oil, to reduce the material inputs at operation of the installation.

8 cl, 2 dwg

FIELD: rubber industry.

SUBSTANCE: invention relates to preparation of petroleum-origin plasticizers for synthetic rubber and tires. In particular, extract obtained from purification of petroleum oil fractions with selective solvents is treated by dimethylsulfoxide at weight ratio 1:(2.0-4.0), respectively, at 30-120°C and resulting raffinate is used as target product. Advantageously, extract is preliminarily diluted with paraffin-naphthene solvent at weight ratio 1:(0.1-0.5), respectively. Extract is of residual type or a mixture of the latter with distillate extract.

EFFECT: reduced level of carcinogenic polycyclic aromatics in plasticizer.

3 cl, 1 tbl, 7 ex

FIELD: chemical industry; petrochemical industry; other industries; methods and the devices for removal of the sulfur from the streams of the fluid medium containing the hydrocarbons.

SUBSTANCE: the invention is pertaining to the method and the installation for removal of the sulfur from the streams of the fluid medium containing the hydrocarbons. The method of desulfurization includes the following stages: a) contacting of the hydrocarbon-containing stream of the fluid medium with the solid particles of the sorbent in the reactor, (b) the increase of the pressure in the reactor airlock storage bin up to the filling pressure, (c) transportation of the sulfur filled particles of the sorbent from the reactor into the being under pressure airlock storage bin of the reactor, (d) reduction of the pressure in the filled airlock storage bin to the pressure of release, (e) transportation of the sulfur filled particles of the sorbent from the filled and being under low pressure airlock storage bin of the reactor into the recuperator and (f) contacting of the sorbent particles with the oxygen-bearing recuperation stream. The installation of desulfurization contains the reactor with the fluidized layer of the sorbent, the receiver of the reactor for reception of the sulfur filled particles of the sorbent, the airlock storage bin of the reactor, the receiver of the recuperator for reception of the recuperated particles of the sorbent, the airlock storage bin of the recuperator for reception of the recuperated particles of the sorbent and the installation of the recuperation. The control system of transmission of the finely dispersed solid particles from the first container into the second container contains the airlock storage bin disposed streamwise between the first and second containers, the valve for filling up by the particles disposed streamwise between the first container and the airlock storage bin, the valve for release of the particles disposed streamwise between the airlock storage bin and the second container, the first gaseous line hydraulically linked to the airlock storage bin and including the first gaseous valve for control over the flow of the first gas through the first gaseous line, the line of a blowing through hydraulically linked to the airlock storage bin and including the outlet valve for the flow control of the fluid medium through the blowing line, the pressure control detector for determination of the pressure in the airlock storage bin, and the electronic control device intended for connection with the valve for filling up by the particles, the valve of the release of the particles, the first gaseous valve, the outlet valve and the pressure control device. The electronic control device is programmed so that to execute the following serial stages: (a) to open the first gaseous valve; (b) to close the first gaseous gate in reply to the first reading of the pressure control device; (c) to open the valve for filling up with the particles; (d) to close the valve filling up with the particles; (e) to open the release valve; (f) to close the release valve in reply to the second reading of the pressure of the pressure control device; (g) to open the valve o the particles release; and (h) to close the valve of the particles release The invention allows to increase efficiency of the hydrocarbons desulfurization.

EFFECT: the invention allows to increase efficiency of the hydrocarbons desulfurization.

29 cl, 6 dwg, 7 tbl

FIELD: petroleum processing.

SUBSTANCE: invention relates to petroleum products (crude oil, kerosene, diesel, and other fractions) purification processes, in particular to those involving use of adsorbents. Purification is conducted in centrifugal field of rotating (at 60-2500 ppm) rotor-drum by common rotation of dispersion mixture of adsorbent and starting petroleum products at adsorbent/petroleum product weight ratio (1.5-2.0):1.0 in rotor-drum. In addition, dispersion mixture is exposed to vertical electrical field with intensity E=1000-15000 v/m, while continuously feeding adsorbent and petroleum product at indicated ration into rotor-drum. Dispersion mixture is continuously poured off through outer side of rotor-drum into pot from which mixture is passed to separation step to separate petroleum products from adsorbent. Purified petroleum products are sent to consumer and adsorbent to regeneration and then to reuse in petroleum product purification stage. Residence time of adsorbent/petroleum product dispersion mixture moving from the center to rotor-drum periphery ranges from 10 to 30 min. In instances when electrical conductivity of petroleum products is less than that of natural water by more than one order of magnitude, dispersion mixture including adsorbent, fine conducting powder, and petroleum product is composed at weight ratio (1.0-2.0):(0.1-1.0):1.0, respectively, and the process is conducted as above with the exception that adsorbent/fine conducting powder is regenerated and reused instead of only adsorbent.

EFFECT: increased productivity, enabled continuous desulfurization of freshly produced crude oil, enabled continuous desulfurization of kerosene and diesel fraction under production conditions, and reduced expenses.

3 cl, 2 dwg, 3 ex

FIELD: petroleum processing.

SUBSTANCE: invention relates to petroleum products (crude oil, kerosene, diesel, and other fractions) purification processes, in particular to those involving use of adsorbents. Purification is conducted in centrifugal field of rotating (at 60-2500 ppm) rotor-drum by common rotation of dispersion mixture of adsorbent and starting petroleum products at adsorbent/petroleum product weight ratio (1.5-2.0):1.0 in rotor-drum. In addition, dispersion mixture is exposed to vertical electrical field with intensity E=1000-15000 v/m, while continuously feeding adsorbent and petroleum product at indicated ration into rotor-drum. Dispersion mixture is continuously poured off through outer side of rotor-drum into pot from which mixture is passed to separation step to separate petroleum products from adsorbent. Purified petroleum products are sent to consumer and adsorbent to regeneration and then to reuse in petroleum product purification stage. Residence time of adsorbent/petroleum product dispersion mixture moving from the center to rotor-drum periphery ranges from 10 to 30 min. In instances when electrical conductivity of petroleum products is less than that of natural water by more than one order of magnitude, dispersion mixture including adsorbent, fine conducting powder, and petroleum product is composed at weight ratio (1.0-2.0):(0.1-1.0):1.0, respectively, and the process is conducted as above with the exception that adsorbent/fine conducting powder is regenerated and reused instead of only adsorbent.

EFFECT: increased productivity, enabled continuous desulfurization of freshly produced crude oil, enabled continuous desulfurization of kerosene and diesel fraction under production conditions, and reduced expenses.

3 cl, 2 dwg, 3 ex

FIELD: petrochemical industry; other industries; methods of production of the hydrogen for the fuel composition.

SUBSTANCE: the invention is pertaining to the method of production of hydrogen for the fuel composition. The method of production of hydrogen for the fuel composition from the hydrocarbon fuel composition includes the following stages: preparation of the hydrocarbon fuel composition, which is produced: i) injection of the liquid hydrocarbon raw including the alkylating agent, in contact with the acid catalyst in the conditions, which are effective for alkylation, at least, of the parts of the hydrocarbon raw, where the liquid hydrocarbon raw additionally includes the aromatic compounds, which are alkylated at the stage of the alkylation; and ii) separation from the stage of the alkylation of the low-boiling fraction containing the hydrocarbons and the aromatic hydrocarbons with the lowered concentration in the capacity of the hydrocarbon fuel composition, transformation of the hydrocarbon fuel composition into the hydrogen and optional injection of the produced hydrogen into the fuel composition. The invention makes it possible to raise efficiency of the production process.

EFFECT: the invention ensures the increased efficiency of the production process.

10 cl, 3 tbl, 3 ex

FIELD: synthesis gas reaction catalysts.

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

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

59 cl, 1 dwg, 1 tbl, 7 ex

FIELD: synthesis gas reaction catalysts.

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

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

59 cl, 1 dwg, 1 tbl, 7 ex

FIELD: chemical engineering.

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

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

17 cl, 3 dwg

FIELD: disproportionation reaction catalysts.

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

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

13 cl, 2 dwg, 1 tbl, 5 ex

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

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

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

9 cl, 5 tbl, 5 ex

FIELD: petrochemical process catalyst.

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

EFFECT: optimized catalyst preparation procedure.

23 cl, 2 dwg, 1 tbl, 12 ex

FIELD: alternate fuel production.

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

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

FIELD: petrochemical processes.

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

EFFECT: improved process technology.

10 cl, 8 dwg, 7 ex

FIELD: organic synthesis catalysts.

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

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

33 cl, 9 dwg, 1 tbl, 10 ex

FIELD: organic chemistry, chemical technology.

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

EFFECT: improved method of synthesis.

8 cl, 3 tbl, 4 ex

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

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

EFFECT: increased efficiency of cleaning method.

23 cl, 1 dwg

FIELD: 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

Up!