EP2658951A1 - Processus intégré aval-amont d'amélioration de pétrole brut lourd avec capture de co2 ; installation connexe pour la mise en oeuvre dudit processus - Google Patents

Processus intégré aval-amont d'amélioration de pétrole brut lourd avec capture de co2 ; installation connexe pour la mise en oeuvre dudit processus

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Publication number
EP2658951A1
EP2658951A1 EP11817421.8A EP11817421A EP2658951A1 EP 2658951 A1 EP2658951 A1 EP 2658951A1 EP 11817421 A EP11817421 A EP 11817421A EP 2658951 A1 EP2658951 A1 EP 2658951A1
Authority
EP
European Patent Office
Prior art keywords
stream
oil
asphaltenes
combustion
crude oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11817421.8A
Other languages
German (de)
English (en)
Inventor
Maria Andrei
Alberto Delbianco
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eni SpA
Original Assignee
Eni SpA
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Filing date
Publication date
Application filed by Eni SpA filed Critical Eni SpA
Publication of EP2658951A1 publication Critical patent/EP2658951A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/14—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003—Solvent de-asphalting
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/164—Injecting CO2 or carbonated water
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E21B43/2406—Steam assisted gravity drainage [SAGD]
    • E21B43/2408—SAGD in combination with other methods
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • C10G2300/206—Asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/70—Combining sequestration of CO2 and exploitation of hydrocarbons by injecting CO2 or carbonated water in oil wells

Definitions

  • UPSTREAM-DOWNSTREAM INTEGRATED PROCESS FOR THE UPGRADING OF A HEAVY CRUDE OIL WITH CAPTURE OF C0 2 AND RELATIVE PLANT FOR THE EMBODIMENT THEREOF
  • the present invention relates to an upstream- downstream integrated process for the upgrading of a heavy crude oil with capture of C0 2 and the relative embodiment plant .
  • the present invention relates to an upstream-downstream integrated process for the upgrading of a heavy crude oil which can be used in an upstream applicative context of marginal fields having a medium-small production capacity (1,000-5,000 barrels/day) wherein the by-products of the upgrading process are conveniently used in tertiary recovery processes for the production of additional oil.
  • the C0 2 produced in the integrated process of the present invention is captured and used in Enhanced Oil Recovery (EOR) or Enhanced Gas Recovery (EGR) processes and/or is sequestered in the subsoil.
  • EOR Enhanced Oil Recovery
  • EGR Enhanced Gas Recovery
  • vapour produced in the oxy-combustion process can be used.
  • vapour can be used in Steam Assisted Gravity Drainage (SAGD) , Steam Flooding or Cyclic Steam Stimulation (CSS) processes.
  • SAGD Steam Assisted Gravity Drainage
  • CSS Cyclic Steam Stimulation
  • the power produced by the vapour can be conveniently used in alternative EOR thermal recovery processes, for feeding Electrical Heaters, electric cables which are lowered into the well and are capable of reducing the viscosity of the crude oil, enhancing its recovery (EEOR, Electrically Enhanced Oil Recovery) .
  • Heavy crude oils are characterized by a high viscosity (from 100 to 10,000 cP) , a factor which strongly limits their mobility and transportation in pipelines. Heavy crude oils can, in many cases, be produced spontaneously or with the assistance of pumps, exploiting the high temperature of the field which guarantees a low viscosity under reservoir conditions; once the oil has reached the surface, however, the temperature of the oil decreases and the viscosity consequently increases at the well head to such an extent as to not satisfy the specifications for transportability in pipelines.
  • the viscosity of the crude oil therefore represents a limiting factor for transportation in pipelines : with an increase in the viscosity, the transportation costs increase, for example as a result of the higher consumption of energy due to the pumping systems .
  • a diluent/fluxing agent this consists in the addition of a light hydrocarbon fraction (gas oil, naphtha, etc..) to the heavy oil, in volumes in the order of 10-50% with respect to the volume of the crude oil to be transported, which allows a reduction in the viscosity of the heavy oil.
  • This system leads to a reduction in the transporting capacity of crude oil in the pipelines.
  • Mixing and separation stations are also required, together with specific transporting ducts for the diluent;
  • thermal methods these exploit the decrease in viscosity associated with an increase in the temperature. Insulated pipelines and heating stations are used. The methods are demanding from an energy and economic point of view. In addition, they can be applied in limited sections of the pipeline and, preferably, on-shore;
  • thermo methods for partial upgrading at the well head are partial crackings (for example, mild-visbreaking processes) which can be applied at the well head, demanding from an energy point of view.
  • a hydrocarbon stream is put in contact with a solvent (or mixture of solvents) at a certain temperature.
  • the contact with the solvent generates a deasphalted oil (DAO) , mainly composed of saturated and aromatic hydrocarbons with a low condensation degree and a precipitate of asphaltenes containing the heaviest, polar hydrocarbon -fractions, which is separated from the DAO.
  • DAO deasphalted oil
  • the solvents used in SDA processes are light paraffin compounds, such as propane, butane, pentane, hexane.
  • the process temperature is selected so as to allow the dissolution of the residue in the solvent.
  • the DAO fraction obtained from the deasphalting process has a lower viscosity with respect to the starting oil and can be suitably transported in pipelines to the final destination (to the refinery, for example, where it can be processed for the production of fuels and lubricants) .
  • the application of the SDA process in the upgrading of heavy oils, ultra-heavy oils and bitumens has led to the development of technologies ad hoc in which the classical extraction unit is often combined with other processes. This is the case of the OrCrudeTM process, specifically developed for the upgrading of Canadian bitumens by ORMAT Industries Ltd.
  • the process provides for: i) distillation of the bitumen (atmospheric and vacuum) , ii) deasphalting treatment of the residue through which the asphaltenes are removed, iii) Thermal Cracking of the DAO, and finally iv) recycling of the cracking products charged to the process in order to recover the distillates and separate the asphaltene component produced with the thermal treatment.
  • the OrCrudeTM process produces distillates and a heavy residue (asphaltenes) which is used as feedstock for gasification plants which produce synthesis gas for the generation of energy and vapour necessary for the extraction of bitumens by means of the Steam Assisted Gravity Drainage (SAGD) technique, in addition to the hydrogen necessary for the further upgrading of the products .
  • SAGD Steam Assisted Gravity Drainage
  • the asphaltene stream can be suitably upgraded.
  • the fraction of asphaltenes separated from the DAO is used in various ways. It can be used, for example, as fuel for producing energy (energy upgrading) , it can be used for the preparation of road tars, it can be subjected to gasification processes (partial oxidation with oxygen deficiency) to produce synthesis gas or it can be used in coking processes.
  • IGCC Integrated Gasification Combined Cycle
  • the oil refinery residues are subjected to gasification in air (oxygen) with the production of hydrogen and carbon monoxide (synthesis gas) which can be used, after abatement of the H 2 S present, in combined cycle power plants for the generation of electric energy.
  • oxygen oxygen
  • synthesis gas hydrogen and carbon monoxide
  • IGCC processes Although highly efficient, IGCC processes have the disadvantage of being complex to run, not very reliable, in addition to having high plant investment costs .
  • the oxy-combustion process (also called oxy-fuel process) has been proposed in the state of the art.
  • the comburent is represented by pure oxygen instead of air.
  • Oxy-combustion is characterized by the high thermal combustion yield of asphaltenes, the improved flame characteristics which lead to a reduced production of unburned (ashes) . With oxy-combustion, moreover, the amount of exhausted fumes emitted into the atmosphere is significantly reduced.
  • the greater efficiency of the oxy-combustion process is mainly due to the absence of nitrogen in the comburent .
  • Oxy-combustion processes have the disadvantage of having to be effected in relatively complex, voluminous plants, and with high investment costs.
  • Oxy-combustion plants require, in their immediate vicinity, the presence of a plant for the production of oxygen (normally by means of cryogenic separation from the air) , whose dimensions are proportional to the power of the oxy-combustion plant.
  • An oxy-combustion plant for example, for the production of 500 MW, requires the production of 10,000 t/day (tons per day or tpd) of oxygen, thus necessitating the installation of at least two air fractioning units.
  • the objective of the present invention is to overcome the drawbacks revealed in the state of the art .
  • a first object of the present invention relates to an upstream-downstream integrated process for the upgrading (refining) of a heavy crude oil with the capture of C0 2 , comprising the following operative steps :
  • the above process preferably also includes a phase g) for mixing the DAO obtained in phase c) with at least a part of the distilled fraction obtained in phase b) with the formation of a reconstituted crude oil and/or a phase h) for the production of power through the water vapour generated in the oxy- combustion phase for possibly feeding electric cables lowered into the well/formation (Electrical Heaters) for EOR purposes EEOR, Electrically Enhanced Oil Recovery) .
  • the above process can possibly comprise the following phase:
  • a second object of the present invention relates to a plant for implementing the upstream-downstream integrated process for the upgrading of a heavy crude oil according to claim 1, comprising:
  • a solvent deasphalting unit for treating said hydrocarbon residue containing asphaltenes with the formation of a precipitate of asphaltenes and a deasphalted oil
  • IVa a combustion unit for subjecting said precipitate of asphaltenes to oxy-combustion with the formation of a stream of exhausted gases comprising C0 2 and water vapour;
  • IVb or, alternatively to the unit defined in IVa) , a combustion unit for subjecting said precipitate of asphaltenes to a gasification process in pure oxygen with the formation of a stream of syngas which can be subsequently transformed into a gas stream comprising C0 2 and H 2 ;
  • V a separation unit for separating a substantially pure gaseous stream of C0 2 from said exhausted gas stream, or from said gas stream comprising C0 2 and H 2 ;
  • the Applicant has found an integrated process which allows the transportability of a heavy crude oil to be enhanced, through the separation of the asphaltene stream, allowing the transportability specifications in pipelines, to be reached. At the same time, the process allows the asphaltene stream separated from the process to be upgraded.
  • the expression "heavy crude oil” means a crude oil having a density lower than 22 °API and a viscosity within the range of 100-10,000 CP or bitumen, i.e. a mixture of hydrocarbons extracted from natural deposits or obtained from asphaltic rocks or oil sands, having a density lower than 10°API and a viscosity higher than 10,000 Cp.
  • bitumens are not mobile under reservoir conditions.
  • the process comprises sending the heavy crude oil to an extraction unit (Solvent DeAsphalting, SDA) in order to separate the high-quality fraction of the crude oil (DeAsphalted Oil, DAO) from the remaining stream of residual asphaltenes, reaching, for this high-quality fraction, viscosity characteristics which ensure its pumpability into the pipeline.
  • Solvent DeAsphalting, SDA Solvent DeAsphalting
  • DAO DeAsphalted Oil
  • viscosity characteristics which ensure its pumpability into the pipeline.
  • the poison content heavy metals, nitrogen, CCR
  • this fraction can be processed in the refinery (in Fluid Catalytic Cracking (FCC) units or hydrocracking units) without particular expedients.
  • FCC Fluid Catalytic Cracking
  • the asphaltenes which in this type of heavy crude oil are typically present in a quantity in the order of 20-40% by weight, separated from the SDA process, are then subjected to combustion in a pure oxygen atmosphere (process known as oxy-combustion) in order to generate power and an off-gas stream containing pure C0 2 and S0 2 .
  • oxy-combustion a pure oxygen atmosphere
  • the pure C0 2 can, in specific contexts, be used for assisted recoveries of the EOR/EGR type or sequestered in the reservoir.
  • Oxy-combustion therefore allows the production of carbon- free electric energy, i.e. without input of C0 2 into the atmosphere.
  • the process is particularly versatile and applicable in various operative contexts, as the choice of the solvent with which the deasphalting process is effected allows the yield to deasphalted oil or the yield to asphaltenes to be maximized, in contexts in which the energy requirement is high.
  • the process of the present invention integrates a solvent deasphalting process (SDA) of a hydrocarbon residue deriving from a heavy crude oil with an oxy- combustion process of the residue containing asphaltenes deriving from the same SDA process.
  • SDA solvent deasphalting process
  • the oxy-combustion of the asphaltene precipitate produces vapour and/or energy with a high yield and provides a substantially pure gaseous stream of C0 2 , which can be advantageously exploited for the assisted recovery of oil or gas from a reservoir by means of EOR or EGR treatment and/or sequestered in a geological formation, thus preventing its dispersion into . the atmosphere .
  • the oxy-combustion phase of asphaltenes is substituted by a gasification phase in the presence of pure oxygen .
  • a particular advantage of the present invention lies in the unexpected fact that the production of additional quantities of oil and/or gas from a reservoir, made possible by the use of the C0 2 deriving from the oxy-combustion of the asphaltene fraction, vapour or energy deriving from the same process, can adequately compensate the energy and plant investment costs associated with the use of oxy-combustion.
  • the integrated process of the present invention is also particularly versatile and can be easily adapted to different operating contexts of the oil industry.
  • the integrated process, object of the present invention therefore represents a promising technological alternative for upgrading heavy crude oils making them transportable, by means of the deasphalting process, exploiting the asphaltene stream for producing energy/vapour and a stream of pure C0 2 which can be suitably used for EOR.
  • Asphaltenes are hydrocarbons insoluble in solvents of the n-alkane type, for example n-heptane or n- pentane, and soluble in aromatic solvents such as benzene and toluene . Asphaltenes comprise a wide variety of molecular structures. The composition of asphaltenes can vary significantly in relation to the nature of the residue subjected to SDA.
  • the integrated process, object of the present invention is applied in the context of the upgrading of heavy crude oils.
  • the process according to the present invention exploits hydrocarbon residues containing asphaltenes deriving from fractionation processes of these crude oils.
  • Phase a) of the integrated process according to the present invention comprises the extraction of heavy crude oil from a reservoir. Once produced at the well head, the heavy crude oil is subjected to the usual preliminary treatment (oil separation, washing, etc.) before being sent for distillation (phase b) .
  • the distillation of the heavy crude oil which can be effected at atmospheric pressure or under vacuum, separates a distilled fraction and a hydrocarbon residue containing asphaltenes .
  • the subsequent phase c) of the process comprises a SDA treatment of the hydrocarbon residue (feedstock) .
  • the SDA treatment is effected according to the techniques and with the equipment known to experts in the field.
  • the feedstock is put in contact with a solvent inside an extractor.
  • the solvents used are C 3 -C 6 alkanes, such as propane, butane (and its isomers) , pentane (and its isomers) , hexane or mixtures thereof.
  • the solvent/heavy crude oil ratio in the SDA process ranges from 4:1 to 13:1.
  • the solvent extraction produces a first fluid phase consisting of a deasphalted oil (DAO) and a second phase, which is separated from the first, consisting of a mass containing the asphaltenes precipitated (hereafter, asphaltene precipitate) .
  • DAO deasphalted oil
  • asphaltene precipitate a mass containing the asphaltenes precipitated
  • asphaltene precipitate in addition to asphaltenes, there are also polluting compounds, such as metals, compounds based on sulfur, nitrogen and aggregates of high-molecular-weight molecules having a high tendency towards the formation of coke.
  • polluting compounds such as metals, compounds based on sulfur, nitrogen and aggregates of high-molecular-weight molecules having a high tendency towards the formation of coke.
  • the DAO obtained in phase a) has a lower density, viscosity, carbonaceous residue and concentration of S, N and metals with respect to the starting feedstock and it is therefore easier to move and be further processed. Furthermore, it is more valuable from an economic point of view.
  • the yield and composition of the DAO and that of the asphaltene precipitate depend on the operating conditions adopted for the SDA process.
  • the choice of solvent to be used in the SDA process plays a fundamental role in determining the yield and quality of the DAO, as the nature and quantity of components of the hydrocarbon residue which can be extracted depends on the solvent or mixture of solvents used.
  • an increase in the quantity of DAO produced generally corresponds to a deterioration in its quality, as a greater quantity of aromatic components and impurities, such as sulfur, nitrogen and metals, is also extracted from the hydrocarbon residue.
  • the solubility of the feedstock in the solvent depends on the density of the solvent used. By increasing the density of the solvent (passing for example from propane to butane and pentane) the dissolution capacity of the resins and pollutants contained in the feedstock increases .
  • the yield and quality of the DAO which can be obtained also depends on the temperature at which the extraction is carried out.
  • the solubility of the hydrocarbons of the feedstock having a higher molecular weight decreases with an increase in the temperature .
  • the paraffinic hydrocarbons present in the feedstock become more soluble in the extraction solvent with respect to the aromatic hydrocarbons .
  • phase c) is preferably carried out under such conditions as to maximize the yield to DAO; in this case, the yield to DAO is in relation to the characteristics of the DAO to be obtained in terms of viscosity for transportation and properties required for the possible subsequent refining step.
  • the asphaltene precipitate is separated from the solvent at the outlet of the extractor.
  • the separation of the solvent can be effected in various ways known to experts in the field.
  • the separation is typically effected by stripping at a temperature slightly above the critical temperature of the solvent.
  • the oil (DAO) and part of the resins are separated from the solvent, which is thus recovered.
  • SDA processes are the DEMEX ® process of UOP and the ROSE process of (Kellog Brown & Root, Inc . ) . Both of the above processes recover the solvent under supercritical conditions .
  • SDA processes known in the art and which can be used for the purposes of the present invention are the PASD ® process of Petrobras and the SOLVAHL ® process of Axens .
  • the process envisages a phase g) for mixing the DAO obtained in the solvent deasphalting phase c) with at least a part of the distilled fraction from the heavy- crude oil obtained in phase b) with the formation of a reconstituted crude oil (also called Synthetic Crude Oil) .
  • the integrated process according to the present invention comprises a phase dl) for the oxy-combustion of the asphaltene precipitate obtained in phase c) .
  • Oxy-combustion (or oxy-fuel combustion or oxy- firing) is a combustion process which uses pure oxygen, instead of air, as primary oxidant.
  • phase dl The oxy-combustion of phase dl can be effected according to the techniques and with the equipment known to experts in the field.
  • the oxy-combustion process is characterized by a high recirculation of discharge gas.
  • the pure oxygen is previously diluted with a stream of recirculated discharge gas .
  • the use of a comburent mixture formed by the combination of a stream of pure oxygen and a dilution stream of exhausted gases allows the combustion of the asphaltene precipitate to be effected within a wide temperature range (600-1200°C) .
  • the pure oxygen used in phase dl is typically produced in a specific air separation unit, for example a cryogenic distillation unit.
  • pure oxygen indicates gaseous oxygen having a purity degree equal to or higher than 95% by volume.
  • the oxy-combustion is effected by putting the fuel in contact with the comburent mixture containing oxygen in a high-pressure combustion chamber (30-100 bar) .
  • the oxy-combustion produces a stream of exhausted gases substantially comprising vapour and C0 2 .
  • the presence in the asphaltene precipitate of compounds based on nitrogen and sulfur can produce small quantities of sulfur oxides (SOx) and nitrogen oxides (NOx) in the stream of exhausted gases.
  • phase dl With respect to conventional combustion processes in air, the oxy-combustion of phase dl) produces much lower volumes of discharge gas (up to 75% less) , it is characterized by reduced heat losses and produces much lower quantities of NOx and SOx.
  • phase dl the process envisages a gasification phase d2) of the asphaltene precipitate in pure oxygen, instead of in air, and the subsequent transformation of this into a stream of gas comprising C0 2 and H 2 .
  • Syngas can be burnt directly in internal combustion engines, used for producing methanol or hydrogen, or converted by means of the Fischer-Tropsch process into synthetic fuel.
  • the process is carried out at high temperatures (higher than 700-800 °C) and pressures of 20-30 bar, in the presence of a substoichiometric percentage of oxygen .
  • Syngas generally contains pollutants whose concentration must be reduced to levels which depend on the final use of the gas.
  • the syngas is treated in a conditioning section which typically provides: 1) a cooling system of the syngas which allows the vapour to be condensed, with the production of energy; 2) a purification system of the syngas to remove particulate, sulfur and other pollutants present; 3) a transformation system of the syngas which depends on the type of application for which the syngas is destined.
  • the C0 2 to be used in EOR/EGR treatment or to be sequestered in a geological formation is obtained from the CO-Shift process which converts syngas into C0 2 and H 2 .
  • Gasification in oxygen is preferred with respect to oxy-combustion in contexts in which use is made of the H 2 produced (for example, refineries or integrated upstream-downstream complexes) .
  • the stream of exhausted gases leaving phase dl) or the stream of gas comprising C0 2 and H 2 leaving phase d2) is subjected to a separation process of the C0 2 (phase c) .
  • a part of the stream of exhausted gases is preferably recycled as dilution stream for forming the comburent mixture fed to the oxy-combustion of phase dl) .
  • the stream of exhausted gases leaving phase dl is generally subjected to conventional purification treatment to remove possible impurities of SOx and NOx.
  • phase e the separation of the stream of C0 2 can be effected according to various treatment techniques .
  • phase d) is an oxy-combustion phase
  • the separation of C0 2 from the stream of exhausted gases can be effected by cooling the exhausted gases to remove the water and subsequently removing the inert gases possibly present.
  • the C0 2 can be compressed.
  • phase f) of the process according to the present invention the stream of C0 2 leaving phase e) is injected into the subsoil.
  • the objective of injection into the subsoil can be the assisted recovery of oil (EOR) or gas (EGR) from a reservoir.
  • EOR assisted recovery of oil
  • EGR gas
  • the injection of C0 2 into the subsoil can have the purpose of permanently sequestering this gas in a geological formation.
  • the assisted recovery of oil or gas (hydrocarbon fluids) in a reservoir is an extraction technique which allows the displacement of the hydrocarbon fluid from the reservoir exceeding the volumes which can be obtained with conventional primary recovery processes.
  • These processes are also known as tertiary recovery processes and are effected by the injection of a fluid containing chemical additives or polymers (chemical/polymer injection) , gases such as C0 2 , N 2 or hydrocarbon gases (gas injection) or by means of thermal recovery with the injection of vapour (steam flooding) or again with electrical heaters.
  • phase i) of the process according to the present invention the vapour stream leaving phase dl) is injected into the subsoil for EOR purposes.
  • Vapour can be used in Cyclic Steam Stimulation (CSS) process, in Steam Assisted Gravity Drainage (SAGD) process and in Steam Flooding process.
  • CSS Cyclic Steam Stimulation
  • SAGD Steam Assisted Gravity Drainage
  • the electric energy produced by the vapour can be used for feeding electric cables ⁇ electrical heaters) for EOR purposes (EEOR, Electrically Enhanced Oil Recovery) .
  • the objective is to push (displace) the hydrocarbon fluid towards the production wells.
  • wells are excavated in the oil field for the injection of the immiscible fluid (also called displacement fluid) which are arranged so as to create a thrust front in the subsoil, of the hydrocarbon fluid which is as uniform as possible.
  • immiscible fluid also called displacement fluid
  • phase f) the gaseous stream of C0 2 leaving phase dl) or d2) is injected into a coal bed methane reservoir, where it produces a displacement effect with respect to the methane present, allowing its production at the surface.
  • the above stream of C0 2 is permanently sequestered in suitable geological formations, such as exhausted oil or gas reservoirs or deep saltwater reservoirs .
  • C0 2 in underground reservoirs also called geological storage
  • geological storage The sequestering of C0 2 in underground reservoirs, also called geological storage, can be effected with the equipment and according to techniques known in the field.
  • the integrated process of the present invention also preferably comprises a phase h) for feeding the water vapour stream obtained in phase dl) , once separated from the C0 2 , to a thermal and/or electric energy production process .
  • the stream of water vapour produced in the oxy- combustion and gasification phases can also be used for EOR treatments, such as SAGD, CSS, Steam Flooding processes or for oil recovery processes by means of thermal methods .
  • the implementation of the integrated process of the present invention on the same oil fields is in any case advantageous, as the overall environmental impact of the extraction of oil from the reservoir is significantly reduced.
  • the oil 1 extracted from a production well PP is 5 fed, from the wells area AP, to the oil separation unit SO, and subsequently to the desalination unit DS, where the saline compounds contained therein are removed by washing with water.
  • a distillate 4 containing light hydrocarbon fractions leaves the distillation unit DF, together with a hydrocarbon residue containing5 asphaltenes 5.
  • the distillate 4 can be further processed in the refinery in order to obtain hydrocarbon products having a commercial value.
  • the hydrocarbon residue containing asphaltenes 5 is subjected to a deasphalting process in a deasphalting 0 unit SDA. The solvent extraction effected in this unit produces a DAO 6 and an asphaltene precipitate 7.
  • the DAO 6 leaving the SDA unit is mixed with at least a part of the distillate 4 in order to obtain a reconstituted5 crude oil 10 having the density and viscosity specifications necessary for allowing it to be easily moved towards the subsequent processing phases in a refinery R.
  • the asphaltene precipitate 7 leaving the deasphalting unit SDA is fed as fuel to a combustion unit OCG, in which the oxy-combustion of the asphaltene precipitate 7 is effected (or its gasification in pure oxygen followed by transformation of the syngas by means of the CO-Shift reaction) , with the production of vapour/energy and a stream of exhausted gases 8 substantially comprising C0 2 and H 2 0.
  • the stream of exhausted gases 8 is fed to a separation and compression unit of the C0 2 SC, in which a stream of high-purity C0 2 9 is obtained, together with a stream of water vapour 11.
  • the stream of high-purity C0 2 9 is recycled to the well area AP, into an injection unit IN, where it can be exploited for the assisted recovery of gas or oil from the reservoir or it can be injected into the subsoil in order to permanently sequester it in a geological formation.
  • the stream of water vapour 11 is fed to an energy production unit PE, for generating thermal and/or electric energy, which can be used for the feeding of electric cables (electrical heaters) for EOR purposes.
  • This technique is particularly convenient in relatively shallow reservoirs, in which the EOR techniques with vapour cannot be typically applied due to the lack of the mineralogical coverage necessary for preventing the discharge of the vapour injected.
  • the stream of water vapour can be used, alternatively to or combined with the production of energy, in. an injection unit IN, where it can be exploited for assisted oil recovery from the reservoir.
  • an injection unit IN where it can be exploited for assisted oil recovery from the reservoir.
  • the C0 2 is compressed in a specific compression unit (not shown in figure 1) generally comprising five compression steps, each with a liquid vapour separator (knock-out drum) in suction and air cooling in supply.
  • Table 2 indicates the water content of the two crude oils tested and the weight percentage of the different hydrocarbon fractions obtained by atmospheric distillation (percentages referring to the overall weight of the starting heavy crude oil) .
  • PI ⁇ 60°C mixture of the hydrocarbon products distilled from PI (initial distillation point, in this case room temperature) to 60 °C.
  • the distilled fractions up to 250°C were separated from the residue (R250°C+) , to allow subsequently mixing, if necessary, with the DAO deriving from the solvent deasphalting of the residue R250°C+.
  • the viscosity and density specifications of the DAO can be adjusted to the minimum acceptable conditions for its transportation (250 est at 40°C) , by mixing with the distillates.
  • the solvent was mixed with the hydrocarbon residue (feedstock) in a flask at room temperature and atmospheric pressure.
  • the feedstock was mixed with an excess of solvent.
  • the asphaltene precipitate was separated from the liquid phase (mixture DAO-solvent) through vacuum filtration.
  • the solvent was subsequently separated from the DAO by distillation in a rotating evaporator at 55°C.
  • the feedstock, the separated asphaltene fraction and DAO were quantified for determining the material balance .
  • the solvent extraction was effected in batch, in a stirred autoclave, heated by two electric coils.
  • the feedstock was mixed with an excess of solvent (mass ratio 1:5).
  • the separation of DAO was effected by decanting the asphaltenes flocculated at a temperature of about 60°C.
  • the supernatant liquid was poured, through a plunged pipe and a heated line, into a second autoclave, where the solvent was separated from the DAO by evaporation at about 55 °C and degassing to atmospheric pressure.
  • the decanted asphaltene precipitate was subjected to a second solvent extraction treatment.
  • the asphaltene precipitate was discharged and recovered from the first autoclave, whereas the DAO was discharged and recovered by drainage from the bottom of the second autoclave.
  • Table 5 indicates the yields of the SDA process applied to R250°C+ of Crude oil 15, in terms of DAO and asphaltene precipitate, and also the results of the characterization of the products obtained.
  • the example shows the importance in the selection of solvent deasphalting, which must be effected according to the type of application and DAO characteristics expected.
  • Table 6 show the characteristics of Crude oil 15, reconstituted by mixing DAO (obtained by means of SDA with n-pentane and n-butane) with 7.6% by weight of the corresponding distilled fraction PI250°C- (percentage referring to the weight of the (anhydrous) feedstock subjected to SDA) .
  • Table 7 shows the yields of the SDA process applied to the residue R250°C+ of Crude oil 10, in terms of DAO and asphaltenes, and also some characteristics of the products obtained. The tests were carried out following the same procedures illustrated in the case of Crude oil 15.
  • Table 8 indicates the characteristics of Crude oil 10 reconstituted by mixing DAO (obtained by means of SDA with n-pentane) with 13.3% by weight of the corresponding distilled fraction PI250°C- (percentage referring to the weight of the anhydrous feedstock subjected to SDA) .
  • the DAO can be mixed with the distillate fraction PI250°C- to form 1239 tpd of reconstituted Crude oil.
  • the oxy-combustion of 1193 tpd of asphaltene precipitate is effected using 3722 tpd of pure oxygen which can be obtained by separation of 15510 tpd of air (nitrogen separated: 11800 tpd) .
  • the following products are obtained with the oxy- combustion of the asphaltene precipitate:
  • vapour produced can be suitably transformed (totally or partially) into electric energy, for a maximum of 152 MW of electric energy (assuming an electric generation yield equal to 35% on the lower calorific power (pci) of the asphaltene precipitate) ;
  • the amount of the electric energy available is equal to electric 106 MW.
  • the vapour produced can be used in EOR processes such as SAGD, CSS and Steam Flooding, wherein the ratio between the volume of vapour to be injected and the volume of additional oil that can be produced (SOR, Steam to Oil Ratio) can vary within the range of 3-5 (for 3-5 volumes of vapour injected, 1 volume of additional oil can be produced) .
  • the electric energy available can also be used for the following reasons.
  • the power density varies within the range of 200- 300 W/m of electric cable.
  • the DAO can be mixed with the distillate fraction PI250°C- of the previous example, to form 1833 tpd of reconstituted Crude oil.
  • vapour produced can be suitably transformed (totally or partially) into electric energy for a maximum of 76.4 MW of electric energy (assuming an electric generation yield equal to 35% on the lower calorific power (pci) of the asphaltene precipitate) ;
  • the amount of the electric energy available for other uses (or for sale) is equal to electric 53.5 MW.
  • C0 2 resulting from the oxy-combustion for EOR recoveries can favour the additional production of oil, quantifiable as 1 t of oil per 1-5 t of C0 2 injected, depending on whether the mechanism is of the miscible type (1 t oil per 1-3 t of C0 2 injected) or non-miscible type (1 t oil per 3-5 t of C0 2 injected) .

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Abstract

Cette invention concerne un processus intégré aval-amont d'amélioration de pétrole brut lourd avec capture de CO2. Le processus comprend les opérations suivantes : production de pétrole brut lourd extrait d'un réservoir; b) distillation dudit pétrole brut lourd, à la pression atmosphérique ou sous vide, avec séparation de la fraction distillée et d'un résidu hydrocarboné contenant des asphaltènes; c) désasphaltage par solvant dudit résidu hydrocarboné contenant des asphaltènes avec formation d'un précipité d'asphaltènes et d'une huile désasphaltée (DAO); d1) oxycombustion dudit précipité d'asphaltènes dans de l'oxygène pur avec formation d'un flux de gaz épuisés comprenant du CO2 et de la vapeur d'eau; d2) en variante de l'oxycombustion, gazéification dudit précipité d'asphaltènes dans de l'oxygène pur avec formation d'un flux de gaz de synthèse transformé ensuite en un flux gazeux comprenant du CO2 et H2; e) séparation du flux gazeux sensiblement pur de CO2 du flux de gaz épuisés ou dudit flux gazeux comprenant CO2 et H2;f) injection dudit flux gazeux de CO2 dans le sous-sol en vue de la récupération du pétrole ou de l'huile par déplacement depuis un réservoir et/ou de la séquestration du flux gazeux de CO2 dans une formation géologique. L'invention concerne également une installation pour mise en œuvre du processus intégré susmentionné.
EP11817421.8A 2010-12-30 2011-12-29 Processus intégré aval-amont d'amélioration de pétrole brut lourd avec capture de co2 ; installation connexe pour la mise en oeuvre dudit processus Withdrawn EP2658951A1 (fr)

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IT002464A ITMI20102464A1 (it) 2010-12-30 2010-12-30 Processo integrato di upstream-downstream per l'upgrading di un greggio pesante con cattura della co2 e relativo impianto per la sua attuazione
PCT/IB2011/056009 WO2012090178A1 (fr) 2010-12-30 2011-12-29 Processus intégré aval-amont d'amélioration de pétrole brut lourd avec capture de co2 ; installation connexe pour la mise en œuvre dudit processus

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CA2825645A1 (fr) 2012-07-05

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