KR102098307B1 - Catalyst regenerator having liquid fuel reformer - Google Patents

Abstract

According to an embodiment of the present invention, a liquid fuel having a high calorific value is reformed into a solid carbon and a gas state and supplied to a reaction chamber to regenerate the catalyst in the reaction chamber and increase the temperature of the catalyst, wherein the temperature balance in the reaction chamber To form It relates to a catalyst regenerator comprising a liquid fuel reformer. A catalyst regenerator including a liquid fuel reformer according to an embodiment of the present invention is a reaction chamber that regenerates and heats a caulking catalyst entering the regeneration space through an inlet, and then sends the regenerated catalyst to an outlet, and is connected to the reaction chamber, the liquid fuel Partial oxidation of hydrogen to form a reforming gas containing hydrogen, carbon monoxide and solid carbon to supply to the regeneration space, a liquid fuel reforming unit, and installed in the regeneration space to burn the reformed gas to regenerate and heat the coking catalyst It includes an air supply for supplying combustion air.

Description

Catalyst regenerator including liquid fuel reformer {CATALYST REGENERATOR HAVING LIQUID FUEL REFORMER}

The present invention relates to a catalyst regenerator, and more specifically, to be used in a fluidized bed catalytic reactor, thereby removing and regenerating carbon on the surface of the cokeed catalyst, and a catalyst regenerator including a liquid fuel reformer to increase the temperature of the catalyst. will be.

In general, ethylene is a representative material of basic raw materials in petrochemicals. The petrochemical process produces various substances through various processes based on olefin compounds such as ethene and propylene.

Catalysts are used to produce olefins from naphtha. The catalyst is coking in the process via a naphtha cracking reaction. That is, carbon particles cover the surface of the catalyst.

After regeneration, the caulking catalyst covered with carbon is mixed with naphtha again to undergo circulation used for the decomposition reaction of naphtha. However, when the catalyst is cocked, it is difficult for the decomposition reaction of the naphtha to occur smoothly.

As disclosed in U.S. Patent No. 7,153,479, when regenerating a coking catalyst, a method of supplying fuel uses a method of injecting fuel oil into a catalyst fluidized bed in the form of a powder with a nozzle.

That is, the liquid fuel compensates for the insufficient temperature in the catalyst regenerator used in the fluidized bed catalytic reactor. The liquid fuel is injected at a high pressure into the reaction chamber of the catalyst regenerator to increase the temperature of the catalyst by the heat of combustion.

However, the injection of liquid fuel causes temperature imbalance in the reaction chamber due to the low dispersibility of the fuel. Accordingly, hot spots are generated in the reaction chamber, the catalyst is aged, and the performance of the catalyst is deteriorated. Therefore, it is necessary to solve these problems.

According to an embodiment of the present invention, a liquid fuel having a high calorific value is reformed into a solid carbon and a gas state and supplied to a reaction chamber to regenerate the catalyst in the reaction chamber and increase the temperature of the catalyst, wherein the temperature balance in the reaction chamber To form It relates to a catalyst regenerator comprising a liquid fuel reformer.

A catalyst regenerator including a liquid fuel reforming unit according to an embodiment of the present invention is a reaction chamber that regenerates and heats a caulking catalyst entering the regeneration space through an inlet, and then sends the regenerated catalyst to an outlet, and is connected to the reaction chamber, the liquid fuel Partial oxidation of hydrogen to form a reforming gas containing hydrogen, carbon monoxide and solid carbon to supply to the regeneration space, a liquid fuel reforming unit, and installed in the regeneration space to burn the reformed gas to regenerate and heat the coking catalyst It includes an air supply for supplying combustion air.

The liquid fuel reforming unit is installed in a housing connected to the reaction chamber, a lean combustion region forming a first hot gas flow with first liquid fuel and first air supplied from one side of the housing, and inside the lean combustion region. It may include a rich combustion region to form a second hot gas flow to the second liquid fuel supplied through the fuel supply pipe.

The housing may further include an inner tube installed through a spacer therein in the rich combustion region.

The outer surface of the inner tube and the inner surface of the housing set a first hot gas flow passage between each other to flow a first hot gas, and the inner surface of the inner tube set a second hot gas flow passage to form a second hot gas You can let gas flow.

The rich combustion zone may be burned at a higher equivalent ratio than in the lean burn zone.

The housing may further include an external tube installed outside the rich combustion region.

The outer surface of the housing and the inner surface of the outer tube may establish a second air flow passage between each other to allow the second air to flow.

The housing includes an expansion portion that is formed to be expanded in the lean combustion region rather than in the rich combustion region, and is installed in the expansion portion to generate plasma by first liquid fuel and first air and to ignite and burn a plasma ignition / combustion portion It may further include.

The housing may further include a high temperature exposure increasing member installed in the rich combustion region to increase a high temperature exposure time. The high temperature exposure increasing member may further include a metal foam, a metal mesh, or a ceramic monolith.

The housing further includes a heating member installed on the outer surface to increase the internal temperature. The heating member may include an insulating material, an electric heater or a heat exchanger.

The liquid fuel reforming unit may be arranged in plural in the lower side of the reaction chamber.

As described above, an embodiment of the present invention is equipped with a liquid fuel reformer, and generates a reforming gas containing hydrogen, carbon monoxide, and solid carbon by partial oxidation of the liquid fuel, thereby supplying the reforming gas to the regeneration space of the reaction chamber. It is possible to form a temperature balance in the reaction chamber to regenerate the catalyst and heat the temperature of the catalyst. Therefore, generation of hot spots in the reaction chamber is prevented, and aging of the catalyst is prevented. That is, the performance of the catalyst can be maintained.

1 is a cross-sectional view of a catalyst regenerator including a liquid fuel reformer according to a first embodiment of the present invention.
FIG. 2 is a cross-sectional view of a liquid fuel reformer applied to FIG. 1.
3 is a cross-sectional view taken along line III-III of FIG. 2.
FIG. 4 is a graph showing the equivalence ratio and temperature relationship for the lean burn region and the rich burn region of the liquid fuel reformer in FIG. 2.
5 is a cross-sectional view of a liquid fuel reformer applied to a second embodiment of the present invention.
6 is a cross-sectional view of a liquid fuel reformer applied to a third embodiment of the present invention.
7 is a cross-sectional view of a liquid fuel reformer applied to a fourth embodiment of the present invention.
8 is a cross-sectional view of a catalyst regenerator including a liquid fuel reformer according to a fifth embodiment of the present invention.
9 is a cross-sectional view of a liquid fuel reformer applied to a sixth embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. In the drawings, parts not related to the description are omitted in order to clearly describe the present invention, and the same reference numerals are attached to the same or similar elements throughout the specification.

1 is a cross-sectional view of a catalyst regenerator including a liquid fuel reformer according to a first embodiment of the present invention. Referring to FIG. 1, the catalyst regenerator 1 of the first embodiment includes a reaction chamber 10, a liquid fuel reforming unit 20 and an air supply unit 30, and is configured to regenerate and heat the coking catalyst.

Although not shown, the fluidized bed reactor mixes the reactant and the catalyst (new catalyst or regenerated catalyst) in a riser (not shown) to cause a decomposition reaction of the reactant, and then separates the caulked caulking catalyst and product with a cyclone to separate them. The coking catalyst is dropped into the catalyst regenerator 1 (see Fig. 1).

As an example, a process of generating olefin using naphtha as a reactant, that is, a process of producing olefin in the form of fluid catalyst cracking (FCC) corresponds to the preceding process of the first embodiment.

In the previous step, the naphtha and the catalyst are mixed to cause a decomposition reaction of the naphtha, and the coke catalyst and the produced olefin are separated from a cyclone (not shown), and the coking catalyst is dropped into the catalyst regenerator 1.

That is, the naphtha is injected into the bottom of the riser and begins to decompose through a catalytic reaction while encountering a high temperature catalyst (including a regenerated catalyst). As the naphtha rises along the riser, it continues to decompose by endothermic catalysis.

After the decomposition reaction of the naphtha, the catalyst covered with solid carbon particles, that is, the coking catalyst and the olefin produced by the decomposition reaction are introduced into the cyclone and separated from each other. The coking catalyst separated from the cyclone falls into the catalyst regenerator 1. That is, the catalyst of the previous process falls to the inlet 11 and is supplied to the catalyst regenerator 1.

The catalyst regenerator 1 of the first embodiment reforms the (first, second) liquid fuel having a high calorific value into solid carbon and gas, and supplies it to the reaction chamber 10 to balance the temperature in the reaction chamber 10 It is configured to form.

The catalyst regenerator 1 of the first embodiment regenerates and heats the catalyst while oxidatively removing carbon remaining on the surface of the caulking catalyst with combustion air that is additionally supplied to solid carbon and reforming gas in a gaseous state (hydrogen, carbon monoxide) .

In the first embodiment, the reaction chamber 10 is configured to regenerate and heat the caulking catalyst entering the regeneration space (RGS) through the inlet 11 in the regeneration space (RGS) and then send the regenerated catalyst to the outlet (12). do.

The liquid fuel reformer 20 is configured to partially oxidize the (first and second) liquid fuels to generate reformed gas containing hydrogen, carbon monoxide, and solid carbon, and supply them to the regeneration space (RGS).

The air supply unit 30 is installed in the regeneration space (RGS) inside the reaction chamber 10 to burn the reformed gas to supply combustion air to the regeneration space (RGS) to regenerate and heat the coking catalyst.

FIG. 2 is a cross-sectional view of the liquid fuel reformer applied to FIG. 1, and FIG. 3 is a cross-sectional view taken along line III-III of FIG. 2. 2 and 3, the liquid fuel reformer 20 includes a housing 21, a lean burn region (LBA), and a rich burn region (RBA).

The housing 21 is connected to the reaction chamber 10 and supplies reformed gas generated by reforming by partial oxidation to the regeneration space RGS in the reaction chamber 10. The lean burn region LBA forms a first hot gas HG1 flow with first liquid fuel and first air supplied from one side of the housing 21. The first hot gas (HG1) flow is formed by general combustion by the first liquid fuel and the first air.

The rich combustion region RBA forms a second hot gas (HG2) flow with the second liquid fuel LF2 supplied through the fuel supply pipe 22 installed inside the lean combustion region LBA. The second liquid fuel LF2 supplied to the fuel supply pipe 22 is supplied to the first hot gas (HG1) stream and is partially oxidized due to lack of air.

The housing 21 is formed to include an extension 211 that extends in the lean burn region LBA rather than in the rich burn region RBA. Therefore, the housing 21 greatly increases the supply amount of the first air compared to the supply amount of the first liquid fuel in the lean burn region LBA through the expansion portion 211, thereby enabling a more complete lean burn and allowing the first hot gas. Can produce and supply.

FIG. 4 is a graph showing the equivalence ratio and temperature relationship for the lean burn region and the rich burn region of the liquid fuel reformer in FIG. 2. Referring to FIG. 4, the second hot gas (HG2) flow is formed by partial oxidation of the first hot gas and the second liquid fuel (LF2). Therefore, the rich combustion zone (RBA) is burned at a higher equivalent ratio than in the lean burn zone (LBA).

In the lean burn region (LBA), the equivalence ratio and the combustion temperature appear in a roughly proportional relationship. Approximately inversely related.

At this time, due to the partial oxidation of the second liquid fuel LF2, a reforming gas containing hydrogen, carbon monoxide and solid carbon is generated. Therefore, the second hot gas flow passage P2 set inside the inner tube 24 supplies the reformed gas containing solid carbon to the reaction chamber 10.

Referring again to FIGS. 2 to 3, in detail, the housing 21 further includes an inner tube 24 installed through a spacer 23 therein in the rich combustion region RBA. The spacers 23 are provided in plural, and are spaced apart along the circumferential direction from the inner surface of the housing 21 and the outer surface of the inner tube 24.

Therefore, the outer surface of the inner tube 24 and the inner surface of the housing 21 establish a first hot gas flow passage P1 between each other and between adjacent spacers 23. As a result, the first hot gas flow passage P1 flows the first hot gas burned in the lean burn region LBA.

In addition, the inner surface of the inner tube 24 sets the second hot gas flow passage P2 to flow the second hot gas. The second hot gas (HG2) flow formed by partial oxidation of the first hot gas (HG1) and the second liquid fuel (LF2) is generated by the first hot gas (HG1) flow flowing into the first hot gas flow passage (P1). , Insulated to enable high temperature flow of the second hot gas (HG2). The second hot gas (HG2) is a reforming gas containing hydrogen, carbon monoxide and solid carbon.

Therefore, the inner wall surface of the inner tube 24 that sets the second hot gas flow passage P2 maintains the reformed gas at a high temperature, thereby minimizing the adsorption of solid carbon contained in the reformed gas to the inner wall surface. You can.

In addition, the inner tube 24 is the first and second hot gas flow passage (P1) to guide the first hot gas (HG1) via the first hot gas flow passage (P1) to the second hot gas flow passage (P2) ( P1, P2) is provided with an induction port 25 at the ends.

The induction port 25 is provided in plural, and is provided at equal intervals along the circumferential direction of the inner tube 24, so that the first hot gas HG1 can be uniformly supplied to the second hot gas HG2. . In addition, since the induction port 25 is formed adjacent to the reaction chamber 10, the first and second hot gases HG1 and HG2 can be supplied to the regeneration space RGS of the reaction chamber 10.

At this time, at the longitudinal ends of the housing 21 and the inner tube 24 (adjacent to the reaction chamber 10), the spacer 26 is completely circumferentially between the housing 21 and the inner tube 24. It can be sealed.

In addition, a plurality of spacers 26 may be provided to be disposed at equal intervals along the circumferential direction. In this case, the first hot gas HG1 may be supplied to the reaction chamber 10 through the first and second hot gas flow passages P1 and P2.

Referring back to FIG. 1, the second hot gas flow passage P2 or the first and second hot gas flow passages P1 and P2 of the liquid fuel reformer 20 is supplied to the reaction chamber 10. 1, the second hot gas (HG1, HG2) is further combusted by the combustion air supplied from the regeneration space (RGS), while continuously regenerating the catalyst by sintering the carbon on the catalyst surface to raise the temperature of the catalyst.

As described above, the first embodiment reforms the solid carbon and gas while supplying the liquid fuel having a high calorific value to the reaction chamber 10, thereby reforming the caulking catalyst and raising the temperature of the catalyst. ) To form a temperature balance. That is, the occurrence of hot spots in the reaction chamber 10 is prevented.

The regenerated and heated catalyst flows out through outlet 12. For example, the effluent regenerated catalyst is used to mix the naphtha and the catalyst to cause a decomposition reaction of the naphtha. In this process, the cokeed catalyst and the produced olefin are separated from a cyclone (not shown), and the cokeed catalyst is supplied to the catalyst regenerator 1 and regenerated and heated to be reused.

Hereinafter, various embodiments of the present invention will be described. Descriptions of the same parts as in the first embodiment and the previously described embodiments are omitted, and different parts are described.

5 is a cross-sectional view of a liquid fuel reformer applied to a second embodiment of the present invention. Referring to FIG. 5, in the liquid fuel reforming unit 220 of the second embodiment, the housing 21 is plasma-ignited / expanded to the expansion 211 formed in the lean combustion region LBA than in the rich combustion region RBA. The combustion unit 27 is further included.

Since the plasma ignition / combustion unit 27 generates plasma by the first liquid fuel and the first air, the plasma ignition / combustion unit acts as an ignition combustion, thereby realizing a lean combustion of the first liquid fuel and the first air as compared to the first embodiment. , More stable combustion can be realized in the lean burn region (LBA).

Therefore, in the second embodiment, partial oxidation of the second liquid fuel LF2 supplied through the fuel supply pipe 22 in the rich combustion region RBA is possible, compared to the first embodiment, such as hydrogen, carbon monoxide, and solid phase. The reformed gas containing carbon is generated and supplied to the reaction chamber 10.

As described above, since the second embodiment stably implements combustion in the lean burn region (LBA) using the plasma ignition / combustion unit 27, the solid carbon generated by effectively implementing partial oxidation in the rich burn region (RBA) Coking catalyst is reformed by supplying a reforming gas comprising a to the reaction chamber 10.

Therefore, compared to the first embodiment, the second embodiment further forms a temperature balance in the reaction chamber 10, and further prevents the occurrence of hot spots in the reaction chamber 10.

6 is a cross-sectional view of a liquid fuel reformer applied to a third embodiment of the present invention. Referring to FIG. 6, in the liquid fuel reformer 320 of the third embodiment, the housing 21 includes a high temperature exposure increasing member 28 installed in the rich combustion region RBA to increase the high temperature exposure time.

The high temperature exposure increasing member 28 has heat resistance. As an example, the high temperature exposure increasing member 28 further includes a metal form, a metal mesh, or a ceramic monolith.

 The high temperature exposure increasing member 28 exposes the first hot gas flow of the first hot gas HG1 burned in the lean burn region LBA and the second liquid fuel LF2 supplied to the fuel supply pipe 22 for a long time. , The second liquid fuel (LF2) is vaporized and reformed. Therefore, the liquid fuel reforming unit 320 supplies reforming gas containing partially oxidized hydrogen, carbon monoxide and solid carbon in the lean combustion region LBA to the reaction chamber 10.

As described above, the third embodiment effectively implements partial oxidation in the rich combustion region (RBA) using the high temperature exposure increasing member 28 to supply the reformed gas containing solid carbon generated to the reaction chamber 10 The coking catalyst is reformed and heated.

Therefore, compared to the first embodiment, the third embodiment can further form a temperature balance in the reaction chamber 10, and further prevent the occurrence of hot spots in the reaction chamber 10.

7 is a cross-sectional view of a liquid fuel reformer applied to a fourth embodiment of the present invention. Referring to FIG. 7, in the liquid fuel reforming unit 420 of the fourth embodiment, the housing 21 is further provided with a heating member 29 installed on the outer surface to increase the internal temperature.

As an example, the heating member 29 includes an insulating material, an electric heater or a heat exchanger. More specifically, the heating member 29 is installed in the rich combustion area RBA of the housing 21. The heating member 29 heats the inside of the inner tube 24 when reforming the second liquid fuel in the rich combustion region RBA.

The solid carbon has a characteristic that the higher the temperature, the less the adsorption and growth on the inner surface of the inner tube 24. Therefore, the heating member 29 increases the temperature in the inner tube 24 to prevent solid carbon generated during partial oxidation of the second liquid fuel LF2 from being adsorbed on the inner surface of the inner tube 24. The solid carbon is adsorbed on the inner surface of the inner tube 24 is most affected by temperature.

As described above, the fourth embodiment uses the heating member 29 to supply the reformed gas containing solid carbon generated by effectively implementing partial oxidation in the rich combustion region (RBA) to the reaction chamber 10 and caulking. The catalyst is regenerated and heated.

Therefore, compared to the first embodiment, the fourth embodiment can further form a temperature balance in the reaction chamber 10, and further prevent the occurrence of hot spots in the reaction chamber 10.

8 is a cross-sectional view of a catalyst regenerator including a liquid fuel reformer according to a fifth embodiment of the present invention. Referring to FIG. 8, the catalyst regenerator 5 of the fifth embodiment has a plurality of liquid fuel reforming parts disposed below the reaction chamber 210.

For example, the liquid fuel reforming unit may include N liquid fuel reforming units 521 to 52N. At this time, the N liquid fuel reforming units 521 to 52N have solid carbon as a main component, and supply reforming gas containing other gaseous gases to the regeneration space RGS in the reaction chamber 10, and regeneration space RGS. While burning by the combustion air, the temperature of the catalyst is raised while regenerating the catalyst by continuously sequencing the cokeed carbon on the catalyst surface.

9 is a cross-sectional view of a liquid fuel reformer applied to a sixth embodiment of the present invention. Referring to FIG. 9, in the liquid fuel reforming unit 620 of the sixth embodiment, the housing 21 further includes an outer tube 31 installed outside the rich combustion region RBA.

The outer surface of the housing 21 and the inner surface of the outer tube 31 set the second air flow passage P3 between each other to flow the second air A2.

In the second air A2 supplied through the second air flow passage P3, the temperature of the rich combustion region RBA is excessive depending on the mixing ratio of the first liquid fuel, the second liquid fuel LF2 and the first air. When it is high, since the outer surface of the housing 21 is cooled, it is possible to stably maintain and implement the temperature of the second hot gas flow passage P2 formed on the inner surface of the inner tube 24.

Although the preferred embodiment of the present invention has been described through the above, the present invention is not limited thereto, and it is possible to carry out various modifications within the scope of the claims and detailed description of the invention and the accompanying drawings. Naturally, it is within the scope of the invention.

1: catalytic regenerators 10, 210: reaction chamber
11: inlet 12: outlet
20, 220, 320, 521 ~ 52N, 620: liquid fuel reformer
21: housing 22: fuel supply pipe
23, 26: spacer 24: inner tube
25: induction port 27: plasma ignition / combustion unit
28: high temperature exposure increasing member 29: heating member
30: air supply 31: outer tube
211: extension A2: second air
HG1: First hot gas HG2: Second hot gas
LBA: lean burn zone LF2: second liquid fuel
P1: First hot gas flow passage P2: Second hot gas flow passage
P3: 2nd air flow passage RBA: Thick combustion area
RGS: Play area

Claims (13)

A reaction chamber that regenerates and heats the caulking catalyst entering the regeneration space through the inlet and then sends the regenerated catalyst to the outlet;
A liquid fuel reformer connected to the reaction chamber to generate a reforming gas containing hydrogen, carbon monoxide, and solid carbon through partial oxidation of liquid fuel and supplying it to the regeneration space; And
An air supply unit installed in the regeneration space to supply combustion air to regenerate and heat the coking catalyst by burning the reformed gas.
It includes,
The liquid fuel reformer
A lean combustion region connected to the reaction chamber and forming a first hot gas flow with supplied first liquid fuel and first air, and
A rich combustion zone that forms a second hot gas stream with a second liquid fuel supplied inside the lean combustion zone.
Catalyst regenerator comprising a. A reaction chamber that regenerates and heats the caulking catalyst entering the regeneration space through the inlet and then sends the regenerated catalyst to the outlet;
A liquid fuel reformer connected to the reaction chamber to generate a reforming gas containing hydrogen, carbon monoxide, and solid carbon through partial oxidation of liquid fuel and supplying it to the regeneration space; And
An air supply unit installed in the regeneration space to supply combustion air to regenerate and heat the coking catalyst by burning the reformed gas.
It includes,
The liquid fuel reformer
A housing connected to the reaction chamber,
A lean combustion region forming a first hot gas flow with the first liquid fuel and the first air supplied from one side of the housing, and
A rich combustion zone that forms a second hot gas stream from the second liquid fuel supplied through a fuel supply pipe installed inside the lean combustion zone.
Catalyst regenerator comprising a. According to claim 2,
The housing,
An inner tube installed through a spacer in the rich combustion region.
Catalyst regenerator further comprising a. According to claim 3,
The outer surface of the inner tube and the inner surface of the housing set a first hot gas flow passage between each other to flow the first hot gas,
The inner surface of the inner tube is a catalyst regenerator that sets a second hot gas flow passage to flow the second hot gas. According to claim 2,
The rich combustion area
A catalyst regenerator that burns at a higher equivalent ratio than in the lean burn zone. According to claim 2,
The housing
External tube installed outside the rich combustion area
Catalyst regenerator further comprising a. The method of claim 6,
The outer surface of the housing and the inner surface of the outer tube
A catalyst regenerator that sets the second air flow passage between each other to flow the second air. According to claim 2,
The housing
And an extension portion that is formed to be expanded in the lean burn region than in the rich burn region.
Plasma ignition / combustion unit installed in the expansion unit to generate plasma and ignite and burn plasma by first liquid fuel and first air
Catalyst regenerator further comprising a. According to claim 2,
The housing
A catalyst regenerator further comprising a high temperature exposure increasing member installed in the rich combustion region to increase a high temperature exposure time. The method of claim 9,
The high temperature exposure increasing member
Catalyst regenerator further comprising a metal foam, metal mesh or ceramic monolith. According to claim 2,
The housing
A catalyst regenerator further comprising a heating member installed on the outer surface to increase the internal temperature. The method of claim 11,
The heating member is a catalyst regenerator comprising an insulating material, an electric heater or a heat exchanger. According to claim 2,
The liquid fuel reformer
A catalyst regenerator disposed in plurality in the lower side of the reaction chamber.

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