JP2006104311A - Method for reforming unutilized heavy oil and apparatus therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stably reform an unutilized heavy oil without causing choking by coking. <P>SOLUTION: Supercritical water or subcritical water is fed from the outside of a reaction vessel 11 through a feed part 21a into a reaction pipe 21 installed in the interior of the reaction vessel 11 and the supercritical water or subcritical water is discharged through a discharge part 21b to the outside of the reaction vessel 11. The unutilized heavy oil is fed to a mixer 36 provided in a feed pipe 32 for feeding the supercritical water or subcritical water to the reaction pipe 21 to mix the supercritical water or subcritical water fed to the reaction pipe 21 with the unutilized heavy oil. Thereby, the unutilized heavy oil mixed with the supercritical water or subcritical water is reacted with the supercritical water or subcritical water in the reaction pipe 21 and converted into a reformed oil. The resultant reformed oil is separated and recovered from the supercritical water or subcritical water discharged through the discharge part 21b to the outside of the reaction vessel 11. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for reforming unused heavy oil and an apparatus therefor, in which unused heavy oil is converted into reformed oil by reacting with supercritical water or subcritical water.

  Conventionally, crude oil, which is a fossil fuel, is refined by an atmospheric distillation column, a vacuum distillation column, etc., and superheavy oil that accumulates in the lowest part of the vacuum distillation column is considered to have low utility value other than asphalt. It was. In recent years, however, it has been proposed that such unused heavy oil be converted to reformed oil by reacting with supercritical water or subcritical water, and that the reformed oil be used as fuel for power generation of gas turbines, etc. (For example, refer to Patent Document 1). Here, subcritical water means a state of water at a temperature of 200 to 374 ° C. and a pressure of 15.68 to 21.07 MPa. The supercritical state of water means a state of water at a temperature of 374 to 900 ° C. and a pressure of 21.07 to 49.00 MPa. Therefore, in an apparatus for reforming unused heavy oil, a reaction vessel that stores such high-temperature and high-pressure supercritical water or subcritical water is used.

As shown in detail in FIG. 3, the conventional reaction vessel 1 has a container body 2 that is open at the top and configured to store supercritical water or subcritical water, and an upper opening 2 a of the container body 1 is opened. And a lid 3 that closes as possible. A lower concave groove 2d for packing is formed continuously in the circumferential direction in the container body 2, and an upper concave groove 3b is formed continuously in the circumferential direction at a portion corresponding to the lower concave groove 2d of the lid 3. The The packing 4 is attached to the upper and lower concave grooves 3b and 2d, and the upper opening 2a of the container body 2 is closed by the lid 3. On the other hand, the lid 3 is provided with a high-pressure water supply pipe 6, a heavy oil supply pipe 7, and a reformed oil discharge pipe 8 penetrating through the lid 3. And a heater 9 is provided for converting the high-pressure water supplied to the reaction vessel 1 through the high-pressure water supply pipe 6 into supercritical water or subcritical water. In the reaction vessel 1, unused heavy oil is supplied to the reaction vessel 1 via the heavy oil supply pipe 8, and the unused heavy oil is stored in the reaction vessel 1 with supercritical water or After being converted to reformed oil by reacting with subcritical water, the reformed oil is discharged from the reaction vessel 1 via the reformed oil discharge pipe 8.
JP 2003-286491 A ("Conventional Technology" column)

However, in the above-described conventional reformer, the heavy oil supply pipe 7 and the reformed oil discharge pipe 8 are provided by penetrating the lid 3 of the reaction vessel 1 around which the heater 9 is provided. Therefore, the heavy oil supply pipe 7 and the reformed oil discharge pipe 8 are also heated together with the reaction vessel 1 by the heat generated from the heater 9 and the high-temperature and high-pressure supercritical water. Here, since the unused heavy oil supplied from the heavy oil supply pipe 7 to the reaction vessel 1 is generally coked at 430 ° C. or higher, when the temperature of the reaction vessel 1 rises, the heavy oil near the inner wall thereof Has a problem of causing caulking and adhering to its inner wall. Further, when the temperature of the supply pipe 7 provided through the lid body 3 rises, there is a problem that heavy oil causes coking inside the supply pipe 7 and closes the supply pipe 7. In particular, this phenomenon occurs for about 1 to 2 hours at 430 ° C after the oil has passed. However, since the caulking speed increases at high temperatures, it may be possible to cause clogging in a shorter time. For this reason, it is difficult for a conventional reformer using a reaction vessel to stably reform unused heavy oil for a relatively long time.
An object of the present invention is to provide a method for reforming unused heavy oil and an apparatus therefor that can stably reform unused heavy oil without causing blockage due to coking.

  In the invention according to claim 1, as shown in FIG. 1, supercritical water or subcritical water is supplied to the reaction tube 21 provided inside the reaction vessel 11 from the outside of the reaction vessel 11 through the supply unit 21 a. In addition, supercritical water or subcritical water is discharged to the outside of the reaction vessel 11 through the discharge unit 21 b, supercritical water or subcritical water supplied to the reaction tube 21 by supplying unused heavy oil to the reaction tube 21. Water and unused heavy oil are mixed, and unused heavy oil mixed with supercritical water or subcritical water is reacted with supercritical water or subcritical water in a reaction tube 21 to be converted into reformed oil. This is a method for reforming unused heavy oil in which reformed oil is separated and recovered from supercritical water or subcritical water discharged to the outside of the reaction vessel 11 through the discharge unit 21b.

  The invention according to claim 3 is a reaction vessel 11 and a reaction that is provided spirally or meandering inside the reaction vessel 11, and the supply portion 21 a and the discharge portion 21 b at both ends penetrate the vessel wall 13 of the reaction vessel 11. Supercritical water or subcritical water is supplied to the reaction tube 21 from the tube 21 and from the outside of the reaction vessel 11 through the supply unit 21a, and supercritical water or subcritical water is supplied to the outside of the reaction vessel 11 through the discharge unit 21b. And the supercritical water or the sublimation water supplied to the reaction tube 21 by supplying unused heavy oil to the mixer 36 provided in the supply pipe 32 constituting the critical water supply unit 31. It is modified from heavy oil supply means 37 for mixing critical water and unused heavy oil, and supercritical water or subcritical water connected to the discharge part 21b and discharged to the outside of the reaction vessel 11 through the discharge part 21b. Oil moisture to separate and recover quality oil The reaction tube 21 is converted to reformed oil by reacting with the supercritical water or subcritical water the unused heavy oil flowing in the mixture after mixing with supercritical water or subcritical water. An unused heavy oil reforming apparatus characterized by being guided to the outside of the post-reaction vessel 11.

  In the method for reforming unused heavy oil described in claim 1 and the reformer for unused heavy oil described in claim 3, the conversion of unused heavy oil is performed by supercritical water or subcritical water. By causing the water to flow inside the reaction tube 21 flowing at a relatively high speed, coking of unused heavy oil can be prevented, and the blocking of the reaction tube 21 due to coking of unused heavy oil is effectively performed. It can be avoided.

The invention according to claim 2 is the invention according to claim 1 and is supplied to the reaction tube 21 based on the temperature change state of unused heavy oil mixed with supercritical water or subcritical water in the reaction tube 21. The amount of supercritical water or subcritical water to be controlled is controlled.
The invention according to claim 4 is the invention according to claim 3, wherein the temperature sensors 61 and 62 for measuring the temperature of the unused heavy oil mixed with the supercritical water or subcritical water flowing through the reaction tube 21; The reformer further includes a controller 63 that controls the critical water supply means 31 based on detection outputs of the temperature sensors 61 and 62.
In general, unused heavy oil starts coking at 430 ° C. or more, and the portion at 430 ° C. is about 1 to 2 hours. In the method for reforming unused heavy oil described in claim 2 and the reformer for unused heavy oil described in claim 4, supercritical water or subcritical water in the reaction tube 21 is 430. If the amount of supercritical water or subcritical water supplied to the reaction tube 21 when the temperature exceeds ° C. is increased, the time for the supercritical water or subcritical water to pass through the reaction tube 21 can be shortened. . As a result, it is possible to avoid a situation in which heavy oil components cause coking in the reaction tube 21, and it is possible to continuously reform unused heavy oil continuously supplied to the reaction tube 21. .

  In the present invention, the conversion of the unused heavy oil is performed inside the reaction tube in which supercritical water or subcritical water flows at a relatively high speed. It is possible to effectively prevent such a situation that the reaction tube is blocked. Then, by controlling the amount of supercritical water or subcritical water supplied to the reaction tube in accordance with the degree of increase in the temperature of the supercritical water or subcritical water in the reaction tube, the supercritical water is controlled. Alternatively, the time for the subcritical water to pass through the reaction tube can be shortened. As a result, it is possible to avoid the situation where heavy oil coking inside the reaction tube, and to stably and continuously reform unused heavy oil continuously supplied to the reaction tube.

The best mode of the present invention will be described below.
As shown in FIG. 1, the unused heavy oil reforming apparatus 10 of the present invention includes a reaction vessel 11 for storing supercritical water or subcritical water. Examples of unused heavy oils include super heavy oils such as oil sand oil and oil shale oil, and unusable super heavy oils generated from petroleum refining processes. As shown in detail in FIG. 2, the reaction vessel 11 is configured such that the upper portion of the reaction vessel 11 is open so that supercritical water or subcritical water can be stored, and the upper opening 12 a of the vessel body 12 can be opened. And a lid 13 for closing. The container body 12 and the lid body 13 are each made by cutting a bulk body made of a metal such as stainless steel by cutting. A flange portion 12b is formed on the periphery of the upper portion of the container body 12 so as to protrude outward. A plurality of female screw holes 12c are formed in the flange portion 12b in the vertical direction, and a lower concave groove 12d for packing is formed on the upper surface thereof. Are continuously formed in the circumferential direction.

On the other hand, the lid body 13 is formed in a disk shape having an outer diameter corresponding to the outer diameter of the flange portion 12b, an attachment hole 13a is formed at a position corresponding to the female screw hole 12c, and a portion corresponding to the lower concave groove 12d. The upper concave groove 13b is continuously formed in the circumferential direction. Packing 14 is mounted in the upper and lower concave grooves 13b, 12d, and the lid 13 is fitted into the female screw hole 12c in this state, so that the lid 13 is placed in the upper opening 12a of the container body 12. Configured to close.
The lid body 13 is provided with a high-pressure water supply pipe 17 and a high-pressure water discharge pipe 18 through the lid body 13. A reaction tube 21 is provided inside the reaction vessel 11 so as to be separated from the vessel wall of the reaction vessel 11. The reaction tube 21 in this embodiment has a spiral shape, and a supply portion 21a and a discharge portion 21b are formed at both ends thereof. The supply unit 21a and the discharge unit 21b are respectively provided through the lid 13 which is a container wall of the reaction vessel 11, and the reaction tube 21 itself is supported by the supply unit 21a and the discharge unit 21b to be inside the reaction vessel 11. Are spaced apart from the container wall.

  Returning to FIG. 1, the ends of the high-pressure water supply pipe 17 and the high-pressure water discharge pipe 18 outside the reaction vessel 11 are respectively connected to the water storage tank 22, and the high-pressure water supply pipe between the reaction vessel 11 and the water storage tank 22. 17, a high-pressure water supply pump 23 that supplies water stored in the water storage tank 22 to the reaction vessel 11 and a temperature-control heater 24 that controls the temperature of the high-pressure water flowing through the high-pressure water supply pipe 17 are provided in this order. It is done. On the other hand, an electromagnetic valve 26 is provided in the high-pressure water discharge pipe 18 between the reaction vessel 11 and the water storage tank 22, and the high-pressure water supply pump 23 is driven in a state where the high-pressure water discharge pipe 18 is shut off by the electromagnetic valve 26. The reaction vessel 11 is configured to be filled with high-pressure water by supplying high-pressure water from the water storage tank 22 via the high-pressure water supply pipe 17. A heater 27 is provided outside the reaction vessel 11 to heat the high-pressure water supplied into the reaction vessel 11 into supercritical water or subcritical water.

  In addition, a critical water supply unit 31 is provided outside the reaction vessel 11 to supply supercritical water or subcritical water to the reaction tube 21 from the outside of the reaction vessel 11 via the supply unit 21a. The critical water supply means 31 in this embodiment includes the water storage tank 22 described above, a supply pipe 32 connecting the water storage tank 22 and the supply unit 21a, and water stored in the water storage tank 22 provided in the supply pipe 32. And a heater 34 for further heating the supercritical water or the subcritical water that is pressurized and circulates through the supply pipe 32. In the critical water supply means 31, when the critical water supply pump 33 is driven, high-temperature and high-pressure supercritical water or subcritical water supplied from the water storage tank 22 and heated by the heater 34 is supplied from the outside of the reaction vessel 11. While being supplied to the reaction tube 21 through 21a, the supercritical water or subcritical water is discharged to the outside of the reaction vessel 11 through the discharge part 21b.

  In addition, a mixer 36 is provided in the supply pipe 32 constituting the supply means 31, and supercritical oil supplied to the reaction pipe 21 by supplying unused heavy oil to the mixer 36 outside the reaction vessel 11. A heavy oil supply means 37 for mixing unused heavy oil with water or subcritical water is provided. The heavy oil supply means 37 in this embodiment includes a heavy oil storage tank 38 provided outside the reaction vessel 11 for storing unused heavy oil, and a heavy oil storage tank 38 connected to the mixer 36. A heavy oil supply pipe 39, a heavy oil supply pump 41 provided in the heavy oil supply pipe 39 for supplying unused heavy oil from the heavy oil storage tank 38 to the mixer 36, and the heavy oil supply pipe 39 And a heat retaining heater 42 that retains the heavy oil that circulates. In this heavy oil supply means 37, a mixer in which unused heavy oil supplied from the heavy oil storage tank 38 and kept warm by the heat retaining heater 42 when the heavy oil supply pump 41 is driven is provided in the supply pipe 32. The mixer 36 is configured to mix the supercritical water or subcritical water supplied to the reaction tube 21 with the unused heavy oil.

  On the other hand, the reaction tube 21 reacts unused heavy oil that is mixed with supercritical water or subcritical water and flows through the reaction with the supercritical water or subcritical water to convert it into reformed oil, and then the reaction vessel 11. From the supercritical water or subcritical water that is connected to the discharge portion 21b of the reaction tube 21 and is discharged to the outside of the reaction vessel 11 through the discharge portion 21b. Oil / water separation means 46 for separating and recovering the reformed oil mixed with the supercritical water or subcritical water is provided. The oil / water separation means 46 in this embodiment is connected to the flash separation tank 47 provided outside the reaction vessel 11 for separating the hydrocarbon-based heavy reforming oil, and the flash separation tank 47 and the discharge part 21b. A gas which is connected to the critical water discharge pipe 48, the flash separation tank 47 and the cooler 52a and from which the heavy reformed oil is separated in the flash separation tank 47 is separated into gas, light reformed oil and water. An oil / water separation tank 52 and a pressure reducing valve 51 provided in the critical water discharge pipe 48 are provided. Note that a heat exchanger 49 is separately provided in the critical water discharge pipe 48 upstream of the pressure reducing valve 51 from the viewpoint of effective use of heat.

  Furthermore, the supply unit 21a of the reaction tube 21 is provided with a first temperature sensor 61 that measures the temperature of the unused heavy oil mixed with the supercritical water or subcritical water in the supply unit 21a. The discharge part 21b is provided with a second temperature sensor 62 for measuring the temperature of the reformed oil mixed with the supercritical water or subcritical water in the discharge part 21b. The reaction vessel 11 is further provided with a third temperature sensor 64 that measures the temperature of supercritical water or subcritical water in the reaction vessel 11. The detection outputs of the first and second temperature sensors 61 and 62 and the third temperature sensor 64 are connected to the input terminal of the controller 63, and the control outputs of the controller 63 are the high-pressure water supply pump 23, the critical water supply pump 33, It is connected to the heavy oil supply pump 41, the electromagnetic valve 26 and the heater 27. The controller 63 is configured to control the critical water supply pump 33 and the heavy oil supply pump 41 based on the detection outputs of the first temperature sensor 61 and the second temperature sensor 62, and the detection output of the third temperature sensor 64. Is configured to control the high-pressure water supply pump 23, the electromagnetic valve 26, and the heater 27.

Next, the unused heavy oil reforming method of the present invention using such an unused heavy oil reforming apparatus will be described.
(a) Supplying process of supercritical water or subcritical water Supercritical water or subcritical water is supplied to the reaction tube 21 provided inside the reaction vessel 11 from the outside of the reaction vessel 11 via the supply unit 21a. However, as a precondition, supercritical water or subcritical water is filled in the reaction vessel 11 around the reaction tube 21. The supercritical water or subcritical water filling the reaction vessel 11 was obtained by heating the high-pressure water supplied into the reaction vessel 11 by the high-pressure water supply pump 23 through the high-pressure water supply pipe 17 with the heater 27. Is. If supercritical water or subcritical water is filled in the reaction vessel 11 in this way, high-temperature and high-pressure supercritical water or subcritical water is also present around the reaction tube 21. The balance with the supercritical water or subcritical water supplied to the water is maintained, and breakage of the reaction tube 21 due to the loss of the balance can be effectively prevented.
The supercritical water or subcritical water is supplied by the critical water supply means 31, and the supercritical water or subcritical water supplied from the water storage tank 22 and heated by the heater 34 by driving the critical water supply pump 33. Water is supplied from the outside of the reaction vessel 11 to the reaction tube 21 via the supply unit 21a. Then, the supplied supercritical water or subcritical water passes through the reaction tube 21 to reach the discharge part 21b, and is discharged from the discharge part 21b to the outside of the reaction vessel 11.

(b) Heavy oil supply conversion step Next, unused heavy oil is supplied to the mixer 36 provided in the supply pipe 32 for supplying supercritical water or subcritical water to the reaction pipe 21 to the reaction pipe 21. The supplied supercritical water or subcritical water and unused heavy oil are mixed, and the unused heavy oil mixed with the supercritical water or subcritical water is mixed in the reaction tube 21 with the supercritical water or subcritical water. React with water to convert to reformed oil. That is, the conversion of unused heavy oil is performed inside the reaction tube 21 in which supercritical water or subcritical water flows at a relatively high speed, thereby preventing coking of unused heavy oil. This effectively prevents a situation where the reaction tube 21 is blocked due to the coking. Here, the supply of the unused heavy oil is performed by the heavy oil supply means 37, and the heavy oil supply pump 41 is driven to drive the unused heavy oil from the heavy oil storage tank 38 to the unused heavy oil. Oil is supplied to the mixer 36, and the unused heavy oil is mixed with supercritical water or subcritical water supplied to the reaction tube 21 in the mixer 36.

  The amount of supercritical water or subcritical water supplied to the reaction tube 21 is controlled based on the temperature change state of the supercritical water or subcritical water in the reaction tube 21. This control is performed by the controller 63, which controls the critical water supply pump 33 according to the detection outputs of the first temperature sensor 61 and the second temperature sensor 62 and supplies supercritical water or sub-water supplied to the reaction tube 21. Control the amount of critical water. Here, the unused heavy oil generally starts coking at 430 ° C. or higher, and the portion at 430 ° C. is about 1 to 2 hours. For this reason, the controller 63 controls to increase the amount of supercritical water or subcritical water supplied to the reaction tube 21 according to the degree to which the supercritical water or subcritical water in the reaction tube 21 exceeds 430 ° C. The time for the supercritical water or subcritical water to pass through the reaction tube 21 is shortened. As a result, it is possible to avoid the occurrence of coking of heavy oil components in the reaction tube 21 and to continuously improve unused heavy oil continuously supplied to the reaction tube 21.

(c) Recovered oil reforming step The reformed oil mixed with the supercritical water or subcritical water is separated and recovered from the supercritical water or subcritical water discharged from the discharge unit 21b to the outside of the reaction vessel 11. The reformed oil is separated and recovered by the oil / water separation means 46, and the reformed oil discharged together with the supercritical water or the subcritical water via the discharge portion 21b is then heat exchanger 49 together with the supercritical water or the subcritical water. The pressure is reduced by the pressure reducing valve 51. The mixed fluid composed of supercritical water or subcritical water and reformed oil cooled under reduced pressure in this way is sent to the flash separation tank 47, and the hydrocarbon-based heavy reformed oil is first separated. The remaining liquid from which the heavy reforming oil has been separated in the flash separation tank 47 is further cooled by the cooler 52a, and then separated into gas, light reforming oil, and water in the gas oil water separation tank 52. The separated gas is used as fuel for a power generation boiler (not shown). The separated heavy and light reformed oils are used as fuel for boilers (not shown) or the like, or used as intermediate raw materials for petroleum refining plants.

It is a block diagram which shows the reforming apparatus of this invention. It is an expanded sectional view which shows the structure of the reaction container used for it. It is sectional drawing corresponding to FIG. 2 which shows the conventional reaction container.

Explanation of symbols

11 reaction vessel 13 lid (container wall)
21 reaction tube 21a supply unit 21b discharge unit 31 critical water supply unit 32 supply tube 36 mixer 37 heavy oil supply unit 46 oil / water separation unit 61, 62 temperature sensor 63 controller

Claims (4)

Supercritical water or subcritical water is supplied to the reaction tube (21) provided inside the reaction vessel (11) from the outside of the reaction vessel (11) via the supply unit (21a) and the discharge unit (21b). The supercritical water or subcritical water is discharged to the outside of the reaction vessel (11) through
Supplying unused heavy oil to the reaction tube (21) and mixing supercritical water or subcritical water and unused heavy oil supplied to the reaction tube (21),
Unused heavy oil mixed with supercritical water or subcritical water is reacted with supercritical water or subcritical water in the reaction tube (21) to be converted into reformed oil,
A method for reforming unused heavy oil, in which reformed oil is separated and recovered from the supercritical water or subcritical water discharged to the outside of the reaction vessel (11) through the discharge section (21b).   Control the amount of supercritical water or subcritical water supplied to the reaction tube (21) based on the temperature change of unused heavy oil mixed with supercritical water or subcritical water in the reaction tube (21). The reforming method according to claim 1. A reaction vessel (11),
A reaction tube provided inside the reaction vessel (11) in a spiral or meandering manner, and the supply portion (21a) and the discharge portion (21b) at both ends penetrate the vessel wall (13) of the reaction vessel (11), respectively. (21) and
Supercritical water or subcritical water is supplied from the outside of the reaction vessel (11) to the reaction tube (21) through the supply unit (21a) and the supercritical water or through the discharge unit (21b). Critical water supply means (31) for discharging subcritical water to the outside of the reaction vessel (11);
Supercritical water or sub-phase supplied to the reaction tube (21) by supplying unused heavy oil to the mixer (36) provided in the supply tube (32) constituting the critical water supply means (31). Heavy oil supply means (37) for mixing critical water and unused heavy oil;
Oil-water separation means for separating and recovering reformed oil from the supercritical water or subcritical water connected to the discharge unit (21b) and discharged to the outside of the reaction vessel (11) through the discharge unit (21b) ( 46) and
The reaction tube (21) is a mixture of supercritical water or subcritical water that reacts with the unused heavy oil flowing inside to react with the supercritical water or subcritical water to convert it into a reformed oil, and then the reaction. An apparatus for reforming unused heavy oil, characterized in that it is configured to guide the container (11) to the outside. A temperature sensor (61, 62) for measuring the temperature of the unused heavy oil mixed with supercritical water or subcritical water flowing through the reaction tube (21), and the detection output of the temperature sensor (61, 62) The reformer according to claim 3, further comprising a controller (63) for controlling the supply means (31).

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