CA2691794C - Process for the conversion of heavy hydrocarbon feedstocks to distillates with the self-production of hydrogen - Google Patents

Process for the conversion of heavy hydrocarbon feedstocks to distillates with the self-production of hydrogen Download PDF

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CA2691794C
CA2691794C CA2691794A CA2691794A CA2691794C CA 2691794 C CA2691794 C CA 2691794C CA 2691794 A CA2691794 A CA 2691794A CA 2691794 A CA2691794 A CA 2691794A CA 2691794 C CA2691794 C CA 2691794C
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hydrotreatment
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Alberto Delbianco
Nicoletta Panariti
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Eni SpA
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    • 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
    • C10G67/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • C10G67/0454Solvent desasphalting
    • C10G67/049The hydrotreatment being a hydrocracking
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • 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
    • C10G21/00Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003Solvent de-asphalting
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    • 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
    • C10G47/02Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02Fixed-bed gasification of lump fuel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • C10J3/78High-pressure apparatus
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/047Composition of the impurity the impurity being carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/063Refinery processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00Details of gasification apparatus
    • C10J2200/33Laboratory scale gasifiers
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/093Coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0943Coke
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0959Oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0966Hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0973Water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983Additives
    • C10J2300/0989Hydrocarbons as additives to gasifying agents to improve caloric properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656Conversion of synthesis gas to chemicals
    • C10J2300/1659Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/16Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Process for the conversion to distillates of heavy feedstocks selected from heavy and extra-heavy crude oils, distillation residues from crude oil or from catalytic treatment, "visbreaking tars", "thermal tars", bitumens from "oil sands" liquids from coals of different origins and other high-boiling feedstocks of a hydrocarbon origin, known as "black oils", comprising the following steps: - sending the heavy feedstock to a first distillation zone (D1) having one or more atmospheric and/or vacuum distillation steps, whereby one or more light fractions are separated from the distillation residue; - sending the single light fraction or one or more light fractions coming from the first distillation zone (D1) to a hydrotreating (HT) zone wherein hydrogen is introduced; -sending the fraction consisting of the distillation residue of the first distillation zone (D1) to a deasphalting zone (SDA) in the presence of solvents, obtaining two streams, one consisting of deasphalted oil (DAO), the other containing asphaltenes; - sending the effluent stream from the hydrotreatment (HT) zone to a second distillation zone (D2), consisting of one or more flash steps and/or one or more atmospheric distillation steps, through which the different fractions are separated, coming from the hydrotreatment of the distillation residue which is recycled to the first distillation zone (D1) and/or to the deasphalting zone (SDA); - mixing of the stream consisting of deasphalted oil (DAO) with a suitable hydrogenation catalyst and sending the mixture obtained to a hydrocracking (HCK) zone in which hydrogen is added and from which the effluent stream is sent to the hydrotreatment (HT) zone and/or to the second distillation (D2) zone; - sending the stream containing asphaltenes to a gasification zone (PO x) so as to obtain a mixture of H2 and CO; - sending the mixture of H2 and CO obtained in the gasification zone (PO x) to a gas separation zone (GS) to recover the H2 to be used as reactive atmosphere for the hydrotreatment (HT) and hydrocracking (KCK) sections.

Description

PROCESS FOR THE CONVERSION OF HEAVY HYDROCARBON FEED-STOCKS TO DISTILLATES WITH THE SELF-PRODUCTION OF HYDRO-GEN
The present invention relates to a high-productivity process for the total conversion to distillates alone, with no contextual production of fuel oil or coke, of heavy feedstocks, among which heavy crude oils also with a high metal content, distillation residues, heavy oils coming from catalytic treatment, "visbreaker tars", "thermal tars", bitumens from "oil sands" possibly ob-tained from mining, liquids from different types of coal and other high-boiling feedstocks of a hydrocarbon na-ture, known as "black oils", also comprising hydrogenat-ing treatment in which hydrogen, self produced in the same process, is used.
The conversion of heavy feedstocks to liquid prod-ucts can be substantially effected through two methods:
one of the thermal type, the other based on hydrogenating treatment. The increasing demand for high-quality dis-tilled products and the parallel reduction in the demand for by-products such as coke and fuel oil, make it neces-sary to look for new integrated processes which allow the complete conversion of heavy feedstocks.
Thermal processes, mainly coking and Visbreaking, have certain advantages as they allow feedstocks having a high polluting level to be fed. The high production of coke and tar, however, is such that its validity is greatly limited in some cases. In addition, the poor quality of the distillates leads to the necessity of se-vere hydrogenating treatment to favour the removal of heteroatoms and bring the products to specification.
Visbreaking allows very low yields to distillates to be obtained together with low-quality products, ob-taming, on the contrary, high amounts of tar.
Coking, in addition of having higher investment costs, also produces low-quality distillates and high quantities of coke.
As far as the hydrogenating processes are concerned, these consist of treating the feedstock in the presence of hydrogen and suitable catalysts, following various ob-jectives:
= to demolish the high molecular weight asphaltene structures, favouring the removal of Ni and V (hy-drodemetallation, HDM) and, contemporaneously, reduce
-2-the content of asphaltenes in the feedstock = to remove S and N through hydrogenation and hydro-genolysis reactions (hydrodesulphurization, HDS and hydrodenitrogenation HDN, respectively) = to reduce CCR (Conradson Carbon Residue) by means of Hydrocracking (HC) and Hydrodearomatization (HDA) re-actions = to transform high molecular weight molecules into light molecules (distillates) through Hydrocracking (HC) reactions.
The hydroconversion technologies currently used make use of fixed bed or ebullated bed reactors and adopt catalysts generally consisting of one or more transition metals (Mo, W, Ni, Co, etc.) supported on silica and/or alumina or another oxide support.
Fixed bed technologies, even in the most advanced versions, have severe- limitations both with respect to the flexibility of the feedstock fed (as the presence of high concentrations of metals and other pollutants would imply excessively frequent regeneration cycles of the catalyst) and also because they do not allow the conver-sion of heavy feedstocks to levels higher than 30-40. As a result of said limitations, fixed bed hydroconversion technologies prove to be completely inadequate for con-figuring total conversion schemes of heavy feedstocks to
-3-
4 PCT/EP2008/005210 distillates.
In order to at least partly overcome these limita-tions, ebullated bed processes were developed, wherein the catalytic bed, even if confined in a certain part of the reactor, is moveable and can expand due to the effect of the reagent flow in liquid and gaseous phase. This al-lows the reactor to be equipped with mechanical appara-tuses for removing the exhausted catalyst and feeding the fresh catalyst in continuous, without interrupting the running. As a result of this possibility of continuously substituting the exhausted catalyst, ebullated bed tech-nologies can process heavy feedstocks with a metal con-tent of up to 1,200 ppm Ni + V. Even if the ebullated bed technology benefits from the improvements provided by the continuous regeneration of the catalyst, it allows con-version levels to distillates of up to a maximum of 60%
to be obtained. It is possible to reach a conversion of 80% by operating under high severity conditions and recy-cling an aliquot of the products, encountering however problems of stability of the fuel oil produced by the separation of the non-converted asphaltene phase, which, in this case too, represents the heart of the problem.
For the above reasons, neither is the ebullated bed tech-nology suitable for total conversion processes to distil-lates, as it is associated with a significant production of fuel oil.
Processes have been proposed which use catalysts ho-mogeneously dispersed in the reaction medium (slurry), as an alternative to hydroconversion processes based on the use of catalysts supported on a fixed bed or ebullated bed. These slurry processes are characterized by the presence of catalyst particles with very small average dimensions and uniformly dispersed in the hydrocarbon phase. The catalytic activity is consequently scarcely influenced by the presence of metals or carbonaceous residues deriving from the degradation of asphaltenes.
With respect to thermal processes, hydroconversion technologies of residues also have limitations due to the high investment costs.
They also require considerably high hydrogen consump-tions.
This latter element represents a very critical fac-tor, mainly in certain cases in which there is a limited availability of natural gas. It can therefore be impor-tant to produce hydrogen starting from alternative sources, for example through the gasification of by-products such as coke, residues, tar, asphaltenes, etc..
For the above reasons, the effecting of integrated processes in which it is possible to use low-value by-products for the production of hydrogen for internal use,
-5-represents an advantageous solution from all points of view.
Deasphaltation, a liquid-liquid extraction treatment based on the use of paraffins, allows a variable aliquot of DAO, deasphalted oil, to be separated, which can have qualitative characteristics (in terms of metal content, carbonaceous residue, etc..) which are such as to favour the subsequent conversion. This process has several ad-vantages with respect to coking: significantly lower in-vestment costs, the possibility of modulating the yield and quality of DAO and asphaltenes according to neces-sity, the production of a by-product (the same asphalte-nes) which can be fed to the gasification process.
As is known, deasphalting does not produce distil-lates: it is therefore necessary to subject the DAO to subsequent cracking treatment.
In US.6274003 of Ormat Industries a process is claimed for the primary upgrading of heavy hydrocarbons, which combines distillation, solvent deasphalting and thermal cracking to produce a synthetic crude oil, par-tially upgraded, substantially without metals and asphal-tenes. In the upgrading process, the feedstock is first distilled to produce a lighter fraction, substantially with no asphaltenes, and a residue containing metals and asphaltenes.
-6-An aliquot of the distilled fraction is sent to a hv-drotreating unit, whereas the residual fraction is deasphalted to produce an oil (DAO) and an asphaltene residue. DAO, and possibly an aliquot of the hydrotreat-ing product (which acts as a diluent, hydrogen donor) are joined and sent to thermal cracking: the cracking product returns to the distillation column, from which the frac-tions forming the partially upgraded syncrude, are col-lected.
The process scheme is improved in subsequent patents of the same owner (W003060042, US-6,702,936, US-20040118745, EP1,465,967) claiming the use of a treatment which also comprises the gasification of asphaltenes to produce synthesis gas, the treatment of the synthesis gas with the production of hydrogen and the hydroprocessing of the distillates. In patent application IT-2004A002446 a conversion process of heavy feedstocks is claimed, which allow the complete transformation of the same ("zero residue refinery"). In said patent application IT-2004A002446 a process is described more specifically in-cluding the use of the following units: solvent deasphalting (SDA), DAO hydroconversion with slurry phase catalysts, distillation. The residue from the hydrotreat-ing stream, together with the catalyst in slurry phase contained therein, is recycled to the hydrotreatment sec-
-7-tion. The asphaltene stream can be sent to a gasification section (P0x) in order to obtain a mixture of H2 and CO.
We have surprisingly found that, by subjecting the DAO obtained from the deasphalting of the distillation residue of the heavy feedstock to hydrocracking in the presence of low concentrations of dispersed catalyst, high yields to distillate can be obtained with an optimum control on the formation of coke and gases. In this way, it is not necessary to recycle the non-converted residue to the hydrocracking section. This residue can be di-rectly recycled to the initial fractionation column or to the deasphalting zone, from which, in addition to the as-phaltenes present in the feedstock, the side-products possibly formed in the hydrocracking phase can be re-moved, said by-products thus being used, at the same time self-producing the hydrogen necessary for the hydrogenat-ing treatment envisaged, by sending the asphaltene stream to a gasification section. By comparing this solution with that comprising a thermal cracking step for the DA0 conversion, it is possible to optimize the process selec-tivity, maximizing the yield to distillates and minimiz-ing the production of coke and gas. With respect to the solution claimed in patent application IT-2004A002446, which includes the use of high catalyst concentrations and the recycling of the same together with the distilla-
-8-tion residue from the hydrotreatment, the new solution proposed herein allows the use of minimum concentrations of catalyst, which can be used only once, greatly simpli-fying the scheme; even at low catalyst concentrations, its formulation allows an optimal hydrogenation of the feedstock, preventing or minimizing the formation of coke. The sending of the hydrotreatment residue to the deasphalting section allows the possible recovery of fur-ther quantities of DAO to be converted and, at the same time, to send to gasification the most concentrated frac-tion of pollutants (metals deriving from the feedstock, together with traces of catalyst).
The process, object of the present invention, for the conversion of heavy feedstocks, comprises the following steps:
= sending the heavy feedstock to a first distillation zone (D1) having one or more atmospheric and/or vac-uum distillation steps whereby one or more light fractions are separated from the distillation resi-due;
= sending the single light fraction or one or more light fractions from the first distillation zone (D1) to a hydrotreating zone (HT) in which hydrogen is in-troduced;
= sending the fraction consisting of the distillation
-9-residue of the first distillation zone (D1) to a deasphalting zone (SDA) in the presence of solvents, obtaining two streams, one consisting of deasphalted oil (DAO), the other containing asphaltenes;
= sending the effluent stream from the hydrotreatment zone (HT) to a second distillation zone (D2), con-sisting of one or more flash steps, and/or of one or more atmospheric distillation steps, whereby the dif-ferent fractions coming from the hydrotreatment reac-tion are separated from the distillation residue, which is recycled to the first distillation zone (D1) and/or to the deasphalting zone (SDA);
= mixing the stream consisting of deasphalted oil (DAO) with a suitable hydrogenation catalyst and sending the mixture thus obtained to a hydrocracking zone (HCK) in which hydrogen is introduced and from which the effluent stream is sent to the hydrotreatment zone (HT) and/or to the second distillation zone (D2);
= sending the stream containing asphaltenes to a gasi-fication zone (P0x) in order to obtain a mixture of H2 and CO;
= sending the mixture of H2 and CO obtained in the gas-ification zone (P0x) to a gas separation zone (GS) to recover H2 to be used as reactive atmosphere for the
-10-hydrotreatment (HT) and hydrocracking (HCK) sections.
The heavy feedstocks treated can be of different kinds:
they can be selected from heavy feedstocks, distillation residues, "heavy oils" from distillation residues, for example "unconverted oils" from hydrotreatment with fixed or ebullated beds, "heavy cycle oils" from catalytic cracking treatment, "thermal tars" (coming, for example, from visbreaking or similar thermal processes), bitumens from "oil sands", different kinds of coals and any high-boiling feedstock of a hydrocarbon origin, generally known in the art as "black oils".
The choice of sending the recycling of the distillation residue of the second distillation zone to the first distillation zone (D1) and/or the deasphalting zone (SD) is influenced by how the second distillation zone is effected: it is in fact preferable to send this residue completely, or at least partially, to the deasphalting area (SDA) if said second area consists of one or more atmospheric distillation steps.
In the case of the contemporaneous sending of the effluent stream from the hydrocracking zone to both the hydrotreatment (HT) zone and the second distillation zone (D2), a separation of said effluent stream is preferably effected by means of separators in order to obtain a gaseous phase and a liquid phase to be sent to the hy-
-11-drotreatment zone (HT) and to the second distillation zone (D2), respectively.
The first distillation zone (D1) preferably consists of one or more atmospheric distillation steps or one or more distillation steps and one vacuum step.
The heavier fraction of the light fractions separated in the first distillation zone, can possibly be at least partially sent to the hydrocracking zone (HCK).
The fraction sent to the hydrotreatment zone (HT) is preferably the lighter stream from the single step or from the last distillation step.
The gasification can be effected by feeding the stream containing asphaltenes to the gasifier, together with oxygen and vapour which react under exothermic con-ditions at a temperature of over 1,300 C and a pressure ranging from 30 to 80 bar, to produce mainly H2 and CO.
The separation of H2 from the mixture of H2 and CO
obtained from the gasification is preferably effected by means of molecular sieves.
A portion of the syngas stream, i.e. a mixture of H2 and CO, obtained from the gasification, can be further upgraded as fuel for the generation of vapour or by com-bustion with combined cycles (IGCC) or it can be trans-formed into paraffin hydrocarbons through Fischer-Tropsch synthesis or it can be converted to methanol, dimethyl-
-12-ether, formaldehyde and, more generally, into the series of products deriving from Cl chemistry.
Furthermore, before being sent to the separation zone (GS), the mixture of H2 and CO obtained in the gasifica-tion zone (P0x) is sent to a water-gas-shift zone (WGS) to generate hydrogen by reaction with water.
The same paraffin hydrocarbons obtained through Fischer-Tropsch can be mixed to the various cuts obtained from the distillation or flash step, improving the compo-sitional characteristics.
The hydrotreatment step (HT) is preferably carried out at a temperature ranging from 360 to 450 C, prefera-bly from 380 to 440 C, at a pressure of between 3 and 30 MPa, preferably between 10 and 20 MPa.
Hydrogen is fed to the hydrotreatment reactor which can operate in the down-flow or, preferably, up-flow mode. This gas can be fed to several sections of the re-actor.
The distillation steps are preferably carried out at a reduced pressure ranging from 0.001 to 0.5 MPa, pref-erably between 0.1 and 0.3 MPa.
The hydrotreatment step (HT) can consist of one or more fixed bed reactors operating within the range of conditions mentioned above. A portion of the distillates produced in the first reactor can be recycled to the sub-
-13-sequent reactors of the same step.
Catalysts normally used for the hydroconversion of . oil products, such as, for example, Ni-Mo, Ni-V, Ni-Co catalytic systems, etc.., can be used for said step.
The deasphalting step (SDA), effected by means of ex-traction with a hydrocarbon or non-hydrocarbon solvent is generally carried out at temperatures ranging from 40 to 200 C and pressures of between 0.1 and 7 MPa.
Furthermore, the same can be composed of one or more sections operating with the same solvent or different solvents; the recovery of the solvent can be carried out under sub-critical or super-critical conditions, with several steps, thus allowing a further fractionation be-tween deasphalted oil and resins.
It is advisable for the solvent of this deasphalting step to be selected from light paraffins having from 3 to 6 carbon atoms, preferably from 4 to 5 carbon atoms, or a mixture of the same.
The hydrocracking HCK) step is carried out in the presence of catalysts in slurry phase, preferably at tem-peratures ranging from 380 to 480 C, more preferably from 420 to 470 C, at a pressure ranging from 2 to 20 MPa, more preferably from 10 to 18 MPa.
Hydrogen is fed to the hydrocracking reactor which can operate both in the down-flow and, preferably, up-
-14-flow mode. This gas can be fed to different sections of the reactor.
The catalyst precursors used can be selected from those obtainable from easily decomposable oil-soluble precursors (metal naphthenates, metal derivatives of phosphonic acids, metal-carbonyls, etc..) or from pre-formed compounds based on one or more transition metals such as Ni, Co, Ru, W and Mo: the latter is preferred thanks to its higher catalytic activity.
The concentration of the catalyst, defined according to the concentration of the metal or metals present in the hydrocracking reactor, ranges from 50 to 5,000 ppm, preferably from 50 to 900 ppm.
The process claimed allows the production of a com-pletely deasphalted and demetallized "light syncrude"
(atmospheric and vacuum distillates) and also upgraded in terms of density, viscosity, CCR sulphur content.
An embodiment of the present invention is now pro-vided with the help of the enclosed figure 1, which should not be considered as limiting the scope of the in-vention itself.
In Fig. 1, the heavy feedstock (1) is fractionated in a first distillation zone (D1) from which the light frac-tions are separated (2) and (3) from the distillation residue (4).
-15-The lighter fraction (2) separated in the first dis-tillation zone (D1) is mixed with the catalyst (5) to form the stream (6) fed to the hydrotreating (HT) reac-tor.
The stream (7) leaving the hydrotreatment step (HT) is sent to a second distillation zone (D2).
The first distillation residue (4) is sent to a deasphalting unit (SDA), said operation being effected by means of solvent extraction (8).
Two streams are obtained from the deasphalting unit (SDA): one (9) consisting of deasphalted oil (DAO), the other containing asphaltenes (10).
Once the stream consisting of deasphalted oil (9) had been freed from the solvent used for the extraction, it is sent to a hydrocracking zone (HCK).
The stream containing asphaltenes (10) is sent to a gasification section (P0x) in order to obtain syngas, i.e. a gaseous mixture of H2 and CO (11) which is sent to a separation area (GS), whereby a stream essentially con-sisting of CO (12) is separated and a stream essentially consisting of H2 (13) of which a part (14) is sent to the hydrocracking step, another part (15) to the hydrotreat-ment step, thus providing the necessary quantity of hy-drogen for effecting the hydrocracking and hydrotreatment reactions.
-16-The stream (16) leaving the hydrocracking step (HCK) is either sent (17) to the hydrotreatment step (HT) or it is sent (18) to the second distillation zone (D2).
In the second distillation zone (D2), consisting of a distillation column, possibly preceded by a flash, the lighter fractions (D21, D"2, D23, ...D2n) are separated from the heavier fraction (19) at the bottom, which is recycled (20) to the first distillation zone (D1) and/or (21) to the deasphalting zone (SDA).
At least part (22) of the heavier light fraction (3), separated in the first distillation zone (D1), can possi-bly be sent to the hydrocracking (HCK) zone.
Some examples are provided hereunder for a better il-lustration of the invention, it being understood that the same should not be considered as being limited thereto or thereby.
Example 1: Preparation of a deasphalted oil * Feedstock: 250 g of atmospheric residue * Deasphalting agent: about 2.5 1 of n-pentane * Temperature: 180 C
* Pressure: 16 atm.
The residue and a volume of n-pentane equal to 8-10 times the residue volume are charged into an autoclave.
The mixture of feedstock and solvent is heated to a tem-perature of 180 C, with stirring (800 rpm) by means of a
-17-mechanical stirrer for a period of 30 minutes. At the end of this operation, the two phases are decanted and sepa-rated, the asphaltene phase which is deposited on the bottom of the autoclave and the deasphalted oil phase di-luted in the solvent. The decanting lasts for about two hours. The DAO-solvent phase is then transferred to a second tank, by means of a suitable recovery system. The DAO-pentane phase is subsequently recovered, and the sol-vent is then eliminated by evaporation.
The yield obtained using the procedure described above is equal to 89.8% by weight of deasphalted oil with respect to the starting residue.
Example 2: Hydrocracking of the deasphalted oil with n-pentane.
The test was effected making use of a stirred micro-autoclave of 30 cm3, according to the following general operative procedure:
- about 10 g of the feedstock are charged into the reac-tor, and the catalyst precursor is added;
- the system is pressurized with hydrogen and brought to temperature by means of an electrically heated oven;
- during the reaction the system is kept under stirring by a swinging capillary system operating at a rotation rate of 900 rpm; furthermore, the total pressure is kept constant by means of an automatic reintegration
-18-system of the hydrogen consumed;
- at the end of the test, quenching of the reaction is effected; the autoclave is then depressurized and the gases collected in a sampling bag; the gaseous samples are then sent to gas chromatographic analysis;
- the solids are separated from the products present in the reactor by filtration; the liquid products are analyzed in order to determine: the yields to distil-lates, sulphur content, nitrogen content, carbonaceous residue and metal content.
The reaction was carried out by feeding the feedstock produced in example 1, under the same operative condi-tions indicated in Table 1. The distribution data ob-tained are shown in Table 2.
Example 3: Thermal cracking of the deasphalted oil with n-pentane.
The test was effected according to the operative procedure described in Example 2, without the addition of catalyst and by substituting hydrogen with nitrogen. The reaction was carried out by feeding the feedstock pro-duced in example 1, under the operative conditions indi-cated in Table 1. The product distribution data are shown in Table 2.
-19-Table 1: Operative conditions Operative conditions Test A ¨ Example 2 Test B ¨ Example 3 Temperature 460 C 460 C
Residence time 2 hours 2 hours Pressure 160 bar H2 160 bar N2 Molybdenum 100 ---Table 2: Product distribution Product distribution Test A ¨ Example 2 Test B ¨ Example 3 (w%) Gas C1-C4 8.4 15.6 C5 ¨ 160 C 26.7 18.1 160-220 C 16.9 10.5 220-365 C 27.3 15.8 365-500 C 12.5 5.7 500 C + 4.3 2.0 Solids 3.9 32.3
-20-

Claims (24)

WHAT IS CLAIMED IS:
1. A
process for the conversion to distillates of heavy feedstocks selected from heavy and extra-heavy crude oils, distillation residues from crude oil or from catalytic treatment, visbreaking tars, thermal tars, bitumens from oil sands liquids from coals of different origins and other high boiling feedstocks of a hydrocarbon origin, known as black oils, comprising the following steps:
.cndot. sending the heavy feedstock to a first distillation zone (D1) having one or more atmospheric and/or vacuum distillation steps, whereby one or more light fractions are separated from the distillation residue;
.cndot. sending the single light fraction or one or more light fractions coming from the first distillation zone (D1) to a hydrotreatment (HT) zone into which hydrogen is introduced;
.cndot. sending the fraction consisting of the distillation residue of the first distillation zone (D1) to a deasphalting zone (SDA) in the presence of solvents, obtaining two streams, one consisting of deasphalted oil (DAO), the other containing asphaltenes;
.cndot. sending the effluent stream from the hydrotreatment (HT) zone to a second distillation zone (D2), consisting of one or more flash steps and/or one or more atmospheric distillation steps, whereby the separation is effected on the different fractions coming from the hydrotreatment of the distillation residue which is recycled to the first distillation zone (D1) and/or to the deasphalting zone (SDA);
.cndot. mixing the stream consisting of deasphalted oil (DAO) with a suitable hydrogenation catalyst and sending the mixture obtained to a hydrocracking (HCK) zone into which hydrogen is introduced and from which the effluent stream is sent to the hydrotreatment (HT) zone and/or to the second distillation (D2) zone;
.cndot. sending the stream containing asphaltenes to a gasification zone (PO) in order to obtain a mixture of H2 and CO;

.cndot. sending the mixture of H2 and CO obtained in the gasification zone (PO) to a gas separation zone (GS) to recover the H2 to be used as reactive atmosphere for the hydrotreatment (HT) and hydrocracking (HCK) sections.
2. The process according to claim 1, wherein, in the case of the contemporaneous sending of the effluent stream from the hydrocracking zone to both the hydrotreatment (HT) zone and to the second distillation zone (D2), a separation is effected on said effluent stream by means of separators, in order to obtain a gaseous and a liquid phase to be sent to the hydrotreatment (HT) zone and to the second distillation zone (D2), respectively.
3. The process according to claim 1, wherein the gasification is effected by feeding the stream containing asphaltenes to the gasifier together with oxygen and vapour, which react under exothermic conditions at a temperature of over 1,300°C
and a pressure ranging from 30 to 80 bar, to produce mainly H2 and CO.
4. The process according to claim 1, wherein, before being sent to the separation (GS) zone, the mixture of H2 and CO obtained in the gasification zone (PO) is sent to a water-gas-shift (WGS) zone to generate hydrogen by means of reaction with water.
5. The process according to claim 1, wherein the first distillation zone (D1) consists of one or more atmospheric distillation steps.
6. The process according to claim 1, wherein the first distillation zone (D1) consists of one or more distillation steps and a vacuum step.
7. The process according to claim 5 or 6, wherein the fraction sent to the hydrotreatment zone (HT) is the lighter stream from the single step or the last distillation step.
8. The process according to claim 1, wherein the heavier fraction of the light fractions separated in the first distillation zone, is at least partially sent to the hydrocracking zone (HCK).
9. The process according to claim 1, wherein the distillation steps are carried out at a reduced pressure of between 0.001 and 0.5 MPa.
10. The process according to claim 9, wherein the distillation steps are carried out at a reduced pressure of between 0.01 and 0.3 MPa.
11. The process according to claim 1, wherein the hydrotreatment step (HT) is carried out at a temperature ranging from 360 to 450°C and at a pressure of between 3 and 30 MPa.
12. The process according to claim 11, wherein the hydrotreatment step (HT) is carried out at a temperature ranging from 380 to 440°C and at a pressure of between 10 and 20 MPa.
13. The process according to claim 1, wherein the deasphalting step (SDA) is carried out at temperatures ranging from 40 to 200°C and pressures of between 0.1 and 7 MPa.
14. The process according to claim 1, wherein the solvent of the deasphalting step (SDA) is a light paraffin or a mixture of light paraffins having a number of carbon atoms ranging from 3 to 6.
15. The process according to claim 14, wherein the deasphalting solvent is a light paraffin or a mixture of light paraffins, having a number of carbon atoms ranging from 4 to 5.
16. The process according to claim 1, wherein the deasphalting step (SDA) is carried out with the recovery of the solvent under supercritical conditions.
17. The process according to claim 1, wherein the hydrocracking step (HCK) is carried out at temperatures ranging from 380 to 480°C, and at a pressure ranging from 2 to 20 MPa.
18. The process according to claim 17, wherein the temperatures range from to 470°C.
19. The process according to claim 17 or 18, wherein the pressure is between 10 and 18 MPa.
20. The process according to any one of claims 17 to 19, wherein the hydrocracking step (HCK) is carried out at temperatures ranging from 420 to 470°C, and at a pressure ranging from 10 to 18 MPa.
21. The process according to claim 1, wherein the hydrogenation catalyst for hydrocracking is an easily decomposable precursor or a pre-formed compound based on one or more transition metals.
22. The process according to claim 21, wherein the transition metal is molybdenum.
23. The process according to claim 1, wherein the concentration of the catalyst in the hydrocracking reactor, defined on the basis of the concentration of the metal or metals present, ranges from 50 to 5,000 ppm.
24. The process according to claim 23, wherein the concentration of the catalyst in the hydrocracking reactor ranges from 50 to 900 ppm.
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