WO2018224310A1 - Procédé et dispositif de purification pour éliminer des métaux alcalins, alcalino-terreux et lourds à partir de pétrole brut et de pétrole lourd - Google Patents

Procédé et dispositif de purification pour éliminer des métaux alcalins, alcalino-terreux et lourds à partir de pétrole brut et de pétrole lourd Download PDF

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Publication number
WO2018224310A1
WO2018224310A1 PCT/EP2018/063496 EP2018063496W WO2018224310A1 WO 2018224310 A1 WO2018224310 A1 WO 2018224310A1 EP 2018063496 W EP2018063496 W EP 2018063496W WO 2018224310 A1 WO2018224310 A1 WO 2018224310A1
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Prior art keywords
phase
water
heavy
oil
crude
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PCT/EP2018/063496
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German (de)
English (en)
Inventor
Markus Kinzl
Ansgar Kursawe
Original Assignee
Siemens Aktiengesellschaft
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Priority to EP18730248.4A priority Critical patent/EP3601487A1/fr
Publication of WO2018224310A1 publication Critical patent/WO2018224310A1/fr

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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
    • C10G21/003—Solvent de-asphalting
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • 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
    • 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
    • C10G2300/4081—Recycling aspects

Definitions

  • Raw and heavy oils are only of limited use for power generation in gas turbines, since modern gas-cooled high-performance gas turbines, such as the H-class, only low concentrations of heavy metals, especially nickel and vanadium, and alkali and alkaline earth metals (eg sodium and potassium) tolerate in the fuel.
  • the upper concentration limit for the said heavy metals is in the range of 0.5 ppm.
  • standard gas turbines, such as the E-Class tolerate higher levels of heavy metals (floating limit up to 100 ppm), but an additive (magnesium salts) must be added to suppress the corrosive effects of heavy metals. These additives in turn lead to an increased service effort, since they form crusts together with the heavy metals and these must be removed regularly from the turbine blades during a shutdown.
  • alkali and alkaline earth metals are in the range of less than or equal to 0.5 ppm for all gas turbine classes. As raw and heavy oils typically significantly higher
  • Patents GB 2145730 and FR 2550545 describe a process in which water and an anti-solvent (deasphalting agent) are added to the oil.
  • anti-solvent typically short-chain alkanes are used.
  • a phase separation takes place in a separator to form three phases: an oil phase consisting of the deasphalted oil and the antisolvent, an asphaltene phase and a water phase in which the alkali metal and alkaline earth metal salts removed from the oil are in dissolved form ,
  • Deemulsifier be added.
  • Asphaltene solubility in non-polar oil is reduced. Our own investigations have shown, however, that no appreciable asphaltene separation from oils can be detected if no anti-solvent is added.
  • oils can be used in conventional standard gas turbines after water washing / desalination, it is always necessary to add inhibitors, since these oils still contain high concentrations of vanadium and nickel. A sufficient heavy metal separation by
  • Deasphalting always requires the addition of an anti-solvent. Added water can only yield the deasphalting yield and possibly the morphology of the asphalt Particles improve, which proves to be advantageous in the subsequent solid-liquid separation.
  • the patent specification US 2010/0089797 describes a deasphalting process.
  • the fouling problem can also be expected in this deasphalting process, because at the moment of supersaturation, no surface other than that of the pipes or containers together with internals is available.
  • the object of this invention is to provide a cost effective method and apparatus by which the depletion of both the water-soluble and the water-insoluble impurities, especially alkali, alkaline earth and heavy metals from crude or heavy oil, can be carried out efficiently.
  • the known from the prior art disadvantages, especially fouling should be avoided.
  • the directed to a method object of the invention for the substantial removal of alkali, alkaline earth and heavy metals from crude or heavy oil is achieved by the independent method claim 1.
  • the raw or heavy oil, a largely or completely metal-free water and an antisolvent is added and the resulting mixture in a mixing unit mixed together such that a multi-phase mixture is formed.
  • the water-soluble alkali metals and alkaline earth metals are dissolved from the crude or heavy oil in the form of their salts in the phase of the metal-free water, and water-insoluble heavy metals from the crude or heavy oil fall through
  • the multiphase mixture is purified by phase separation in a working up step
  • Raw or heavy oil which is desalted and substantially free of alkali, alkaline earth and heavy metals, in alkaline and alkaline earth metal-rich water, and in heavy metal-rich, suspended _.
  • the suspended asphalt particles obtained in the process are recycled through a return line into the crude oil or heavy oil in the area at which the antisolvent is added.
  • An essential aspect of the invention is that the crude or heavy oil desalted by water washing and simultaneously by
  • alkali metal and alkaline earth metal-free or water-free water and an antisolvent are added to the process.
  • the products obtained are heavy metal-rich asphalt particles, alkaline and alkaline earth metal-rich water and purified oil, whereby at least one oil product stream is obtained which has reduced heavy metal concentrations and can therefore be used advantageously in vanadium-tolerant standard turbines.
  • another oil product stream can be obtained which has greatly reduced heavy metal concentrations in the range of less than or equal to 0.5 ppm so that it can be used in heavy metal sensitive high performance turbines.
  • the product oils have been greatly depleted of alkali and alkaline earth metals, so that the remaining residual concentrations of these components do not limit the use in gas turbines.
  • the core of the invention is that already suspended asphalt particles are present at the point where the antisolvent is added to the crude or heavy oil.
  • suspended asphalt particles are recycled to the crude or heavy oil which had previously been formed by the continuous process.
  • the deasphalting step is not affected by fouling.
  • the crude or heavy oil to be deasphalted and the antisolvent are intensively mixed with the aid of a mixing unit (eg a pump).
  • a mixing unit eg a pump
  • a recycle stream of suspended asphalt particles is ensured that in place the supersaturation already solid asphalt particles are available on the surface of which can be deposited from the oil asphaltenes. The unwanted growth on pipe and container surfaces (fouling) which frequently occurs in conventional deasphalting is thus prevented.
  • suspended asphalt particles are used, and no dry-solid particles.
  • the task of reducing the concentrations of alkali, alkaline earth and heavy metals in crude and heavy oils before the oils are used as gas turbine fuels is achieved by a combination of water washing (desalination) and deasphalting.
  • the water wash removes the water-soluble alkali and alkaline earth metals in the form of their salts, while the water-insoluble heavy metals are separated together with the asphaltenes in which they occur in very high concentrations (deasphalting).
  • Washing processes complement each other. Both of them are necessary because heavy metals can not be removed by dewaxing from oils with water washes and alkali / alkaline earth metals.
  • the combined crude oil purification allows the use of crude and heavy oils as gas turbine fuels. Highly contaminated raw or heavy oils, which may not be used in the uncleaned state due to their high concentrations of corrosive metals or metal salts, are made usable by cleaning, and crude or heavy oils, which may be used only with high service costs, after Cleaning be emitted at significantly reduced operating costs.
  • the multiphase mixture is maintained in intimate phase contact for a period of time prior to being phase separated until equilibration by bulk transport operations is about 95% complete. This will ensure that the concentration of heavy metals is in the range of less than 0.5 ppm and the alkali, alkaline earth metals have almost completely transferred into the aqueous phase.
  • desalting and deasphalting are carried out together in one step.
  • the multiphase mixture is passed before the phase separation in a mixing unit downstream of the container, wherein a partial flow of the multiphase mixture with suspended asphalt particles from the container into the
  • the wash water is thus present in the deasphalting, which has a positive side effect: the expert is aware that the oil added to water positively influences deasphalting, because the highly polar water attaches to the slightly polar surface of the asphaltenes and thus polarized this surface additionally, so that the asphaltene solubility in the non-polar oil is reduced.
  • the deasphalting yield can increase and the particle properties can be improved, resulting in improved separation in the subsequent solid-liquid separation.
  • this integrated process saves a mixing stage for the combination of oil and water compared to the sequential variants, since the mixing devices (mixing pump and mixing tank) already present in the deasphalting stage can be used.
  • phase separation in a work-up stage (separator), wherein the phase with the oil antisolvent with residues of asphalt particles and salt-laden water is fed to a separator in which the light oil antisolvent phase is separated from heavy components from the oil antisolvent phase.
  • phase of suspended asphalt particles is fed to a solid-liquid separation stage in which the asphalt particles are separated from their mother liquor.
  • the levels of the separate phases in the separator are controlled by suitable sensors to ensure that the discharges are each fed with the correct phase.
  • the separation of the phases can take place in successive stages of separation.
  • the mixing unit is preceded by a water wash device and a phase separator, wherein the crude or heavy oil and the largely or completely metal-free water are fed to the water wash device and mixed with each other to form an emulsion which is fed to the phase separator ,
  • a phase of salt-laden water is separated, and a residual phase of desalted oil is fed to the mixing unit together with the antisolvent.
  • the raw or heavy oil is supplied to a concentration stage before being fed into the water wash device, in which it is concentrated by evaporation and / or distillation, wherein volatile components are separated off.
  • the asphalt particles separated in all variants are also a valuable product of the process. These can be supplied to the production of road asphalt or electricity in thermal power plants.
  • one or more additives can advantageously be added.
  • the additives may be added before the mixing unit, and / or in the mixing unit, and / or in the circuit between mixing unit and phase separator. Alternatively or additionally, the additives may also be added in the container, and / or in the circuit between the mixing unit and the container.
  • Advantageously suitable as additives are phosphoric acid and / or phosphorous acid.
  • the ratio between the crude or heavy oil (1) and the water (2) is preferably set in a range of 5: 1 and 50: 1. Further advantageous is a ratio of 10: 1.
  • a de-emulsifier is added to the emulsion to improve the phase separations carried out in the phase separator.
  • the device-oriented object of the invention for the substantial removal of alkali, alkaline-earth and heavy metals. from crude and heavy oils is dissolved by a cleaning device with a mixing unit and a treatment stage.
  • the crude or heavy oil, a largely or completely metal-free water and an antisolvent fed, and mixed in the mixing unit together to form a multi-phase mixture, that in the multiphase mixture, the water-soluble alkali and alkaline earth metals from the crude or heavy oil in Dissolve the form of their salts in the phase of the metal-free water, and precipitate water-insoluble heavy metals from the crude or heavy oil by deasphalting with the antisolvent in the form of suspended asphalt particles.
  • the multiphase mixture can be separated into a purified crude or heavy oil, which is desalted and largely freed of alkali metals, alkaline earth metals and heavy metals, an alkali and alkaline earth metal-rich water and heavy metal-rich asphalt particles.
  • the suspended asphalt particles obtained in the cleaning apparatus are returned to the crude oil or heavy oil by means of a return line, in the area where the antisolvent is located
  • the multiphase mixture is in intimate phase contact in a residence time before the processing step until the equilibration by material transport operations in about 95% is completed.
  • a container is provided between the work-up stage and the mixing unit, the container being connected to the mixing unit by the return line, so that a partial stream of the multiphase mixture with suspended acids phalt particles from the container in the mixing unit is traceable.
  • the work-up stage is followed by a separator and a solid-liquid separation stage, wherein the phase with the oil-antisolvent with residues of asphalt particles and salt-laden water can be fed to the separator, in which the light oil antisolvent phase of heavy Components from the light oil antisolvent phase is separated,
  • phase of suspended asphalt particles is deliverable to the solid-liquid separation stage where asphalt particles (400) are separated from their mother liquor.
  • the water wash device is a
  • Heavy oil can be fed so that volatile components can be separated by evaporation and / or distillation and thus the crude or heavy oil can be concentrated.
  • additives can be introduced, which bring about an improvement in the separation of the asphalt particles formed in the deasphalting.
  • additives can be introduced into the container and / or in the circuit between the mixing unit and the container.
  • phosphoric acid and / or phosphorous acid are preferably added.
  • a ratio between the crude or heavy oil and the water is set between 5: 1 and 50: 1.
  • the ratio is about 10: 1.
  • a de-emulsifier can be added to improve the phase separations of the emulsion carried out in the phase separator.
  • the crude oil can be separated off at least into a first and a second product stream.
  • the first product stream is heavily depleted in heavy metals, so it has vanadium and / or nickel concentrations of less than or equal to 0.5 ppm, and is combustible in a high-performance gas turbine.
  • the second product stream is only lightly stored on heavy metals, and has a vanadium and / or nickel concentration of greater than 0.5 ppm, and is combustible in a standard gas turbine.
  • FIG. 1 shows a circuit diagram of the invention with the educt
  • FIG. 2 shows a first embodiment of the invention with sequentially sequential process steps
  • FIG. 3 shows a second embodiment of the invention with sequentially sequential process steps with concentration stage
  • FIG. 4 shows a further embodiment of the invention with integrated method steps
  • Figure 1 shows a schematic diagram of the process according to the invention with the educt and product streams of the process.
  • the cleaning device H a crude or heavy oil 1, a substantially or completely metal-free water 2 and an anti-solvent 3 are added.
  • the antisolvent does not need to be added separately because it is generated within the cleaning device H.
  • the purifier leaves a purified crude oil or heavy oil 100, volatile components 200, salt laden wastewater 300 and an asphalt particle end product 400.
  • Asphalt particles are already available as asphalt particles, so that no fouling occurs due to asphaltenes precipitating from the oil, which could deposit on pipe or container walls in the absence of particles.
  • the stream of purified crude oil or heavy oil 100 may be fed to gas turbines and thus used for the production of electric power, while the asphalt particles 400 are sent for recovery (production of road asphalt or power generation in thermal power plants) and the salt laden wastewater 300 (aqueous salt solution) is subjected to a wastewater treatment.
  • the processes for the purification of crude and heavy oil 1 can be subdivided into two groups. On the one hand a sequential execution of water washing and deasphalting and on the other hand an integrated execution of these purification steps.
  • FIG. 2 shows a first embodiment of the invention, with process steps taking place sequentially one behind the other.
  • the water washing for oil desalting and the deasphalting take place in succession in separate steps.
  • the water 2 added to the oil wash, which extracts the alkali metal and alkaline earth metal salts from the oil, is again separated in a stream 300 before deasphalting occurs.
  • the water purifier T2 is a mixed unit, in which the crude or heavy oil 1 is mixed with a stream of substantially or completely metal-free water 2, wherein a water-in-oil emulsion 1 'is formed.
  • the ratio between the crude or heavy oil and the water 2 is about 10: 1. Due to the fine distribution of the phases insoluble in one another (emulsification), a large phase interface is generated, via which all water-soluble salts, in particular alkali metal and alkaline earth metal salts, are wholly or partially extracted from the oil into the water.
  • the water-in-oil emulsion 1 ' is fed to a phase separator T3 which separates the phases to form a salt laden waste water 300 and a desalted oil 1 "
  • the desalted oil is fed to a mixing unit A in power plants.
  • a de-emulsifier can be added to the emulsion 1 '.
  • the phases are thoroughly mixed in the mixing unit T2
  • the phases do not yet separate macroscopically. These remain in the emulsified state, which allows an intensive mass transfer over the large phase interface.
  • the action of the de-emulsifier prevails, whereby the phases separate out.
  • the mixing unit A is next to the desalted oil 1 "a
  • the liquids are mixed.
  • Antisolvent 3 is a solvent which has already been recovered from crude or heavy oil 1 within the process.
  • the desalted oil 1 ", the antisolvent 3 and the stream 5 are intensively mixed by the mixing unit A (eg a mixing pump) using a mixture 4 of desalted oil, antisolvent and asphalt particles arises.
  • Mixture 4 is fed to vessel B, where a residence time is provided for the deasphalting initiated by the addition of anti-solvent 3. Due to the residence time, the de-Asphaltmaschine begins, which forms a mixture of crude or heavy oil 1, antisolvent 3 and already failed asphalt particles.
  • a part of the present mixture is fed to the mixing unit A in the form of a backflow 5, so that there are suspended asphalt particles at the point of mixing, at which the asphalts precipitating from the supplied desalted oil 1 "can grow up, whereby the fouling becomes successful
  • the container B leaves a stream of the mixture 6 at the top and a stream of the mixture 9 at the bottom.
  • the stream with the mixture 6 is fed to a separator C in which there is a phase separation based on density differences.
  • the phase separation can be enhanced by centrifugal action (hydrocyclone).
  • hydrocyclone centrifugal action
  • a light, depleted of asphalt particles oil antisolvent phase 100 ' is separated, which is fed to the antisolvent recovery.
  • the antisolvent recovery can be carried out advantageously by distillation.
  • the purified crude or heavy oil 100 remaining in the anti-solvent recovery which still contains heavy metal residues (the concentrations are, however, in the tolerable range) can now be supplied as a product of a standard turbine.
  • Separator C also produces a mixture 7 of concentrated, solid asphalt particles in a 01 antisolvent mixture, which is recycled in a stream into container B.
  • the withdrawn from the container B stream with the mixture 9 is fed to the separator E.
  • the function of the separator E is likewise based on a density-dependent separation, which can be partially reinforced by centrifugal action (eg hydrocyclone).
  • a light oil anti-solvent phase 8 is formed, which is returned to the container B.
  • the solid asphalt particle enriched phase 10 is fed as a stream to the solid-liquid separation stage G, where the solid asphalt particles are separated from adherent mother liquor 14.
  • the liquid phase 14 is returned to the container B.
  • the asphalt particles 400 recovered in the solid-liquid separation step G and the above-mentioned sewage 300 are end products of the process, the oil antisolvent stream 100 'may be supplied for anti-solvent recovery.
  • the purified crude or heavy oil 100 remaining after separation of the antisolvent is supplied as power to a standard turbine.
  • Figure 3 shows a second embodiment of the invention with sequential successive process steps with an additional concentration level.
  • a concentration stage T1 is connected in the pipeline for crude oil or heavy oil 1, by means of which readily volatile components from the crude or heavy oil 2 are introduced Concentrate can be deducted.
  • the concentration stage T1 is preferably carried out in the form of an evaporation and / or distillation.
  • the asphalt particles 400 and the above-mentioned waste water 300 obtained from the solid-liquid separation stage G are obtained as end products of the process, while the oil anti-solvent stream 100 'is supplied to the anti-solvent recovery in which the antisolvent is recovered to be re-deasphalted into the mixing unit A after mixing with the C4-C6 low boilers.
  • the after separation of the anti-insulating remaining purified crude or heavy oil 100 is supplied as power to a standard turbine.
  • the crude or heavy oil 1 is deprived of the readily volatile components (low-boiling components, typically C4-C6 components) before washing the water in the water-washing device T2.
  • low boilers are combined with the distillate stream obtained in the later antisolvent recovery and then used as an anti-solvent in the deasphalting by being fed as anti-solvent 3 to the mixing unit A.
  • the concentration stage T1 leaves a stream of vaporized, volatile components 200 which are virtually metal-free and can be delivered to heavy metal sensitive high performance gas turbines.
  • the sequential methods have the advantage that no three-phase mixtures occur, whereby the phase separation is facilitated.
  • standard apparatuses available on the market can be used.
  • the positive effect of water on deasphalting which is an advantage of the integrated process, is eliminated.
  • Concentration stage Tl which in the sequential method of Figure 3 is shown.
  • a mixing unit A becomes a stream of crude or heavy oil
  • a stream of substantially or completely metal-free water 2, and a stream of antisolvent 3 supplied, the Antisolvent 3 as described above, is recovered within the process of the crude oil.
  • the streams fed to the mixing unit A are intensively mixed, whereby a fine distribution of the components results and a large phase boundary is created for the mass transfer necessary in water washing and deasphalting.
  • the resulting three-phase mixture 4 ' is fed to the intensively mixed container B, where residence time is provided for the two purification processes without the phases separating from each other.
  • the resulting deasphalting is favorably influenced by the presence of water, while at the same time the desalting of the oil takes place by a migration of the water-soluble salts into the water phase.
  • the mixing unit A in the form of a recycle stream 5.
  • a stream of a mixture 6 is fed to the separator C. Separation according to density takes place in the separator, for example by a phase separation based on density differences, which is produced by centrifugal action. can be strengthened (hydrocyclone). In this case, a light oil antisolvent phase 100 'is separated off, which is fed as a stream of antisolvent recovery (advantageously by distillation). The resulting in separator C heavy mixture 7 with concentrated solid asphalt particles is returned to the container B.
  • a stream 9 is withdrawn from the container B with solid asphalt particles, which consists of a light oil antisolvent phase and the water phase containing the water-soluble salts.
  • the stream 9 of solid asphalt particles is fed to the separator E, whose function is also based on a separation by density, which can be enhanced by centrifugal action (hydrocyclone).
  • a light oil antisolvent phase 8 is returned to the container B, while a heavy phase with water and asphalt - particles with remaining residues of the oil antisolvent phase as mixture 10/13 fed to a solid-liquid separation stage G for further processing becomes.
  • the three phases (solid asphalt particles, oil with antisolvent and water) are advantageously finally separated from each other in a single workup stage F.
  • residues of the light oil antisolvent phase which is not completely separated in the separator E, separate out as the upper phase.
  • a water phase is formed, which contains the water-soluble salts, which were previously washed out of the oil, as well as the phase of the water-and oil-insoluble asphalt particles.
  • the water phase 300 is supplied as a stream of wastewater treatment while the still oil wet asphalt particles 15 are supplied as a stream to the solid-liquid separation stage G, where the solid asphalt particles are separated from adherent mother liquor 14, which is again fed to the phase separation stage F.
  • the levels of the three mentioned in the separator phases are controlled by suitable sensors, for example, based on conductivity, so that it is ensured that the derivatives are each fed with the correct phase.
  • the oil antisolvent phase formed in the separator F contains residues of asphalt particles and salt-laden water 11. These are fed as stream for further purification to the separator D whose separation effect is likewise based on density differences (preferably the separator is designed as a hydrocyclone).
  • the light oil antisolvent phase 100 "deposited there is fed to the anti-solvent recovery, while the heavy components 12 are fed as stream again to a phase separator F.
  • solid asphalt particles, oil with antisolvent and water also occurs sequentially.
  • the three existing phases are not separated simultaneously in a single three-phase separator but in succession.
  • the light oil antisolvent phase can be separated in a separator before the remaining asphaltene particles are separated from the water phase by solid-liquid separation, or else a different order is selected for the separation of the three-phase mixture 10.
  • a three-phase separator is simple in terms of apparatus, but can only be used if the separation behavior is favorable, so that the three-phase mixture 10 separates well from one another and the phases can be discharged separately.
  • a de-emulsifier can be added to the mixing unit A or the container B to improve the phase separations carried out in the subsequent stages.
  • the phases do not separate macroscopically yet. They remain in the emulsified state, which enables an intensive substance exchange over the large phase interface.
  • the action of the emulsifier prevails, whereby the phases separate out.
  • the asphalt particles 400 recovered in the solid-liquid separation and the waste water 300 are end products of the process, while the oil antisolvent streams 100 'and 100 "are fed to the antisolvent recovery, in which the antisolvent is recovered Mixing with the C4-C6
  • Figure 5 describes a further advantageous embodiment of the invention, in which the described method can be carried out in a simplified apparatus form, when the deasphalting and the water washing done instantaneously, so do not require any significant residence time.
  • the residence time container B is dispensed with.
  • the mixing unit A continues to produce three-phase mixture (4M from the oil, water and antisolvent streams (1, 2, 3).)
  • the three-phase mixture (4) is fed directly to a phase separator F, where the phases This can advantageously be accelerated by the addition of a de-emulsifier
  • the three phases oil / antisolvent, aqueous salt solution and asphalt particles which are already present in the embodiments of the invention according to FIGS.
  • the backflow 5 required to prevent fouling is provided to the mixing unit A, as well as the further purification of the oil antisolvent phase in separator D and the residual wet asphalt particles in the solid-liquid Separation stage G.
  • the asphalt particles 400 and the effluent 300 are the final products of the process while the oil antisolvent stream 100 "is fed to the anti-solvent recovery 16.
  • the separation of the three-phase mixture 4 it is also possible to separate the light oil antisolvent phase in a separator before the remaining asphalt particles are separated from the water phase by solid-liquid separation , or a different order is chosen for the separation of the three-phase mixture.
  • additives before the deasphalting, which bring about an improvement in the properties of the asphalt particles formed in the deasphalting and thus positively influence the subsequent separation of the asphalt particles.
  • additives may be added before the mixing unit A, in the mixing unit A, in the tank B or in the circuit between the mixing unit A and the tank B.
  • they can be admixed with the crude oil 1, the water 2, the anti-solvent 3 or mixtures formed in the process.
  • Examples include phosphoric acid and phosphorous acid. It is known that both additives, which are water-soluble and thus can preferably be mixed into the water stream 2, influence the properties of the asphalt particles formed.

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

Abstract

La présente invention concerne un procédé et un dispositif de purification pour éliminer sensiblement les métaux alcalins, alcalino-terreux et lourds à partir de pétrole brut ou de pétrole lourd (1). Tout d'abord, sont ajoutés au pétrole brut ou au pétrole lourd (1) une eau (2) sensiblement ou totalement exempte de métaux et un antisolvant (3). Le mélange ainsi obtenu est malaxé dans une unité de mélangeage (A) de manière à donner un mélange multiphase (4, 4'). Dans le mélange multiphase (4, 4'), les métaux alcalins et alcalino-terreux hydrosolubles provenant du pétrole brut ou du pétrole lourd (1) se dissolvent sous forme de leurs sels dans la phase de l'eau (2) exempte de métaux, et les métaux lourds non hydrosolubles précipitent à partir du pétrole brut ou du pétrole lourd (1) par désasphaltage avec l'antisolvant (3) sous la forme de particules d'asphalte en suspension. Le mélange multiphase (4, 4') est décomposé par séparation de phase, lors d'une étape de traitement (F), en pétrole brut ou pétrole lourd (100) purifié qui est dessalé et sensiblement débarrassé des métaux alcalins, alcalino-terreux et lourds, en eau (300) riche en métaux alcalins et alcalino-terreux et en particules d'asphalte (400) en suspension et riches en métaux lourds. Selon l'invention, les particules d'asphalte en suspension obtenues dans le procédé sont renvoyées par une conduite de retour (5) dans le pétrole brut ou le pétrole lourd (1), dans la zone où est ajouté l'antisolvant (3).
PCT/EP2018/063496 2017-06-06 2018-05-23 Procédé et dispositif de purification pour éliminer des métaux alcalins, alcalino-terreux et lourds à partir de pétrole brut et de pétrole lourd WO2018224310A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021335A (en) * 1975-06-17 1977-05-03 Standard Oil Company (Indiana) Method for upgrading black oils
FR2550545A1 (fr) 1983-08-08 1985-02-15 Elf Aquitaine Procede et appareil pour deshydrater, dessaler et desasphalter simultanement un melange d'hydrocarbures
RU2000312C1 (ru) 1992-07-15 1993-09-07 Салимов М.Х. Способ деасфальтизации нефти и т желых нефт ных остатков
US20060283776A1 (en) * 2005-06-21 2006-12-21 Kellogg Brown And Root, Inc. Bitumen Production-Upgrade with Common or Different Solvents
US20100089797A1 (en) 2008-10-15 2010-04-15 Sudhakar Chakka Devices And Processes For Deasphalting And/Or Reducing Metals In A Crude Oil With A Desalter Unit
WO2016173732A1 (fr) * 2015-04-28 2016-11-03 Siemens Aktiengesellschaft Dispositif et procédé pour la séparation d'asphaltènes d'un combustible contenant de l'huile

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021335A (en) * 1975-06-17 1977-05-03 Standard Oil Company (Indiana) Method for upgrading black oils
FR2550545A1 (fr) 1983-08-08 1985-02-15 Elf Aquitaine Procede et appareil pour deshydrater, dessaler et desasphalter simultanement un melange d'hydrocarbures
GB2145730A (en) 1983-08-08 1985-04-03 Elf Aquitaine Process and apparatus for simultaneously dewatering, desalting and deasphalting a mixture of hydrocarbons
RU2000312C1 (ru) 1992-07-15 1993-09-07 Салимов М.Х. Способ деасфальтизации нефти и т желых нефт ных остатков
US20060283776A1 (en) * 2005-06-21 2006-12-21 Kellogg Brown And Root, Inc. Bitumen Production-Upgrade with Common or Different Solvents
US20100089797A1 (en) 2008-10-15 2010-04-15 Sudhakar Chakka Devices And Processes For Deasphalting And/Or Reducing Metals In A Crude Oil With A Desalter Unit
WO2016173732A1 (fr) * 2015-04-28 2016-11-03 Siemens Aktiengesellschaft Dispositif et procédé pour la séparation d'asphaltènes d'un combustible contenant de l'huile

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