WO2010056153A1 - Process for obtaining light petroleum products and plant for implementing this process - Google Patents

Process for obtaining light petroleum products and plant for implementing this process Download PDF

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Publication number
WO2010056153A1
WO2010056153A1 PCT/RU2009/000613 RU2009000613W WO2010056153A1 WO 2010056153 A1 WO2010056153 A1 WO 2010056153A1 RU 2009000613 W RU2009000613 W RU 2009000613W WO 2010056153 A1 WO2010056153 A1 WO 2010056153A1
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WO
WIPO (PCT)
Prior art keywords
activator
organomineral
hpr
mixture
solvent
Prior art date
Application number
PCT/RU2009/000613
Other languages
French (fr)
Inventor
Eugeniy Grigorievich Gorlov
Boris Konstantinovich Nefedov
Aleksey Gennadievich Poliakov
Vladimir Mikhailovich Kapustin
Aleksandr Ivanovich Kotov
Yuriy Nikolaevich Kitashov
Yuriy Nikolaevich Kartashev
Aleksandr Nikolaevich Andriyash
Pavel Yurievich Nikonov
Original Assignee
Zakrytoe Aktsionernoe Obschestvo "Buguruslanneftepererabotka" (Zao "Bnp")
Enerlink Limited
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Application filed by Zakrytoe Aktsionernoe Obschestvo "Buguruslanneftepererabotka" (Zao "Bnp"), Enerlink Limited filed Critical Zakrytoe Aktsionernoe Obschestvo "Buguruslanneftepererabotka" (Zao "Bnp")
Publication of WO2010056153A1 publication Critical patent/WO2010056153A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/22Non-catalytic cracking in the presence of hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/107Atmospheric residues having a boiling point of at least about 538 °C

Definitions

  • the present matter relates to petroleum industry and, specifically, to the processes used for converting heavy petroleum residues (HPR) into fuel distillates by thermal cracking thereof with use of donor solvent processes.
  • HPR heavy petroleum residues
  • a process for obtaining liquid products from HPR (RF Patent No. 2178448, published on Jan. 20, 2002) by converting the HPR into light products, wherein a homogenous blend is prepared from the HPR and finely crushed sapropelite (particle size, 20-30 ⁇ m) specially dried and subjected to mechanochemical treatment in a vibrating mill with subsequent thermal cracking of the thus obtained mixture at 390-420 °C and 0.2-5 MPa and recovery of the cracked products.
  • the mechanochemical treatment is performed in an inert medium at a pressure of 0.05 atm. with the vibrating mill working in stream with a vibrating sieve, while the components are continuously fed for mixing by a screw feeder having an adjustable feed rate.
  • Combustible shale, sapromyxite, rabdopissite, boghead and cannel coal are used as a sapropelite.
  • this process has some disadvantages, such as the need for a thorough drying and very fine crushing of the sapropelite, heating of the stock in a pipe still with inevitable coking of the stock, the need to carry out the process in an inert medium, including fine crushing of the sapropelite, the use of external high pressure reactors, and the need to use the water steam for extraction of the spent organomineral catalyst from the products of the reaction.
  • the combustible shale and shale oil fraction are added in a desired proportion to the stock (mass %) from 1.0 to 5.0 and from 1.0 to 6.0, respectively.
  • the homogenization is performed in an agitator at a temperature of 80-100 °C, while the combustible shale is additionally finely crushed to a particle size of 30-100 ⁇ m during its mechanochemical activation.
  • This process has a comparatively high cost and is generally insufficient in its effectiveness of obtaining the end product.
  • plants for thermal cracking of heavy petroleum residues with use of an organomineral catalyst, for example as described in RF Patents Nos 2178446 and 2178447, published on Jan. 20, 2002.
  • the plants include stock mixers, stock blend heating furnaces with a reaction chamber, disintegrators, external reactors, separators, atmospheric column for separation of thermal cracking products.
  • the disadvantage of such plants resides in their complex hardware configuration.
  • RF Patent No. 2261265 published on Sept. 27, 2005, describes a plant for obtaining light petroleum products comprising a bunker for receiving organomineral activator, e.g., combustible shale, a crusher with a bag filter all series-connected to said activator and a disintegrator, a bunker for temporary storage of organomineral activator, a reservoir with a hydrogen donor additive, a reservoir with the HPR, connected to the agitator, which in turn is connected to the furnace for heating the mixture of hydrogen donor additive with the HPR and organomineral activator, a reactor connected to the furnace and a heat exchanger connected to a hot separator and to a high pressure separator through a cooling system, a low pressure separator connected through an accumulator tank with a rectifying tower, and a refrigerator connected through a centrifuge to the rectifying tower.
  • organomineral activator e.g., combustible shale
  • the present matter provides a process of converting the heavy petroleum residues into fuel distillates by thermal cracking with the use of donor solvent processes.
  • a process for obtaining light petroleum products comprising mixing of heavy petroleum residues (HPR) with an organomineral activator, such as finely crushed combustible shale, and a hydrogen donor additive, added in a desired proportion to the stock, homogenization of the blend in an agitator at a temperature of 80-100 0 C and thermal cracking of the resultant mixture with subsequent recovery of the end products.
  • HPR heavy petroleum residues
  • organomineral activator such as finely crushed combustible shale
  • a hydrogen donor additive added in a desired proportion to the stock, homogenization of the blend in an agitator at a temperature of 80-100 0 C and thermal cracking of the resultant mixture with subsequent recovery of the end products.
  • the process uses, as a hydrogen donor additive, a solvent- refined oil extract containing 0.1 - 15 % of active hydrogen, added in the amount of 0.5 - 15 mass % to the mixture of the HPR with an organomineral activator, such as finely crushed
  • the solvent-refined oil extract is first mechanically mixed with the organomineral activator, following which the HPR is mixed with the blend of the solvent-refined oil extract and organomineral activator, and the resultant mixture is mechanically homogenized, while the organomineral activator is added in the amount of 1 - 15 mass % to the mixture.
  • the thermal cracking in the process, is performed at a temperature of 380 - 490 °C, a pressure of 0.2 - 5 MPa and space velocity of feeding the mixture of HPR, solvent-refined oil extract and organomineral activator equal to 0.5 - 4 hour "1 .
  • the solvent-refined oil extract, used in the process is mixed with an organomineral activator, preliminarily finely crushed in a mechanical crusher, at a temperature of 50 - 100 °C to a particle size of 5 - 100 ⁇ m with production of a suspension with a viscosity of 0.5 - 1.0 Pa • s at 80 °C.
  • the organomineral activator used is selected from combustible shales, sapropelites, sapromyxites and other liptobiolith coals, and added in the amount of 1 - 15 mass % to the mixture.
  • a blend of solvent-refined oil extract and combustible shale is admixed with a portion of HPR in the process.
  • a process for obtaining light petroleum products wherein heavy petroleum residues (HPR) are mixed by the mechanochemical method with an organomineral activator, such as finely crushed combustible shale, added in the amount of 1 - 15 mass % to the mixture, with a blend of solvent-refined oil extract containing 0.1 - 15 % of active hydrogen added in the amount of 0.5 - 15 mass % to a blend of the heavy petroleum residues (HPR).
  • the solvent-refined oil extract is first mixed by the mechanical method with an organomineral activator. Then, the thus obtained three-component mixture is homogenized in an agitator at a temperature of 80 - 100 °C and is subjected to thermal cracking with subsequent recovery of the end product(s).
  • the present matter provides a plant for obtaining light petroleum products.
  • a plant for obtaining light petroleum products comprising a bunker for receiving an organomineral activator, such as combustible shale, a crusher with a bag filter and a disintegrator series-connected thereto, a bunker for temporary storage of an organomineral activator, a reservoir with a hydrogen donor additive, a reservoir with a heavy petroleum residue (HPR) connected to an agitator, which is connected to a furnace for heating the mixture of hydrogen donor additive with HPR and organomineral activator, a reactor connected to the furnace and heat exchanger connected to a hot separator and a high pressure separator through a cooling system, a low pressure separator connected through an accumulation tank to a rectifying tower and a refrigerator connected through a centrifuge to the rectifying tower.
  • organomineral activator such as combustible shale
  • a bunker for temporary storage of an organomineral activator a reservoir with
  • the plant includes a unit for preparing a mixture of an organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent-refined oil extract, the unit being connected to a bunker for temporary storage of the organomineral activator, to a reservoir with a hydrogen donor additive and to an agitator, as well as mechanochemical activation device connected to the agitator and a furnace for heating the blend of hydrogen donor additive with HPR and organomineral activator.
  • an organomineral activator such as combustible shale
  • a hydrogen donor additive such as solvent-refined oil extract
  • the reactor, in the plant is made up of sections whose number is from one to three.
  • the unit for preparing a mixture of an organomineral activator with a hydrogen donor additive, within the plant is made up of a series-connected mixer and mechanical activation mill.
  • Figure 1 is a schematic diagram of the plant according to the present matter for implementation of the process described herein.
  • the process described herein increases the effectiveness of HPR processing, improves the quality and decreases the production cost of the end product as well as decreasing the coke formation by replacing the expensive liquid aromatic additive (shale oil fraction) by a cheaper one (solvent-refined oil extract).
  • the process includes preliminary mechanical mixing of the solvent-refined oil extract with the organomineral activator, mixing of the HPR with a blend of solvent-refined oil extract with organomineral activator and homogenization of the resultant mixture by the mechanochemical method.
  • the process provides an increased yield of light petroleum products, decreased coke formation as well as decreased production cost of the end product.
  • the process for obtaining light petroleum products described herein comprises mixing HPR with an organomineral activator, such as finely crushed combustible shale, and a hydrogen donor additive, taken in a desired proportion with the stock. Homogenization of the blend in an agitator occurs at a temperature of 80-100 0 C followed by thermal cracking of the resultant mixture with subsequent recovery of the end products.
  • organomineral activator such as finely crushed combustible shale
  • the process uses, as a hydrogen donor additive, a solvent-refined oil extract containing 0.1-15 mass % of active hydrogen, added in the amount of 0.5-15 mass % to the HPR blend with an organomineral activator, such as finely crushed combustible shale, while the solvent-refined oil extract is first mechanically mixed with an organomineral activator, following which the HPR is mixed with the blend of solvent-refined oil extract with the organomineral activator, and the resultant mixture is homogenized by a mechanochemical method, while an organomineral activator is added to the mixture in the amount of 1 - 15 mass %.
  • an organomineral activator such as finely crushed combustible shale
  • the process described herein uses, as a hydrogen donor additive, a solvent-refined oil extract containing 0.1 - 15% of active hydrogen added in the amount of 0.5 - 15 mass % to an HPR mixture with an organomineral activator, which promotes optimization of the HPR treatment process.
  • the use of the solvent-refined oil extract in this process includes the content of active hydrogen in the range of 0.1 - 15 mass %, while the content of the extract itself is in the range of 0.5 - 15 mass %.
  • an organomineral activator e.g., combustible shale
  • active hydrogen in the solvent-refined oil extract are interrelated, so a decreased amount of combustible shale requires an increased amount of hydrogen and vice versa.
  • This factor sets the ranges of the contents of active hydrogen, solvent-refined oil extract and organomineral activator.
  • the solvent-refined oil extract is first mechanically mixed with an organomineral activator and only after that a HPR is mixed with a blend of solvent-refined oil extract with organomineral activator, following which the resultant mixture is homogenized by a mechanochemical method.
  • the preliminary mixing of the solvent-refined oil extract with an organomineral activator allows mixing the given mixture by a mechanical, not mechanochemical, method, which aids in decreasing the production cost of the process for obtaining light petroleum products by reducing the energy expenses, while the mixing of the given blend with a HPR and homogenization of the resultant mixture increases the yield of light petroleum products.
  • the homogenization of the resultant ternary blend by a mechanochemical method aids in lowering the temperature of the cracking process and decreasing the coke formation.
  • Combustible shale, sapropelites, sapromyxites and other liptobioliths added in the amount of 1-15 mass % to the mixture can be used as the organomineral activator.
  • the experiments have shown that the given amount is preferred, since the use of an organomineral activator in an amount less than 1 mass % does not ensure proper quality of the end products, whereas the amounts greater than 15 mass % do not change the quality, while the obtained end products become more expensive.
  • the hydrogen donor additive is mixed with an organomineral activator, which was first finely crushed in a mechanical crusher at a temperature of 50-100 °C to a particle size of 5-100 ⁇ m to obtain a suspension with a viscosity of 0.5-1.0 Pa-S at 80 °C. If necessary, to obtain a suspension of this viscosity, a part of the HPR is added to the mixture of hydrogen donor additive with an organomineral activator.
  • the thermal cracking process is preferably carried out at a temperature of 380-490°C, pressure of 0.2-5 MPa and space velocity of feeding of three-component reaction mixture equal to 0.5 - 4 hour "1 .
  • Any residual petroleum products like straight-run or recycled fuel oil (mazout), tar (goudron), cracking residues, heavy pyrolysis resins, asphalt-free oils, heavy crude oils and oils extracted from oil-bearing rocks, etc. may be used as the HPR.
  • the solvent-refined oil extract is a byproduct of production of various grades of oil at all petroleum refineries of the Russian Federation, where oil production facilities are used.
  • the formulation of the solvent-refined oil extract contains a significant amount of aromatic hydrocarbons (64.0 - 77.6 %), inclusive of 30.3 - 38.5 mass % of polycyclic.
  • HPR processing is optimization of the reaction for transfer of hydrogen from the donor liquid aromatic additive to the HPR molecules.
  • the degree of transformation of the HPR is markedly affected by the presence of the hydrogen donors and carriers.
  • Hydrogenation is a reducing process, and dehydration is an oxidizing process. If the reaction results in transfer of the atoms of hydrogen from one molecule to another (hydrogen transfer reaction), the molecule donating hydrogen is a donor molecule, and that accepting it is called an acceptor molecule.
  • Transfer of hydrogen from a donor to carriers occurs stepwise in the manner of a free radical mechanism, and the strength of the bond between hydrogen and the atoms of carbon in the donor molecule is essential.
  • the aromatic liquid additive should easily give away the atomic hydrogen in the course of thermal cracking and dissolve well the asphaltenes. This quality is observed in the liquid aromatic additives containing naphta-aromatic hydrocarbons, specifically, the solvent-refined oil extract. During the thermal cracking the atomic hydrogen interacts with unsaturated radicals resulting from destruction of petroleum residues, thus preventing the reactions of consolidation and coke formation.
  • the present matter also provides a high-capacity plant for obtaining light petroleum products.
  • the plant for producing light petroleum products comprises a bunker for receiving an organomineral activator, such as combustible shale, a crusher with a bag filter and disintegrator all series-connected to said bunker, a bunker for temporary storage of the organomineral activator, a reservoir with a hydrogen donor additive, an HPR reservoir connected to an agitator which is connected to a furnace for heating the mixture of a hydrogen donor additive with a HPR and organomineral activator, a reactor connected to the furnace and a heat exchanger connected to a hot separator and to a high pressure separator through a cooling system, a low pressure separator connected through an accumulation tank to a rectifying tower, and a refrigerator connected through a centrifuge to the rectifying tower.
  • an organomineral activator such as combustible shale
  • a crusher with a bag filter and disintegrator all series-connected to said bunker
  • the plant includes a unit for preparing a mixture of organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent- refined oil extract, the unit being connected to a bunker for temporary storage of the organomineral activator, to a reservoir with a hydrogen donor additive and to an agitator, as well as with a mechanochemical activation device connected to an agitator and furnace for heating the mixture of hydrogen donor additive with HPR and organomineral activator.
  • organomineral activator such as combustible shale
  • a hydrogen donor additive such as solvent- refined oil extract
  • a unit for preparing a mixture of organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent- refined oil extract makes it possible to use a more economical mechanical method of agitation and so speed up the preparation of the mixture consisting of an HPR and a blend of combustible shale with solvent-refined oil extract.
  • the plant comprises bunker 1 for receiving the organomineral activator, such as combustible shale, crusher 2 with a bag filter, disintegrator 3, bunker 4 for temporary storage of the organomineral activator, unit 5 for preparing a mixture of the organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent- refined oil extract, reservoir 6 with a hydrogen donor additive, reservoir 7 with an HPR, agitator 8, device 9 for mechanochemical activation, furnace 10 for heating the mixture of a hydrogen donor additive with an organomineral activator and an HPR, reactor 11 made up of one to three sections, heat exchanger 12, hot separator 13, cooling system 14, high pressure separator 15, low pressure separator 16, accumulation tank 17, refrigerator 18, centrifuge 19, and rectifying tower 20.
  • a hydrogen donor additive such as solvent- refined oil extract
  • furnace 10 for heating the mixture of a hydrogen donor additive with an organomineral activator and an HPR
  • reactor 11 made up of one to three sections, heat exchange
  • Bunker 1 for receiving an organomineral activator is series-connected to crusher 2, disintegrator 3, bunker 4 for temporary storage of the organomineral activator and to unit 5 for preparing a mixture of organomineral activator with hydrogen donor additive, which, in turn, is connected to reservoir 6 with hydrogen donor additive and to agitator 8 connected to
  • HPR reservoir 7 and device 9 for mechanochemical activation Reactor 1 1 is connected to furnace 10 and to heat exchanger 12.
  • Hot separator 13 is connected to heat exchanger 12, cooling system 14 and refrigerator 18.
  • High pressure separator 15 is connected to low pressure separator 16 and to cooling system 14.
  • Refrigerator 18 is connected to centrifuge
  • the plant operates as follows:
  • a 25-250 mm lump of organomineral activator, such as combustible shale, or 0-25 mm fines thereof are delivered from a railway car to a storage area. From the storage area, the combustible shale is delivered to bunker 1 for receiving combustible shale. From bunker 1 for receiving combustible shale, the combustible shale is transferred by a belt conveyer into crusher 2 fitted with a bag filter, where the shale is finely crushed to a particle size of up to 8 mm.
  • Disintegrator 3 mechanically activating mill
  • Disintegrator 3 has a cyclone separator, air filter, a bag filter, and a sector feeder (not shown in the diagram).
  • the finely crushed shale goes through the latter's relief passage onto the vibrating sieve (not shown in the diagram) with a mesh of to 140 ⁇ m, and then comes to bunker 4 for temporary storage.
  • the entire system used for crushing the shale has a control panel with safe start equipment.
  • the vibrating sieve is designed to separate shale particles greater than 140 ⁇ m in size.
  • the shale which is finely crushed to a particle size of 100 ⁇ m, is fed into the unit for preparing the stock, that is, the mixture of organomineral activator, such as combustible shale, taken from bunker 4 with hydrogen donor additive, such as solvent- refined oil extract from reservoir 6.
  • This stage is essential for the entire chain process.
  • the stock is prepared in the following steps. At first, a blend of organomineral activator and hydrogen donor additive is prepared in unit 5 for preparation of this blend. Unit 5 consists of a series-connected mixer and a mechanical activation mill.
  • the mechanical activation is performed in the prior art units, type Desi-14, as well as in prior art dispersers (homogenizers), disperser-mixers, disintegratorax, etc.
  • the HPR from tank 7 is added to the thus obtained mixture.
  • the temperature in agitator 8 (used for mixing and mechanical activation of the initial HPR with a blend of organomineral activator and hydrogen donor additive) is maintained within 80 - 100 °C to ensure pumpability of the petroleum residue.
  • the operations involving feeding the three components of the raw mixture are performed when the agitator is working to prevent settlement of the organomineral activator on the agitator. Should the agitator fail to assure effective mixing of the 3 -component blend, dispersion pumps are used for a more thorough mixing (homogenization). From agitator 8, the raw mixture comes into mechanochemical activation device 9, said activation being effected, say, with the aid of the magnetic vortex field.
  • the ready raw mixture is first fed into furnace 10 for heating the stock (the mixture of hydrogen donor additive with organomineral activator and HPR) and then into reactor 1 1 having from 1 to 3 sections.
  • the temperature at the outlet from furnace 10 is from 380 to 490 0 C, depending on the type of the stock processed.
  • the steam-gas flow goes into heat exchanger 12 and, then, into hot separator 13 where the temperature is maintained at 270 - 320 °C and pressure at 10 MPa.
  • the fractions boiling away at temperatures below 360 - 380 °C mostly pass at the top of the hot separator, while the fractions boiling away at temperatures above 360 - 380 °C pass, mixed with solid products, at the bottom portion of the hot separator.
  • the top flow of the hot separator is accumulated, along with a hydrogen bearing gas (HBG), in high pressure separator 15, where the HBG is separated from the liquid fractions.
  • HBG hydrogen bearing gas
  • the product received at the bottom of hot separator 13 passes through a restrictor valve into refrigerator 18 for cooling and then is delivered through a pipeline to decanting centrifuge 19.
  • the liquid fractions are passed, along with the liquid fractions from accumulation tank 17, into rectifying tower 20 for distillation with obtaining a gasoline fraction with boiling point of up to 180 0 C, a diesel fraction with boiling point of 180 - 360 °C, gas oil fraction with boiling point or 360 - 500 °C and a residue boiling out at temperatures above 500 °C (recycling temperature).
  • Example 1 The initial mixture is prepared by mixing the tar (goudron) with 10 mass % of solvent-refined oil extract containing 5 mass % of active hydrogen and with 7 mass % of combustible shale finely crushed to particle size of 50 ⁇ m. The mixing is performed in a heated agitator at a temperature not below 90 0 C to obtain a suspension with a viscosity of 1.0 Pa s at 80 0 C. Then the mixture is subjected to mechanochemical activation and processing at 90 0 C by a magnetic vortex field. Thermal cracking of the obtained product is then performed at a pressure of 5 MPa, temperature of 45O 0 C, and space velocity of 2 hour '1 .
  • the resultant liquid products are distilled to form fractions with boiling points (b. p.) of to 180 0 C (gasoline) - 26 mass %, 180 - 360 0 C (diesel) - 56 mass %, 360 - 500 0 C (gas oil) - 10 mass %, and a residue with boiling point above 500 0 C.
  • the amount of coke is 0.07 % mass %.
  • Example 2 The initial mixture is prepared by mixing 15 mass % of solvent-refined oil extract containing 0.1 mass % of active hydrogen and 5 mass % of sapropelite finely crushed at 60 0 C to particle size of 75 ⁇ m. Then, the thus obtained blend is admixed with an HPR, such as asphalt- free oil, in the amount of 15 mass % (of its initial quantity). The obtained mixture is subjected to the mechanochemical activation and processing at 8O 0 C. Then the remaining asphalt-free oil is added to the blend, following which the blend is subjected to additional homogenization in a disintegrator.
  • HPR such as asphalt- free oil
  • Example 3 The initial mixture is prepared by mixing 0.1 mass % of solvent-refined oil extract containing 15 mass % of active hydrogen and 15 mass % of sapromyxite finely crushed at 60 0 C to particle size of 5 ⁇ m. Then, the thus obtained blend is admixed with
  • HPR such as the tar or goudron in the amount of 15 mass % (of its initial quantity).
  • the resultant mixture is subjected to mechanochemical activation and processing at 8O 0 C. Then the remaining amount of tar is added to the mixture, following which the mixture is subjected to additional homogenization in a disintegrator.
  • Example 4 The initial mixture is prepared by mixing 0.2 mass % of solvent-refined oil extract containing 12 mass % of active hydrogen and 1 mass % of sapromyxite finely crushed at 60 0 C to particle size of 100 ⁇ m. Then, the thus obtained blend is admixed with HPR, such as the tar or goudron, in the amount of 15 mass % (of its initial quantity). The resultant mixture is subjected to mechanochemical activation and processing at 8O 0 C. Then the remaining amount of tar is added to the mixture, following which the mixture is subjected to additional homogenization in a disintegrator.
  • HPR such as the tar or goudron
  • Example 5 The initial mixture is prepared by mixing 0.5 mass % of solvent-refined oil extract containing 1 1.5 mass % of active hydrogen and 6 mass % of sapromyxite finely crushed at 60 0 C to particle size of 20 ⁇ m. Then, the thus obtained blend is admixed with HPR, such as the tar or goudron, in the amount of 15 mass % (of its initial quantity). The resultant mixture is subjected to mechanochemical activation and processing at 8O 0 C. Then the remaining amount of tar is added to the mixture, following which the mixture is subjected to additional homogenization in a disintegrator.
  • HPR such as the tar or goudron
  • Thermal cracking of the resultant product is performed at a pressure of 3 MPa, temperature of 430 0 C and space velocity of 4 hour "1 .
  • the obtained liquid products are then distilled to form fractions with b. p. of to 180 0 C (gasoline) - 26.5 mass %, 180 - 360 0 C (diesel) - 49 mass %, 360 - 500 0 C (gas oil) - 10.0 mass %, and a residue with boiling point above 500 0 C.
  • the amount of coke is 0.08 mass %.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present matter relates to the petroleum industry and, more particularly, to a process of converting the heavy petroleum residues into fuel distillates by thermal cracking with use of the donor solvent processes.

Description

PROCESS FOR OBTAINING LIGHT PETROLEUM PRODUCTS AND PLANT FOR IMPLEMENTING THIS PROCESS
TECHNICAL FIELD
The present matter relates to petroleum industry and, specifically, to the processes used for converting heavy petroleum residues (HPR) into fuel distillates by thermal cracking thereof with use of donor solvent processes.
BACKGROUND ART
Known in the art is a process for obtaining liquid products from HPR (RF Patent No. 2178448, published on Jan. 20, 2002) by converting the HPR into light products, wherein a homogenous blend is prepared from the HPR and finely crushed sapropelite (particle size, 20-30 μm) specially dried and subjected to mechanochemical treatment in a vibrating mill with subsequent thermal cracking of the thus obtained mixture at 390-420 °C and 0.2-5 MPa and recovery of the cracked products. The mechanochemical treatment is performed in an inert medium at a pressure of 0.05 atm. with the vibrating mill working in stream with a vibrating sieve, while the components are continuously fed for mixing by a screw feeder having an adjustable feed rate. Combustible shale, sapromyxite, rabdopissite, boghead and cannel coal are used as a sapropelite.
However, this process has some disadvantages, such as the need for a thorough drying and very fine crushing of the sapropelite, heating of the stock in a pipe still with inevitable coking of the stock, the need to carry out the process in an inert medium, including fine crushing of the sapropelite, the use of external high pressure reactors, and the need to use the water steam for extraction of the spent organomineral catalyst from the products of the reaction.
An alternative fuel distillate production process is described in RF Patent No. 2261265, published on Sept. 27, 2005, comprising mixing of the residual petroleum stock
(heavy petroleum residues or HPR for short) with a finely crushed sapropelite and a liquid activating additive. Homogenization and thermal conversion or hydraulic cracking of the resultant blend with a subsequent recovery of the end products occurs wherein the finely crushed sapropelite is subjected, before homogenization, to mechanochemical activation in at least one disperser. Combustible shale containing 45-60 mass % of the mineral part and 40-55 mass % of the organic part is used as a sapropelite, and a shale oil fraction having a cut boiling range of 200-400°C and containing at least 10.0 mass % of hydrogen is used as a liquid activating additive. The combustible shale and shale oil fraction are added in a desired proportion to the stock (mass %) from 1.0 to 5.0 and from 1.0 to 6.0, respectively. The homogenization is performed in an agitator at a temperature of 80-100 °C, while the combustible shale is additionally finely crushed to a particle size of 30-100 μm during its mechanochemical activation.
This process has a comparatively high cost and is generally insufficient in its effectiveness of obtaining the end product.
Also known in the art are plants for thermal cracking of heavy petroleum residues (HPR) with use of an organomineral catalyst, for example as described in RF Patents Nos 2178446 and 2178447, published on Jan. 20, 2002. The plants include stock mixers, stock blend heating furnaces with a reaction chamber, disintegrators, external reactors, separators, atmospheric column for separation of thermal cracking products. The disadvantage of such plants resides in their complex hardware configuration.
RF Patent No. 2261265, published on Sept. 27, 2005, describes a plant for obtaining light petroleum products comprising a bunker for receiving organomineral activator, e.g., combustible shale, a crusher with a bag filter all series-connected to said activator and a disintegrator, a bunker for temporary storage of organomineral activator, a reservoir with a hydrogen donor additive, a reservoir with the HPR, connected to the agitator, which in turn is connected to the furnace for heating the mixture of hydrogen donor additive with the HPR and organomineral activator, a reactor connected to the furnace and a heat exchanger connected to a hot separator and to a high pressure separator through a cooling system, a low pressure separator connected through an accumulator tank with a rectifying tower, and a refrigerator connected through a centrifuge to the rectifying tower. The disadvantage of this prior art plant is its insufficient production capacity.
SUMMARY In one aspect the present matter provides a process of converting the heavy petroleum residues into fuel distillates by thermal cracking with the use of donor solvent processes.
In one embodiment, there is described a process for obtaining light petroleum products, comprising mixing of heavy petroleum residues (HPR) with an organomineral activator, such as finely crushed combustible shale, and a hydrogen donor additive, added in a desired proportion to the stock, homogenization of the blend in an agitator at a temperature of 80-100 0C and thermal cracking of the resultant mixture with subsequent recovery of the end products. The process uses, as a hydrogen donor additive, a solvent- refined oil extract containing 0.1 - 15 % of active hydrogen, added in the amount of 0.5 - 15 mass % to the mixture of the HPR with an organomineral activator, such as finely crushed combustible shale. The solvent-refined oil extract is first mechanically mixed with the organomineral activator, following which the HPR is mixed with the blend of the solvent-refined oil extract and organomineral activator, and the resultant mixture is mechanically homogenized, while the organomineral activator is added in the amount of 1 - 15 mass % to the mixture.
In a further embodiment the thermal cracking, in the process, is performed at a temperature of 380 - 490 °C, a pressure of 0.2 - 5 MPa and space velocity of feeding the mixture of HPR, solvent-refined oil extract and organomineral activator equal to 0.5 - 4 hour"1 .
In a further embodiment the solvent-refined oil extract, used in the process, is mixed with an organomineral activator, preliminarily finely crushed in a mechanical crusher, at a temperature of 50 - 100 °C to a particle size of 5 - 100 μm with production of a suspension with a viscosity of 0.5 - 1.0 Pa s at 80 °C.
In a further embodiment the organomineral activator used is selected from combustible shales, sapropelites, sapromyxites and other liptobiolith coals, and added in the amount of 1 - 15 mass % to the mixture.
In a further embodiment a blend of solvent-refined oil extract and combustible shale (organomineral activator) is admixed with a portion of HPR in the process.
In an alternative embodiment there is provided a process for obtaining light petroleum products wherein heavy petroleum residues (HPR) are mixed by the mechanochemical method with an organomineral activator, such as finely crushed combustible shale, added in the amount of 1 - 15 mass % to the mixture, with a blend of solvent-refined oil extract containing 0.1 - 15 % of active hydrogen added in the amount of 0.5 - 15 mass % to a blend of the heavy petroleum residues (HPR). The solvent-refined oil extract is first mixed by the mechanical method with an organomineral activator. Then, the thus obtained three-component mixture is homogenized in an agitator at a temperature of 80 - 100 °C and is subjected to thermal cracking with subsequent recovery of the end product(s).
In another aspect the present matter provides a plant for obtaining light petroleum products.
In one embodiment there is provided a plant for obtaining light petroleum products, comprising a bunker for receiving an organomineral activator, such as combustible shale, a crusher with a bag filter and a disintegrator series-connected thereto, a bunker for temporary storage of an organomineral activator, a reservoir with a hydrogen donor additive, a reservoir with a heavy petroleum residue (HPR) connected to an agitator, which is connected to a furnace for heating the mixture of hydrogen donor additive with HPR and organomineral activator, a reactor connected to the furnace and heat exchanger connected to a hot separator and a high pressure separator through a cooling system, a low pressure separator connected through an accumulation tank to a rectifying tower and a refrigerator connected through a centrifuge to the rectifying tower. The plant includes a unit for preparing a mixture of an organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent-refined oil extract, the unit being connected to a bunker for temporary storage of the organomineral activator, to a reservoir with a hydrogen donor additive and to an agitator, as well as mechanochemical activation device connected to the agitator and a furnace for heating the blend of hydrogen donor additive with HPR and organomineral activator.
In one embodiment, the reactor, in the plant, is made up of sections whose number is from one to three.
In another embodiment the unit for preparing a mixture of an organomineral activator with a hydrogen donor additive, within the plant, is made up of a series-connected mixer and mechanical activation mill.
BRIEF DESCRIPTION OF THE DRAWINGS
The present matter will now be described in further detail with reference to the attached Figures in which:
Figure 1 is a schematic diagram of the plant according to the present matter for implementation of the process described herein.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The process described herein increases the effectiveness of HPR processing, improves the quality and decreases the production cost of the end product as well as decreasing the coke formation by replacing the expensive liquid aromatic additive (shale oil fraction) by a cheaper one (solvent-refined oil extract). The process includes preliminary mechanical mixing of the solvent-refined oil extract with the organomineral activator, mixing of the HPR with a blend of solvent-refined oil extract with organomineral activator and homogenization of the resultant mixture by the mechanochemical method.
The process provides an increased yield of light petroleum products, decreased coke formation as well as decreased production cost of the end product.
In one aspect, the process for obtaining light petroleum products described herein, comprises mixing HPR with an organomineral activator, such as finely crushed combustible shale, and a hydrogen donor additive, taken in a desired proportion with the stock. Homogenization of the blend in an agitator occurs at a temperature of 80-100 0C followed by thermal cracking of the resultant mixture with subsequent recovery of the end products. The process uses, as a hydrogen donor additive, a solvent-refined oil extract containing 0.1-15 mass % of active hydrogen, added in the amount of 0.5-15 mass % to the HPR blend with an organomineral activator, such as finely crushed combustible shale, while the solvent-refined oil extract is first mechanically mixed with an organomineral activator, following which the HPR is mixed with the blend of solvent-refined oil extract with the organomineral activator, and the resultant mixture is homogenized by a mechanochemical method, while an organomineral activator is added to the mixture in the amount of 1 - 15 mass %.
As stated above, the process described herein, uses, as a hydrogen donor additive, a solvent-refined oil extract containing 0.1 - 15% of active hydrogen added in the amount of 0.5 - 15 mass % to an HPR mixture with an organomineral activator, which promotes optimization of the HPR treatment process.
Experiments, examples of which are provided below, have shown that, in the preferred embodiment, the use of the solvent-refined oil extract in this process includes the content of active hydrogen in the range of 0.1 - 15 mass %, while the content of the extract itself is in the range of 0.5 - 15 mass %. This is because the content of an organomineral activator, e.g., combustible shale, and active hydrogen in the solvent-refined oil extract are interrelated, so a decreased amount of combustible shale requires an increased amount of hydrogen and vice versa. This factor sets the ranges of the contents of active hydrogen, solvent-refined oil extract and organomineral activator.
In the process described herein the solvent-refined oil extract is first mechanically mixed with an organomineral activator and only after that a HPR is mixed with a blend of solvent-refined oil extract with organomineral activator, following which the resultant mixture is homogenized by a mechanochemical method.
The preliminary mixing of the solvent-refined oil extract with an organomineral activator allows mixing the given mixture by a mechanical, not mechanochemical, method, which aids in decreasing the production cost of the process for obtaining light petroleum products by reducing the energy expenses, while the mixing of the given blend with a HPR and homogenization of the resultant mixture increases the yield of light petroleum products.
In the process described herein the homogenization of the resultant ternary blend by a mechanochemical method aids in lowering the temperature of the cracking process and decreasing the coke formation.
Combustible shale, sapropelites, sapromyxites and other liptobioliths added in the amount of 1-15 mass % to the mixture can be used as the organomineral activator. The experiments have shown that the given amount is preferred, since the use of an organomineral activator in an amount less than 1 mass % does not ensure proper quality of the end products, whereas the amounts greater than 15 mass % do not change the quality, while the obtained end products become more expensive. In one embodiment the hydrogen donor additive is mixed with an organomineral activator, which was first finely crushed in a mechanical crusher at a temperature of 50-100 °C to a particle size of 5-100 μm to obtain a suspension with a viscosity of 0.5-1.0 Pa-S at 80 °C. If necessary, to obtain a suspension of this viscosity, a part of the HPR is added to the mixture of hydrogen donor additive with an organomineral activator.
The thermal cracking process is preferably carried out at a temperature of 380-490°C, pressure of 0.2-5 MPa and space velocity of feeding of three-component reaction mixture equal to 0.5 - 4 hour"1.
Any residual petroleum products like straight-run or recycled fuel oil (mazout), tar (goudron), cracking residues, heavy pyrolysis resins, asphalt-free oils, heavy crude oils and oils extracted from oil-bearing rocks, etc. may be used as the HPR.
The solvent-refined oil extract is a byproduct of production of various grades of oil at all petroleum refineries of the Russian Federation, where oil production facilities are used.
The formulation of the solvent-refined oil extract contains a significant amount of aromatic hydrocarbons (64.0 - 77.6 %), inclusive of 30.3 - 38.5 mass % of polycyclic.
One of the problems of HPR processing is optimization of the reaction for transfer of hydrogen from the donor liquid aromatic additive to the HPR molecules. During hydrogenation, the degree of transformation of the HPR is markedly affected by the presence of the hydrogen donors and carriers.
Hydrogenation is a reducing process, and dehydration is an oxidizing process. If the reaction results in transfer of the atoms of hydrogen from one molecule to another (hydrogen transfer reaction), the molecule donating hydrogen is a donor molecule, and that accepting it is called an acceptor molecule.
Transfer of hydrogen from a donor to carriers (molecules of aromatic compounds) occurs stepwise in the manner of a free radical mechanism, and the strength of the bond between hydrogen and the atoms of carbon in the donor molecule is essential.
The aromatic liquid additive (hydrogen donor) should easily give away the atomic hydrogen in the course of thermal cracking and dissolve well the asphaltenes. This quality is observed in the liquid aromatic additives containing naphta-aromatic hydrocarbons, specifically, the solvent-refined oil extract. During the thermal cracking the atomic hydrogen interacts with unsaturated radicals resulting from destruction of petroleum residues, thus preventing the reactions of consolidation and coke formation.
The fine crushing of a solid activator additive and subsequent homogenization of the 3-component blend are attended by a fairly effective activation of the stock, while the sizes of molecules of the additives (0.3 - 0.5 nm) are commensurate with that of molecules of the heavy petroleum stock (0.4 - 0.7 nm). This circumstance is preferred for creating the conditions for the optimal contact of the activator additives with the molecules of the stock.
The present matter also provides a high-capacity plant for obtaining light petroleum products. The plant for producing light petroleum products, comprises a bunker for receiving an organomineral activator, such as combustible shale, a crusher with a bag filter and disintegrator all series-connected to said bunker, a bunker for temporary storage of the organomineral activator, a reservoir with a hydrogen donor additive, an HPR reservoir connected to an agitator which is connected to a furnace for heating the mixture of a hydrogen donor additive with a HPR and organomineral activator, a reactor connected to the furnace and a heat exchanger connected to a hot separator and to a high pressure separator through a cooling system, a low pressure separator connected through an accumulation tank to a rectifying tower, and a refrigerator connected through a centrifuge to the rectifying tower. The plant includes a unit for preparing a mixture of organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent- refined oil extract, the unit being connected to a bunker for temporary storage of the organomineral activator, to a reservoir with a hydrogen donor additive and to an agitator, as well as with a mechanochemical activation device connected to an agitator and furnace for heating the mixture of hydrogen donor additive with HPR and organomineral activator.
The inclusion in the plant of a unit for preparing a mixture of organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent- refined oil extract, makes it possible to use a more economical mechanical method of agitation and so speed up the preparation of the mixture consisting of an HPR and a blend of combustible shale with solvent-refined oil extract.
Introduction of a mechanochemical activation device connected to an agitator and furnace for heating the mixture of hydrogen donor additive with an HPR and organomineral activator increases the production capacity of the plant.
The plant, described herein, is illustrated by the schematic shown in Figure 1 of the plant for implementation of the claimed process.
The plant comprises bunker 1 for receiving the organomineral activator, such as combustible shale, crusher 2 with a bag filter, disintegrator 3, bunker 4 for temporary storage of the organomineral activator, unit 5 for preparing a mixture of the organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent- refined oil extract, reservoir 6 with a hydrogen donor additive, reservoir 7 with an HPR, agitator 8, device 9 for mechanochemical activation, furnace 10 for heating the mixture of a hydrogen donor additive with an organomineral activator and an HPR, reactor 11 made up of one to three sections, heat exchanger 12, hot separator 13, cooling system 14, high pressure separator 15, low pressure separator 16, accumulation tank 17, refrigerator 18, centrifuge 19, and rectifying tower 20.
Bunker 1 for receiving an organomineral activator is series-connected to crusher 2, disintegrator 3, bunker 4 for temporary storage of the organomineral activator and to unit 5 for preparing a mixture of organomineral activator with hydrogen donor additive, which, in turn, is connected to reservoir 6 with hydrogen donor additive and to agitator 8 connected to
HPR reservoir 7 and device 9 for mechanochemical activation. Reactor 1 1 is connected to furnace 10 and to heat exchanger 12. Hot separator 13 is connected to heat exchanger 12, cooling system 14 and refrigerator 18. High pressure separator 15 is connected to low pressure separator 16 and to cooling system 14. Refrigerator 18 is connected to centrifuge
19, which is connected to accumulation tank 17 and to rectifying tower 20.
The plant operates as follows:
A 25-250 mm lump of organomineral activator, such as combustible shale, or 0-25 mm fines thereof are delivered from a railway car to a storage area. From the storage area, the combustible shale is delivered to bunker 1 for receiving combustible shale. From bunker 1 for receiving combustible shale, the combustible shale is transferred by a belt conveyer into crusher 2 fitted with a bag filter, where the shale is finely crushed to a particle size of up to 8 mm. Then the shale which is finely crushed to a particle size of 8 mm is fed into disintegrator 3 (mechanically activating mill), where the shale is milled to a particle size less than 100 μm. Disintegrator 3 has a cyclone separator, air filter, a bag filter, and a sector feeder (not shown in the diagram).
Downstream of the disintegrator the finely crushed shale goes through the latter's relief passage onto the vibrating sieve (not shown in the diagram) with a mesh of to 140 μm, and then comes to bunker 4 for temporary storage. The entire system used for crushing the shale has a control panel with safe start equipment. The vibrating sieve is designed to separate shale particles greater than 140 μm in size.
Then the shale, which is finely crushed to a particle size of 100 μm, is fed into the unit for preparing the stock, that is, the mixture of organomineral activator, such as combustible shale, taken from bunker 4 with hydrogen donor additive, such as solvent- refined oil extract from reservoir 6. This stage is essential for the entire chain process. The stock is prepared in the following steps. At first, a blend of organomineral activator and hydrogen donor additive is prepared in unit 5 for preparation of this blend. Unit 5 consists of a series-connected mixer and a mechanical activation mill.
The mechanical activation is performed in the prior art units, type Desi-14, as well as in prior art dispersers (homogenizers), disperser-mixers, disintegratorax, etc.
Then, the HPR from tank 7 is added to the thus obtained mixture. The temperature in agitator 8 (used for mixing and mechanical activation of the initial HPR with a blend of organomineral activator and hydrogen donor additive) is maintained within 80 - 100 °C to ensure pumpability of the petroleum residue. The operations involving feeding the three components of the raw mixture are performed when the agitator is working to prevent settlement of the organomineral activator on the agitator. Should the agitator fail to assure effective mixing of the 3 -component blend, dispersion pumps are used for a more thorough mixing (homogenization). From agitator 8, the raw mixture comes into mechanochemical activation device 9, said activation being effected, say, with the aid of the magnetic vortex field. After mixing, the ready raw mixture is first fed into furnace 10 for heating the stock (the mixture of hydrogen donor additive with organomineral activator and HPR) and then into reactor 1 1 having from 1 to 3 sections. The temperature at the outlet from furnace 10 is from 380 to 490 0C, depending on the type of the stock processed. Downstream of reactor 1 1, the steam-gas flow goes into heat exchanger 12 and, then, into hot separator 13 where the temperature is maintained at 270 - 320 °C and pressure at 10 MPa.
Now the fractions boiling away at temperatures below 360 - 380 °C mostly pass at the top of the hot separator, while the fractions boiling away at temperatures above 360 - 380 °C pass, mixed with solid products, at the bottom portion of the hot separator. After passing cooling system 14, the top flow of the hot separator is accumulated, along with a hydrogen bearing gas (HBG), in high pressure separator 15, where the HBG is separated from the liquid fractions.
From high pressure separator 15, the liquid fractions pass into low pressure separator
16 and then go through a pipeline into accumulation tank 17 for further processing.
The product received at the bottom of hot separator 13 (the so-called sludge) passes through a restrictor valve into refrigerator 18 for cooling and then is delivered through a pipeline to decanting centrifuge 19. The liquid fractions are passed, along with the liquid fractions from accumulation tank 17, into rectifying tower 20 for distillation with obtaining a gasoline fraction with boiling point of up to 180 0C, a diesel fraction with boiling point of 180 - 360 °C, gas oil fraction with boiling point or 360 - 500 °C and a residue boiling out at temperatures above 500 °C (recycling temperature).
Listed below are examples of the process described herein.
Example 1 : The initial mixture is prepared by mixing the tar (goudron) with 10 mass % of solvent-refined oil extract containing 5 mass % of active hydrogen and with 7 mass % of combustible shale finely crushed to particle size of 50 μm. The mixing is performed in a heated agitator at a temperature not below 90 0C to obtain a suspension with a viscosity of 1.0 Pa s at 80 0C. Then the mixture is subjected to mechanochemical activation and processing at 90 0C by a magnetic vortex field. Thermal cracking of the obtained product is then performed at a pressure of 5 MPa, temperature of 45O0C, and space velocity of 2 hour'1. Now the resultant liquid products are distilled to form fractions with boiling points (b. p.) of to 180 0C (gasoline) - 26 mass %, 180 - 360 0C (diesel) - 56 mass %, 360 - 500 0C (gas oil) - 10 mass %, and a residue with boiling point above 500 0C. The amount of coke is 0.07 % mass %.
Example 2: The initial mixture is prepared by mixing 15 mass % of solvent-refined oil extract containing 0.1 mass % of active hydrogen and 5 mass % of sapropelite finely crushed at 600C to particle size of 75 μm. Then, the thus obtained blend is admixed with an HPR, such as asphalt- free oil, in the amount of 15 mass % (of its initial quantity). The obtained mixture is subjected to the mechanochemical activation and processing at 8O0C. Then the remaining asphalt-free oil is added to the blend, following which the blend is subjected to additional homogenization in a disintegrator.
Thermal cracking of the resultant product is performed at a pressure of 3 MPa, temperature of 4000C and space velocity of 3 hour"1. The obtained liquid products are then distilled to form fractions with b. p. of to 180 0C (gasoline) - 27 mass %, 180 - 360 0C
(diesel) - 52 mass %, 360 - 500 0C (gas oil) - 5.0 mass %, and a residue with boiling point above 500 0C. The amount of coke is 0.075 mass %.
Example 3 : The initial mixture is prepared by mixing 0.1 mass % of solvent-refined oil extract containing 15 mass % of active hydrogen and 15 mass % of sapromyxite finely crushed at 60 0C to particle size of 5 μm. Then, the thus obtained blend is admixed with
HPR, such as the tar or goudron in the amount of 15 mass % (of its initial quantity). The resultant mixture is subjected to mechanochemical activation and processing at 8O0C. Then the remaining amount of tar is added to the mixture, following which the mixture is subjected to additional homogenization in a disintegrator.
Thermal cracking of the resultant product is performed at a pressure of 0.2 MPa, temperature of 490 0C and space velocity of 0.5 hour"1. The obtained liquid products are then distilled to form fractions with b. p. of to 180 0C (gasoline) - 26.5 mass %, 180 - 360
0C (diesel) - 54 mass %, 360 - 500 0C (gas oil) - 10.0 mass %, and a residue with boiling point above 500 0C. The amount of coke is 0.07 mass %. Example 4: The initial mixture is prepared by mixing 0.2 mass % of solvent-refined oil extract containing 12 mass % of active hydrogen and 1 mass % of sapromyxite finely crushed at 600C to particle size of 100 μm. Then, the thus obtained blend is admixed with HPR, such as the tar or goudron, in the amount of 15 mass % (of its initial quantity). The resultant mixture is subjected to mechanochemical activation and processing at 8O0C. Then the remaining amount of tar is added to the mixture, following which the mixture is subjected to additional homogenization in a disintegrator.
Thermal cracking of the resultant product is performed at a pressure of 4 MPa, temperature of 380 0C and space velocity of 1.5 hour"1. The obtained liquid products are then distilled to form fractions with b. p. of to 180 0C (gasoline) - 27.5 mass %, 180 - 360
0C (diesel) - 58.5 mass %, 360 - 500 0C (gas oil) - 6.0 mass %, and a residue with boiling point above 500 0C. The amount of coke is 0.1 mass %.
Example 5. The initial mixture is prepared by mixing 0.5 mass % of solvent-refined oil extract containing 1 1.5 mass % of active hydrogen and 6 mass % of sapromyxite finely crushed at 60 0C to particle size of 20 μm. Then, the thus obtained blend is admixed with HPR, such as the tar or goudron, in the amount of 15 mass % (of its initial quantity). The resultant mixture is subjected to mechanochemical activation and processing at 8O0C. Then the remaining amount of tar is added to the mixture, following which the mixture is subjected to additional homogenization in a disintegrator.
Thermal cracking of the resultant product is performed at a pressure of 3 MPa, temperature of 430 0C and space velocity of 4 hour"1. The obtained liquid products are then distilled to form fractions with b. p. of to 180 0C (gasoline) - 26.5 mass %, 180 - 360 0C (diesel) - 49 mass %, 360 - 500 0C (gas oil) - 10.0 mass %, and a residue with boiling point above 500 0C. The amount of coke is 0.08 mass %.
For the conditions used for preparing the feedstock, thermal cracking and for the quantities of the products obtained in the process, refer to Table 1 below. Table 1
Figure imgf000015_0001
The presented results, shown in the above examples, demonstrate the advantages of the process described herein showing that the use of the process and plant, described herein, make it possible to achieve the desired result, namely, to increase the yield of light products to 82-86 mass % and decrease the coke formation as well as decrease the production cost of the end products by using inexpensive feedstock components.
While this invention has been described with reference to illustrative embodiments and examples, the description is not intended to be construed in a limiting sense. Thus, various modification of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments. Further, all of the claims are hereby incorporated by reference into the description of the preferred embodiments.
Any publications, patents and patent applications referred to herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety.

Claims

WHAT IS CLAIMED IS:
1. A process for obtaining light petroleum products, comprising mixing of the heavy petroleum residues (HPR) with an organomineral activator, such as finely crushed combustible shale, and a hydrogen donor additive, added in a desired proportion to the stock, homogenization of the blend in an agitator at a temperature of 80-100 °C and thermal cracking of the resultant mixture with subsequent recovery of the end products, wherein used as a hydrogen donor additive is solvent-refined oil extract containing 0.1 - 15 % of active hydrogen, added in the amount of 0.5 - 15 mass % to the mixture of the HPR with an organomineral activator, such as finely crushed combustible shale, said solvent-refined oil extract being first mechanically mixed with the organomineral activator, following which the HPR is mixed with the blend of the solvent-refined oil extract and organomineral activator, and the resultant mixture is mechanically homogenized, while the organomineral activator is added in the amount of 1 - 15 mass % to the mixture.
2. A process according to claim 1, wherein thermal cracking is performed at a temperature of 380 - 490 °C, pressure of 0.2 - 5 MPa and space velocity of feeding the mixture of HPR, solvent-refined oil extract and organomineral activator equal to 0.5 - 4 hour"1 .
3. A process according to claim 1, wherein the solvent-refined oil extract is mixed with an organomineral activator preliminarily finely crushed in a mechanical crusher at a temperature of 50 - 100 °C to a particle size of 5 - 100 μm with production of a suspension with a viscosity of 0.5 - 1.0 Pa s at 80 °C.
4. A process according to claim 1, wherein used as an organomineral activator are combustible shales, sapropelites, sapromyxites and other liptobiolith coals, added in the amount of 1 - 15 mass % to the mixture.
5. A process according to claim 1, wherein a blend of solvent-refined oil extract and combustible shale (organomineral activator) is admixed with a portion of HPR.
6. A plant for obtaining light petroleum products, comprising a bunker for receiving an organomineral activator, such as combustible shale, a crusher with a bag filter and a disintegrator series-connected thereto, a bunker for temporary storage of an organomineral activator, a reservoir with a hydrogen donor additive, a reservoir with a heavy petroleum residue (HPR) connected to an agitator, which is connected to a furnace for heating the mixture of hydrogen donor additive with HPR and organomineral activator, a reactor connected to the furnace and heat exchanger connected to a hot separator and a high pressure separator through a cooling system, a low pressure separator connected through an accumulation tank to a rectifying tower, a refrigerator connected through a centrifuge to the rectifying tower, wherein the plant has a unit for preparing a mixture of an organomineral activator, such as combustible shale, with a hydrogen donor additive, such as solvent-refined oil extract, the unit being connected to a bunker for temporary storage of the organomineral activator, to a reservoir with a hydrogen donor additive and to an agitator, as well as mechanochemical activation device connected to the agitator and a furnace for heating the blend of hydrogen donor additive with HPR and organomineral activator.
7. A plant according to claim 6, wherein the reactor is made up of sections whose number is from one to three.
8. A plant according to claim 6, wherein the unit for preparing a mixture of an organomineral activator with a hydrogen donor additive is made up of series- connected mixer and mechanical activation mill.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60120791A (en) * 1983-12-02 1985-06-28 Asahi Chem Ind Co Ltd Conversion of heavy hydrocarbon to light hydrocarbon
RU2178448C1 (en) * 2000-08-08 2002-01-20 Горлов Евгений Григорьевич Process for production of liquid products from heavy petroleum residue
RU2261265C1 (en) * 2001-07-12 2005-09-27 Закрытое акционерное общество "Научно-производственная компания Панджшер-Холдинг" Fuel distillates production process
RU2288940C1 (en) * 2005-07-20 2006-12-10 Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный технологический институт (технический университет)" Process for thermochemical processing of heavy petroleum residues

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60120791A (en) * 1983-12-02 1985-06-28 Asahi Chem Ind Co Ltd Conversion of heavy hydrocarbon to light hydrocarbon
RU2178448C1 (en) * 2000-08-08 2002-01-20 Горлов Евгений Григорьевич Process for production of liquid products from heavy petroleum residue
RU2261265C1 (en) * 2001-07-12 2005-09-27 Закрытое акционерное общество "Научно-производственная компания Панджшер-Холдинг" Fuel distillates production process
RU2288940C1 (en) * 2005-07-20 2006-12-10 Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный технологический институт (технический университет)" Process for thermochemical processing of heavy petroleum residues

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