KR101892589B1 - Method using asphaltene for improving bitumen recovery and transportation from oilsands - Google Patents

Method using asphaltene for improving bitumen recovery and transportation from oilsands Download PDF

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KR101892589B1
KR101892589B1 KR1020150081863A KR20150081863A KR101892589B1 KR 101892589 B1 KR101892589 B1 KR 101892589B1 KR 1020150081863 A KR1020150081863 A KR 1020150081863A KR 20150081863 A KR20150081863 A KR 20150081863A KR 101892589 B1 KR101892589 B1 KR 101892589B1
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South Korea
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oil
asphaltene
asphaltenes
bitumen
oil sand
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KR1020150081863A
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Korean (ko)
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KR20160145368A (en
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고강석
편원범
최선웅
노남선
김종득
김광호
권은희
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한국에너지기술연구원
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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
    • C10G27/00Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/34Arrangements for separating materials produced by the well

Abstract

The present invention relates to a method for inducing oxidation of asphaltenes contained in an oil sands and utilizing asphaltenes from oil sands, and more particularly, to a method for producing asbestos from oil sands, Which serves as an additive upstream in the process, leading to the precipitation of asphaltene along with a reduction in the amount of solvent used and serves as a diluent in the downstream process, thereby controlling the viscosity for transfer to the reforming process It is possible to remove the asphaltenes or to reduce the viscosity of the oil sand during transportation, so that the organic solvent or the diluent is not used or the usage amount can be reduced compared with the conventional method.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for asphaltene recovery and transportation from oilsands for recovering and transporting bitumen from an oil sludge,

The present invention relates to a method for removing asphaltene from an oil sand corresponding to a low-grade fuel source, and more particularly, to a method for removing asphaltene from an oil sand, To act as an additive upstream in the foaming process, leading to precipitation of asphaltene with reduced solvent usage and as a diluent in the downstream process to control the viscosity for transfer to the reforming process will be.

Oil Sands has emerged as a substitute for crude oil as one of the fossil fuels to replace petroleum since the first oil shock in 1973, and since the oil prices have continued since 2000 and large-scale separation process technology has been introduced, It became active.

In case of Korea, Korea National Oil Corporation (KNOC) has been participating in oil sands development project since 1999 in order to secure overseas crude oil.

Oil sands are made up of bitumen, sand, water, clay and trace minerals, of which bitumen is a key ingredient in making oil sands meaningful as petroleum resources.

Bitumen contained in oil sands is a complex combination of polar and nonpolar materials. These bitumen are divided into asphaltene and maltene (maltene or petrolenes), and bitumen buried in nature has viscosity It must be diluted in an appropriate manner or reduced in viscosity using chemical methods and transported to the refinery through the pipeline.

On the other hand, the production cost for extracting bitumen from oil sands is about 20 ~ 25 dollars per barrel, which is higher than the conventional crude oil production cost, which is not economical. However, the trend of increasing R & D and demand as an alternative fuel to be.

The commonly known bitumen extraction methods can be roughly divided into two methods: extracting the oil sand, extracting the bitumen (extraction method after extraction), and extracting the bitumen directly from the site (in-situ).

As for the specific extraction method, the hot water extraction process which can recycle about 90% of the non-tuyman by injecting and mixing the heated water which is tried for the first time in the 19th century is a method of extracting the bittern after mining the oil sand.

By injecting steam of high pressure and high temperature (about 350 ° C) into the buried oil sands, the oil sand lumps are crushed by the steam pressure, the bitumen is melted by the high temperature of the steam, A cyclic steam stimulation (CSS) method is used to excise two parallel horizontal wells, then steam is injected into the upper well to generate hot heat to lower the viscosity of the crude oil, The SAGD (steam assisted gravity drainage) method is applied to the in situ extraction method.

In addition, the open-pit mining method includes the steps of collecting an oil sand (sand containing bitumen) existing on the ground surface, grinding sand and stone by putting the collected oil sand into a crusher, adding hot water to the oil sand Separating the sand and bitumen by putting the oil-sand mixture into a decomposition vessel, and removing the bubbles and extracting the bitumen through a centrifugal separator.

In addition, similar to SAGD technology, VAPEX (vapor extraction process) technology, which extracts bitumen using gravity by forming a vapor-chamber underneath by injecting a vaporized solvent such as ethane or propane instead of water Is also known.

Meanwhile, in the conventional bitumen extraction method, in order to heat water or produce steam, a large amount of water or fuel for heating is required additionally, consuming a lot of energy, There is a problem that a purification cost for waste treatment is additionally required.

Although the method of extracting the bitumen by lowering the viscosity by injecting an organic solvent has been evaluated to solve the above problem to some extent, there is still a technical problem to completely separate or recover the injected organic solvent.

Especially in Canada where oil sands are mainly distributed, crude oil extracted from oil sands has increased from 600,000 barrels per day in 2000 to 2.2 million barrels per day in 2015, and an enormous amount of water It is urgent to develop a technology that can replace the water used for the mining, transport and refining of oil sands, considering that the waste water is converted into wastewater and serious water pollution is caused by environmentalists.

In addition to the above-mentioned use of a large amount of water, the present technology is used to reduce the operating cost due to the use of naphtha or paraffin oil in order to separate bitumen mixed with water at the time of mining, and to lower the viscosity for transportation through the pipeline after the water is separated Can be used as a means for solving the cost aspect of the diluent being used.

US 6,475,396 B1 US 2003-0079879 A1

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems and it is an object of the present invention to provide a method and apparatus for recovering and transporting bitumen from an oil sand without using conventional high temperature steam, water, solvent or the like, It is an object of the present invention to provide a method of eliminating the use of a diluent or transporting a non-toxic product more effectively than before.

In order to solve the above-mentioned object, the present invention provides a method for producing a slurry-containing oil sludge, comprising the steps of: mining oil sands located on the surface of the ground and underground; transferring the oil sand in the slurry state; And an asphaltene removal step of removing asphaltenes from the bitumen-containing foam, comprising the steps of: removing an underground oil sand, an oil sand in a submerged slurry, And an oxidation step of separating and oxidizing the asphaltenes contained in any one or more of the bitumen in the foam state and the asphaltene oil occurring in the refining process, and a method of utilizing the asphaltene from the oil sand .

The method may further include a transfer step of transferring the bitumen through the bubble processing step to the reforming process.

In addition, the oxidized asphaltenes produced through the oxidation step may be introduced as a mixture of bitumen and water in the process or as an additive for separating asphaltenes, or as a diluent for lowering the viscosity in the transfer step to facilitate transfer of the oil sand in the process can do.

Further, in the oxidation step, an oxidizing agent may be added to oxidize the separated asphaltenes.

Further, when only the asphaltenes contained in the oil sands located underground are oxidized, the separated asphaltenes and the oxidizing agent may be further injected into the oil sand placed underground.

Also, the oxidized asphaltenes generated through the oxidation step may include a mining step of mining the oil sand located on the surface and the ground, a transfer step of transferring the oil sand in the mined slurry state, a step of transferring the oil sand from the oil sand in the slurry state, A foaming step of producing a foam containing a tymene, a foaming step of foaming the asphaltene from the foam containing the bitumen, and a transfer step of transferring the bitumen through the foam processing step to the reforming step Can be injected.

Also, the oxidized asphaltenes generated through the oxidation step may include a mining step of mining the oil sand located on the surface and the ground, a transfer step of transferring the oil sand in the mined slurry state, a step of transferring the oil sand from the oil sand in the slurry state, The asphalt and the oxidized asphaltenes separated in one or more of the bubble generation step to produce the bubble containing the tymene and the foaming step to the asphaltene from the bubble containing the bitumen can be recovered.

It may also include an oxidized asphaltene separator and / or a bypass tube between the oil sand extraction step and the foam generation step.

The oxidizing agent may be at least one selected from the group consisting of potassium permanganate (KMnO 4 ), ozone, hydrogen peroxide water (H 2 O 2 ), permanganate compounds, cerium compounds, chromate compounds, dichromate compounds, tetroxide compounds, Compounds, sulfuric acid compounds, halogen compounds, and derivatives thereof.

In addition, a catalyst may be further added to promote oxidation of the asphaltene.

The catalyst may be one or more of vanadium, titanium, tungsten, molybdenum, and a compound thereof.

Also, the recovered asphaltene and oxidized asphaltene are produced by producing synthetic gas through the production of asphaltene oxide and gasification process, producing light oil through hydrocracking process, producing synthetic oil through Fischer-Trop process, and producing steam And as a fuel for the cement burning process.

According to the present invention, it is possible to remove asphaltenes or lower the viscosity of the oil sand by utilizing the oxidized asphaltenes generated through the oxidation process of asphaltene, and as a result, An organic solvent used for separation and removal of asphaltenes, and a diluent used for lowering the viscosity of the bitumen, or to reduce the amount of the diluent used compared to the conventional method.

In addition, it is possible to economically and effectively perform the mining and bubble treatment processes of oil sand such as energy problems consumed in water heating and steam production, purification costs for discharged wastewater and waste treatment, separation and recovery of organic solvents used .

Further, the present invention can remove the remaining sediments (oil phase sand, bitumen) in the oil sand together, increase the removal rate of asphaltenes, and increase the throughput per unit time as well.

1 is a flow chart of a conventional process for separating asphaltenes from an oil sand;
Fig. 2 is a flow chart of a process for utilizing asphaltenes from an oil sand according to the first embodiment of the present invention
FIG. 3 is a flow chart of the process of utilizing asphaltenes from the oil sludge according to the second embodiment of the present invention
4 is a flow chart of a process for utilizing asphaltenes from an oil sludge according to a third embodiment of the present invention
5 is a flow chart of a process for utilizing asphaltenes from an oil sand according to the fourth embodiment of the present invention
6 is a flow chart of a process for utilizing asphaltenes from an oil sludge according to a fifth embodiment of the present invention
7 is a flow chart of a process for utilizing asphaltenes from an oil sludge according to a sixth embodiment of the present invention
8 is a flow chart of a process for utilizing asphaltenes from an oil sludge according to a seventh embodiment of the present invention

Bitumen in oil sands contains asphaltene, oil and resin maltene consisting of highly concentrated aromatic compounds with polar functional groups with many chemically heteroatoms.

Of these, asphaltene is the most molecular weight substance in heavy oil, dissolved in benzene but insoluble in n-pentene, forming cokes in the feed pipe or reactor, inactivating the catalyst, plugging, and sedimentation. Therefore, it is possible to control the degree of oxidation of asphaltene from oil sands and to improve the dispersibility of asphaltenes in the oil during transport through the pipeline, thereby lowering the viscosity of the oil, thereby enabling efficient transfer. In the paraffin bubble treatment process, The degree of oxidation of the asphaltene is determined according to the content of oxygen, and may be more than 0 wt% to less than 100 wt%, preferably 2 wt% to 80 wt% Or less, more preferably 10 wt% or more and 40 wt% or less. When the oxidation degree is lower than the oxidation degree, the effect of aggregation or dispersion may be low depending on the change of the zeta potential value. Even if the oxidation degree is higher than the oxidation degree, the effect of aggregation or dispersion .

It is also clear that the agglomeration or dispersibility of asphaltenes in the oil sand changes depending on the amount of the asphaltene oxide having the same oxygen content. The throughput rate of the oil sand to the injection amount of the asphaltene oxide may be more than 0 and less than 1, preferably not less than 0.01 and not more than 0.8, and more preferably not less than 0.1 and not more than 0.4. If the ratio is lower than the above ratio, the effect of coagulation or dispersion may be lowered, and if it is higher than the above ratio, the effect of coagulation or dispersion may be less.

This is because the resin contained in the oil sand disperses the asphaltene agglomerates, so that the separation is not easy, and even if the resin is removed, the dispersed state of the asphaltenes becomes unstable and aggregates.

The structure of asphaltene is controversial, but according to the Yen-Mullins model, asphaltenes contain aromatic and naphthalene-based ring units linking the paraffin chain and the pendant group. Oxidation of asphaltenes with this structure results in conversion of the paraffin chains and pendant groups of asphaltenes to carboxyl groups, which has stronger hydrophilicity compared to asphaltene before oxidation. That is, the oxidized asphaltenes have both aromaticity and hydrophilicity due to the aromatic and naphthalene-based ring units of asparten before the oxidation reaction and the carboxyl groups generated after the oxidation reaction. When the asphaltenes are oxidized as described above, since they have both aromaticity and hydrophilicity, the affinity with asphaltenes in the oil sand is increased, so that the asphaltenes in the oil sand can be precipitated as a water phase to remove asphaltenes from the oil sand. Oil sand, bitumen) can be removed together. Also, the removal rate of asphaltenes increases, and the throughput per unit time also increases.

Fig. 1 shows a series of processing steps in which an oil sludge buried in the ground is mined on the ground, and asphaltenes are separated from the mined oil sands to be converted into crude oil.

As shown in FIG. 1, a process for separating the bitumen component from the oil sand and removing the asphaltenes contained in the bitumen includes an oil preparation step (Ore Preparation Step), a foam production step (Froth Production Step, and Froth Treatment Step.

More specifically, in the Ore Preparation Step, heated water, high-pressure steam, and high-temperature steam are injected into a buried oil sludge consisting of bitumen, sand, clay, and the like. Since the oil sand is highly viscous and heavy, and because the above materials are combined and aggregated, it is impossible to extract the oil sand directly to the ground. Therefore, the heated sand must be poured at the point where the oil sand is located to lower the viscosity, It is possible to transfer the oil to the ground through the oil sludge and easily separate the oil as the desired substance from the oil sludge.

The slurry oil sand having a lower viscosity through the preparation step is transferred to the primary separation cell (PSC) through an operation such as pumping. The slurry oil sands containing water injected in the crude oil preparation stage are separated into three layers by the specific gravity difference in the first separation tank. In other words, the lightest bitumen on the top layer forms a foam layer, and the middle layer contains sand, clay and a small amount of bitumen. In the lowest layer, a mixed layer of sand, clay and water having the largest specific gravity is formed. Of course, in order to improve the separation efficiency of the materials, warmed water or the like may be further added in the primary separation tank.

The mixture of sand, clay and water present in the lowest layer in the first separation tank is transported to a place called Tailing Pond and then discharged after discharging various contaminants contained in water and then reused in the preparation stage of oil sands extraction .

Here, the mixture present in the lowest layer of the primary separation tank contains various mineral minerals such as barium, calcium, iron, and magnesium contained in the oil sand including pure water. In addition to the above materials, dissolved hydrocarbons such as methane, ethane and propane, radioactive materials such as radium isotopes (Naturally occurring radioactive materials: NORM), and the like, must be reprocessed for the purpose of final use.

Processes used for reprocessing of the above components include aerobic biofiltration, oxidation, coagulation, sedimentation, filtration using activated carbon, dissolved air flotation (DAF), sand filtration using multi media, general water treatment methods such as chlorine income A membrane separation step included in the advanced water treatment technique, freezing evaporation using thermal techniques, adsorption, ion exchange, crystallization, and the like can be used.

Since the middle layer contains a small amount of bitumen, some bitumen can be recovered by forming a bitumen foam through air injection or the like. The bitumen recovered in this process is mixed with the bitumen foam layer formed on the upper layer to be described later, or the bitumen is recovered through a separate transfer line.

In the first separation tank, the bitumen foam layer formed on the uppermost layer is collected in a separate storage tank. The foam is removed by removing the asphaltenes contained in the bitumen through a process of mixing, Step to the step of reforming into synthetic crude oil.

More specifically, the bitumen foam layer contains about 30% of water and 10% of solid by weight. Therefore, the bitumen foam layer is washed in a foam processing plant or the like, and the bitumen foam layer Separate organic solvents will be used to separate and remove the asphaltenes contained in the feed and vortex. The organic solvent may be a low molecular weight alkane solvent such as propane, butane, pentane, hexane or butane, or a surfactant. However, the viscosity of the bitumen foam layer is lowered and the asphalt is easily separated from the bitumen by phase separation There is no particular restriction on the solvent.

On the other hand, the organic solvent added to the foam removing step is recovered through a recovery process such as evaporation and condensation, and then reused.

The most significant feature of the present invention is that in a series of processes including the above-described oil sand extraction preparation step (Ore Preparation step), froth production step (Froth Production step), and froth treatment step, Further comprising a step of separating the tungsten component and oxidizing the asphaltene to effectively remove the asphaltenes contained in the bitumen.

In the present specification, asphaltene oxidation is used in a sense including both partially oxidized or peroxidized, regardless of oxidation of asphaltenes.

A first preferred embodiment of the present invention will be described with reference to FIG.

In the first embodiment of the present invention, it is possible to oxidize the asphaltenes contained in the bitumen in the foamed state separated from the oil sand in the slurry state.

Two kinds of effects can be expected depending on the degree of oxidation when oxidized asphaltenes with controlled oxidation degree in the oxidation unit are injected. When the degree of oxidation is low, it causes coagulation and when the degree of oxidation is high, it has dispersibility. The degree of oxidation of asphaltene for determining the dosage of asphaltene oxide for agglomeration is determined according to the oxygen content and may be more than 0 wt% to less than 100 wt%, preferably 2 wt% to 80 wt% Or less, more preferably 10 wt% or more and 40 wt% or less. If the oxidation level is lower than the oxidation level, the effect of coagulation may be lowered according to the change of the zeta potential value. Even if the oxidation level is higher than the oxidation level, the coagulation effect may be less depending on the change of the zeta potential value

It is also apparent that the cohesiveness of asphaltenes in the oil sand changes depending on the amount of the asphaltene oxide to be injected with the same oxygen content. The throughput rate of the oil sand to the injection amount of the asphaltene oxide may be more than 0 and less than 1, preferably not less than 0.01 and not more than 0.8, and more preferably not less than 0.1 and not more than 0.4. If the ratio is lower than the above ratio, the coagulation effect may be lowered, and if it is higher than the above ratio, the coagulation effect may be lowered.

Also, the degree of oxidation of asphaltene for the injection of the asphaltene oxide for dispersibility according to the above purpose is determined according to the oxygen content, and may be more than 0 wt% to less than 100 wt%, preferably 2 wt% to 80 wt% or less, and more preferably 10 wt% or more to 40 wt% or less. When the oxidation degree is lower than the oxidation degree, the effect of dispersion may be lowered according to the change of the zeta potential value, and even when the oxidation degree is higher than the oxidation degree, the effect of dispersion may be less depending on the change of the zeta potential value .

It is also apparent that the dispersibility of asphaltenes in the oil sand changes depending on the injection amount of the asphaltene oxide having the same oxygen content. The throughput rate of the oil sand to the injection amount of the asphaltene oxide may be more than 0 and less than 1, preferably not less than 0.01 and not more than 0.8, and more preferably not less than 0.1 and not more than 0.4. If the ratio is lower than the above ratio, the effect of dispersion may be low, and if it is higher than the above ratio, the effect of dispersion may be less.

Some of the asphaltenes contained in the bitumen are removed, and the oil sand viscosity in the slurry state is lowered due to oxidized asphaltenes. The change in the bitumen property of the foam state is advantageous in that the amount of the organic solvent injected in the foam removing step is not reduced or used. Therefore, the cost of removing the asphalt from the oil sand can be drastically reduced, And as a viscosity reducer capable of lowering the viscosity by injecting it as a diluent for reducing the viscosity of the diluent, there is an advantage that the cost of using the diluent for transporting can be reduced.

The effect of asphaltene oxide in the foam removal process is to effectively separate the asphaltene from the bitumen and water present in the extracted oil sand.

Specifically, the asphaltene oxidizing process may be implemented by various methods known to those skilled in the art.

The asphaltene oxidizing agent can oxidize asphaltene by using potassium permanganate (KMnO 4 ), ozone, hydrogen peroxide (H 2 O 2 ) and the like.

In addition, a permanganate compound, a cerium compound, a chromate compound, a dichromate compound, a tetroxide compound, a nitrate compound, a nitric acid compound, a sulfuric acid compound, a halogen compound and a derivative thereof may be used.

Further, in the oxidation step, a catalyst may be further used for promoting oxidation.

As the oxidation catalyst, various oxidation catalysts known in the art may be used. Specific oxidation catalysts may be vanadium, titanium, tungsten, molybdenum, radium and compounds thereof.

3 is a process diagram showing a second preferred embodiment of the present invention.

The second embodiment may further include the step of performing the injection of asphaltenes in the oil sand extraction preparation step. That is, by injecting the asphaltenes and the oxidizing agent contained in the bitumen in the foamed state separated from the oil sand in the slurry state directly into the oil sand buried underground, the buried underground by the injected asphaltene, The direct oxidation concept, which can lower the viscosity through oxidation of the oil sand components, can be achieved by injecting asphaltenes and oxidants in the oil sand extraction preparation stage.

In the general oil sands extraction preparation step, warmed water, high-pressure steam and high-temperature steam are injected into the oil sand buried in the oil sand to lower the viscosity of the oil sand. In the second embodiment, however, The viscosity of the component can be lowered through oxidation. The oxidation of the asphaltene component is characterized by being oxidized by oxygen and heat generated in the field.

When the viscosity of the oil sand is lowered under the buried underground, the water or steam can not be injected separately or the amount of the injection can be reduced, so that the energy required for the steam heating can be reduced, and a large amount of wastewater And the processing cost can be reduced. In addition, since the organic solvent is not used or the consumption amount can be reduced in the depletion step of removing the asphaltene, the cost for removing the asphaltene from the oil sand, such as the equipment cost for recovering the organic solvent and the recovery cost of the organic solvent used, .

Meanwhile, the oxidizing agent and the oxidation catalyst used in the oxidation process in the second embodiment may be the same as those in the first embodiment, and thus will not be described.

4 is a process diagram showing a third preferred embodiment of the present invention.

In a third preferred embodiment of the present invention, the method may further comprise the step of adding asphalt oxide to oxidize the asphaltenes contained in the slurry oil sands. That is, the transfer of the oil sand containing the asphaltene in the slurry state can be effectively accomplished by oxidizing the asphaltenes contained in the oil sand in the slurry state in which the warmed water or the high-pressure, high-temperature steam is injected and transported . When the oxidation process is performed on the oil sand in the slurry state, some asphaltenes contained in the oil sand are removed and the oil sand viscosity in the slurry state is further lowered due to oxidized asphaltenes. Such a change in properties of the slurry state facilitates the transfer of the slurry through a pipe or the like due to the reduced viscosity. In addition, since the layer separation in the foam production stage is facilitated and the use amount of the organic solvent injected in the foaming step is not reduced or used, the cost of removing the asphaltene from the oil sand can be drastically reduced.

In particular, in the second embodiment, the oxidizing agent and the oxidation catalyst are directly injected into the basement where the oil sand is buried, so that it is difficult to control the reaction temperature and the reaction time. In the third embodiment, however, Which is a slurry state, can be optimized.

Meanwhile, the oxidizing agent and the oxidation catalyst used in the oxidation process in the third embodiment may be the same as those in the first embodiment, and therefore will not be described.

5 is a process diagram showing a fourth preferred embodiment of the present invention.

The fourth embodiment is a modified example of the first to third embodiments, specifically, the step of oxidizing the asphaltenes contained in the foamed bitumen separated from the slurry oil sand (the first embodiment , A step of performing oxidation of asphaltenes in the oil sand extraction preparing step (second embodiment), and a step of oxidizing the asphaltenes contained in the oil sand in the slurry state (third embodiment) (Fig. 5).

Specifically, as in the second embodiment, a part of the asphaltene is oxidized in the oil sand extraction preparing step, and water and warm steam are injected together to mined the oil sand into the slurry state. Then, as in the third embodiment, Oxidation of some unoxidized asphaltenes contained in the oil sand, and finally oxidizing the asphaltenes contained in the bitumen of the unoxidized foam state of the first embodiment.

As described above, by inducing the oxidation of asphaltenes contained in the oil sand preparation step, the slurry state transfer step and the foam transfer step, it is possible not only to reduce the amount of water or steam but also to use the organic solvent or to reduce the amount There is an advantage.

6 is a process diagram showing a fifth preferred embodiment of the present invention.

Hereinafter, referring to FIG. 6, the present invention further includes an asphaltene oxide separator for recovering oxidized asphaltenes through the first to fourth embodiments.

Specifically, by recovering oxidized asphaltenes (TSRU) through any one of the second to third embodiments, the viscosity of the oil sand, oil sand slurry or foam state in each step is lowered .

Asphaltenes containing recovered oxidized asphaltenes can be used as fuels for other processes such as reusable boiler fuel.

7 is a process diagram showing a sixth preferred embodiment of the present invention.

The difference from Example 6 is that it can further include an asphalt oxide separator and a bypass pipe for separating the asphaltene oxide contained in the transferred slurry. That is, when the viscosity of the transferred slurry is higher than a predetermined value, a part of the oxidized asphaltene is recovered, and if the viscosity of the slurry is lower than a predetermined value, the oxidized asphaltene separation tank is transferred to the foam production step without passing through.

8 is a process diagram showing a seventh preferred embodiment of the present invention.

The seventh embodiment is advantageous in that the viscosity is reduced by injecting the asphaltene oxide as a viscosity reducing agent in the diluent input step for the transfer to the reforming process, thereby reducing the transportation cost and reducing the amount of the diluent used.

The method of utilizing asphaltenes from the oil sands according to the present invention comprises the steps of: mining the oil sand placed underground, transferring the oil sand in the mined slurry state, transferring the oil sand from the transferred slurry oil sand, A method for utilizing asphaltenes from an oil sand comprising the steps of producing a froth containing oil and a step of removing asphaltenes from the bitumen-containing froth, characterized in that the oil sand is a submerged oil sand, Characterized in that the asphaltenes contained in at least one of the bitumen in the foamed state are oxidized.

The asphaltenes usable in the present invention are applicable to asphaltenes on residues generated from the bottom of the column after the heat treatment in the peripheral refining process, deasphalting and distillation in addition to the asphaltenes to be mined.

The method of utilizing asphaltenes from the oil sands according to the present invention may further comprise the steps of adding asphaltenes contained in the foamed bitumen, asphaltenes contained in the oil sands located in the underground, and oil sands in the mined slurry state And oxidizing the asphaltenes.

The method for utilizing asphaltenes from the oil sand according to the present invention is characterized in that the asphaltenes contained in the foamed bituminous material and the asphaltenes contained in the oil sand in the slurry state are oxidized.

The method for utilizing asphaltenes from the oil sands according to the present invention is characterized in that the asphaltenes contained in the foamed bitumen and the asbestos contained in the oil sands located in the underground are oxidized.

The method of utilizing asphaltenes from the oil sands according to the present invention is characterized in that water or steam is further injected into the oil sands located in the underground.

The method of utilizing asphaltenes from the oil sands according to the present invention may further comprise recovering the oxidized asphaltenes in the foam removing step and recovering the recovered oxidized asphaltenes by using an oil sand placed underground, To the at least one of the bitumen in the frozen state.

The method for utilizing asphaltenes from the oil sands according to the present invention further comprises an asphaltene separating tank and a bypass line between the oil sand extracting step and the foam producing step and further separating the asphaltene oxide separated from the asphaltene separating tank And is supplied to at least one of an oil sand placed in an underground or an oil sand in a mined slurry.

Hereinafter, effects of the present invention will be described with reference to specific experimental examples and comparative examples related to the embodiments.

<Example 1> Precipitation effect using asphaltene oxide

The oxidized asphaltenes were added to effectively remove the asphaltenes contained in the bitumen. When the bitumen is mined, it is extracted into a mixture of water and bitumen, where n-pentane is added to remove asphaltenes. 5 mL of water, 5 mL of n-pentane, 1 g of bitumen and 40 mg of asphaltene oxide were vigorously mixed for 10 minutes, and then the mixture was poured into a twist shaker for 1 hour to precipitate.

Oxygen content
(wt.%)
Oxygen per carbon
(g-oxygen / g-carbon)
Settling rate (%)
Example 1-1 23.0 0.34 16.3 Examples 1-2 24.7 0.39 18.3 Example 1-3 28.4 0.39 19.0 Examples 1-4 28.4 0.42 20.9 Examples 1-5 29.7 0.44 30.0 Comparative Example 1 Control group   - 15.8

As can be seen from Table 1, it was found that the precipitation rate was improved by adding asphaltene oxide, and that the higher the oxygen content of the oxidized asphaltene was, the more precipitated. Here, the oxygen content (wt.%) = Oxygen / (asphaltene oxide) X100 means that the amount of oxygen in the additive is a controlled variable.

Especially, as shown in Table 2 below, the SARA of the precipitate was analyzed. As a result, it was found that 58.8% of the resin and 56% of the asphaltene in the case of adding 24.7 wt.% Of oxygenated asphaltene (Example 1-2) And 7.9% of resin and 88.5% of asphaltene were precipitated when most of the asphaltene was removed by adding 29.7 wt.% Of oxygenated asphaltene (Example 1-5).

  bitumen
Oxygen content 24.7 wt.%
(Example 1-2)
Oxygen content 29.7 wt.%
(Example 1-5)
ingredient Bitumen (mg) % Of precipitated component (%)  Amount of precipitation (mg) Percent removed from bitumen (%) % Of precipitated component (%) Amount of precipitation (mg) Percent removed from bitumen (%) Saturate 217 3.182 5.83 2.69   3.958 10.29 4.74 Aromatic 221 17.195 31.53 14.27   15.665 40.71 18.42 Resin 358 17.203 31.54 8.81   10.959 28.48 7.96 Asphaltene 204  62.460 114.53 56.14   69.418 180.42 88.49 Oxidized asphaltene (0.04)  - (0.04) -  - (0.04) - Total 1,000 100 183.4 - 100 299.9 -

<Example 2> Viscosity reduction effect using asphaltene oxide

In order to confirm the effect of decreasing the viscosity due to addition of asphaltene oxide, the results obtained by adding diluents as Examples 2-1 to 2-3, in which asphalt oxide was added to bitumen, and a control group, are shown in Table 3.

In Examples 2-1 to 2-3, asphalt oxide having different oxygen contents was added in an amount corresponding to 1 wt%, toluene in an amount corresponding to 20 wt% was added as a control, and the mixture was stirred at 80 ° C .

As can be seen from the following Table 3, the viscosity of Examples 2-1 to 2-3 added with 1wt.% Of asphaltene oxide was lower than that of Comparative Example 2-1 in which toluene was added in an amount corresponding to 20wt. . Also, it can be seen that the larger the oxygen content of the asphaltene oxide is, the greater the effect of decreasing the viscosity is.

Addition amount (wt.%) Oxygen content (wt.%) Viscosity, 30 (cP)  Viscosity, 50 (cP) Comparative Example 2-1 bitumen
(20 wt.%)
- 576.6 198.6
Example 2-1 Asphaltene oxide (1 wt.%) 23.0 574.0 196.2 Example 2-2 24.7 528.9 179.9 Example 2-3 27.3 486.9 171.9

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described herein are merely the most preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that there are various equivalents and modifications that can be substituted at the time of the present application It should be understood.

Claims (14)

A mining step for mining the oil sands located on the surface and the ground, a transfer step for transferring the oil sand in the mined slurry state, a bubble generation step for generating the bitumen-containing bubbles from the transferred slurry- A method for utilizing asphaltenes removed from an oil sand comprising the step of foaming asphaltenes from a foam containing the foam,
An oxidation step of separating and oxidizing asphaltenes contained in one or more of the oil sands located underground, the oil sludge in the mined slurry state, the bitumen in the foam state, and the asphaltene oil generated in the refinery process In addition,
An asphalt oxide separator or a bypass pipe between the oil sand mining step and the foam generation step,
Further comprising a transfer step of transferring the bitumen through the foam processing step to the reforming process,
The oxidized asphaltene produced through the oxidation step is introduced as a mixture of bitten and water in the process or as an additive for separating asphaltenes or as a diluent for lowering the viscosity in the transfer step to facilitate transfer of the oil sand in the process,
Wherein the oxygen content of the asphaltene oxide is 10 wt% or more to 40 wt% or less.
delete delete The method of claim 1, wherein the oxidizing step comprises introducing an oxidizing agent for oxidation of the separated asphaltenes.
The method as claimed in claim 1, wherein when the asbestos contained in the oil sands located in the ground is oxidized, the separated asphaltenes and the oxidizing agent are further injected into the oil sands located in the underground, How to use it.
The method as claimed in claim 1, wherein the oxidized asphaltenes produced through the oxidation step include a mining step of mining the oil sand located on the surface and underground, a transfer step of transferring the oil sand in the mined slurry state, A foaming step of producing a foam containing bitumen from the oil sand, a foaming step of foaming the asphaltene from the foam containing bitumen, and a transferring step of transferring the bitumen through the foam processing step to the reforming process or Lt; RTI ID = 0.0 &gt; 2, &lt; / RTI &gt;
7. The method as claimed in claim 6, wherein the oxidized asphaltenes produced through the oxidation step include a mining step of mining the oil sand located on the surface and underground, a transfer step of transferring the oil sand in the mined slurry state, Recovering separated asphaltene and oxidized asphaltene from any one or more of the bubbling step of bubbling the asphaltene from the foam containing the bitumen and the bubbling step of producing the bitumen containing foam from the oil sand &Lt; RTI ID = 0.0 &gt; a &lt; / RTI &gt; oil sands.
delete The method of claim 4, wherein the oxidizing agent is selected from the group consisting of potassium permanganate (KMnO 4 ), ozone, hydrogen peroxide water (H 2 O 2 ), permanganate compounds, cerium compounds, chromate compounds, dichromate compounds, tetroxide compounds, A nitrate compound, a nitric acid compound, a sulfuric acid compound, a halogen compound and derivatives thereof.
5. The method of claim 4, further comprising a catalyst for promoting oxidation during the asphaltene oxidation.
11. The method of claim 10, wherein the catalyst is one or more of vanadium, titanium, tungsten, molybdenum, radium and a compound thereof.
8. The method of claim 7, wherein the recovered asphaltene and oxidized asphaltene are produced by producing a synthetic gas through the production of asphaltene oxide and a gasification process, producing a light oil through a hydrocracking process, producing a synthetic oil through a Fischer- , As boiler fuel for steam production, or as fuel for cement burning process. The method of utilizing asphaltene from an oil sludge.
delete The method of claim 1, wherein the ratio of throughput of the oil sand to the amount of injected oxidized asphaltenes may be greater than 0 and less than 1.
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