RU2674160C1 - Method of hydroconversion residue of atmospheric distillation of gas condensate - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: invention relates to methods for processing heavy hydrocarbon raw materials with an extremely high content of paraffin-naphthenic hydrocarbons and a low content of native resins and asphaltenes and can be used in the processing of the residue of atmospheric distillation of gas condensate ADGC. In the method of hydroconversion of highly paraffin residue of atmospheric distillation of gas condensate before hydroconversion, the raw material is mixed with a suspension of ultrafine Mo-containing catalyst with particle sizes of 5–300 nm and a catalyst concentration of 1 % by weight (in terms of molybdenum), obtaining a homogeneous stable suspension of ultrafine catalyst in raw materials containing 0.05–0.2 % wt. catalyst (in terms of molybdenum) on the mass of raw materials. First suspension is preliminarily prepared by dispersing a catalytically active molybdenum compound in the residue of atmospheric distillation of the hydrogenate. Hydroconversion of the prepared mixture is carried out by mixing with hydrogen and hydrogenating the raw materials in a reactor with an upward flow of raw materials at a temperature of 380–450 °C and pressure of 7–10 MPa. Hydroconversion products are separated to produce a hydrogen-containing gas that is returned to hydrogenation as hydrogen from distillate fractions with a boiling point of up to 350 °C, which are derived as marketable products, and the residue of atmospheric distillation of hydrogenate with a boiling point above 350 °C. Part of the latter (stream I) is returned to the hydroconversion process and used to prepare a suspension of fresh catalyst, part (stream II) is returned to mixing with the raw material, and part (stream III) is removed from the hydroconversion process to extract and regenerate the catalyst. Preferably, an ultrafine Mo-containing catalyst promoted with nickel is used from the condition of the mass ratio Mo:Ni=(100–10):1. Amount of metals of the fresh catalyst dispersed in stream I must be equal in mass to the amount of metals discharged with stream III. Mass ratio of raw materials and flows is: raw materials: [stream I+stream II+stream III]=1:(0.25–0.8). Ratio of the mass of raw materials and stream III is 1:(0.05–0.3). Hydrocarbon portion of the residue above 350 °C of stream III after separation of the catalyst and other metals is recycled. Mass of stream I is calculated by the formula (1), where M_(I) M_(III) – the mass streams (I) and (III), respectively (the same units); C₍₃₅₀₎ – the content of catalysts (in terms of metals) in the residue of atmospheric distillation of hydrogenation, % wt. M_(I)=M_(III)C₍₃₅₀₎/(1-C₍₃₅₀₎) (1).

EFFECT: increasing the depth of conversion of raw materials, improving the sustainability of the process, simplifying the method, reducing capital and energy costs, environmental safety.

7 cl, 1 dwg, 1 tbl, 6 ex

Description

The invention relates to methods for processing heavy hydrocarbons with an extremely high content of paraffin-naphthenic hydrocarbons and a low content of native resins and asphaltenes under hydrogen pressure in the presence of heterogeneous nanosized catalysts and can be used in the processing of the residue of atmospheric distillation of gas condensate (AOGC).

The process of hydrogenation processing of heavy raw materials in the presence of heterogeneous nanoscale and ultrafine catalysts to produce hydrocarbon fractions with a lower boiling point than the feedstock, was called "hydroconversion".

Currently, industrial processes for the hydrogenation processing of heavy raw materials are carried out mainly with the use of heterogeneous catalysts supported by active catalytic metals. Granular or ball supported catalysts in a stationary or fluidized bed quickly lose activity as a result of the deposition of metals and coke, and therefore are not sufficiently effective. To increase the conversion from raw materials, it is necessary to first remove the metals, for example, by deasphalting by solvents or by catalytic adsorption, which significantly complicates the process and reduces the yield of light products.

In recent years, new processes have been intensively developed and existing processes for the hydrogenation processing of heavy raw materials have been used using highly dispersed nanoscale and ultrafine catalysts uniformly distributed in the feed in the form of a suspension of catalytic particles of molybdenum, nickel, cobalt, tungsten metals with sizes of 50 - 5000 nm. The process takes place in a slurry reactor in the presence of a catalyst formed from a catalyst precursor (precursor) previously introduced into the raw material or introduced as a suspension in a hydrocarbon medium.

Known methods for the hydrogenation processing of heavy oil feedstocks based on the use of water-soluble or oil-soluble organic derivatives of molybdenum, nickel, cobalt as precursors.

So, in accordance with PCT WO 93/03117, C10G 47/06, 1993, a process for the hydrogenation conversion of heavy hydrocarbons to lower boiling products at temperatures of 343-515 ° C in the presence of hydrogen (3.5-14 MPa) with the addition of a catalyst concentrate is proposed . The catalyst concentrate is preliminarily prepared as follows:

a) a catalyst preconcentrate is obtained by mixing hydrocarbon oil, excluding fractions with a boiling point above 570 ° C, with an aqueous solution of a metal compound, from groups II, III, IV, V, VIB, VNB and VIII of the Periodic system in an amount providing 0.2- 2.0% of the mass of metal on the specified oil; b) heating the preconcentrate without adding hydrogen at temperatures of 275-450 ° C using elemental sulfur as a sulfidizing agent with a ratio (atomic) S: metal from 1: 1 to 8: 1, a catalyst concentrate is obtained.

The disadvantage of this method is the need for an additional complex stage of preparation under special conditions of catalysis concentrate

torus, in the use of relatively expensive phosphoformolybdic acid, as well as in the absence of a solution to issues related to catalyst regeneration.

In the method according to patent RU 2472842 CI, C10G31 / 00, C10G11 / 02, C10G35 / 06, C10G7 / 00, publ. 01/20/2013, as an additive to increase the depth of processing of hydrocarbon-containing raw materials in thermocatalytic processes, an organic salt of the formula M (OOC-R) _n , or M (SOC-R) _p , or M (SSC-R) _n , where R denotes alkyl, aryl, isoalkyl, tert-alkyl, alkyl aryl, possibly including hydroxyl, keto, amino, carboxyl, thiocarbamine groups, n is 1-3, and M denotes a transition metal from elements of the Periodic system of elements. Metal from elements of group VIII of the Periodic system of elements is selected from the group of: iron, nickel, cobalt, palladium, platinum, metal from elements of group VII is selected from manganese, metal from elements of group VI is selected from the group consisting of chromium, molybdenum, tungsten. These organic compounds are converted into an ultrafine metal suspension under thermal exposure conditions, i.e. receive metal nanoparticles, which, in turn, catalyzes all kinds of hydrocarbon conversion processes: hydrogenation, dehydrogenation, destruction. Heavy hydrocarbons with a density of more than 0.850 g / cm ^{3 are} predominantly used as hydrocarbon-containing raw materials, for example, heavy oils, vacuum gas oils, straight-run fuel oils, tars, semi-tars, cracked residues, oil sludges individually or in a mixture, as well as mixtures thereof with combustible minerals ( oil shale, tar sands).

The disadvantages of the process are the complexity of the synthesis and the high cost of catalyst precursors.

A known method of processing heavy hydrocarbons described in US patent No. 4134825, class. 208 - 108, 1979, according to which the process is carried out in the presence of oil-soluble compounds of Mo, V or Cg. As the latter, salts of tar and naphthenic acids containing these metals are used. The oil soluble compound is converted to a catalyst by

pre-heating a solution of this compound in the temperature range 325-415 ° C and a pressure of 3.5-35 MPa in the presence of a hydrogen-containing gas, which contains 1-90 mol%. hydrogen sulfide. Then, the oil product with the solid colloidal catalyst contained inside it is introduced into the hydroconversion zone carried out at a temperature of 343-538 ° C and a partial pressure of hydrogen of 3.5-35 MPa.

The disadvantage of the described method is the complexity and high cost of the catalyst and the need for preliminary preparation of the latter.

Oil-soluble precursors are distributed in the volume of raw materials at the molecular level and decompose under hydroconversion conditions to obtain catalyst suspensions with the formation of particles of minimum size and maximum activity. However, oil soluble precursors are expensive and difficult to regenerate. Therefore, it was proposed to use another method for the synthesis of ultrafine catalysts, the emulsion one, for hydroconversion of TUS.

According to the invention according to the patent of the Russian Federation No. 2400525, C10G49 / 04, publ. 09/27/2010, hydrocarbon feedstock hydroconversion is carried out in the presence of a molybdenum-containing catalyst distributed in the feedstock, at elevated temperature and hydrogen pressure. The raw materials are pre-homogenized in a mixture with a modifier, which is used as oil fractions of secondary origin, at a temperature of 80-95 ° С, a molybdenum-containing catalyst precursor and a surfactant-lecithin are introduced, the resulting mixture is dispersed to form a stable emulsion with an average droplet diameter equal to 45-260 nm, and hydrogenation is carried out, then distillate fractions, boiling at temperatures up to 520 ° C, and the residue boiling at temperatures above 520 ° C are isolated from the reaction products, and, possibly about, return the residue to recycling in the amount of 5-60% of the mass, to the stage of dispersion.

The disadvantages of the method are the use of a modifier and emulsifier, a high consumption of modifier is from 1 to 4% and a relatively high coke formation is 0.25 - 1.38%.

The known method according to patent RU 2146274 CI, C10G47 / 06, publ. 03/10/2000, in which the processing of high molecular weight hydrocarbon feedstock is carried out by hydrogenation with uniform distribution in the feedstock of the catalyst obtained directly in the reaction zone from an emulsion formed by mixing the feedstock with an aqueous solution containing a salt of molybdenum acid, for example, ammonium paramolybdate and ammonia taken in a mass ratio of ammonia: molybdenum equal to 0.15-0.39: 1, and having a droplet diameter of 0.3-5 microns. The resulting organic compounds with a boiling point below 350 ° C are distilled off. The residue with a boiling point above 350 ° C is burnt completely or partially at 800-1000 ° C and the catalyst is removed from the ash and slag residues in the form of ammonium paramolybdate recycled to the process, as well as rare and precious metals contained in the feedstock.

The disadvantage of this process is the complexity of the composition and operations of preparing the emulsion of the catalyst precursor in the feed and the low yield of distillate fractions with a boiling point below 350 ° C.

All of the above methods were used to process heavy oil residues from the processing of light, medium, heavy and superheavy oils, natural bitumen, and other types of heavy raw materials, characterized by a high content of asphalt-resinous substances 10-40% by weight, metals 100-10000 mg / kg.

Unlike traditional types of raw materials (light, medium, superheavy oils and natural bitumen, etc.), AOGC is characterized by a low content of polar components - resins, asphaltenes, hetero-organic metal-containing compounds that have surface-active properties and are natural stabilizers of particles of a dispersed phase of oil

dispersed systems. In addition, AOGC is characterized by an extremely high content of saturated paraffin-naphthenic hydrocarbons having a low polarity, respectively, a low ability to stabilize particles of a dispersed phase.

The hydrocarbon composition of the original AOGC contains neutral resins of -1.2% by weight, acidic resins - 2.5% of the mass, asphaltenes - 1.6% of the mass. , paraffin-naphthenic hydrocarbons - 52.8% of the mass, aromatic hydrocarbons -42% of the mass, including light aromatics - 8% of the mass, medium aromatics of 4.5% of the mass, heavy aromatics - 29.5% of the mass. AOGK contains an insignificant amount of metals (V + Ni -0.9 mg / kg, Fe -9 mg / kg), the content of boiling above fractions of 350 ° С - 75.8% of the mass. A low content of asphalt-resinous substances leads to a low value of AOGC viscosity, which contributes to the aggregation of nanoparticles and creates additional difficulties in obtaining a stable suspension of catalyst nanoparticles in the reaction medium.

In view of the specific properties and hydrocarbon composition of AOGCs, the direct conversion of such raw materials using suspension technology using nanosized catalysts formed in situ from inverse emulsions of reverse emulsions is a very difficult task and requires the development of special methods for hydroconversion.

In this regard, the use of ex situ dispersed ultrafine catalyst dispersed in raw materials is promising.

A known method of hydroprocessing of heavy raw materials, including atmospheric residue of gas condensate, according to the patent of the Russian Federation No. 2241022, class. IPC C10G69 / 06, publ. 11/27/2004, which includes hydrofining of the feedstock with a ratio of water to molybdenum in the feedstock (0.005-0.05) :( 0.001-0.002): 1 when heated and increased pressure in the presence of a catalyst-molybdenum sulfide, which is formed in the reaction zone during the interaction of dispersed in raw materials of water and a molybdenum-containing salt with a sulfidizing agent, which is used as an aqueous solution of sulfide or poly-

ammonium sulfide at a ratio in the solution of sulfur to molybdenum (0.6-3.2): 1, subsequent separation or vacuum distillation of hydrofined fractions to obtain low boiling and high boiling fractions of hydrocarbons, and after vacuum distillation of the fraction with a boiling point up to 500 ° C, it is subjected to pyrolysis or at a temperature of 650-720 ° C and a residence time of the raw material in the reaction zone of 1.2-0.6 seconds. with the predominant production of aromatic carbons in the form of a pyrolysis resin, or at a temperature of 720-850 ° C and a residence time in the reaction zone of 1.5-0.3 sec. with the predominant production of ethylene and propylene in the form of an exhaust gas phase. According to examples for hydroprocessing (i.e., hydroconversion) of the atmospheric residue of gas condensate, the catalyst is prepared from a precursor, ammonium paramolybdate, by mixing it with raw materials and a sulfonating agent, ammonium sulfide, and emulsifying them in a disk dispersant (i.e., the catalyst is prepared ex situ). The prepared emulsion is subjected to hydrofining in a flow reactor at a temperature of 450 ° C, a hydrogen pressure of 6 MPa, a volumetric rate of 2 h " ¹ and a volumetric ratio of H ₂ : feedstock = 900 nl / L. The resulting hydrogenation is subjected to vacuum distillation to obtain a distillate fraction" n .-500 ° C "and the residue into which the precious metals pass. The residue is subjected to combustion with the recovery of metals and regeneration of the catalyst.

This method, as the closest to the one chosen by us for the prototype.

The disadvantage of the prototype method is the use of a reverse emulsion rather than a suspension of ultrafine catalyst in raw materials, since it is not possible to create a highly dispersed emulsion of a catalyst precursor (dispersed phase) in a dispersion medium represented by highly paraffinic feedstock, the emulsion will be unstable due to agglomeration and sedimentation of its particles.

Another disadvantage of the prototype is that when used as raw materials AOGK with a boiling point up to 300 ° C get distillate

fraction with a boiling point of up to 500 ° C, which requires pyrolysis at temperatures of at least 650 ° C to obtain marketable products, which is associated with the complexity of the hardware design, increased capital costs and energy costs. In addition, during the pyrolysis of the high sulfur distillate fraction, sulfur oxides are formed, which have an adverse effect on the environment and entail additional costs for environmental measures.

The objectives of the invention is to develop an effective, environmentally friendly method of processing AOGC using nanosized catalysts using suspension technology, implemented on domestic industrial equipment and providing an increase in the depth of conversion of raw materials, increasing process stability by reducing the degree of agglomeration and deposition of particles of the dispersed phase in the reaction system, simplifying the method , as well as a reduction in capital and energy costs.

To solve the problem in the proposed method, the hydroconversion of the high-paraffin residue of atmospheric distillation of gas condensate, including hydroconversion at elevated temperature and pressure in the presence of the obtained ex situ Mo-containing ultrafine catalyst dispersed in the feed by mixing with hydrogen and hydrogenation of the feed, separation of the reaction products into distillate fractions and high-boiling residue, from which metals and spent catalyst are sent for regeneration, before g drokonversiey raw material is mixed with a suspension of ultrafine Mo-containing catalyst with a particle size of 5-300 nm and a catalyst concentration of 1% by weight. (in terms of molybdenum), previously prepared by dispersing the catalytically active compound of molybdenum in the residue of atmospheric distillation of the hydrogenated product, to obtain a homogeneous stable suspension of ultrafine catalyst in a feed containing 0.05-0.2% wt. catalyst (in terms of molybdenum) to the mass of raw materials, conduct hydroconversion prepared-

hydroconversion products are separated in order to obtain hydrogen-containing gas, which is returned to hydrogenation as hydrogen, distillate fractions with a boiling point up to 350 ° С, which are separated into a reactor with an upward flow of raw materials at a temperature of 380-450 C and a pressure of 7-10 MPa. removed as commercial products, and the residue of atmospheric distillation of the hydrogenate with a boiling point above 350 ° C, part of which - stream I - is returned to the hydroconversion process and used to prepare a suspension of fresh catalyst, part - stream II - return They are mixed with raw materials, part of stream III is removed from the hydroconversion process to extract and regenerate the catalyst.

Preferably, an ultrafine Mo-containing catalyst promoted with nickel is used from the condition of the mass ratio Mo: Ni = 100: (1-10).

The amount of metals of the fresh catalyst dispersed in stream I should be equal in weight to the amount of metals removed from stream III.

The ratio of the masses of raw materials and flows is: raw materials: [stream I + stream II + stream III] = 1: (0.25-0.8).

The ratio of the mass of raw materials and stream III is 1: (0.05 - 0.3).

The hydrocarbon portion of the residue above 350 ° C. of stream III, after separation of the catalyst and other metals, is recycled.

The mass of stream I is calculated by the formula:

where M (i) and M (III) are the masses of flows I and III, respectively (identical units); C (350) is the content of catalysts (in terms of metals) in the residue of atmospheric distillation of hydrogenate,% wt.

The mass of stream II is determined by the properties of the raw material and can be from less than 1 to 80% by weight of the raw material.

The process is as follows (Figure 1).

Raw materials - the residue of atmospheric distillation of gas condensate (stream 1) and a suspension of ultrafine catalyst (stream 2) are fed to the raw material preparation unit 3. The raw material preparation unit also receives the hydroconversion residue with a boiling point of 350 ° С containing a recirculating catalyst (stream 10 ) According to one embodiment of the invention, a hydroconversion residue with a boiling point of 350 ° C., not containing a catalyst, enters the raw material preparation unit (stream 16). The components are mixed (dispersed) at a temperature of 50-80 ° C to obtain a stable homogeneous suspension working composition. The content of active metals in the raw material mixture is 0.05 - 0.2% for metals based on raw materials. Next (stream 4) is sent to the heating and reaction unit 5. The feed with the catalyst enters the hydroconversion unit (5). Before the hydroconversion reactor, the feed is mixed with hydrogen (stream 27) and a circulating hydrogen-containing gas (HSG) (stream 24). The feed with a catalyst and hydrogen is heated to a temperature of 380-450 ° C and sent to a reactor in which hydroconversion occurs in an upward flow of a gas-liquid mixture at a ratio of hydrogen: feed: (500 - 1000): 1 nl / l, temperature 380 - 450 ° C , a pressure of 7-10 MPa in the presence of an ultrafine molybdenum-containing catalyst.

The reaction products (stream 6) are sent to the separation unit 7, where they are separated (separated) into a hydrogen-containing gas (stream 13), distillate fractions with a boiling point up to 350 ° C (stream 8) and the remainder of the atmospheric distillation of hydrogenate with a boiling point above 350 ° C (stream 9) containing a dispersed catalyst. Stream 9 is divided into 3 streams. A portion of the stream (stream 11) is withdrawn for catalyst recovery with its subsequent regeneration in the demetallization unit 14. The extraction and regeneration of the catalyst from stream 11 is carried out by known demetallization methods. Other metals are also recovered. The demetallized distillation residue (stream 15) from block 14 can partially be returned to the preparation of the suspension

fresh catalyst (stream 16), and partially withdrawn (stream 17). Another part of the hydrogenation residue distillation residue (stream 10) containing the ultrafine catalyst is returned to the hydroconversion process to the feed preparation unit 3. A portion of the hydrogenation distillation residue (stream 12) is used to prepare the catalyst suspension in the catalyst preparation block 28. Distillate products boiling up to 350 ° С (stream 8) are sent to separation unit 29, where a gasoline fraction (stream 20), a diesel fraction (stream 19), a fraction above 350 ° C (stream 22) are separated, which are withdrawn from the installation as commercial products, as well as carbohydrate hydrogen gases (stream 21).

Hydrogen-containing gas (stream 13) and hydrocarbon gases (stream 21) are sent to the purification unit 23 of hydrogen sulfide and ammonia. The purified hydrocarbon gas (stream 25) is sent to the fuel network, the hydrogen-containing gas is recycled (stream 24).

In the catalyst preparation unit 28, the catalytically active molybdenum compound (stream 26) is dispersed in the residue of atmospheric distillation of the hydrogenate (stream 12) to obtain a suspension of an ultrafine Mo-containing catalyst with a particle size of 5-300 nm and a catalyst concentration of 1% wt. (in terms of molybdenum). According to one embodiment of the invention, a molybdenum catalyst promoted with nickel is introduced into the suspension at a weight ratio of Mo: Ni = (100-10): 1. The catalyst is introduced based on the preparation of a suspension with a content of Me - 10000 ppm (Me is the total content of catalytic metals) . To obtain a homogeneous stable suspension of catalyst in an organic medium, known equipment is used - dispersants, grinders, homogenizers.

The invention is illustrated by the following examples. The percentages given in the examples are expressed in% wt.

Example 1 (comparative).

The feedstock is the atmospheric residue of gas condensate (AOGK) with the following properties: boiling point above 350 ° C, density at 20

0 3 0 2

C - 951 kg / m, viscosity at 50 C is 33.8 mm / s, the content of fractions of boiling over 350 C is 85.8%. AOGC contains neutral resins - 1.2% of the mass, acidic resins - 2.5% of the mass, asphaltenes - 1.6% of the mass, paraffin-naphthenic hydrocarbons - 52.8% of the mass, aromatic hydrocarbons - 42 % of the mass, including light - 8% of the mass, medium - 4.5% of the mass and heavy -29.5% of the mass.

Molybdenum-containing catalyst (M0S2) is introduced into 0.4 kg of raw material heated to 80 ° C based on the preparation of a suspension with a Mo concentration of 1%. The suspension is homogenized using a disk dispersant for 1 hour. The average particle diameter of the dispersed phase in the suspension is 420 nm. 0.2 kg of the prepared suspension is mixed with 1.8 kg of raw material. The mixture is further homogenized by passing through a disk dispersant. In the resulting feed mixture, the catalyst content was 0.05% of the mass of the feed. The feed mixture is subjected to hydroconversion in a flow-through hydro-conversion unit with a reactor volume of 210 cm at a temperature of 450 ° C and a pressure of 10 MPa, a space velocity of 1 h ’ ¹ (200 g / h), the ratio of hydrogen to feedstock = 1000 nl / L. The reaction products are separated, liquid products are subjected to atmospheric distillation to obtain gasoline, diesel fractions and a residue with a temp, the beginning of boiling 350 ° C. The hydrogen-containing gas is returned to the cycle.

The yield of products is shown in table 1. The conversion of raw materials (l,%) is calculated by the formula:

wherein Mz50 (sy _P o) ~~ mass feedstock fraction with a boiling point of 350+ ° C and M350 (from) - mass of product discharged from the process as a residual fuel.

The conversion of raw materials in the experiment was 55.4%. The yield of distillate products is 56.3% with a relatively high yield of coke - 0.14%. The consumption of catalyst is 0.05 % for raw materials.

Example 2

The feedstock, experimental setup, and hydroconversion conditions are the same as in Example 1. In the feed mixture entering the reactor, the catalyst content was 0.05% of the feed weight. To disperse the Mo catalyst, a part of the hydrogenation product distillation residue with a boiling point above 350 ° C is used (stream I). The content of the catalyst in its suspension in the remainder of the distillation of the hydrogenate is 1% wt. Another portion of the hydrogenation distillation residue (stream III) is removed from the process as residual fuel. The mass of stream III is 12% by weight of the raw material. The Mo content in the residue of the hydrogenation distillation is 0.17% in May. The mass of stream I is calculated according to the formula 1: Mf = 12 »0.17 / (1-0.17) = 2.46% by weight of the raw material. Mo stream is introduced into stream I. The amount of fresh catalyst is equal to the loss of catalyst withdrawn from the hydroconversion process with stream III: 12 * 0.17 / 100 = 0.0204% by weight of the feed. The molybdenum-containing catalyst is introduced under constant hydroconversion into the recycle stream I. The mass of the hydrogenation product distillation residue is 36% by weight of the feed. Accordingly, the mass of stream II is 36 - 12 - 2.46 = 21.54% of the mass of raw materials. The product yield is shown in table 1.

The conversion of raw materials in the experiment is 86%. The yield of distillate products is 83.1% with a low coke yield of 0.08%. Catalyst consumption - 0.021% for raw materials

As can be seen from the above results, the dispersion of the Mo catalyst in the hydrogenation distillation residue is more effective than the dispersion of the catalyst in the feed (Example 1), since it allows to increase the conversion of the feed and the yield of distillate products and reduce the loss of catalyst with the stream withdrawn from the process.

Example 3

The raw materials and the experimental setup are the same as in Example 1. Hydroconversion is carried out at a temperature of 440 ° C and a pressure of 7 MPa, a volumetric feed rate of 1.5 h " ¹ (100 g / h), a ratio of hydrogen and feedstock = 500 nl / l. The content of the Mo catalyst in the feed mixture entering the reactor is 0.1% of the mass for the feed. Part of the hydrogenation residue with a boiling point above 350 ° C (stream I) is used to disperse the Mo catalyst. Another part of the residue is hydrogenation distillation (stream III) removed from the process as residual fuel. Mass flow III composition It accounts for 30% of the mass of raw materials. The Mo content in the residue of the hydrogenation distillation is 0.125%. The mass of stream I is calculated by the formula 1: M ₍ i) = 30 ^e 0.125 / (1-0.125) = 4.28% of the mass of raw material. Mo catalyst is introduced in. The amount of fresh catalyst is equal to the loss of catalyst withdrawn from the hydroconversion process with stream III: 30 * 0.125 / 100 = 0.0375 % by weight of the feed.

The molybdenum-containing catalyst is introduced under constant hydroconversion into the recycle stream I. The mass of the hydrogenation product distillation residue is 80.1% by weight of the feed. The mass of stream II is equal to: 80.1 - 30 - 4.28 = 45.82% of the mass of raw materials. The product yield is shown in table 1.

The conversion of raw materials in the experiment is 65%. The yield of distillate products is 66.5% with a low coke yield of 0.09%. The consumption of the catalyst is 0.0375% of the raw material. As can be seen from example 4 with a maximum permissible amount of flow III - 30%, a low ratio of hydrogen containing gas and feed = 500 nl / l and a total yield of the total flows of 1+ 11+ III 80% by weight of the feed, the conversion of the feed and the yield of distillate products remain sufficient high.

Example 4

In Example 4, the feedstock, experimental setup, and hydroconversion conditions are the same as in Example 3. The ratio of hydrogen to feedstock is increased to 800 nl / L. The mass of stream III is also 30% by weight of the feed. Unlike

Example 3 in example 4, the hydrocarbon part of stream III (20% of the mass of raw materials) after metal recovery is returned to the hydroconversion process, and part - 10% is removed from the process as residual fuel. The masses of streams I and II remained the same as in example 4. The results are shown in table 1. As can be seen from the data presented, the return of demetallized stream III to the hydroconversion process increases the depth of conversion of the feed to 88.3% and the yield of distillate products to 85.5 % by weight of raw materials. In this case, the consumption of the catalyst remains the same as in example 4 Example 5.

In Example 5, the feedstock, experimental setup, and hydroconversion conditions are the same as in Example 4. A molybdenum containing catalyst promoted with nickel (M0S2 + NiS) is used. The molybdenum: nickel ratio in the catalyst is 100: 1 (by weight). The amount of catalyst in the raw material mixture is 0.05% in terms of metals per mass of raw material. The mass of stream III is 30%, of which 20.3% is returned to the hydroconversion process after demetallization. The content of Mo in the residue of distillation of the hydrogenate is 0.07%. The mass of stream I is calculated according to the formula 1: Mf = 30 »0.07 / (1-0.07) = 2.26 % by weight of the raw material. Nickel-promoted Mo catalyst is introduced into stream I. The amount of fresh catalyst is equal to the loss of catalyst withdrawn from the hydroconversion process with stream III: 30 * 0.07 / 100 = 0.021% by weight of the feed. The catalyst is introduced at a constant hydroconversion mode into the recycle stream I. The mass of the hydrogenation distillation residue is 71.5% by weight of the feed. The mass of stream II is: 71.5 - 30 -2.26 = 29.24% of the mass of raw materials. The product yield is shown in table 1.

The conversion of raw materials in the experiment was 88.7%. The yield of distillate products is 87.2% with a low coke yield of 0.04 %. As can be seen from the above data, the promotion of the molybdenum catalyst with nickel reduces the catalyst consumption from 0.037 (Example 5) to 0.021%, reduces the formation of coke, and increases the yield of distillate products.

Example 6

In Example 6, the feedstock, experimental setup, and hydroconversion conditions are the same as in Example 4. A molybdenum-containing catalyst promoted with nickel is used. The molybdenum: nickel ratio in the catalyst is 10: 1 (w / w). The amount of catalyst in the raw material mixture is 0.05% in terms of metals per mass of raw material. The mass of stream III is 30% of which 22.5% is returned to the hydroconversion process after demetallization. The Mo content in the residue of the hydrogenation distillation is 0.081%. The mass of stream I is calculated according to the formula 1: M ^ = 30 0,0 0.081 / (1-0.081) = 2.64% of the mass of raw materials. Nickel-promoted Mo catalyst is introduced into stream I. The amount of fresh catalyst is equal to the loss of catalyst withdrawn from the hydroconversion process with stream III: 30 * 0.081 / 100 = 0.024% by weight of the feed. The molybdenum-containing catalyst is introduced under constant hydroconversion into the recycle stream I. The mass of the hydrogenation distillation residue is 62% by weight of the feed. The mass of stream II is equal to: 62 - 30 -2.64 = 29.36 % of the mass of raw materials. The product yield is shown in table 1.

As can be seen from the above data, the promotion of the molybdenum catalyst with nickel can reduce the consumption of the catalyst, reduce coke formation, and increase the yield of distillate products.

* - the catalyst was dispersed in the feed; ** - the catalyst was dispersed in the residue of atmospheric distillation of the hydrogenate; *** - total content of active metals; **** - the amount of catalyst recovered from stream (III) is not taken into account.

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Claims (9)

1. The method of hydroconversion of the residue of atmospheric distillation of gas condensate, including hydroconversion at elevated temperature and pressure in the presence of an ex situ obtained Mo-containing ultrafine catalyst dispersed in the feed by mixing with hydrogen and hydrogenation of the feed, separation of the reaction products into distillate fractions and a high boiling residue, from which metals and spent catalyst are recovered, which are sent for regeneration, characterized in that before the hydroconversion the raw materials are mixed with a suspension of finely dispersed Mo-containing catalyst with a particle size of 5-300 nm and a catalyst concentration of 1% wt. (in terms of molybdenum), previously prepared by dispersing the catalytically active compound of molybdenum in the residue of atmospheric distillation of the hydrogenated product, to obtain a homogeneous stable suspension of ultrafine catalyst in a feed containing 0.05-0.2% wt. catalyst (in terms of molybdenum) to the mass of raw materials, hydroconversion of the prepared mixture is carried out in a reactor with an upward flow of raw materials at a temperature of 380-450 ° C and a pressure of 7-10 MPa, the hydroconversion products are separated to obtain a hydrogen-containing gas, which is returned to hydrogenation as hydrogen , distillate fractions with a boiling point up to 350 ° С, which are discharged as commercial products, and the residue of atmospheric distillation of hydrogenate with a boiling point above 350 ° С, part of which - stream I - is returned to the process rsii and used to prepare fresh catalyst slurry, a part - Feed II - recycled for mixing with a feed part - Feed III - outputted from the hydroconversion process for the recovery and regeneration of the catalyst. 2. The method according to p. 1, characterized in that they use an ultrafine Mo-containing catalyst promoted with nickel from the condition of the mass ratio Mo: Ni = (100-10): 1. 3. The method according to one of claims 1 or 2, characterized in that the amount of metals of the fresh catalyst dispersible in stream I should be equal in weight to the number of metals removed from stream III. 4. The method according to p. 1, characterized in that the ratio of the masses of raw materials and flows is: raw materials: [stream I + stream II + stream III] = 1: (0.25-0.8). 5. The method according to p. 1, characterized in that the ratio of the mass of raw materials and stream III is 1: (0.05-0.3). 6. The method according to p. 1, characterized in that the hydrocarbon portion of the residue above 350 ° C of stream III after separation of the catalyst and other metals is recycled. 7. The method according to p. 1, characterized in that the mass of stream I is calculated by the formula:

where M _(I) and M _(III) are the masses of flows (I) and (III), respectively (identical units); C ₍₃₅₀₎ is the content of catalysts (in terms of metals) in the residue of atmospheric distillation of hydrogenate,% wt.

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