WO2011048642A1

WO2011048642A1 - Device for reforming heavy oil and method of reforming heavy oil

Info

Publication number: WO2011048642A1
Application number: PCT/JP2009/006855
Authority: WO
Inventors: 永松茂樹; 粥川智生; 江上日加里; 藤本高義
Original assignee: 日揮株式会社; 独立行政法人石油天然ガス・金属鉱物資源機構
Priority date: 2009-10-20
Filing date: 2009-12-14
Publication date: 2011-04-28
Also published as: CA2774062C; ECSP12011824A; JP2011088964A; EA022662B1; CA2774062A1; EA201270444A1; CO6511243A2

Abstract

A device and method for reforming a heavy oil are provided with which it is possible to control the degree of progress of the thermal cracking of the heavy oil when the heavy oil is reformed using supercritical water. A reactor (1) is kept at a temperature and a pressure which are equal to or higher than the critical points of water, and a heavy oil is brought into contact with supercritical water. While thermal cracking of the heavy oil is allowed to proceed, the reaction mixture is separated into a first phase comprising heavy-oil matter obtained by the thermal cracking of the heavy oil and supercritical water dissolved in the heavy-oil matter and a second phase comprising supercritical water and light-oil matter extracted and dissolved in the supercritical water. An interface detector (75) detects the level of the interface between the first phase and the second phase in the reactor. A control unit (7) controls, on the basis of the volume of the first phase determined from the level of the interface, the discharge rate of the mixed fluid composed of the heavy-oil matter and the supercritical water dissolved therein, so that the residence time of the heavy-oil matter/supercritical water mixed fluid is a first residence time preset.

Description

Heavy oil reforming apparatus and heavy oil reforming method

The present invention relates to a technology for reforming heavy oil using supercritical water.

In the future, while demand for crude oil is expected to increase mainly in developing countries such as China and India, the production of light crude oil, which has been used in the past, is reaching its peak, and it has not been used so far. There is an increasing need to use high-quality and ultra-heavy crude oil. Among super heavy oils, Canadian oil sand bitumen and Venezuelan orinocotal have already established economical production methods and their production is increasing.

These ultra-heavy crude oils have very high density and viscosity, so they cannot be transported as they are using pipelines to transport them from wells in production areas to refineries in consumption areas. Therefore, at the well site, a dilution method in which a diluent is mixed to lower the viscosity, and a reforming method to produce a light synthetic crude oil by constructing a plant called pyrolyzer and hydrotreating, which is called an upgrader, is nearby. The two methods are selected.

However, the dilution method has a problem that a sufficient diluent such as condensate must be secured, and a problem that the transportation cost increases because the transportation amount increases by the amount of dilution. Also, the reforming method requires a large plant as well as a refinery at the well site, so there is a problem that it is economical only in the vicinity of a large oil field, and processing of by-products such as coke and sulfur. The problem of having to secure the hydrogen required for reforming occurs.

Also, existing heavy oil upgrading technologies include pyrolysis processes such as delayed coker and fluid coker, and hydrocracking processes such as H-Oil and LC-Fining. The pyrolysis process is a technology that pyrolyzes heavy oil to produce cracked oil, gas, and coke. The by-products such as coke and sulfur produced in large quantities here have problems such as being forced to pile up in areas where there is no use.

On the other hand, the hydrocracking process is a technique for cracking heavy oil using a catalyst under high-temperature and high-pressure hydrogen conditions. Since a large amount of hydrogen is required here, naphtha and natural gas are required, and the supply thereof becomes a problem. Furthermore, it is necessary to consider the supply of the catalyst and the disposal of the used catalyst.
As described above, in the existing technology, processing of by-products, hydrogen production, catalyst supply, and waste catalyst processing become problems.

In response to these problems, the present inventors modified heavy crude oil and super heavy crude oil (hereinafter referred to as heavy oil) using supercritical water, and required a diluent with a simple reforming scheme. We focused on the technology to produce synthetic crude oil that can be transported by pipeline. In this technology, the pyrolysis reaction of heavy oil due to the contact between heavy oil and supercritical water inside the reactor and the extraction of light oil produced by pyrolysis to the supercritical water side are performed in parallel. The synthetic light crude oil that can be transported by pipeline can be obtained by separating and recovering the extracted light oil. In addition, heavy oil that has not been extracted into supercritical water can be used as residual oil in applications such as boiler fuel.

As a technique for reforming heavy oil using supercritical water, for example, Patent Document 1 supplies heavy oil vertically downward from the upper part of the reactor, and supercritical water (or subcritical water) from the lower part. Is separated into a light oil dissolved in supercritical water and a heavy oil not dissolved in the supercritical water.

Patent Document 2 discloses a primary pyrolysis section that heats and mixes heavy oil with supercritical water in the lower part of a vertical reactor, decomposes a part of the raw material into light components, and vaporizes the reactor. There has been proposed a reformer having a secondary decomposition section that decomposes a part of the vaporized light component into a reformed component at a higher temperature from the center to the top in the inner vertical direction. In the primary pyrolysis section, a pyrolysis vessel is provided in the reactor, and heavy oil is reacted in the reactor. On the other hand, the liquid overflowing from the pyrolysis vessel without pyrolysis is left as a residual oil from the bottom of the reactor. Discharged. In addition, in Patent Document 3, heavy oil is reacted with supercritical water in a reactor to produce coke together with the reformed oil emulsion, and the reformed oil emulsion is continuously extracted while the coke is intermittently discharged. The technology to be extracted is disclosed.

Japanese Patent No. 4117262: Claim 1, paragraphs 0030 to 0033, FIG. JP 2008-208170 A: claim 1, paragraphs 0012 to 0017, FIG. Japanese Patent Laying-Open No. 2007-51224: Claim 1, paragraphs 0024 to 0030, FIG.

Among the above-mentioned prior arts, the technique described in Patent Document 1 is made by bringing heavy oil into contact with supercritical water and dissolving a light oil component on the supercritical water side, so that vanadium contained in heavy oil, etc. It removes heavy metals and has obtained gas turbine fuel that is unlikely to cause high temperature corrosion. At this time, the heavy metal contained in the heavy oil is concentrated on the heavy oil side that does not dissolve in the supercritical water, and this heavy oil is used as a fuel for a boiler or the like.

In particular, in paragraph 0012 of Patent Document 1, although reforming proceeds when the heavy oil component is brought into contact with supercritical water, the main point of the technology is to dissolve the light oil component on the supercritical water side. It is specified that heavy components that do not dissolve are settled and separated without further modification. Therefore, Patent Document 1 does not disclose a technique for producing a synthetic crude oil by modifying a heavy oil that has not been dissolved in supercritical water to reduce density and viscosity.

Further, according to the technique described in Patent Document 2, the primary pyrolysis section is heated to 380 ° C. to 450 ° C., and the upper secondary pyrolysis section is 450 ° C. to 550 ° C. higher than the primary pyrolysis section. By heating to 0 ° C., heavy oil brought into contact with supercritical water is decomposed into light oil and further decomposed into reforming components in two stages. However, if the light components are actively decomposed as in the case of this technology, the amount of gas generated due to excessive decomposition (decrease in liquid yield) and the concentration of olefins in the light components will be increased. It cannot be said that the technology is suitable for the manufacturing technology.

Here, in paragraph 0018 of Patent Document 2, the reaction time of heavy oil in the pyrolysis vessel arranged in the primary pyrolysis section is adjusted by changing the supply amount of heavy oil and the volume of the pyrolysis vessel. In addition, it is described that the reaction time in the secondary pyrolysis section is adjusted by changing the flow rate of supercritical water or by filling the secondary pyrolysis section with a filler and changing its internal volume. Yes.

However, in the specification of Patent Document 2, for example, the space between the primary pyrolysis unit and the secondary pyrolysis unit or the gap between the pyrolysis container and the reactor disposed in the reactor of the primary pyrolysis unit, Further, there is no disclosure of temperature conditions at the bottom of the reactor where liquid overflowing from the pyrolysis volume accumulates. However, it is considered that the light components and liquids that flow through the space, such as those that come into contact with the space that reaches 380 ° C. to 550 ° C., are decomposed and polymerized. It is difficult to control the reaction sufficiently.

The technique described in Patent Document 3 is operated by actively selecting conditions for generating coke, and coke processing becomes a problem. Moreover, under severe conditions that generate coke, there are concerns about an increase in gas production (reduction in liquid yield) and an increase in olefin concentration in the reformed oil due to excessive decomposition of light oil.

The present invention has been made under such circumstances, and its purpose is to control the degree of thermal decomposition of heavy oil when reforming heavy oil using supercritical water. An object of the present invention is to provide a possible heavy oil reforming apparatus and reforming method.

The heavy oil reforming apparatus according to the present invention is maintained at a temperature and pressure above the critical point of water, while bringing the heavy oil and supercritical water into contact with each other while advancing thermal decomposition of the heavy oil. A first phase consisting of a heavy oil obtained by pyrolyzing the heavy oil and supercritical water dissolved in the heavy oil; the supercritical water; and the supercritical water extracted into the supercritical water. A reactor for separation into a second phase consisting of a light oil component,
A heavy oil supply section for supplying heavy oil to the reactor;
A supercritical water supply for supplying supercritical water to the reactor;
A first extraction portion for extracting a mixed fluid of heavy oil and supercritical water from the first phase;
A second extraction portion for extracting a mixed fluid of supercritical water and light oil from the second phase;
An interface detector for detecting a height position of an interface between the first phase and the second phase in the reactor;
The volume of the first phase is obtained based on the height position of the interface detected by the interface detector, and the heavy oil component and the supercritical dissolved in the heavy oil component are obtained based on the volume of the first phase. A control unit that controls the amount of the mixed fluid extracted from the heavy oil and the supercritical water so that the residence time of the mixed fluid of water becomes a preset first residence time. .

Further, the heavy oil reforming apparatus according to another invention is maintained at a temperature and pressure above the critical point of water, and the heavy oil and the supercritical water are brought into contact with each other to advance thermal decomposition of the heavy oil. However, the first phase comprising the heavy oil obtained by pyrolyzing the heavy oil and the supercritical water dissolved in the heavy oil, the supercritical water, and extraction into the supercritical water. A reactor for separating into a second phase consisting of
A heavy oil supply section for supplying heavy oil to the reactor;
A supercritical water supply for supplying supercritical water to the reactor;
A first extraction portion for extracting a mixed fluid of heavy oil and supercritical water from the first phase;
A second extraction portion for extracting a mixed fluid of supercritical water and light oil from the second phase;
Based on the supply amount of the heavy oil, the heavy oil component and the heavy oil component so that the residence time of the mixed fluid of supercritical water dissolved in the heavy oil component becomes a preset first residence time. And a control unit for controlling the amount of fluid extracted from the supercritical water.

The heavy oil reforming apparatus may have the following characteristics.
(A) In order to suppress the formation of coke in the heavy oil, the control unit is a mixed fluid of the heavy oil and supercritical water so that the first residence time is 3 minutes or more and 95 minutes or less. Control the amount of extraction.
(B) The first residence time is a residence time during which the pyrolysis of the heavy oil proceeds within a range where the amount of coke produced is 0% by weight or more and 20% by weight or less of the heavy oil. .
(C) The first residence time is a residence time during which thermal decomposition of the heavy oil proceeds until the kinematic viscosity of the heavy oil at 350 ° C. becomes 3.0 × 10 ⁻⁵ m ² / s or less. There is.
(D) The control unit obtains the volume of the second phase based on the height position of the interface detected by the interface detection unit, and determines the supercritical water and the supercritical water based on the volume of the second phase. To control the supply amount of supercritical water so that the residence time of the mixed fluid of light oil extracted in the critical water becomes a preset second residence time.
(E) Based on the supply amount of the heavy oil, the control unit has a second residence time set in advance for the mixed fluid of the supercritical water and the light oil extracted into the supercritical water. To control the amount of supercritical water supplied.
(F) In order to suppress excessive decomposition of the light oil, the control unit controls the supply amount of supercritical water so that the second residence time is 1 minute or more and 25 minutes or less.
(G) The second residence time is a residence time during which thermal decomposition of the heavy oil proceeds within a range where the amount of gas generated by overdecomposition is 0% by weight or more and 5% by weight or less of the heavy oil. Be.
(H) The second residence time is a residence time during which the thermal decomposition of the heavy oil proceeds until the kinematic viscosity of the light oil at 10 ° C. is 5.0 × 10 ⁻³ m ² / s or less. thing.
(I) The heavy oil is selected from the group of heavy oils consisting of oil sand bitumen, orinocotal, atmospheric distillation residue oil, and vacuum distillation residue oil.

A method for reforming heavy oil according to still another invention includes a step of supplying heavy oil to a reactor,
Supplying supercritical water to the reactor;
Maintaining the reactor at a temperature and pressure above the critical point of water, bringing the heavy oil into contact with the supercritical water and proceeding with the thermal decomposition of the heavy oil, A first phase comprising the heavy oil obtained in this manner and supercritical water dissolved in the heavy oil, a second phase comprising the supercritical water and the light oil extracted into the supercritical water. Separating into phases of
Extracting a mixed fluid of heavy oil and supercritical water from the first phase;
Extracting a fluid mixture of supercritical water and light oil from the second phase;
Detecting the height position of the interface between the first phase and the second phase in the reactor;
The volume of the first phase is obtained based on the height position of the interface detected in this step, and the heavy oil and supercritical water dissolved in the heavy oil are based on the volume of the first phase. And a step of controlling the extraction amount of the mixed fluid of the heavy oil and the supercritical water so that the residence time of the mixed fluid becomes a preset first residence time.

A method for reforming heavy oil according to still another invention includes a step of supplying heavy oil to a reactor,
Supplying supercritical water to the reactor;
Maintaining the reactor at a temperature and pressure above the critical point of water, bringing the heavy oil into contact with the supercritical water and proceeding with the thermal decomposition of the heavy oil, A first phase comprising the heavy oil obtained in this manner and supercritical water dissolved in the heavy oil, a second phase comprising the supercritical water and the light oil extracted into the supercritical water. Separating into phases of
Extracting a mixed fluid of heavy oil and supercritical water from the first phase;
Extracting a fluid mixture of supercritical water and light oil from the second phase;
Based on the supply amount of the heavy oil, the heavy oil component and the heavy oil component so that the residence time of the mixed fluid of supercritical water dissolved in the heavy oil component becomes a preset first residence time. And a step of controlling the extraction amount of the fluid mixture with the supercritical water.

Further, the heavy oil reforming method may include the following features.
(J) In order to suppress the formation of coke in the heavy oil component, the first residence time is adjusted within a range of 3 minutes to 95 minutes.
(K) The first residence time is a residence time during which pyrolysis of the heavy oil proceeds in a range where the amount of coke produced is 0% by weight or more and 20% by weight or less of the heavy oil. .
(L) The first residence time is a residence time during which thermal decomposition of the heavy oil proceeds until a kinematic viscosity of the heavy oil at 350 ° C. is 3.0 × 10 ⁻⁵ m ² / s or less. It is characterized by being.
(M) obtaining the volume of the second phase based on the height position of the interface detected in the step of detecting the height position of the interface between the first phase and the second phase, Including the step of controlling the supply amount of supercritical water so that the residence time of the supercritical water in the second phase and the mixed fluid of the light oil extracted in the supercritical water becomes a preset second residence time. .
(N) Based on the supply amount of the heavy oil, the supercritical water and the supercritical water so that the residence time of the mixed fluid of the light oil extracted in the supercritical water becomes a preset second residence time. Including a step of controlling the supply amount of
(O) adjusting the second residence time within a range of 1 minute to 25 minutes in order to suppress overdecomposition of the light oil.
(P) The second residence time is a residence time during which pyrolysis of the heavy oil proceeds within a range where the amount of gas generated by overdecomposition is 0% by weight or more and 5% by weight or less of the heavy oil. Be.
(Q) The second residence time is a residence time during which thermal decomposition of the heavy oil proceeds until the kinematic viscosity of the light oil at 10 ° C. is 5.0 × 10 ⁻³ m ² / s or less. thing.

(R) including a step of cooling and depressurizing the mixed fluid of the heavy oil extracted from the first phase and the supercritical water to separate it into the heavy oil and water.
(S) The step of lowering the temperature of the mixed fluid of the heavy oil extracted from the first phase and the supercritical water to obtain fuel oil containing moisture in the heavy oil is included.
(T) The fluid mixture of the heavy oil extracted from the first phase and the supercritical water contains water in the range of 3 wt% to 100 wt% of the heavy oil.
(U) A step of lowering the temperature of the mixed fluid of supercritical water and light oil extracted from the second phase and reducing the pressure to separate the oil into light oil and water.
(V) including a step of recovering water separated from the heavy oil or light oil for reuse as supercritical water supplied to the reactor.
(W) Lowering the temperature of the mixed fluid of the heavy oil extracted from the first phase and the supercritical water, lowering the pressure, and separating the fluid into the heavy oil and water;
Lowering the temperature of the mixed fluid of supercritical water and light oil extracted from the second phase and lowering the pressure to separate the oil into light oil and water;
Mixing the heavy oil and the light oil after being separated from water.
(X) The heavy oil is selected from the group of heavy oils consisting of oil sand bitumen, orinocotal, atmospheric distillation residue oil, and vacuum distillation residue oil.

According to the present invention, these fluids are brought into the first phase (mixing of heavy oil and supercritical water dissolved in this heavy oil by bringing heavy oil and supercritical water into contact in the reactor. The first phase is constituted by separating into two phases of a fluid phase) and a second phase (a phase consisting of a mixed fluid of the supercritical water and a light oil extracted into the supercritical water). The extraction amount of the mixed fluid of the heavy oil and the supercritical water is adjusted so that the residence time of the mixed fluid in the first phase becomes a preset first residence time. This makes it possible to control the degree of progress of thermal decomposition of the heavy oil that proceeds in the first phase. For example, the thermal decomposition is allowed to proceed to the maximum extent that coke generation from the heavy oil can be suppressed. It is possible to operate the reformer under optimum conditions, such as by allowing thermal decomposition to proceed so that the kinematic viscosity of the heavy oil falls within a desired range.

It is a process flow figure concerning the reforming device of heavy oil of this embodiment. It is explanatory drawing which shows the structure of the reactor provided in the said reformer. It is a process flow figure of the experimental device concerning an example. It is explanatory drawing which shows the interface of the 1st phase and 2nd phase which are formed in a reactor.

First, the overall configuration of the heavy oil reforming apparatus according to the present embodiment will be described with reference to the process flow diagram of FIG. The reformer according to the present embodiment is installed at a well where a high-density, high-viscosity crude oil such as oil sand bitumen or orinocotal is produced, and the heavy oil is synthesized with low-density, low-viscosity. Plays a role in reforming crude oil.

As shown in FIG. 1, the reformer reforms the heavy oil by bringing heavy oil and supercritical water into contact with each other, and separates the heavy oil into the light oil and the reactor 1. A high-pressure separator 2 that separates a mixed fluid of light oil and supercritical water flowing out of the oil under a pressure condition similar to that in the reactor 1, for example, and a combination of light oil and water flowing out of the high-pressure separator 2 The mixed fluid of the low pressure separator 3 that separates the mixed fluid into oil and water under a lower pressure condition than the high pressure separator 2 and the heavy oil and supercritical water that has flowed out of the reactor 1 A flash drum 4 for separation and a recycled water tank 5 for recycling the water after oil-water separation are provided.

The reactor 1 thermally decomposes the heavy oil by bringing the heavy oil and supercritical water, which have been heated and pressurized, into contact with each other, for example, in countercurrent. This serves to separate and extract the light oil and heavy oil obtained separately. The reactor 1 is a pressure vessel having a hollow interior and formed in, for example, a tower shape. A heavy oil for receiving heavy oil from a heavy oil supply source 11 is provided on, for example, an upper side wall portion of the reaction vessel. A supply line 110 is connected. The heavy oil supply source 11 is composed of, for example, a tank for storing heavy oil.

In the heavy oil supply line 110, the heavy oil received from the heavy oil supply source 11 is increased to a critical pressure of water of 22.1 MPa or more, for example, 25 MPa to 30 MPa, and sent to the reactor 1. For example, a heating pump for heating the heavy oil supplied to the reactor 1 to 300 ° C. to 450 ° C., for example, is provided. A heater 113 is interposed. Here, the heavy oil is supplied at a temperature lower than the temperature in the reactor 1 (for example, 374 ° C. to 500 ° C.) in order to prevent polycondensation in the heavy oil supply line 110 and the heater 113. The heavy oil supply line 110, the heavy oil supply pump 111, the flow rate control valve 112, the heater 113, and the like correspond to the heavy oil supply unit of the present embodiment.

On the other hand, a supercritical water supply line 120 for supplying water received from a water supply source 12 such as a water storage tank to the reactor 1 in a supercritical state is connected to the lower side wall portion of the reaction vessel, for example. Yes. In the supercritical water supply line 120, a supercritical water supply pump 121 that boosts the water received from the water supply source 12 to a critical pressure (22.1 MPa) or higher, for example, 25 MPa to 30 MPa, and sends it to the reactor 1, A flow control valve 122 that adjusts the supply amount of supercritical water, and a heating furnace for heating the supercritical water supplied to the reactor 1 to, for example, 450 ° C. to 600 ° C. above its critical temperature (374 ° C.) The heater 123 which consists of these etc. is interposed. As described above, the heavy oil supplied from the heavy oil supply line 110 is supplied at a temperature lower than the temperature in the reactor 1 for the purpose of preventing polycondensation. Is supplied at a temperature higher than the temperature in the reactor 1 to supply heat necessary for the pyrolysis reaction of heavy oil. The supercritical water supply line 120, the supercritical water supply pump 121, the flow control valve 122, the heater 123, and the like correspond to the supercritical water supply unit of the present embodiment.

In addition, at the top of the reactor 1, for example, at the top of the column, a light oil component is extracted to extract a mixed fluid formed by extracting a light oil component obtained by decomposing heavy oil in the reactor 1 into the supercritical water. Line 130 is connected. A light oil content extraction line 130 includes a cooler 132 including a heat exchanger for cooling the mixed fluid flowing in the light oil content extraction line 130 to a temperature lower than the critical pressure of water, for example, 200 ° C. to 374 ° C. A pressure adjusting valve 131 for adjusting the pressure in the reactor 1 to, for example, 25 MPa to 30 MPa is interposed. The light oil content extraction line 130, the pressure adjustment valve 131, and the cooler 132 correspond to the second extraction portion of the present embodiment.

Downstream of the light oil content extraction line 130, the mixed fluid cooled by the cooler 132 under a pressure substantially equal to the pressure in the reactor 1 is mixed with the light oil content (however, the light oil content also contains moisture). And a high-pressure separator 2 for separation into water. A light oil component line 210 is connected to the upper side of the high pressure separator 2 to extract a light oil component and send it to the low pressure separator 3. The light oil component line 210 cools the light oil component to a temperature of about 40 ° C. to 100 ° C. And a pressure reducing valve 211 for reducing the pressure of the light oil flowing in the line 210 to, for example, about 0.2 MPa to 1.0 MPa higher than normal pressure. It is installed.

On the other hand, a high-pressure separation water line 220 is provided on the bottom side of the high-pressure separator 2 for extracting water separated from the light oil under a pressure of about 25 MPa to 30 MPa and a temperature of about 200 ° C. to 374 ° C. The high-pressure separation water line 220 is connected to a later-described recycle water line 510 so that the separation water from the high-pressure separator 2 can be supplied to the reactor 1 again. A high-pressure separation water recycle pump 221 for feeding the separation water from the high-pressure separator 2 is provided in the high-pressure separation water line 220.

Next, the low pressure separator 3 provided on the downstream side of the light oil content line 210 will be described. The low pressure separator 3 has a pressure of about 0.2 MPa to 1.0 MPa with respect to the light oil content containing water flowing out from the high pressure separator 2, 40 Under the temperature condition of about 100 ° C. to 100 ° C., it again separates into light oil and water. Reference numeral 320 denotes a synthetic crude oil line for delivering light oil separated from water as synthetic crude oil to the synthetic crude oil tank 62.

On the other hand, a low-pressure separation water recycling line 330 is connected to, for example, the bottom of the low-pressure separator 3, and the low-pressure separation water recycling line 330 extracts water separated from light oil and recycles it as supercritical water. It plays the role of sending liquid to the tank 5. In addition, a drainage line 340 for extracting a part of the recycled water from the low-pressure separated water recycling line 330 to the wastewater treatment facility 63 is branched, and it is improved by increasing or decreasing the amount of liquid fed to the wastewater treatment facility 63. The concentration of oil and salinity in the recycled water circulating in the quality device can be adjusted to a predetermined value or less. In the figure, reference numeral 310 denotes an exhaust gas line for sending gas to the exhaust gas treatment facility 61 that has volatilized from the light oil component.

In contrast to the above-described process flow at the top of the reactor 1, heavy oil that has not been extracted into supercritical water from the heavy oil decomposed in the reactor 1, for example, at the bottom of the reactor 1. A heavy oil extraction line 140 for extracting a mixed fluid of the heavy oil and supercritical water dissolved in the heavy oil is connected. The heavy oil content extraction line 140 includes a cooler 141 including a heat exchanger for cooling the mixed fluid flowing in the line 140 to about 200 ° C. to 350 ° C., and a mixture from the bottom of the reactor 1. A flow rate adjustment valve 142 is provided for adjusting the amount of fluid extracted and reducing the pressure of the mixed fluid flowing in the heavy oil content extraction line 140 to, for example, about 0.2 MPa to 1.0 MPa higher than normal pressure. It is installed. The heavy oil content extraction line 140, the cooler 141, and the flow rate adjustment valve 142 correspond to the first extraction portion of the present embodiment.

The flow rate adjusting valve 142 is connected to the flash drum 4, and the flash drum 4 has a heavy oil component and the heavy oil component under a pressure condition of about 0.2 MPa to 1.0 MPa and a temperature condition of about 200 ° C. to 350 ° C. It plays the role of separating water dissolved in it. 410 provided in the flash drum 4 is a drum separation water line for extracting water separated in the flash drum 4 toward the low-pressure separation water recycling line 330 and recycling the water, and 420 is a weight separated from the water. This is a residual oil line for extracting the quality oil to the residual oil tank 64 as residual oil for boiler combustion, for example.

In the residual oil line 420, a total amount or a part of the heavy oil extracted from the flash drum 4 is mixed with the light oil extracted from the low-pressure separator 3 side and sent to the synthetic crude oil tank 62. A crude oil mixing line 430 is branched. By mixing the heavy oil with the light oil, it is possible to improve the yield of synthetic crude oil with high added value compared to boiler fuel. Here, the mixing amount of the heavy oil to the light oil is adjusted to a range in which the compatibility of the synthetic crude oil after mixing is ensured, in other words, a mixing amount in a range where the synthetic crude oil after mixing is not re-separated into the heavy light oil. It has become so.

As an index for judging the compatibility of synthetic crude oil, for example, CII (Colloidal Instability Index) shown in the following formula (1) can be cited. CII is a synthetic crude oil mixed with heavy and light oils. For example, SARA analysis is performed, and saturated oils, aromatic hydrocarbons, resins, asphaltenes (saturated hydrocarbons, aromatics) Asphaltenes) is measured, CII is calculated from equation (1), and the amount of heavy oil mixed is adjusted so that the value is 0.5 or less.
CII = {(saturated content + asphaltene content) / (aromatic content + resin content)} ≦ 0.5 (1)

Next, a water recycling system for supercritical water will be described. The recycled water tank 5 provided downstream of the low-pressure separation water recycling line 330 includes water separated from light oil by the low-pressure separator 3 and the flash drum 4. The water separated from the heavy oil is received, and the water collected in the recycled water tank 5 is resupplied to the supercritical water supply line 120. Here, 510 is a recycle water line connecting the recycle water tank 5 and the supercritical

water supply line

120, and 511 is water discharged from the recycle water tank 5 that has a critical pressure (22.1 MPa) or more, for example, 22.1 MPa to This is a recycled water pump for raising the pressure to 40 MPa and sending it out toward the supercritical water supply line 120. As described above, the recycle water line 510 is joined with the high pressure separation water line 220 for recycling the water separated by the high pressure separator 2. By recycling the water used as supercritical water, it is possible to reduce the amount of new water used, to easily secure the water necessary for reforming heavy oil, and to reduce the environmental load.

Further, as shown in FIG. 2, the reformer includes a control unit 7. The control unit 7 includes a computer having a CPU and a storage unit, for example, and the storage unit is operated by the reformer, that is, the heavy oil and the supercritical water are brought into contact with each other in the reactor 1 to perform thermal decomposition. After proceeding and separating into heavy oil and light oil, water of each oil is removed, and light oil alone or synthetic oil in which light oil and heavy oil are mixed, and residual oil consisting of heavy oil A program in which a group of steps (commands) relating to the control related to the operation for obtaining is assembled is recorded. This program is stored in a storage medium such as a hard disk, a compact disk, a magnetic optical disk, or a memory card, and installed in the computer therefrom.

The reformer according to the present embodiment, which has outlined the overall process flow as described above, includes (1) control that reduces the kinematic viscosity of the heavy oil while suppressing coke generation in the heavy oil, and (2) It is possible to adjust the control for reducing the kinematic viscosity of the light oil component while suppressing the gas generation accompanying the excessive decomposition of the light oil component using independent operating variables. The detailed configuration will be described below.

FIG. 2 schematically shows the internal structure of the reactor 1 described above and the configuration of the control system provided in the reactor 1. The heavy oil heated and heated through the heavy oil supply line 110 is supplied from the upper side of the reactor 1, while the supercritical water heated and heated through the supercritical water supply line 120 is It is supplied from the bottom side of the reactor 1. And when both fluids contact, the thermal decomposition of heavy oil will advance by the heat brought in by supercritical water, and the whole heavy oil will become light. 2, 101 is a heavy oil supply nozzle, and 102 is a supercritical water supply nozzle.

When these fluids are brought into contact with each other, the light oil contained in the heavy oil in advance is extracted into supercritical water, and the heavy oil remaining without being extracted in the supercritical water is thermally decomposed. The light oil produced by the extraction into supercritical water forms a continuous phase consisting of supercritical water and light oil (hereinafter referred to as second phase), and heavy oil that has not been extracted into supercritical water. The oil component forms a continuous phase (hereinafter referred to as the first phase) and separates into two phases. Since the heavy oil has a higher specific gravity than the mixed fluid of supercritical water and light oil, the first phase is formed on the lower side of the reactor 1 and the second phase is formed on the upper side of the reactor 1. Will be.

In practice, depending on the type of heavy oil and the temperature and pressure conditions of the reactor 1, the heavy oil constituting the first phase contains heavy oil (dry condition standard containing no water). 3) to 100% by weight of supercritical water dissolves. In this respect, it can be said that the first phase is composed of a mixed fluid of heavy oil and supercritical water. Thus, when supercritical water dissolves in the heavy oil component, water molecules enter, for example, between the polycyclic aromatic molecules constituting the heavy oil component that undergoes thermal decomposition, and the polycyclic aromatic molecules are separated from each other. The cage effect which suppresses the production | generation of asphaltenes by condensation and the production | generation of coke by the polycondensation of asphaltenes can be exhibited.

In the reactor 1 according to the present embodiment, supercritical water is supplied from the supercritical water supply nozzle 102 into the first phase on the lower side, and the heavy oil supply nozzle 101 is supplied into the second phase on the upper side. Will be supplied with heavy oil. At this time, extraction of light oil to the supercritical water side and dissolution to the heavy oil side of the supercritical water settles the interface with the supercritical water (dispersed phase) that rises the first phase and the second phase. It proceeds at the interface with the heavy oil (dispersed phase) and the contact interface between the first phase and the second phase.

On the other hand, the present inventors have a very fast rising speed of supercritical water rising in the first phase, a very high sedimentation speed of heavy oil settling in the second phase, and each supercritical water and heavy oil is, for example, It is understood that it passes through the first and second phases in several seconds to several tens of seconds. For this reason, the pyrolysis of heavy oil actually proceeds with pyrolysis of the heavy oil in the first phase, and the resulting light oil is extracted to the second phase, and the second In this phase, further thermal decomposition of the light oil component and the light oil component supplied from the first phase side proceeds.

Then, the mixed fluid constituting the first phase is extracted from the heavy oil content extraction line 140 and cooled by the cooler 141, whereby the thermal decomposition of the heavy oil content is stopped, while the second phase is configured. When the mixed fluid to be extracted is extracted from the light oil content extraction line 130 and cooled by the cooler 132, the thermal decomposition of the light oil content is stopped.

According to the thermal decomposition mechanism described above, the degree of thermal decomposition of the heavy oil component is determined by the mixed fluid of the heavy oil component in the first phase and the supercritical water dissolved in the heavy oil component (hereinafter, It can be controlled by the residence time of the first mixed fluid). For heavy oil, the yield of light oil increases as the pyrolysis progresses, and supercritical water is dissolved in the heavy oil and the decomposition of the heavy oil is moderately advanced under the condition that the cage effect is exhibited. As a result, the viscosity of the heavy oil component decreases, and handling of the synthetic crude oil becomes easier when used as boiler fuel or after being mixed with the light oil component. On the other hand, if pyrolysis proceeds to such an extent that the cage effect described above is offset, coke is generated in the heavy oil.

Therefore, in the reformer according to the present embodiment, the kinematic viscosity at 350 ° C. of the heavy oil serving as the residual oil is set to 3.0 × 10 ⁻⁵ m ² / s or less (30 cSt or less), and coke is generated. A mechanism for adjusting the residence time of the first mixed fluid in the first phase so that the thermal decomposition of the heavy oil component proceeds to such an extent that the oil is suppressed.

The degree of progress of thermal decomposition of light oil is determined by the residence time of the mixed fluid of supercritical water in the second phase and the light oil extracted in the supercritical water (hereinafter referred to as the second mixed fluid). Can be adjusted. The light oil component has a kinematic viscosity that decreases as the thermal decomposition proceeds. For example, even in cold regions, it is possible to transport synthetic crude oil without providing special heating equipment. On the other hand, if the light oil component is excessively decomposed, the amount of gas generated from the light oil component increases, and the yield of synthetic crude oil decreases.

Therefore, in this reformer, the kinematic viscosity at 10 ° C. of light crude oil alone or mixed with heavy oil, for example, at 10 ° C. is set to 5.0 × 10 ⁻³ m ² / s or less (5000 cSt or less), and gas Is provided with a mechanism for adjusting the residence time of the second mixed fluid in the second phase so that the thermal decomposition of the light oil proceeds to such an extent that the generation of is suppressed. Here, in order to set the kinematic viscosity of the synthetic crude oil mixed with the heavy oil component to 5.0 × 10 ⁻³ m ² / s or less (5000 cSt or less), it is mixed with the heavy oil component having a relatively large kinematic viscosity. The second residence time is adjusted so that the kinematic viscosity of the light oil alone becomes a lower value.

For example, the residence time of the first mixed fluid in the first _phase is θ _pitch , the residence time of the second mixed fluid in the second _phase is θ _Lt, and the unit time of heavy oil from the heavy oil supply line 110 is F _{Oin is} the supply amount per unit time, F _{Win is} the supply amount per unit time of supercritical water from the supercritical water supply line 120, and the first mixed fluid is extracted from the heavy oil content extraction line 140 per unit time. When the amount is expressed as FW1 _{+ Pitch} and the extraction amount of the second mixed fluid from the light oil content extraction line 130 per unit time is expressed as _{FW2 + Lt} , the supply and extraction balance of the fluid to the reactor 1 is as follows (2) It is expressed by a formula.
F _Oin + F _Win = F _{W1 + Pitch} + F _{W2 + Lt} (2)

Further, the proportion of the light oil extracted in the second phase varies depending on the properties of the heavy oil, the temperature and pressure conditions of the reactor 1, and the degree of progress of thermal decomposition of the heavy oil. For example, a fraction lighter than VGO (Vacuumed Gas Oil: vacuum gas oil) having a boiling point of 540 ° C. or less is extracted as a light oil component to the supercritical water side, and the fraction corresponding to VR (Vacuumed Residue) having a boiling point higher than 540 ° C. Consider the case of using heavy oil extracted as heavy oil not extracted in supercritical water. Here, in the present embodiment, θ _pitch is controlled within, for example, a fluctuation range of about ± 1 minute of the target value, and the degree of progress of thermal decomposition is controlled within a certain range, thereby obtaining the VGO yield (ie, VR). ) Is assumed to be almost constant.

Also, of the heavy oil to be supplied to the reactor 1, the flow rate withdrawn a flow rate withdrawn as heavy oil F _Pitch, as light oil and F _Lt, supercritical water is also fed to the reactor 1 flow rate F _w1 withdrawn from the first phase by dissolving the heavy oil _of, when a flow rate withdrawn from the second phase by extracting light oil and F _w2, the first fluid, the second The amount of fluid extracted is expressed by the following equations (3) and (4).
F _{W1 + Pitch} = F _W1 + F _Pitch (3)
_{FW2 + Lt} = _FW2 + _FLt (4)

When the volume of the first phase in the reactor 1 is expressed as V ₁ and the volume of the second phase is expressed as V ₂ , the residence time θ _pitch of the first mixed fluid in the first phase, the second phase The residence time θ _Lt of the second mixed fluid is expressed by the following equations (5) and (6).
θ _pitch = V ₁ / F _{W1 + Pitch}
= V ₁ / (F _W1 + F _Pitch ) (5)
_{_{_{θ Lt = V 2 / F W2}}} + Lt
= V ₂ / (F _W2 + F _Lt ) (6)

According to the equation (5), when the volume V ₁ of the first phase is constant, the first phase is increased or decreased by increasing / decreasing the extraction amount F _{W1 + Pitch} of the first mixed fluid from the heavy oil content extraction line 140. The residence time θ _pitch of the first mixed fluid can be adjusted. In the reformer according to the present embodiment, by setting the residence time θ _pitch within the range of “3 minutes ≦ θ _pitch ≦ 95 minutes” from the results of the examples described later, the coke in the heavy oil component is reduced. It has been confirmed that the formation can be suppressed and the kinematic viscosity of the residual oil at 350 ° C. can be adjusted to 3.0 × 10 ⁻⁵ m ² / s or less (30 cSt or less).

In addition, since the solubility of supercritical water in the heavy oil is constant under the conditions of constant temperature and pressure, if the outflow amount F _Pitch of the heavy oil extracted from the first phase is determined, The amount F _{W1 of} supercritical water dissolved in the refined oil is a constant value. If the supply amount F _Win of the supercritical water is increased or decreased in this state, it is possible to increase or decrease the amount of supercritical water that does not dissolve in the heavy oil, that is, the amount F _{W2 of the} supercritical water that forms the second phase. It becomes. Dissolution amount F _W1 of supercritical water for outflow F _Pitch of heavy oil, for example it is sufficient to understand due preliminary experiments.

From the above relationship, when the volume V ₂ of the second phase is constant, increasing / decreasing the supply amount F _Win of supercritical water from the supercritical water supply line 120 increases / decreases F _W2 in the equation (6). The residence time θ _Lt of the second mixed fluid in the second phase can be adjusted. In the reformer according to the present embodiment, by setting the residence time θ _Lt within the range of “1 minute ≦ θ _Lt ≦ 25 minutes” from the results of the examples described later, the coke in the heavy oil component is reduced. It is possible to suppress the production and adjust the kinematic viscosity of light crude oil alone at 10 ° C. or the synthetic crude oil after mixing with heavy oil to 5.0 × 10 ⁻³ m ² / s or less (5000 cSt or less). I have confirmed.

Based on the concept described above, the heavy oil content extraction line 140 is provided with a flow rate controller 74 for adjusting the extraction amount _{FW1 + Pitch} of the first mixed fluid, and the indicated value (b ) Is output to the control unit 7. The control unit 7 calculates the residence time θ _pitch based on the equation (5), and increases or decreases the flow rate setting value (e) of the flow rate controller 74 so that the θ _pitch becomes a preset target value. The opening degree of 142 is adjusted.

The supercritical water supply line 120 is provided with a flow rate controller 72 for adjusting the supply amount F _Win (ie, F _W2 ) of supercritical water, and the indicated value (a) of the flow rate controller 72 is a control unit. 7 is output. The controller 7 calculates the residence time θ _Lt based on the equation (6), and increases or decreases the flow rate setting value (d) of the flow rate controller 74 so that the θ _Lt becomes a preset target value. The opening degree of 122 is adjusted.

Further, the reactor 1 is provided with an interface level meter 75 such as a differential pressure type, an ultrasonic type, an X-ray type, etc., which is an interface detection unit of the present embodiment, and the first phase in the reactor 1 and the first phase. When the level of the interface with the second phase exceeds or falls below a preset range, a signal (c) indicating “high interface level” or “low interface level” is output to the control unit 7. . The controller 7 increases or decreases the flow rate set value (f) of the flow rate controller 71 provided in the heavy oil supply line 110 so that the interface level returns to the height position within the set range, thereby supplying the heavy oil supply amount. By adjusting the supply amount F _Oin , the volume V ₁ of the first phase (that is, the volume V ₂ of the second phase) is kept constant.
Here, the pressure in the reactor 1 is performed by opening and closing the pressure reducing valve 211 by a pressure controller (not shown) provided in the light oil content line 210 of the high pressure separator 2 shown in FIG.

An operation of adjusting the residence times θ _pitch and θ _Lt in the reformer having the above-described configuration will be described. Now, assuming that the residence time θ _pitch of the first mixed fluid in the first phase exceeds the set value, according to the equation (5), θ _pitch is reduced by increasing the extraction amount F _Pitch of the first mixed fluid. Can be restored to the set value. However, if the F _Pitch is increased, the interface level is lowered, so the interface level meter 75 outputs a “interface level low” signal, and operates the flow control valve 112 to supply the heavy oil supply amount from the heavy oil supply line 110. Increase F _Oin .

At this time, “ΔF _Pitch ” of the increment ΔF _Oin of the heavy oil supply amount is distributed to the first phase, while “ΔF _Lt ” is distributed to the second phase side. As a result, θ _Lt becomes smaller than the equation (6). With regard to this change, θ _Lt is raised and returned to the set value by reducing the supercritical water supply amount F _Win (ie, F _W2 ). be able to.

On the other hand, if the residence time θ _Lt of the second mixed fluid in the second phase exceeds the set value, the supply amount F _Win (ie, F _W2 ) of the supercritical fluid is increased by the equation (6). θ _Lt is lowered and returned to the set value. Even if F _Win is increased, for example, the amount of extraction from the second phase F F _{2 + Lt} increases in accordance with the amount of increase in F _Win (F _W2 ) so that the pressure in the reactor 1 becomes constant. The interface with the second phase is kept at a constant level.

According to the reformer according to the present embodiment, these fluids are dissolved in the first phase (heavy oil and the heavy oil by bringing heavy oil and supercritical water into contact in the reactor. And the second phase (the phase consisting of the supercritical water and the light oil extracted in the supercritical water) and the second phase (mixed phase constituting the first phase). Heavy oil and supercritical water so that the residence time of the fluid in the first phase becomes a preset first residence time (for example, set to a predetermined value within a range of 3 to 95 minutes). The amount of extraction of the mixed fluid (first mixed fluid) is adjusted. This makes it possible to control the degree of progress of thermal decomposition of the heavy oil that proceeds in the first phase, for example, to proceed with thermal decomposition in a range where the production of coke from the heavy oil is suppressed, It is possible to operate the reformer under optimum conditions, such as by causing thermal decomposition to proceed so that the kinematic viscosity of the heavy oil falls within a desired range.

In addition, the residence time in the second phase of the mixed fluid constituting the second phase becomes a preset second residence time (for example, set to a predetermined value in the range of 1 to 25 minutes). In this way, the amount of the second mixed fluid (mixed fluid of light oil and supercritical water) is adjusted. As a result, it is possible to control the degree of progress of thermal decomposition of the light oil that proceeds in the second phase. For example, thermal decomposition proceeds in a range in which excessive decomposition of the light oil is suppressed and generation of gas is suppressed. Or thermal decomposition can be advanced so that the kinematic viscosity of the synthetic crude oil obtained from the light oil is in a desired range.

Here, in the example shown in FIG. 2, an interface level meter 75 is provided to measure the interface between the first and second phases so that V ₁ and V ₂ are constant. The level meter 75 may not be provided. For example, the yields of lighter fractions and VR fractions than VGO according to the oil type, temperature, pressure conditions, etc. of heavy oil are obtained by experiments in advance, and F _Oin , F _Win , F _Pitch , F The interface level in the reactor 1 is estimated from the values of _Lt , F _w1 , and F _w2 , and V ₁ and V ₂ are kept constant based on the estimated interface level, and each of the values based on the equations (5) and (6) The residence times θ _pitch and θ _Lt may be adjusted.

In the example shown in FIG. 2, an example in which V ₁ and V ₂ are kept constant and the residence times θ _pitch and θ _Lt are adjusted is shown. However, the residence times θ _pitch and θ are changed while V ₁ and V ₂ are changed. It is also possible to adjust _Lt. For example, when the residence time θ _pitch of the first mixed fluid in the first phase exceeds the set value, the extraction amount F _Pitch of the first mixed fluid is increased from the equation (5) and the volume V _{1 of} the first phase is increased. _Is reduced to reduce θ _pitch and return to the set value. As a result, the volume V ₂ of the second phase increases, which affects the residence time θ _Lt of the second mixed fluid, but supplies supercritical water so as to offset the increase in volume V _2. By increasing the amount F _Win (ie, F _W2 ), θ _Lt can be returned to the set value.

Further, in each of the above-described examples, the residence time θ _pitch of the first mixed fluid in the first _phase is adjusted by the extraction amount F _Pitch of the first mixed fluid, and the residence time of the second mixed fluid in the second phase is adjusted. Although the example in which θ _Lt is adjusted by the supply amount F _Win of supercritical water has been shown, these residence times are set to other operating variables shown in the equations (5) and (6), for example, the supply amount F of heavy oil _It does not deny adjusting with _Oin or the extraction amount _{FW2 + Ltout} of the second mixed fluid.

In the process flow diagram shown in FIG. 1, an example is shown in which water is separated from heavy oil by the flash drum 4 and is sent to the residual oil tank 64 as residual oil, but the flash drum 4 is not necessarily provided. Good. For example, when the residual oil is used as boiler fuel in a plant near the reformer, the flash drum 4 can be omitted. For example, it is possible to make the residual oil easier to handle by further reducing the viscosity of the residual oil by using the boiler fuel while the water is dispersed in the residual oil without performing the pressure reduction operation of the first fluid. At the same time, vaporization when used as boiler fuel is promoted by the effect of water dispersed in the residual oil, and the combustibility in the boiler can also be improved.

In the above-described embodiment, the heavy oil to be reformed by the reformer has been described for the case of processing ultra heavy crude oil such as oil sand bitumen or orinocotal, but can be processed by the reformer. Heavy oil is not limited to crude oil. For example, the case of performing reforming treatment of atmospheric distillation residue oil or vacuum distillation residue oil is also included in the technical scope of the present invention.

(Experiment 1)
As a model device of the reformer shown in FIG. 1, the test device shown in FIG. 3 was manufactured and a heavy oil reforming experiment was conducted.

A. Experimental conditions In FIG. 3, reference numeral 200 denotes a gas-liquid separation tank for separating the second mixed fluid extracted from the upper side of the reactor 1 into a mixed fluid of gas and light oil / water, and 143 denotes the reactor 1. It is a ball valve for extracting heavy oil (second mixed fluid) from the lower side. In this apparatus, the residence time θ _pitch of the first mixed fluid was controlled by the amount of extracted residual oil F _Pitch , and the residence time θ _Lt of the second mixed fluid was controlled by the supercritical water supply amount F _Win . As heavy oil, Canadian oil sand bitumen having the properties shown in Table 1 was used.
(Table 1)

Example 1
The experiment was performed under the following conditions.
Reaction temperature in reactor 1: 430 ° C
Reaction pressure in reactor 1: 25 MPa
Water / oil weight ratio: 1.0
Residence time θ _Pitch of the first fluid mixture: 82 minutes Residence time θ _Lt of the second fluid mixture: 2.3 minutes (Example 2)
Reaction temperature in reactor 1: 450 ° C
The experiment was conducted under the same conditions as in Example 1 _{except that} the residence time θ _Pitch of the first mixed fluid was 4.9 minutes and the residence time θ _Lt of the second fluid mixture was 11 minutes.
(Example 3)
Water / oil weight ratio: 0.5
The experiment was performed under the same conditions as in Example 1 _{except that} the residence time θ _Pitch of the first mixed fluid was 38 minutes and the residence time θ _Lt of the second fluid mixture was 22 minutes.
Example 4
The experiment was performed under the same conditions as in Example 1 _{except that} the residence time θ _Pitch of the first mixed fluid was 67 minutes and the residence time θ _Lt of the second fluid mixture was 1.8 minutes.
(Comparative Example 1)
The experiment was performed under the same conditions as in Example 1 _{except that} the residence time θ _Pitch of the first mixed fluid was 105 minutes and the residence time θ _Lt of the second fluid mixture was 1.1 minutes.
The experimental conditions of each example and comparative example are summarized in (Table 2).
(Table 2)

B. Experimental results (Table 3) show the yields of gas, synthetic crude oil (light oil), and residual oil (heavy oil) in each Example and Comparative Example. Table 4 shows the properties of the synthetic crude oil, and Table 5 shows the properties of the residual oil.
(Table 3)

(Table 4)

(Table 5)

Moreover, the yield of each fraction obtained as a result of treating the same oil sand bitumen as used in (Example 1) by a bisbreaker test and a delayed coker test was compared with the results of (Examples 1 and 2). The results are shown in (Table 6). In addition, (Examples 1 and 2) are obtained by synthesizing the yields of synthetic crude oil and residue wafers and converting them into a VGO fraction having a boiling point of 540 ° C. or lower and a VR fraction having a boiling point higher than 540 ° C. , (Table 3) may not match the yield.
(Table 6)

According to the results of (Experiment 1), Example 2 (θ _Pitch : 4.9 minutes) → Example 3 (same: 32 minutes) → Example 1 (same: 95 minutes) and first residence time θ _Pitch As the oil length is increased, the yield of residual oil decreases while the yield of synthetic crude oil increases. Further, in Comparative Example 1 where the θ _pitch was 105 minutes, generation of coke (coking) was observed. Here, in Example 4 (θ _Pitch : 67 minutes) in which the first residence time θ _Pitch is longer than that in Example 3, the residual oil yield is higher than that in Example 3, while the synthetic crude oil yield is The reason for this is not clear, but I think it is due to fluctuation error.

Further, regarding the gas yield, Example 4 (same as 1.8 minutes) → Example 2 (same as 11: except for Example 1 (θ _Lt : 2.3 minutes) with the highest gas yield). Min) → Example 3 (25 minutes in the same order), the gas yield tends to increase as the second residence time θ _Lt is increased. Although the reason why the yield of gas was maximized at 4% by weight in Example 1 in which the second residence time θ _Lt is the second shortest is not clear, it is considered that this is also the influence of the fluctuation error.

According to the measurement results of the kinematic viscosity of the synthetic crude oil shown in (Table 4), in each example, the maximum was 2.8 × 10 ⁻⁵ m ² / s (28 cSt) (standard value 5.0) at 10 ° C. Synthetic crude oil having a kinematic viscosity with no practical problems was obtained, × 10 ⁻³ m ² / s (5000 cSt)). Here, Example 4 ( _θLt : 1.8 minutes) → Example 1 (same: 2.3 minutes) → Example 2 (same: 11 minutes) → Example 3 (same: 25 minutes) and second There is a tendency that the kinematic viscosity of the synthetic crude oil decreases as the residence time θ _Lt is increased. This is considered to be a result of the progress of decomposition of the light oil as the second residence time is increased. This can also be confirmed from the fact that the density of the synthetic crude oil decreases as the second residence time increases.

Next, according to the measurement results of the kinematic viscosity of the residual oil shown in (Table 5), in each example, the maximum is 1.8 × 10 ⁻⁵ m ² / s (18 cSt) at 310 ° C., which is a practical problem. A residual oil with no kinematic viscosity was obtained. When the residual oil is heated to 350 ° C., the kinematic viscosity is further reduced. Then, the first residence is performed in the order of Example 2 (θ _Pitch : 4.9 minutes), Example 3 (same: 32 minutes) → Example 4 (same: 67 minutes) → Example 1 (same: 95 minutes). As the time θ _Pitch is lengthened, the kinematic viscosity of the residual oil tends to increase. This is considered to be the result of the polymerization of the heavy oil proceeding against the cage effect of supercritical water dissolved in the heavy oil as the first residence time is increased. This can also be confirmed from the fact that the density of the residual oil increases as the first residence time increases.

Summarizing the results of Examples 1 to 4 and Comparative Example 1, when oil sand bitumen is used as the raw material heavy oil, the first residence time θ _Pitch should be in the range of about 3 minutes to 95 minutes. For example, the kinematic viscosity at 310 ° C. becomes 1.8 × 10 ⁻⁵ m ² / s (18 cSt) or less while suppressing the generation of coke, and it can be seen that a residual oil that is easy to handle can be obtained. The second residence time θ _Lt is about 1 to 25 minutes, and the gas generation is suppressed to about 4% by mass or less, and the kinematic viscosity at 10 ° C. is 2.8 × 10 ⁻⁵ m. ^It can be said that synthetic crude oil of ² / s (28 cSt) or less can be obtained.

Further, according to the results shown in (Table 6), while the generation of coke is suppressed, the yield of the VGO fraction is higher than that of the bisbreaker, and in Example 1, VGO comparable to the delayed coker is obtained. A fraction yield is obtained. From this, the pyrolysis of heavy oil using supercritical water can control the VGO fraction with high yield while suppressing the generation of coke and gas by appropriately controlling the first and second residence times. It can be seen that this is a pyrolysis process capable of obtaining (light oil content).

(Experiment 2)
A viewing window for internal observation is provided in the reactor 1 of the same experimental apparatus as in (Experiment 1), and it is confirmed that the fluid in the container is separated into the first phase and the second phase, and an interface is formed. did. FIG. 4A shows the result of photographing the inside of the reactor 1 from the viewing window, and FIG. 4B shows a schematic diagram thereof. According to the result of FIG. 4A, the lower side of the reactor 1 has a first phase composed of a heavy oil component and supercritical water dissolved in the heavy oil component, supercritical water, and supercritical water. A second phase consisting of light oil extracted in critical water was confirmed.

1 Reactor 110 Heavy Oil Supply Line 112 Flow Control Valve 120 Supercritical Water Supply Line 122 Flow Control Valve 130 Light Oil Extraction Line 131 Pressure Control Valve 140 Heavy Oil Extraction Line 142 Flow Control Valve 2 High Pressure Separator 3 Low Pressure Separator 4 Flash drum 5 Recycled water tank 7

Control units

71, 72, 74
Flow controller 73 Pressure controller 75 Interface level meter

Claims

Maintained at a temperature and pressure above the critical point of water, obtained by thermally decomposing this heavy oil while bringing the heavy oil and supercritical water into contact with each other and advancing thermal decomposition of the heavy oil Separation into a first phase comprising a heavy oil and supercritical water dissolved in the heavy oil, and a second phase comprising the supercritical water and a light oil extracted into the supercritical water And a reactor to
A heavy oil supply section for supplying heavy oil to the reactor;
A supercritical water supply for supplying supercritical water to the reactor;
A first extraction portion for extracting a mixed fluid of heavy oil and supercritical water from the first phase;
A second extraction portion for extracting a mixed fluid of supercritical water and light oil from the second phase;
An interface detector for detecting a height position of an interface between the first phase and the second phase in the reactor;
The volume of the first phase is obtained based on the height position of the interface detected by the interface detector, and the heavy oil component and the supercritical dissolved in the heavy oil component are obtained based on the volume of the first phase. A control unit that controls the amount of the mixed fluid extracted from the heavy oil and the supercritical water so that the residence time of the mixed fluid of water becomes a preset first residence time. Heavy oil reforming equipment.
Maintained at a temperature and pressure above the critical point of water, obtained by thermally decomposing this heavy oil while bringing the heavy oil and supercritical water into contact with each other and advancing thermal decomposition of the heavy oil Separation into a first phase comprising a heavy oil and supercritical water dissolved in the heavy oil, and a second phase comprising the supercritical water and a light oil extracted into the supercritical water And a reactor to
A heavy oil supply section for supplying heavy oil to the reactor;
A supercritical water supply for supplying supercritical water to the reactor;
A first extraction portion for extracting a mixed fluid of heavy oil and supercritical water from the first phase;
A second extraction portion for extracting a mixed fluid of supercritical water and light oil from the second phase;
Based on the supply amount of the heavy oil, the heavy oil component and the heavy oil component so that the residence time of the mixed fluid of supercritical water dissolved in the heavy oil component becomes a preset first residence time. A heavy oil reforming apparatus, comprising: a control unit that controls the amount of fluid extracted from the supercritical water.
In order to suppress the formation of coke in the heavy oil component, the control unit extracts the mixed fluid of the heavy oil component and the supercritical water so that the first residence time is 3 minutes or more and 95 minutes or less. The heavy oil reforming apparatus according to claim 1 or 2, wherein the reforming apparatus is controlled.
The first residence time is a residence time in which thermal decomposition of the heavy oil proceeds within a range where the amount of coke produced is 0 wt% or more and 20 wt% or less of the heavy oil. The heavy oil reforming apparatus according to claim 1 or 2.
The first residence time is a residence time during which thermal decomposition of the heavy oil proceeds until a kinematic viscosity at 350 ° C. of 3.0 × 10 −5 m 2 / s or less. The heavy oil reforming apparatus according to claim 1 or 2, characterized in that:
The control unit obtains the volume of the second phase based on the height position of the interface detected by the interface detection unit, and in the supercritical water and the supercritical water based on the volume of the second phase. The reforming of heavy oil according to claim 1, wherein the supply amount of supercritical water is controlled so that the residence time of the extracted light oil mixed fluid becomes a preset second residence time. apparatus.
Based on the supply amount of the heavy oil, the control unit is configured so that the residence time of the mixed fluid of the supercritical water and the light oil extracted into the supercritical water becomes a preset second residence time. The heavy oil reforming apparatus according to claim 2, wherein the supply amount of critical water is controlled.
The control unit controls the supply amount of supercritical water so that the second residence time is 1 minute or more and 25 minutes or less in order to suppress excessive decomposition of the light oil component. Or the heavy oil reforming apparatus according to 7;
The second residence time is a residence time during which thermal decomposition of the heavy oil proceeds in a range where the amount of gas generated by overdecomposition is 0% by weight or more and 5% by weight or less of the heavy oil. The heavy reforming apparatus according to claim 6 or 7, wherein:
The second residence time is a residence time during which thermal decomposition of the heavy oil proceeds until the kinematic viscosity of the light oil at 10 ° C. is 5.0 × 10 −3 m 2 / s or less. The heavy oil reforming apparatus according to claim 6 or 7.
The heavy oil modification according to claim 1 or 2, wherein the heavy oil is selected from the group of heavy oils consisting of oil sand bitumen, orinocotal, atmospheric distillation residue oil, and vacuum distillation residue oil. Quality equipment.
Supplying heavy oil to the reactor;
Supplying supercritical water to the reactor;
Maintaining the reactor at a temperature and pressure above the critical point of water, bringing the heavy oil into contact with the supercritical water and proceeding with the thermal decomposition of the heavy oil, A first phase comprising the heavy oil obtained in this manner and supercritical water dissolved in the heavy oil, a second phase comprising the supercritical water and the light oil extracted into the supercritical water. Separating into phases of
Extracting a mixed fluid of heavy oil and supercritical water from the first phase;
Extracting a fluid mixture of supercritical water and light oil from the second phase;
Detecting the height position of the interface between the first phase and the second phase in the reactor;
The volume of the first phase is obtained based on the height position of the interface detected in this step, and the heavy oil and supercritical water dissolved in the heavy oil are based on the volume of the first phase. A step of controlling the amount of extraction of the mixed fluid of the heavy oil and the supercritical water so that the residence time of the mixed fluid becomes a preset first residence time. Modification method.
Supplying heavy oil to the reactor;
Supplying supercritical water to the reactor;
Maintaining the reactor at a temperature and pressure above the critical point of water, bringing the heavy oil into contact with the supercritical water and proceeding with the thermal decomposition of the heavy oil, A first phase comprising the heavy oil obtained in this manner and supercritical water dissolved in the heavy oil, a second phase comprising the supercritical water and the light oil extracted into the supercritical water. Separating into phases of
Extracting a mixed fluid of heavy oil and supercritical water from the first phase;
Extracting a fluid mixture of supercritical water and light oil from the second phase;
Based on the supply amount of the heavy oil, the heavy oil component and the heavy oil component so that the residence time of the mixed fluid of supercritical water dissolved in the heavy oil component becomes a preset first residence time. And a step of controlling a drawing amount of the fluid mixture with supercritical water.
The heavy oil reforming according to claim 12 or 13, wherein the first residence time is adjusted within a range of 3 minutes to 95 minutes in order to suppress coke formation in the heavy oil component. Quality method.
The first residence time is a residence time in which thermal decomposition of the heavy oil proceeds within a range where the amount of coke produced is 0 wt% or more and 20 wt% or less of the heavy oil. The heavy oil reforming method according to claim 12 or 13.
The first residence time is a residence time during which thermal decomposition of the heavy oil proceeds until a kinematic viscosity at 350 ° C. of 3.0 × 10 −5 m 2 / s or less. The heavy oil reforming method according to claim 12 or 13, characterized in that:
The volume of the second phase is determined based on the height position of the interface detected in the step of detecting the height position of the interface between the first phase and the second phase. A step of controlling the supply amount of supercritical water so that the residence time of the supercritical water in the phase and the mixed fluid of the light oil extracted in the supercritical water becomes a second residence time set in advance. The heavy oil reforming method according to claim 12.
Based on the supply amount of the heavy oil, the supply amount of the supercritical water so that the residence time of the mixed fluid of the supercritical water and the light oil extracted into the supercritical water becomes a preset second residence time. The heavy oil reforming method according to claim 13, comprising a step of controlling the oil.
The heavy oil reforming method according to claim 17 or 18, wherein the second residence time is adjusted within a range of 1 minute to 25 minutes in order to suppress overdecomposition of the light oil. .
The second residence time is a residence time during which thermal decomposition of the heavy oil proceeds in a range where the amount of gas generated by overdecomposition is 0% by weight or more and 5% by weight or less of the heavy oil. The heavy oil reforming method according to claim 17 or 18, characterized in that:
The second residence time is a residence time during which thermal decomposition of the heavy oil proceeds until the kinematic viscosity of the light oil at 10 ° C. is 5.0 × 10 −3 m 2 / s or less. The heavy oil reforming method according to claim 17 or 18.
14. The method according to claim 12, further comprising a step of lowering the temperature and reducing the pressure of the mixed fluid of the heavy oil extracted from the first phase and the supercritical water and separating the fluid into the heavy oil and water. Of reforming heavy oil.
13. The method includes a step of lowering a temperature of a mixed fluid of heavy oil extracted from the first phase and supercritical water to obtain a fuel oil containing moisture in the heavy oil. Or the heavy oil reforming method according to 13;
23. The mixed fluid of heavy oil and supercritical water extracted from the first phase contains water in a range of 3 wt% to 100 wt% of the heavy oil. The heavy oil reforming method described in 1.
The mixed fluid of the heavy oil extracted from the first phase and the supercritical water contains moisture in the range of 3 wt% to 100 wt% of the heavy oil. The heavy oil reforming method described in 1.
The heavy fluid according to claim 12 or 13, further comprising a step of lowering the temperature and reducing the pressure of the mixed fluid of the supercritical water extracted from the second phase and the light oil to separate the light oil and the water. Quality oil reforming method.
The heavy oil according to claim 22, further comprising a step of recovering water separated from the heavy oil or light oil to be reused as supercritical water supplied to the reactor. Modification method.
27. The heavy oil according to claim 26, further comprising a step of recovering water separated from the heavy oil or light oil for reuse as supercritical water supplied to the reactor. Modification method.
Lowering the temperature of the mixed fluid of the heavy oil extracted from the first phase and the supercritical water, lowering the pressure, and separating the fluid into the heavy oil and water;
Lowering the temperature of the mixed fluid of supercritical water and light oil extracted from the second phase and lowering the pressure to separate the oil into light oil and water;
The method for reforming heavy oil according to claim 12 or 13, comprising a step of mixing the heavy oil and the light oil after being separated from water.
The heavy oil modification according to claim 12 or 13, wherein the heavy oil is selected from the group of heavy oils consisting of oil sand bitumen, orinocotal, atmospheric distillation residue oil, and vacuum distillation residue oil. Quality method.