Mobile bed adsorption desulfurization device and method
By combining liquid-phase adsorption desulfurization with coke burning regeneration in a co-current moving bed reactor, the problem of high cost of existing heavy oil desulfurization is solved, achieving low-cost and high-efficiency heavy oil desulfurization.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA NAT PETROLEUM CORP
- Filing Date
- 2022-03-29
- Publication Date
- 2026-04-14
AI Technical Summary
Existing heavy oil desulfurization methods mainly rely on hydrotreating, which has high operating costs and high hydrogen consumption, while moving bed liquid phase adsorption desulfurization technology is lacking.
A co-current moving bed reactor is used for liquid phase adsorption desulfurization. The adsorbent is continuously regenerated by the slow movement of the adsorbent between the reactor and the regenerator. The adsorbent activity is restored by coke burning regeneration.
It achieves low-cost desulfurization of heavy oil, reduces operating pressure and hydrogen consumption, and improves desulfurization efficiency and adsorbent activity recovery efficiency.
Smart Images
Figure CN116925807B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of heavy oil desulfurization technology, and more specifically, to a moving bed adsorption desulfurization device and method. Background Technology
[0002] The existing industrialized heavy oil desulfurization is mainly achieved through hydrogenation. However, heavy oil hydrogenation requires high operating pressure, large investment, and consumes a large amount of hydrogen, resulting in high operating costs. Currently, there is no method for heavy oil moving bed liquid phase adsorption desulfurization. Summary of the Invention
[0003] The present invention aims to provide, for example, a moving bed adsorption desulfurization apparatus and method, in which sulfur-containing heavy oil undergoes contact liquid-phase adsorption desulfurization in a co-current moving bed reactor to obtain desulfurized heavy oil with a low sulfur content. The sulfur-containing adsorbent undergoes coke burn-off regeneration in a regeneration system to restore its activity. The adsorbent moves slowly between the reaction system and the regeneration system by means of lifting and gravity, thereby achieving continuous regeneration of the adsorbent.
[0004] The embodiments of the present invention can be implemented as follows:
[0005] In a first aspect, embodiments of the present invention provide a moving bed adsorption desulfurization device, comprising a co-current moving bed reactor, a lower closed hopper, a centrifugal separator, a reactor bottom elevator, a regenerator top separation hopper, a one-stage or multi-stage coke burner regenerator, a flow control hopper, a buffer hopper, a regenerator bottom elevator, a reactor top separation hopper, and an upper closed hopper.
[0006] The co-current moving bed reactor is used to: introduce sulfur-containing heavy oil and, under the action of the regenerated adsorbent, allow the sulfur-containing heavy oil to undergo liquid-phase adsorption desulfurization;
[0007] The lower closed hopper is used to allow the wet sulfur-containing adsorbent after liquid-phase adsorption and desulfurization to enter;
[0008] The centrifuge is used to centrifuge the wet sulfur-containing adsorbent to further separate the heavy oil carried in the wet sulfur-containing adsorbent.
[0009] The reactor bottom elevator is used to: lift the oil-free dry sulfur-containing adsorbent to the top separation hopper of the regenerator;
[0010] The top separation hopper of the regenerator is used to: allow the dry sulfur-containing adsorbent to pass through a ceramic separator blower to remove the adsorbent dust generated in the reaction system;
[0011] The one- or multi-stage coking regenerator is used to: regenerate the sulfur-containing adsorbent by coking.
[0012] The flow control hopper is used to: control the flow rate of the coke-regenerated adsorbent before it enters the buffer hopper, and to adjust and control the circulation rate of the coke-regenerated adsorbent.
[0013] The regenerator bottom lifter is used to: lift the regenerated adsorbent to the reactor top separation hopper at the top of the reactor;
[0014] The top separation hopper of the reactor is used to remove adsorbent dust generated by the regeneration system by a ceramic separator blower.
[0015] The upper locking hopper is used to adjust the pressure to the reaction pressure.
[0016] Furthermore, in an optional embodiment, the upper locking hopper adjusts the reaction pressure to 1.0-5.0 MPag.
[0017] Furthermore, in an optional embodiment, the lower locking hopper is used to adjust the pressure to 0.3-1.0 MPa.
[0018] Furthermore, in an optional embodiment, the regeneration pressure of the sulfur-containing adsorbent in the coke regeneration process of one or more coke regenerators is between 0.1 and 1.0 MPa.
[0019] Furthermore, in an optional embodiment, during the coking process in the one or more coking regenerators, regeneration ends when the sulfur content of the adsorbent is between 0 and 0.5% wt.
[0020] Furthermore, in an optional embodiment, during the coking process in the one or more coking regenerators, the coking temperature does not exceed 600°C.
[0021] Secondly, embodiments of the present invention provide a moving bed adsorption desulfurization method, utilizing the aforementioned moving bed adsorption desulfurization device, wherein the moving bed adsorption desulfurization method includes:
[0022] Sulfur-containing heavy oil is introduced into a co-current moving bed reactor for liquid-phase adsorption desulfurization treatment in the co-current moving bed reactor.
[0023] After the desulfurization treatment, the wet sulfur-containing adsorbent enters the lower closed hopper below the co-current moving bed reactor to reduce the adsorption pressure.
[0024] The wet sulfur-containing adsorbent is centrifuged to further separate the heavy oil carried in the wet sulfur-containing adsorbent;
[0025] The separated sulfur-containing adsorbent is lifted into one or more stages of coking regenerator so that the sulfur-containing adsorbent is coked and regenerated through the one or more stages of coking regenerator.
[0026] The regenerated adsorbent, which has been charred in one or more stages of the char regenerator, is introduced into a co-current moving bed reactor to complete one cycle.
[0027] Furthermore, in an optional embodiment, the top of the one or more coke burner regenerator is provided with a regenerator top separation hopper, and the reactor bottom elevator is used to introduce sulfur-containing adsorbent into the regenerator top separation hopper.
[0028] Furthermore, in an optional embodiment, the bottom of the one or more coke burner regenerator is provided with a flow control hopper, which is used to control the flow of the coke burner regenerated adsorbent before it enters the buffer hopper, thereby adjusting and controlling the circulation rate of the coke burner regenerated adsorbent.
[0029] Furthermore, in an optional embodiment, a regenerator bottom lifter is provided downstream of the flow control hopper, the regenerator bottom lifter being used to lift the regenerated adsorbent to the co-current moving bed reactor so that the regenerated adsorbent can enter the next cycle.
[0030] The moving bed adsorption desulfurization device and method provided in this embodiment: Heavy oil containing 1-5% wt sulfur undergoes a contact adsorption reaction with an adsorbent in a co-current moving bed reactor. As the sulfur-containing heavy oil and adsorbent slowly move within the moving bed reactor, sulfur in the oil phase is gradually adsorbed onto the adsorbent, achieving desulfurization of the heavy oil and meeting the product's sulfur content requirements. Simultaneously, the adsorbent gradually becomes sulfur-saturated, transforming into a sulfur-containing adsorbent. The sulfur-containing adsorbent undergoes dust removal through the top separation hopper of the regenerator and the top separation hopper of the reactor, and is then regenerated through coking in one or more stages of a coking regenerator, thereby achieving adsorbent regeneration and maintaining its activity. The sulfur-containing adsorbent and the regenerated adsorbent move slowly between the reactor and the regenerator through lifting and gravity, achieving continuous regeneration of the adsorbent. Attached Figure Description
[0031] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of the present invention and should not be considered as limiting the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.
[0032] Figure 1 This is a schematic diagram of the moving bed adsorption desulfurization device according to a specific embodiment of the present invention.
[0033] Icons: 1-Sulfur-containing heavy oil; 2-Desulfurized heavy oil; 3-Co-current moving bed reactor; 4-Lower closed hopper; 5-Centrifugal separator; 6-Reactor bottom elevator; 7-Sulfur-containing adsorbent; 8-Regenerator top separation hopper; 9-One or more stages of coke burner regenerator; 10-Flow control hopper; 11-Buffer hopper; 12-Regenerator bottom elevator; 13-Regenerated adsorbent; 14-Reactor top separation hopper; 15-Upper closed hopper. Detailed Implementation
[0034] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
[0035] Please see Figure 1 This invention provides a moving bed adsorption desulfurization device, comprising a co-current moving bed reactor 3, a lower closed hopper 4, a centrifugal separator 5, a reactor bottom elevator 6, a regenerator top separation hopper 8, a single or multiple coke burner regenerator 9, a flow control hopper 10, a buffer hopper 11, a regenerator bottom elevator 12, a reactor top separation hopper 14, and an upper closed hopper 15. The co-current moving bed reactor 3 is used to: introduce sulfur-containing heavy oil 1, and under the action of the regenerated adsorbent 13, cause the sulfur-containing heavy oil 1 to undergo liquid-phase adsorption desulfurization. The lower closed hopper 4 is used to: allow the wet sulfur-containing adsorbent 7 after liquid-phase adsorption desulfurization to enter. The centrifugal separator 5 is used to: centrifuge the wet sulfur-containing adsorbent 7 to further separate the heavy oil carried in the wet sulfur-containing adsorbent 7. The reactor bottom elevator... Unit 6 is used to: lift the oil-free dry sulfur-containing adsorbent 7 to the top separation hopper 8 of the regenerator; the top separation hopper 8 of the regenerator is used to: remove adsorbent dust generated in the reaction system by passing the dry sulfur-containing adsorbent 7 through a ceramic separation fan; a one-stage or multi-stage coking regenerator 9 is used to: regenerate the sulfur-containing adsorbent 7 by coking; the flow control hopper 10 is used to: control the flow of the regenerated adsorbent 13 after coking before it enters the buffer hopper 11, and adjust and control the circulation rate of the regenerated adsorbent 13 after coking; the bottom elevator 12 of the regenerator is used to: lift the regenerated adsorbent 13 to the top separation hopper 14 of the reactor at the top of the reactor; the top separation hopper 14 of the reactor is used to: remove adsorbent dust generated in the regeneration system by passing the ceramic separation fan; the upper locking hopper 15 is used to: adjust the pressure to the reaction pressure.
[0036] Optionally, the upper locking hopper adjusts the reaction pressure to 1.0-5.0 MPag.
[0037] Optionally, the lower locking hopper is used to adjust the pressure to 0.3-1.0 MPa.
[0038] Optionally, the regeneration pressure of the sulfur-containing adsorbent 7 in the coke regeneration of one or more coke regenerators 9 is between 0.1 and 1.0 MPa.
[0039] Optionally, during coking in one or more stages of the coking regenerator 9, regeneration ends when the sulfur content of the adsorbent is between 0 and 0.5% wt.
[0040] Optionally, during coking in one or more coking regenerators 9, the coking temperature does not exceed 600°C.
[0041] This invention also provides a moving bed adsorption desulfurization method, utilizing the aforementioned moving bed adsorption desulfurization device. The moving bed adsorption desulfurization method includes:
[0042] Sulfur-containing heavy oil 1 is introduced into a co-current moving bed reactor 3 to perform liquid-phase adsorption desulfurization treatment on the sulfur-containing heavy oil 1 in the co-current moving bed reactor 3.
[0043] After the desulfurization treatment, the wet sulfur-containing adsorbent 7 enters the lower closed hopper 4 below the co-current moving bed reactor 3, and the adsorption pressure is reduced.
[0044] The wet sulfur-containing adsorbent 7 is centrifuged to further separate the heavy oil carried in the wet sulfur-containing adsorbent 7;
[0045] The separated sulfur-containing adsorbent 7 is lifted into one or more coke burner regenerators 9 so that the sulfur-containing adsorbent 7 can be regenerated by coking through one or more coke burner regenerators 9.
[0046] The regenerated adsorbent 13, which has been charred in one or more stages of the char regenerator 9, is introduced into the co-current moving bed reactor 3 to complete one cycle.
[0047] Optionally, the top of one or more coke burner regenerators 9 is provided with a regenerator top separation hopper 8, and the reactor bottom elevator 6 is used to introduce sulfur-containing adsorbent 7 into the regenerator top separation hopper 8.
[0048] Optionally, a flow control hopper 10 is provided at the bottom of one or more coke burner regenerators 9. The flow control hopper 10 is used to control the flow of the coke burner regenerated adsorbent 13 into the buffer hopper 11, and to adjust and control the circulation rate of the coke burner regenerated adsorbent 13.
[0049] Optionally, a regenerator bottom lifter 12 is provided downstream of the flow control hopper 10. The regenerator bottom lifter 12 is used to lift the regenerated adsorbent 13 to the co-current moving bed reactor 3 so that the regenerated adsorbent 13 can enter the next cycle.
[0050] It should be noted that, in the embodiments of the present invention, the specific steps of the moving bed adsorption desulfurization method are as follows:
[0051] (1) Heavy oil containing 1-5% sulfur enters the co-current moving bed reactor 3 and moves downwards simultaneously with the regenerated adsorbent 13. Liquid phase adsorption desulfurization is carried out during the process, with an adsorption pressure of 1.0-5.0 MPa.
[0052] (2) The sulfur adsorption process in the heavy oil is completed at the bottom of the co-current reactor. After adsorption, the sulfur content of the product meets the product requirements. After initial separation by the conical screen at the bottom of the reactor, the desulfurized heavy oil 2 is used as the product to proceed to the next process, and the wet sulfur adsorbent 7 exits the reactor.
[0053] (3) The wet sulfur-containing adsorbent 7 is first passed through a closed hopper to adjust the pressure to 0.3-1.0 MPa;
[0054] (4) After adjusting the pressure, the wet sulfur adsorbent 7 is centrifuged to further separate the heavy oil carried in the wet sulfur adsorbent 7. The heavy oil separated by centrifugation is used as the product for the next process.
[0055] (4) The oil-free dry sulfur-containing adsorbent 7 is lifted to the top of the regenerator by the elevator;
[0056] (5) The dry sulfur-containing adsorbent 7 is separated in the top hopper of the regenerator and the adsorbent dust generated by the reaction system is removed by the Tao desorption fan.
[0057] (6) The sulfur-containing adsorbent 7 is regenerated by coking in a regenerator. The regeneration pressure is between 0.1-1.0 MPag. One or more stages of coking are used to ensure that the sulfur content on the adsorbent after coking is between 0-0.5% WT.
[0058] (7) After the charring, the regenerated adsorbent 13 enters the buffer hopper 11 after the flow control hopper 10 is used to adjust and control the circulation rate of the adsorbent.
[0059] (8) The regenerated adsorbent 13 is lifted to the top of the reactor via a booster.
[0060] (9) The regenerated adsorbent 13 is separated in the top hopper of the reactor and the adsorbent dust generated by the regeneration system is removed by the Tao separation blower.
[0061] (10) Install a closed hopper at the top of the reactor and adjust the pressure to the reaction pressure;
[0062] (11) The regenerated adsorbent 13 enters the reactor to complete one cycle.
[0063] The key technical points of this invention are:
[0064] (1) The desulfurization process is a contact liquid phase adsorption desulfurization carried out in the co-current moving bed reactor 3;
[0065] (2) The wet sulfur-containing adsorbent 7 after adsorption needs to be centrifuged to separate the oil and ensure that the adsorbent entering the regeneration is a dry adsorbent.
[0066] (3) The adsorbent is regenerated by coking in one or more coking regenerators 9;
[0067] (4) The adsorbent moves slowly between the reaction and regeneration systems to achieve continuous regeneration of the adsorbent;
[0068] (5) Locking hoppers are installed before and after the reactor to achieve pressure switching between the reaction system and the regeneration system;
[0069] The advantages of this invention are as follows: Heavy oil containing 1-5% wt sulfur undergoes a contact adsorption reaction with the adsorbent in a co-current moving bed reactor 3. As the sulfur-containing heavy oil 1 and the adsorbent move slowly within the moving bed reactor, sulfur in the oil phase is gradually adsorbed onto the adsorbent, achieving desulfurization of the heavy oil and meeting the product's sulfur content requirements. Simultaneously, the adsorbent gradually reaches sulfur saturation, becoming a sulfur-containing adsorbent 7. The sulfur-containing adsorbent 7 undergoes dust removal and precipitation in the top separation hopper 8 of the regenerator and the top separation hopper 14 of the reactor, and is regenerated by coking in one or more stages of coking regenerator 9, thereby achieving adsorbent regeneration and maintaining its activity. The sulfur-containing adsorbent 7 and the regenerated adsorbent 13 move slowly between the reactor and the regenerator through lifting and gravity, achieving continuous regeneration of the adsorbent.
[0070] like Figure 1 As shown, heavy oil containing 0.5-5% wt sulfur enters the reactor from the top of the co-current moving bed reactor 3, where it undergoes a contact desulfurization adsorption reaction with the regenerated adsorbent. The reactor pressure is 1.0-5.0 MPa. The sulfur-containing heavy oil 1 and the adsorbent move slowly downwards along the reactor, gradually reaching adsorption saturation, thus achieving desulfurization of the sulfur-containing heavy oil 1. The desulfurized heavy oil 2, meeting product requirements, exits the reactor from the bottom side and proceeds to the next process as the product. The saturated wet sulfur-containing adsorbent 7 enters the lower closed hopper 4 to reduce the system pressure to 0.3-1.0 MPa. The depressurized sulfur-containing adsorbent 7 moves into the centrifugal separator 5, where centrifugal separation further separates the adsorbent from the heavy oil. The separated heavy oil proceeds to the next process as the product. The separated dry adsorbent is lifted to the regeneration section by the reactor bottom elevator 6. The separation efficiency is generally 90-99.9%.
[0071] The sulfur-containing adsorbent 7 is lifted to the top separation hopper 8 of the regenerator via the bottom elevator 6 of the reactor. Here, inert gas is used to precipitate the sulfur-containing adsorbent 7, removing the dust generated during the reaction stage. After precipitation, the sulfur-containing adsorbent 7 enters one or more stages of coking regenerator 9, where oxygen-containing gas is used to coke the sulfur-containing adsorbent 7. The coking temperature generally does not exceed 600℃. When the sulfur content of the adsorbent is 0-0.5%wt, the regeneration is considered to be completed. After coking, the adsorbent enters the flow control hopper 10 to achieve flow control of the adsorbent. Then, it enters the buffer hopper 11 for buffering and cooling. After cooling, the adsorbent is lifted to the reaction section via the bottom elevator 12 of the regenerator.
[0072] The regenerated adsorbent 13 is lifted to the top separation hopper 14 of the reactor via the bottom elevator 12 of the regenerator. Here, inert gas is used to precipitate the regenerated adsorbent 13 to remove the dust generated during the regeneration stage. After precipitation, the regenerated adsorbent 13 enters the upper closed hopper 15, where the system pressure is increased to 2.0-5.0 MPa. The pressurized regenerated adsorbent 13 then enters the co-current moving bed reactor 3 to complete one catalyst cycle.
[0073] The moving bed heavy oil adsorption desulfurization device and method provided in this invention involve desulfurizing sulfur-containing heavy oil 1 through contact liquid-phase adsorption in a co-current moving bed reactor 3 to obtain desulfurized heavy oil 2 with a lower sulfur content. The sulfur-containing adsorbent 7 undergoes coke burn-off regeneration in a regeneration system to restore its activity. The adsorbent moves slowly between the reaction system and the regeneration system by lifting and gravity, thereby achieving continuous regeneration of the adsorbent.
[0074] While the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.
Claims
1. A moving bed adsorption desulfurization device, characterized in that, It includes a co-current moving bed reactor, a lower closed hopper, a centrifugal separator, a reactor bottom elevator, a regenerator top separation hopper, a one-stage or multi-stage coke burner regenerator, a flow control hopper, a buffer hopper, a regenerator bottom elevator, a reactor top separation hopper, and an upper closed hopper. The co-current moving bed reactor is used to: introduce sulfur-containing heavy oil, and under the action of the regenerated adsorbent, allow the sulfur-containing heavy oil to undergo liquid-phase adsorption desulfurization, wherein the sulfur-containing heavy oil contains 1-5 wt% sulfur; The lower closed hopper is used to allow the wet sulfur-containing adsorbent after liquid-phase adsorption and desulfurization to enter; The centrifuge is used to centrifuge the wet sulfur-containing adsorbent to further separate the heavy oil carried in the wet sulfur-containing adsorbent. The reactor bottom elevator is used to: lift the oil-free dry sulfur-containing adsorbent to the top separation hopper of the regenerator; The top separation hopper of the regenerator is used to: allow the dry sulfur-containing adsorbent to pass through a ceramic separator blower to remove the adsorbent dust generated in the reaction system; The one- or multi-stage coke burner is used to: burn and regenerate sulfur-containing adsorbents; The flow control hopper is used to: control the flow rate of the regenerated adsorbent after coking before it enters the buffer hopper, and to adjust and control the circulation rate of the regenerated adsorbent after coking. The regenerator bottom lifter is used to: lift the regenerated adsorbent to the reactor top separation hopper at the top of the reactor; The top separation hopper of the reactor is used to remove adsorbent dust generated by the regeneration system by a ceramic separator blower. The upper locking hopper is used to: adjust the pressure to the reaction pressure; The upper locked hopper adjusts the reaction pressure to 1.0-5.0 MPag; The lower locking hopper is used to adjust the pressure to 0.3-1.0 MPa; The regeneration pressure of sulfur-containing adsorbents in one or more coke burners is between 0.1 and 1.0 MPa.
2. The moving bed adsorption desulfurization device according to claim 1, characterized in that, When the adsorbent is burned in one or more stages of the coking regenerator, the regeneration ends when the sulfur content of the adsorbent is between 0-0.5 wt%.
3. The moving bed adsorption desulfurization device according to claim 2, characterized in that, During the coking process in the one or more coking regenerators, the coking temperature does not exceed 600°C.
4. A moving bed adsorption desulfurization method, utilizing the moving bed adsorption desulfurization device as described in any one of claims 1-3, characterized in that, The moving bed adsorption desulfurization method includes: Sulfur-containing heavy oil is introduced into a co-current moving bed reactor for liquid-phase adsorption desulfurization treatment in the co-current moving bed reactor. After the desulfurization treatment, the wet sulfur-containing adsorbent enters the lower closed hopper below the co-current moving bed reactor to reduce the adsorption pressure. The wet sulfur-containing adsorbent is centrifuged to further separate the heavy oil carried in the wet sulfur-containing adsorbent; The separated sulfur-containing adsorbent is lifted into one or more stages of coking regenerator so that the sulfur-containing adsorbent is coked and regenerated through the one or more stages of coking regenerator. The regenerated adsorbent, which has been charred in one or more stages of the charring regenerator, is introduced into a co-current moving bed reactor to complete one cycle. The top of the one or more coke burner regenerator is provided with a regenerator top separation hopper, and the reactor bottom elevator is used to introduce sulfur-containing adsorbent into the regenerator top separation hopper. The bottom of the one or more coke burner regenerator is provided with a flow control hopper. The flow control hopper is used to control the flow of the coke burner regenerated adsorbent before it enters the buffer hopper, thereby adjusting and controlling the circulation rate of the coke burner regenerated adsorbent. Downstream of the flow control hopper is a regenerator bottom lifter, which is used to lift the regenerated adsorbent to the co-current moving bed reactor so that the regenerated adsorbent can enter the next cycle.
Citation Information
Patent Citations
Method and apparatu of adsorbing desulfurization of catalytically cracked gasoline
CN101067093A
Processing method and system for inferior crude oil
CN107267208A