METHODS AND SYSTEMS FOR HYDROCARBON OIL PROCESSING

Abstract

The invention proposes a method for treating hydrocarbon oil, including step (1): to give hydrocarbon oil, preferably gaseous hydrocarbon oil, contact in hydrogen-free conditions in a desulfurization reactor, with a desulfurization adsorbent consisting of a metal active component M to carry out a selective desulfurization reaction and produce sulfides of the metal active component, known as metal sulfides, to obtain at least partially desulfurized hydrocarbon oil and used desulfurization adsorbent containing metal sulfides; wherein at least part, preferably all, of the sulfides in the hydrocarbon oil are non-thiophene sulfides, and the metal active component M is one or more of the selected types from cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium; preferably step (1) is carried out in a continuous manner. The invention also proposes a system for implementing the method described above.

Description

Method and system for treating hydrocarbon oil Technical Field

[0001] The present invention relates to the field of petrochemical engineering, and in particular to a method and system for treating hydrocarbon oil to desulfurize it. Background Art

[0002] Refineries produce large quantities of liquefied natural gas (LNG), which contains a high sulfur content. The sulfur compounds in LNG are converted into sulfur oxides (SOx) through combustion. Emissions into the atmosphere contribute to acid rain and cause severe environmental pollution, necessitating desulfurization. The sulfides in LNG are primarily hydrogen sulfide, mercaptans, and sulfides. Organic sulfides such as mercaptans are difficult to completely remove using traditional wet desulfurization methods using alcoholamines. Excessive sulfur content in LNG limits its application in downstream processing.

[0003] CN105176615A provides a new method for removing mercaptans from liquefied petroleum gas, which comprises the following steps: a) in completely alkali-free conditions, the liquefied petroleum gas treated with alcoholamine is subjected to a catalyst in a fixed-bed reactor, so that the mercaptans in the liquefied petroleum gas undergo an alkylation reaction with olefins to generate high-boiling-point sulfides; b) the liquefied petroleum gas containing the high-boiling-point sulfides flows out of the fixed-bed reactor and enters a distillation tower, where it is separated into a sulfur-free liquefied petroleum gas component and a sulfur-containing high-boiling-point component through distillation, thereby achieving the purpose of liquefied gas refining. The method has the advantages of high efficiency and no alkali liquid discharge.

[0004] Adsorption is a new technology for removing sulfides from hydrocarbon oils. It utilizes adsorbents to selectively adsorb polar sulfides, such as mercaptans and thiophenes, to remove sulfides from gasoline, diesel, or aromatic hydrocarbons. Currently, the main types of adsorbents reported for hydrocarbon oil desulfurization include oxide adsorbents (γ-Al₂O₃, TiO₂, ZrO₂, ZnO₂, SiO₂), metal-loaded oxide adsorbents (Ni, Na, K, Ca, Ba), molecular sieve adsorbents (A, X, Y, TS-1, SAPO-34, MCM-41), and metal ion-exchange molecular sieve adsorbents. Adsorbents used for aromatic hydrocarbon desulfurization primarily include supported oxide adsorbents loaded with metals (Ni, Pd, Pt, Cu, etc.), as reported in USP 2,876,196, USP 3,485,884, USP 4,419,224, and USP 4,592,829.

[0005] CN103031150A provides a dual-reactor method for simultaneously removing sulfides from hydrocarbon oil and liquefied gas. The hydrocarbon oil feedstock and hydrogen enter a first adsorption reactor from the bottom, flow upward, and come into contact with a desulfurization adsorbent in the reactor to remove sulfides from gasoline. In the upper portion of the first adsorption reactor, the desulfurized oil and gas are separated from the desulfurization adsorbent, and the separated, less active desulfurization adsorbent is introduced into a second adsorption reactor. In the second adsorption reactor, the sulfur-containing liquefied gas comes into contact with the hydrogen and desulfurization adsorbent to remove sulfides from the liquefied gas. This method maximizes the desulfurization activity of the adsorbent, utilizing the adsorbent's remaining desulfurization capacity to remove sulfides from the liquefied gas while simultaneously adsorbing and removing sulfides from the gasoline.

[0006] US Patents US7427581, US6869522 and US6274533 disclose methods for desulfurizing light hydrocarbon oils by adsorption under hydrogen conditions. These methods have the characteristics of high desulfurization depth, low hydrogen consumption and low octane number loss, and can produce fuel oil with a sulfur content of less than 30 micrograms / gram. The adsorbent used in the above methods uses a mixture of zinc oxide, silica and aluminum oxide as a carrier, and the loaded active components are composed of one or more of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, vanadium, etc. At 0.1-10.3MPa, 37.7-537.7℃, and a weight hourly space velocity of 0.5-50h -1 Under the conditions of catalytic cracking and hydrogenation, sulfur in the oil is captured on the adsorbent. The hydrocarbons produced after sulfide cracking are returned to the reaction mass, and the sulfur-containing adsorbent can be recycled through continuous regeneration. In actual industrial applications, this process can remove sulfur from catalytically cracked gasoline to below 10 micrograms / gram by adsorption, and the product's anti-knock index loss does not exceed 0.6 units.

[0007] However, in the prior art, the desulfurization treatment of hydrocarbon oil containing sulfides and olefins is usually carried out under hydrogen conditions, which will cause saturation loss of olefins.

[0008] Chinese patent CN104277877 discloses a process for adsorption desulfurization of cracked gasoline, which combines non-hydrogen physical adsorption desulfurization with a hydrotreatment adsorbent to produce clean gasoline. Catalytic gasoline that has undergone selective hydrodesulfurization is used as the raw material and enters a fixed-bed reactor to contact the desulfurization adsorbent to adsorb thiophene compounds. After the desulfurization adsorbent is saturated with adsorption, the feedstock is stopped, hydrogen is passed through the desulfurization adsorbent bed, and the desulfurization adsorbent is hydrotreated. The hydrotreated adsorbent can then continue to adsorb sulfides in the catalytic gasoline. However, this method is implemented in a fixed bed. Because the desulfurizer has limited adsorption capacity and quickly reaches adsorption saturation, the desulfurization efficiency is low. It can only be operated in an intermittent manner, requiring constant switching of the desulfurization adsorbent and hydrogen, which affects production efficiency and places high demands on reactor safety. Furthermore, the document does not demonstrate that sulfides can be removed efficiently and deeply in a fluidized bed.

[0009] Summary of the Invention

[0010] The object of the present invention is to provide a method for treating hydrocarbon oil that can be carried out continuously, which can avoid the loss of olefins caused by hydrogenation during the desulfurization treatment of hydrocarbon oil and can efficiently and deeply remove sulfides contained in the hydrocarbon oil, especially non-thiophene sulfides.

[0011] In order to achieve the above-mentioned object, the first aspect of the present invention provides a method for treating hydrocarbon oil (especially liquefied gas) containing sulfides and optional olefins, the method comprising the following steps (1): contacting hydrocarbon oil, preferably gaseous hydrocarbon oil, with a desulfurization adsorbent containing a metal active component M under non-hydrogen conditions in a desulfurization reactor to carry out a selective desulfurization reaction and generate a metal active component sulfide called a metal sulfur compound, thereby obtaining at least partially desulfurized hydrocarbon oil and a regenerated desulfurization adsorbent containing the metal sulfide; wherein at least a portion, preferably all, of the sulfides in the hydrocarbon oil are non-thiophene sulfides, and the metal active component M is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium; preferably, step (1) is carried out continuously. As an illustration, in this specification, the term "regenerated desulfurization adsorbent" refers to a desulfurization adsorbent that has at least partially lost its activity and needs to be restored or regenerated.

[0012] According to a preferred technical solution of the first aspect above, the desulfurization adsorbent further comprises a carrier, wherein the carrier contains a sulfur-carrying component in the form of an oxide, and the metal active component M is loaded on the carrier.

[0013] According to a preferred technical solution of the first aspect above, the method further includes the following step (2): transferring the desulfurization adsorbent to be generated into a sulfur transfer reactor and contacting it with a hydrogen donor to carry out a sulfur transfer reaction to reduce the metal sulfide to a metal active component M, and converting the sulfur-carrying component in the form of an oxide into a sulfide to obtain a desulfurization adsorbent with at least partially restored activity, and optionally returning at least a portion of the desulfurization adsorbent with at least partially restored activity to the desulfurization reactor of step (1). Preferably, step (2) is carried out continuously.

[0014] According to one embodiment of the first aspect of the present invention, the method for continuously treating a hydrocarbon oil (particularly liquefied gas) containing sulfides and optionally olefins comprises the following steps:

[0015] (1) contacting a hydrocarbon oil, preferably a gaseous hydrocarbon oil, with a desulfurization adsorbent comprising a metal active component and a carrier containing a sulfur-carrying component in a desulfurization reactor under non-hydrogen conditions to carry out a selective desulfurization reaction to generate metal sulfides, thereby obtaining at least partially desulfurized, or even almost completely desulfurized, hydrocarbon oil and a regenerated desulfurization adsorbent comprising metal sulfides; wherein at least a portion, preferably at least 50%, more preferably 75%, and even more preferably 100%, of the sulfides contained in the hydrocarbon oil are non-thiophene sulfides;

[0016] (2) transferring the desulfurization adsorbent to be regenerated to a sulfur transfer reactor and contacting it with a hydrogen donor to carry out a sulfur transfer reaction to reduce the metal sulfide to the metal active component, wherein the sulfur element is transferred to the sulfur-carrying component to obtain a desulfurization adsorbent with at least partially restored activity, and then returning at least a portion of the desulfurization adsorbent with at least partially restored activity to the desulfurization reactor of step (1).

[0017] According to a second aspect of the present invention, the present invention also provides a system for treating hydrocarbon oil, characterized in that the system includes a non-hydrogen desulfurization reactor (2), wherein the non-hydrogen desulfurization reactor (2) is provided with a hydrocarbon oil inlet at the bottom for the entry of hydrocarbon oil, a desulfurization adsorbent inlet at the lower part, a desulfurization oil and gas outlet at the top and an outlet for the desulfurization adsorbent to be generated at the upper part.

[0018] According to one embodiment of the second aspect of the present invention, the system for treating hydrocarbon oil according to the present invention comprises a non-hydrogen desulfurization reactor (2) and a hydrosulfur transfer reactor (7), wherein the bottom of the non-hydrogen desulfurization reactor (2) is provided with a hydrocarbon oil inlet for supplying hydrocarbon oil, the lower part is provided with a desulfurization adsorbent inlet, the top is provided with a desulfurized oil and gas outlet, and the upper part is provided with an outlet for a desulfurization adsorbent to be regenerated; the bottom of the hydrosulfur transfer reactor (7) is provided with a hydrogen donor inlet, the lower part is provided with an inlet for a desulfurization adsorbent to be regenerated and an optional inlet for a regenerated desulfurization adsorbent, the upper part is provided with an outlet for a desulfurization adsorbent for recovering at least part of its activity, the top is provided with a gas outlet, and the non-hydrogen desulfurization reactor (2) is provided with a hydrocarbon oil inlet for supplying hydrocarbon oil, the lower part is provided with a desulfurization adsorbent inlet, the top part is provided with a desulfurized oil and gas outlet, and the upper part is provided with an outlet for a desulfurization adsorbent to be regenerated. The outlet of the desulfurization adsorbent to be regenerated of the desulfurization reactor (2) is connected to the inlet of the desulfurization adsorbent to be regenerated of the hydrogenation sulfur transfer reactor (7) through a pipeline, and the outlet of the desulfurization adsorbent to be reactivated of the hydrogenation sulfur transfer reactor (7) is connected to the desulfurization adsorbent inlet of the non-hydrodesulfurization reactor (2) through a pipeline; wherein the pipeline (6, 20) is provided with a device for respectively pressing the desulfurization adsorbent to be regenerated and the desulfurization adsorbent that has at least partially recovered its activity into the hydrogenation sulfur transfer reactor (7) and the non-hydrodesulfurization reactor (2) and a device for preventing gas from flowing between the non-hydrodesulfurization reactor (2) and the hydrogenation sulfur transfer reactor (7).

[0019] After extensive research, the inventors surprisingly discovered that when desulfurizing hydrocarbon oils containing non-thiophene sulfides and a large amount of olefins, reactive adsorption of the sulfides can be achieved even under non-hydrogenation conditions. More specifically, by contacting the hydrocarbon oil with a desulfurization adsorbent comprising a metal active component, a support, and an optional sulfur-carrying component in a desulfurization reactor under non-hydrogenation conditions, the non-thiophene sulfides, particularly mercaptans, sulfides, and hydrogen sulfide, contained in the hydrocarbon oil can be rapidly and extensively removed by chemically reacting the sulfur in the sulfides with the metal active component, without hydrogenating the contained olefins. Furthermore, unlike prior art physical adsorption methods, this desulfurization reaction securely encloses the sulfides formed by the sulfur and metal active component within the desulfurization adsorbent. Therefore, the desulfurization reaction can be carried out continuously in a fluidized bed under high temperature and high gas flow rates, allowing the metal sulfides to be continuously removed from the desulfurization reactor along with the desulfurization adsorbent. The desulfurization sorbent containing metal sulfide can then be reduced to a metal active component M in a desulfurization sorbent reactor under hydrogen conditions by reacting with a sulfur-carrying component contained in a carrier. In this case, the desulfurization sorbent is converted into a desulfurization sorbent that has at least partially recovered its activity. At least a portion of the desulfurization sorbent obtained, which has at least partially recovered its activity, can then be recycled to the desulfurization reactor. Because the sulfur transfer reaction can also be carried out in a fluidized bed, the method of the present invention can be carried out continuously without requiring intermittent feeding or replacement of the desulfurization sorbent, thereby saving operating costs and time. Furthermore, the amount of metal active component used in the desulfurization sorbent can be reduced. The inventors believe, without being bound by a specific theory, that the principle of the hydrogen sulfur transfer process may be as follows: Under the action of hydrogen, the metal active component sulfide (e.g., nickel sulfide) in the desulfurization sorbent undergoes a reduction reaction to generate a metal active component (e.g., nickel). Under the catalytic action of the metal active component (e.g., nickel), sulfur combines with the sulfur-carrying component (e.g., zinc oxide) in the desulfurization sorbent to form sulfide, which is then transferred to the sorbent. Since the metal active components on the surface of the adsorbent are released, the non-hydrogen chemical reaction adsorption process of step (1) can be repeated.

[0020] More specifically, without being bound by a particular theory and without limiting the present invention in any way, based on the test results of the products of the non-hydrogen adsorption desulfurization reaction and the hydrosulfur transfer reaction, the inventors believe that when the desulfurization adsorbent of the present invention is used for the desulfurization of sulfides such as methyl mercaptan, the following reactions may occur in the desulfurization reactor and the sulfur transfer reactor, respectively:

[0021] Non-hydrogen adsorption desulfurization reaction: CH3-SH+Ni→CH4+NiS

[0022] Hydrogen-sulfur transfer reaction: NiS+ZnO+H2→Ni+ZnS+H2O.

[0023] As can be seen from the above reactions, the chemical adsorption method of the present invention only displaces the sulfur element in the hydrocarbon oil from the non-thiophene sulfides and carries them out of the desulfurization reactor along with the desulfurization adsorbent, without carrying out the entire sulfide (such as mercaptans). Furthermore, by allowing the sulfide in the hydrocarbon oil to react quickly and fully with the metal active component, sulfur is deeply removed. Therefore, this desulfurization method does not result in the loss of carbon and hydrogen elements in the hydrocarbon oil. In contrast, the physical adsorption under non-hydrogen conditions in the prior art only carries out the entire organic sulfide, such as thiophene, along with the adsorbent, resulting in the loss of some carbon and hydrogen elements in the hydrocarbon oil.

[0024] According to a preferred embodiment, in the method according to the present invention, the desulfurization reactor is a fluidized bed reactor or a moving bed, and / or the sulfur transfer reactor is a fluidized bed reactor or a moving bed; preferably, the desulfurization reactor is a fluidized bed reactor, and / or the sulfur transfer reactor is a fluidized bed reactor.

[0025] According to a preferred embodiment, in the method according to the present invention, the conditions of the selective desulfurization reaction include: a temperature of 150-550°C, preferably 300-450°C, such as 350°C or 400°C; a pressure of 0.1-5MPa, preferably 1.5-4MPa, such as 2.0MPa, 2.5MPa, 3.0MPa or 3.5MPa; a weight hourly space velocity of the hydrocarbon oil containing sulfides and olefins of 0.1-30h -1 , preferably 1-20h -1 , for example 2h -1 , 4h -1 , 6h -1 , 8h -1 , 10h -1 , 12h -1 , 14h -1 , 16h -1 and 18h -1 .

[0026] According to a preferred embodiment, in the method according to the present invention, the sulfur content in the hydrocarbon oil containing sulfides and olefins is 10-5000 μg / g, preferably 30-3000 μg / g, and the mass percentage of olefins is 2-100%, preferably 5-85%.

[0027] According to a preferred embodiment, in the method according to the present invention, the hydrocarbon oil containing sulfides and olefins is selected from one or more of dry gas, liquefied gas, and catalytic gasoline; preferably, the hydrocarbon oil containing sulfides and olefins is selected from one or more of catalytic cracking dry gas, catalytic cracking liquefied gas, catalytic cracking dry gas, catalytic cracking liquefied gas, steam cracking ethylene and / or propylene products, or one or more of C7 and lower light fractions in catalytic cracking gasoline, catalytic cracking gasoline, and steam cracking gasoline. If the hydrocarbon oil is liquid at room temperature, it can be preheated before entering the desulfurization reactor to convert it into a gaseous state.

[0028] According to a preferred embodiment, in the method according to the present invention, the conditions of the sulfur transfer reaction include: temperature of 300-550° C., preferably 350-450° C.; pressure of 0.1-5 MPa, preferably 1.5-4 MPa.

[0029] According to a preferred embodiment, in the method according to the present invention, the hydrogen donor is selected from one or more of hydrogen, a mixed gas containing hydrogen and a hydrogen donor, preferably, the volume fraction of hydrogen in the hydrogen-containing mixed gas is 10-99%, preferably 30-90%; or the hydrogen donor is selected from one or more of cyclohexane, methylcyclohexane, tetralin and decalin, preferably, the volume ratio of hydrogen in the hydrogen donor to the desulfurization adsorbent to be generated is (10-3000):1, preferably 100-2500:1, for example 300:1, 500:1, 800:1, 1200:1, 1500:1 or 2000:1.

[0030] According to a preferred embodiment, in the method according to the present invention, the sulfur content of the at least partially restored desulfurization adsorbent is 0.5-12%, preferably 1-10%, calculated as elemental sulfur, relative to the total weight of the desulfurization adsorbent.

[0031] According to a preferred embodiment, in the method according to the present invention, the method further includes step (3): subjecting the remaining portion of the at least partially restored desulfurization adsorbent obtained in step (2) that is not returned to the desulfurization reactor of step (1) to oxygen-containing char regeneration to obtain a regenerated desulfurization adsorbent, and subjecting the regenerated desulfurization adsorbent to a reduction treatment in a reducing gas atmosphere to obtain a reduced desulfurization adsorbent, and then returning the reduced desulfurization adsorbent to the desulfurization reactor of step (1).

[0032] According to a preferred embodiment, in the method according to the present invention, the oxygen-containing coke is carried out in the presence of an oxygen-containing gas, and the volume fraction of oxygen in the oxygen-containing gas is 5-50 volume %; preferably, the oxygen-containing gas is selected from one of air, a mixture of oxygen and nitrogen, and a mixture of air and nitrogen; preferably, the reaction conditions of the oxygen-containing coke include: a temperature of 300-800°C, preferably 350-600°C; and a pressure of 0.1-3.0 MPa, preferably 0.1-1.0 MPa.

[0033] According to a preferred embodiment, in the method according to the present invention, the conditions for the reduction treatment of the regenerated desulfurization adsorbent include: a temperature of 300-550°C, preferably 350-450°C; a pressure of 0.1-5 MPa, preferably 1.5-4 MPa; a volume space velocity of hydrogen in the reducing gas of 10-3000 h -1 ; Preferably, the reducing gas is selected from one or more of hydrogen, a mixed gas containing hydrogen and a precursor compound capable of producing hydrogen; preferably, the volume fraction of hydrogen in the mixed gas containing hydrogen is 10-99%, preferably 30-95%; preferably, the reduction treatment of the regenerated desulfurization adsorbent is also carried out in the sulfur transfer reactor.

[0034] According to a preferred embodiment, in the method according to the present invention, the metal active component is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium, preferably cobalt and nickel, and / or the sulfur-carrying component is mainly selected from the oxides of IVB, VIIB, VIIIB, IIB, IIB, IIA and IVA metal elements, preferably selected from ZnO, TiO2, ZrO2, MnO2, Fe2O3, CuO, MgO, CaO, SrO, GeO, SnO, PbO; more preferably, selected from ZnO.

[0035] According to a preferred embodiment, in the method according to the present invention, the carrier containing the sulfur-carrying component comprises, based on the weight of the carrier, 20-85wt%, preferably 25-75wt% of the sulfur-carrying component, 10-75wt%, preferably 15-60wt% of alumina, and 5-70wt%, preferably 15-60wt% of silica.

[0036] According to a preferred embodiment, in the method according to the present invention, based on the total weight of the desulfurization adsorbent, the content of the metal active component is 2-30 wt%, and the content of the carrier containing the sulfur-carrying component is 70-98 wt%.

[0037] According to a preferred embodiment, in the method according to the present invention, the sulfide is selected from one or more of mercaptans, sulfides, carbonyl sulfide and hydrogen sulfide.

[0038] According to a second aspect of the present invention, the present invention also provides a system for treating hydrocarbon oil, characterized in that the system includes a non-hydrogen desulfurization reactor (2), wherein the non-hydrogen desulfurization reactor (2) is provided with a hydrocarbon oil inlet at the bottom for the entry of hydrocarbon oil, a desulfurization adsorbent inlet at the lower part, a desulfurization oil and gas outlet at the top and an outlet for the desulfurization adsorbent to be generated at the upper part.

[0039] According to one embodiment of the second aspect of the present invention, the system for treating hydrocarbon oil according to the present invention comprises a non-hydrogen desulfurization reactor (2) and a hydrosulfur transfer reactor (7), wherein the bottom of the non-hydrogen desulfurization reactor (2) is provided with a hydrocarbon oil inlet for supplying hydrocarbon oil, the lower part is provided with a desulfurization adsorbent inlet, the top is provided with a desulfurized oil and gas outlet, and the upper part is provided with a regenerated desulfurization adsorbent outlet; the bottom of the hydrosulfur transfer reactor (7) is provided with a hydrogen donor inlet, the lower part is provided with a regenerated desulfurization adsorbent inlet and an optional regenerated desulfurization adsorbent inlet, the upper part is provided with an outlet for at least partially recovering the activity of the desulfurization adsorbent, the top is provided with a gas outlet, and the non-hydrogen desulfurization reactor (2) is provided with a hydrocarbon oil inlet for supplying hydrocarbon oil, the lower part is provided with a desulfurization adsorbent inlet, the top is provided with a desulfurized oil and gas outlet, and the upper part is provided with a regenerated desulfurization adsorbent outlet. The outlet of the desulfurization adsorbent to be regenerated of the desulfurization reactor (2) is connected to the inlet of the desulfurization adsorbent to be regenerated of the hydrogenation sulfur transfer reactor (7) through a pipeline, and the outlet of the desulfurization adsorbent to be reactivated of the hydrogenation sulfur transfer reactor (7) is connected to the desulfurization adsorbent inlet of the non-hydrodesulfurization reactor (2) through a pipeline; wherein the pipeline (6, 20) is provided with a device for respectively pressing the desulfurization adsorbent to be regenerated and the desulfurization adsorbent that has at least partially recovered its activity into the hydrogenation sulfur transfer reactor (7) and the non-hydrodesulfurization reactor (2) and a device for preventing gas from flowing between the non-hydrodesulfurization reactor (2) and the hydrogenation sulfur transfer reactor (7).

[0040] According to a preferred embodiment, the system for processing hydrocarbon oil of the present invention further comprises a first receiver (5) and a second receiver (19), wherein the first receiver (5) is provided with a first material inlet and a first material outlet, and the second receiver (19) is provided with a second material inlet and a second material outlet; wherein the outlet of the desulfurization adsorbent to be regenerated of the non-hydrodesulfurization reactor (2) is connected to the first material inlet of the first receiver (5), and the first material outlet of the first receiver (5) is connected to the desulfurization adsorbent to be regenerated inlet of the hydrosulfurization transfer reactor (7); and the outlet of the reactivated desulfurization adsorbent of the hydrosulfurization transfer reactor (7) is connected to the second material inlet of the second receiver (19), and the second material outlet of the second receiver (19) can be switchably connected to the desulfurization adsorbent inlet of the non-hydrodesulfurization reactor (2).

[0041] According to a preferred embodiment, the system for processing hydrocarbon oil of the present invention further comprises a lock hopper (11) and a regenerator (14); wherein the bottom of the regenerator (14) is provided with an oxygen-containing gas inlet, the lower part is provided with a regenerated desulfurization adsorbent outlet, the upper part is provided with a desulfurization adsorbent inlet, and the top is provided with a flue gas outlet; the lock hopper (11) is provided with a third material inlet, a third material outlet and a regenerated desulfurization adsorbent inlet; the second material outlet of the second receiver (19) can also be switchably connected to the third material inlet of the lock hopper (11), the third material outlet of the lock hopper (11) can be switchably connected to the desulfurization adsorbent inlet of the regenerator (14), the regenerated desulfurization adsorbent outlet of the regenerator (14) is connected to the regenerated desulfurization adsorbent inlet of the lock hopper (11), and the third material outlet of the lock hopper (11) can also be switchably connected to the regenerated desulfurization adsorbent inlet of the hydrogen sulfur transfer reactor (7).

[0042] According to a preferred embodiment, the system for treating hydrocarbon oil according to the present invention is used to implement the method for treating hydrocarbon oil according to the present invention.

[0043] According to a preferred embodiment, in the system of the present invention, the regenerator (14) is a fluidized bed reactor or a moving bed reactor, preferably a fluidized bed reactor.

[0044] Through the above technical solution, the present invention allows hydrocarbon oil containing sulfides and olefins to contact with a desulfurizer under non-hydrogen conditions to carry out a desulfurization reaction, which not only achieves deep desulfurization of the hydrocarbon oil, but also avoids the loss of olefins and octane number caused by hydrogenation saturation of unsaturated olefins under hydrogen reaction conditions, thereby improving the selectivity of the desulfurization reaction.

[0045] Other features and advantages of the present invention will be described in detail in the following detailed description of the embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:

[0047] FIG1 shows a schematic flow diagram of a system for processing hydrocarbon oil according to one embodiment of the present invention.

[0048] FIG2 shows a schematic flow diagram of a system for processing hydrocarbon oil according to a preferred embodiment of the present invention.

[0049] The reference numerals in Figures 1 and 2 are as follows: 1: hydrocarbon oil and gas inlet 2: desulfurization reactor 3: desulfurized hydrocarbon oil and gas outlet 4: regenerated desulfurization adsorbent outlet 5: first receiver 6: pipeline 7: hydrogen sulfur transfer reactor 8: hydrogen inlet 9: circulating hydrogen outlet 10: pipeline 11: lock hopper 12: pipeline 13: pipeline 14: regenerator 15: gas inlet 16: regenerated flue gas outlet 17: pipeline 18: reactivated desulfurization adsorbent outlet 19: second receiver 20: pipeline Specific implementation plan

[0050] The specific embodiments of the present application are described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application and are not intended to limit the present application.

[0051] Any specific numerical value disclosed herein (including the endpoints of a numerical range) is not limited to the exact value of the numerical value, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Moreover, for a disclosed numerical range, any combination of the endpoints of the range, between the endpoints and the specific points in the range, and between the specific points can be used to generate one or more new numerical ranges, and these new numerical ranges should also be considered to be specifically disclosed herein.

[0052] Unless otherwise specified, the terms used herein have the same meaning as commonly understood by those skilled in the art. If a term is defined herein and its definition is different from the commonly understood meaning in the art, the definition herein shall prevail.

[0053] In this application, except for the contents explicitly stated, any matters or items not mentioned are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are considered part of the original disclosure or original description of the present invention, and should not be regarded as new content not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.

[0054] Unless expressly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising” will be understood to include the stated elements or components but not to exclude other elements or components.

[0055] In this specification, the terms "first", "second", etc. are used to distinguish two different elements or parts, and are not used to limit specific positions or relative relationships. In other words, in some embodiments, the terms "first", "second", etc. can also be interchangeable.

[0056] In this application, the term "olefin" has the meaning commonly understood in the art, i.e., an unsaturated hydrocarbon compound having a carbon-carbon double bond. The olefin may be a chain olefin or a cycloolefin, and may have one, two, or more carbon-carbon double bonds, and the carbon-carbon double bond may be at the end of the carbon chain or in the middle of the carbon chain (i.e., an internal olefin). In addition, the olefin may contain other functional groups, such as hydroxyl groups, aromatic rings, etc. In the method of the present application, the olefin is preferably a monoolefin, and more preferably a linear or branched monoolefin.

[0057] References to the "upper," "lower," "top," or "bottom" of a reactor in this specification refer to the relative horizontal positions of different regions of the reactor. The "top" position may be higher or lower than the "upper" position, the "upper" position may be higher than the "lower," and the "lower" position may be higher or lower than the "bottom." The "top" and "upper" positions of a reactor are generally within the upper half or even one-third of the total height of the reactor, while the "bottom" and "lower" positions of a reactor are generally within the lower half or even one-third of the total height of the reactor.

[0058] All patent and non-patent literature, including but not limited to textbooks and journal articles, mentioned herein are incorporated by reference in their entirety.

[0059] According to a preferred embodiment, the present invention provides a method for treating hydrocarbon oil, in particular liquefied gas, in particular a method for desulfurizing hydrocarbon oil, the method comprising the following steps:

[0060] (1) under non-hydrogen conditions, in a desulfurization reactor, contacting a hydrocarbon oil containing sulfide and optionally olefin with a desulfurization adsorbent comprising a metal active component and a carrier containing a sulfur-carrying component to perform a selective desulfurization reaction and generate metal sulfide, thereby obtaining an at least partially desulfurized hydrocarbon oil and a regenerated desulfurization adsorbent comprising the metal sulfide; wherein the sulfide is a non-thiophene compound;

[0061] (2) The desulfurization adsorbent to be regenerated is directly contacted with a hydrogen donor in a sulfur transfer reactor to carry out a sulfur transfer reaction to reduce the metal sulfide to the metal active component, thereby obtaining a desulfurization adsorbent with at least partially restored activity, and then at least a portion of the desulfurization adsorbent with at least partially restored activity is returned to the desulfurization reactor in step (1).

[0062] The present invention allows hydrocarbon oil containing sulfides and optional olefins, especially liquefied gas, to contact with a desulfurization adsorbent containing a metal active component and a carrier containing a sulfur-carrying component under non-hydrogen conditions to carry out a desulfurization reaction. The one-step desulfurization reaction under hydrogen conditions in the prior art is modified into a non-hydrogen desulfurization and hydrogen sulfur transfer reaction carried out in two steps respectively, thereby avoiding the problem of hydrogenation saturation of olefins in the feedstock during the desulfurization reaction under hydrogen conditions and preventing olefin loss.

[0063] After the desulfurization reaction is carried out under non-hydrogen conditions, the desulfurization adsorbent contacts with hydrogen to carry out a sulfur transfer reaction, releasing metal active centers, at least partially restoring the desulfurization activity of the desulfurization adsorbent, and increasing the sulfur holding capacity of the desulfurization adsorbent, so that the desulfurization adsorbent with at least partially restored activity can be partially recycled back to the desulfurization reactor, and reducing the sulfur burning regeneration intensity of the desulfurization adsorbent in the regenerator.

[0064] When used to desulfurize the light fraction of catalytic gasoline, the method of the present invention can avoid the octane loss caused by existing hydrodesulfurization processes. When applied to the desulfurization of liquefied petroleum gas, the method of the present invention can also avoid the loss of unsaturated olefins due to hydrogenation during hydrodesulfurization, thereby improving the quality of hydrocarbon oil. Compared with traditional alkaline desulfurization, the desulfurization method of the present invention avoids the problem of alkaline liquid discharge and achieves a higher desulfurization depth.

[0065] In the context of the present invention, "at least a portion" means part or all. For example, in one embodiment of the present invention, the desulfurization sorbent that has at least partially recovered its activity can be returned to the desulfurization reactor of step (1) to continue the desulfurization reaction; in another embodiment of the present invention, a portion of the desulfurization sorbent that has at least partially recovered its activity can be returned to step (1) to carry out the desulfurization reaction, and the remaining portion of the desulfurization sorbent that has at least partially recovered its activity can be subjected to oxygen-containing regeneration and reduction in sequence and then returned to the desulfurization reactor in step (1).

[0066] In the context of the present invention, "a desulfurization adsorbent that has at least partially recovered its activity" refers to a desulfurization adsorbent whose metal active components have recovered their desulfurization activity. The regenerated desulfurization adsorbent contacts a hydrogen donor to undergo a sulfur transfer reaction. In the presence of hydrogen, sulfur is transferred from the metal active component to the sulfur-carrying component, releasing metal active centers and recovering at least part of the desulfurization activity of the desulfurization adsorbent. Therefore, after the sulfur transfer reaction, the regenerated desulfurization adsorbent can be recycled back to the desulfurization reactor to continue participating in the desulfurization reaction, greatly increasing the sulfur holding capacity of the desulfurization adsorbent, significantly extending the time the desulfurization adsorbent is used for the desulfurization reaction, reducing the frequency of regeneration of the desulfurization adsorbent by burning sulfur and carbon, and thereby reducing the loss of the desulfurization adsorbent during the regeneration process.

[0067] Preferably, the conditions for carrying out the selective desulfurization reaction in the desulfurization reactor allow the reactor to react in the form of a fluidized bed; preferably, the reaction conditions include: a temperature of 150-550°C, preferably 200-450°C, for example, 250°C, 300°C, 350°C or 400°C; a pressure of 0.1-5MPa, preferably 1.5-4MPa, for example, 2.0MPa, 2.5MPa, 3.0MPa or 3.5MPa; a weight hourly space velocity of the hydrocarbon oil containing sulfides and olefins of 0.1-30h -1 , preferably 1-20h -1 , for example 2h -1 , 4h -1 , 6h -1 , 8h -1 , 10h -1 , 12h -1 , 14h -1 , 16h -1 or 18h -1 Under the above reaction conditions, the catalytic efficiency of the desulfurization reaction of the hydrocarbon oil containing sulfides and olefins in contact with the desulfurization adsorbent is higher. Preferably, the flow rate of the hydrocarbon oil is such that the desulfurization reactor is operated in a fluidized bed mode.

[0068] In the present invention, the hydrocarbon oil containing sulfides and olefins contains C2-C7 olefins and sulfides, wherein at least a portion of the sulfides in the hydrocarbon oil are preferably not all thiophene sulfides, and the sulfides mainly include hydrogen sulfide, mercaptans, sulfides, disulfides or a mixture of one or more thereof.

[0069] The sulfur content of the hydrocarbon oil containing sulfides and olefins is above 10 μg / g, preferably 15-5000 μg / g, preferably 20-45000 μg / g; the mass percentage of olefins is 2-100%; preferably, the sulfur content of the hydrocarbon oil containing sulfides and olefins is 30-3000 μg / g, and the mass percentage of olefins is 5-85%.

[0070] The hydrocarbon oil containing sulfides and olefins may be a hydrocarbon oil from any source. Preferably, the hydrocarbon oil containing sulfides and olefins is selected from one or more of dry gas, liquefied gas, and catalytic gasoline; preferably, the hydrocarbon oil containing sulfides and olefins is selected from one or more of catalytic cracking dry gas, catalytic cracking liquefied gas, catalytic cracking dry gas, catalytic cracking liquefied gas, and steam cracking ethylene and / or propylene products, or is selected from one or more of C7 and lower light fractions in catalytic cracking gasoline, catalytic cracking gasoline, and steam cracking gasoline.

[0071] The sulfur transfer reaction carried out in the sulfur transfer reactor is a reaction between metal sulfide, hydrogen donor and sulfur-carrying component; preferably, the reaction conditions in the reactor allow the reactor to carry out the reaction in the form of a fluidized bed; preferably, the conditions of the sulfur transfer reaction include: a temperature of 300-550°C, preferably 350-450°C, for example, 370°C, 400°C or 420°C; a pressure of 0.1-5MPa, preferably 1.5-4MPa, for example, 2.0MPa, 2.5MPa, 3.0MPa or 3.5MPa. The hydrogen donor can be selected from one or more of hydrogen, a mixed gas containing hydrogen and a precursor capable of producing hydrogen; the volume fraction of hydrogen in the hydrogen-containing mixed gas is 10-99%, preferably 30-90%, for example 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%; the precursor compound capable of producing hydrogen is selected from one or more of cyclohexane, methylcyclohexane, tetralin and decalin; the volume ratio of hydrogen in the hydrogen donor to the desulfurization adsorbent to be generated is (10-3000):1, preferably 50-2000:1, for example 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, 1200:1, 1300:1 or 1400:1.

[0072] The sulfur content of the at least partially recovered desulfurization adsorbent obtained by the sulfur transfer reaction in the sulfur transfer reactor is 0.5-12%, preferably 0.6-8%, such as 2%, 3%, 4%, 5%, 6% or 7%.

[0073] In order to further restore the activity of the desulfurization adsorbent that has at least partially restored its activity, the method for treating hydrocarbon oil according to the present invention further includes: regenerating the remaining part of the desulfurization adsorbent that has at least partially restored its activity by oxygen-containing charring to obtain a regenerated desulfurization adsorbent, and reducing the regenerated desulfurization adsorbent in a reducing gas atmosphere to obtain a reduced desulfurization adsorbent, and then returning the reduced desulfurization adsorbent to the desulfurization reactor of step (1).

[0074] According to a specific embodiment, the desulfurization adsorbent with at least partially restored activity can also be regenerated by oxygen-containing coke with an oxygen-containing gas to burn off the sulfur and carbon adsorbed on the desulfurization adsorbent to obtain a desulfurization adsorbent with fully restored activity. The regenerated desulfurization adsorbent is then reduced under hydrogen conditions, and the reduced regenerated desulfurization adsorbent is returned to the desulfurization reactor to contact with hydrocarbon oil containing sulfides and olefins to carry out a desulfurization reaction.

[0075] According to a specific embodiment, the oxygen-containing charring in the regenerator is carried out in the presence of an oxygen-containing gas, wherein the volume fraction of oxygen in the oxygen-containing gas is 5-50% by volume, preferably 10-45% by volume; the oxygen-containing gas is selected from one of air, a mixture of oxygen and nitrogen, and a mixture of air and nitrogen; preferably, the reaction conditions for the oxygen-containing charring include: a temperature of 300-800°C, preferably 350-600°C; and a pressure of 0.1-3.0 MPa, preferably 0.1-1.0 MPa. The flue gas discharged from the top of the regenerator primarily contains gases such as carbon dioxide and sulfur oxides and requires treatment to meet environmental requirements before being discharged into the atmosphere.

[0076] According to a specific embodiment, the conditions for the reduction treatment of the regenerated desulfurization adsorbent include: a temperature of 300-550°C, preferably 350-450°C; a pressure of 0.1-5MPa, preferably 1.5-4MPa; the sulfur content of the reduced desulfurization adsorbent is 0.3-10%, preferably 0.3-6%; the volume ratio of hydrogen in the reducing gas to the regenerated desulfurization adsorbent is (10-3000):1, preferably (50-2000):1; the reducing gas is selected from one or more of hydrogen, a hydrogen-containing mixed gas and a precursor compound capable of generating hydrogen; the volume fraction of hydrogen in the hydrogen-containing mixed gas is 10-99%, preferably 30-90%; the precursor compound capable of generating hydrogen can be selected from one or more of cyclohexane, methylcyclohexane, tetralin and decalin.

[0077] According to a specific embodiment, the desulfurization adsorbent includes a metal active component and a carrier containing a sulfur-carrying component, wherein the sulfur-carrying component is selected from zinc oxide; based on the weight of the carrier, the carrier includes 20-85wt% of zinc oxide, 10-75wt% of aluminum oxide and 5-70wt% of silica, preferably 25-75wt% of zinc oxide, 15-65wt% of aluminum oxide and 10-60wt% of silica; based on the total weight of the desulfurization adsorbent, the content of the metal active component is 2-30wt%, preferably 10-25wt%, for example, 15wt% or 20wt%; the metal active component is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium, preferably one or more of cobalt, nickel and molybdenum.

[0078] The desulfurization adsorbent of the present invention can be prepared according to general methods known in the art, wherein the support is prepared by slurrying, mixing, shaping, drying, and calcining zinc oxide, aluminum oxide, and silica. The metal active component is loaded onto the support by methods such as impregnation and spraying, followed by drying and calcination, and reduced with hydrogen before use to obtain the desulfurization adsorbent for desulfurization reactions.

[0079] In the present invention, the desulfurization adsorbent may be in any shape, such as microspheres, ellipsoids, strips, sheets, and rings. The specific shape depends on the type of desulfurization reactor, and is preferably in the shape of microspheres.

[0080] In the present invention, the desulfurization reactor may be a fluidized bed or a moving bed, etc. The specific type may be determined according to the properties of the hydrocarbon oil to be processed and the economic efficiency of the operation; preferably, it is a fluidized bed type reactor.

[0081] The second aspect of the present invention provides a system for treating hydrocarbon oil, wherein the system includes a non-hydrogen desulfurization reactor 2 and a hydrosulfur transfer reactor 7, wherein the bottom of the non-hydrogen desulfurization reactor 2 is provided with a hydrocarbon oil inlet for supplying hydrocarbon oil, the lower part is provided with a desulfurization adsorbent inlet, the top is provided with a desulfurized oil and gas outlet, and the upper part is provided with a regenerated desulfurization adsorbent outlet; the bottom of the hydrosulfur transfer reactor 7 is provided with a hydrogen donor inlet, the lower part is provided with a regenerated desulfurization adsorbent inlet and a regenerated desulfurization adsorbent inlet, the upper part is provided with an outlet for recovering at least part of the activity of the desulfurization adsorbent, and the top is provided with a gas outlet, and the regenerated desulfurization adsorbent of the non-hydrogen desulfurization reactor (2) is provided with a hydrogen donor inlet. The adsorbent outlet is connected to the inlet of the desulfurization adsorbent to be regenerated of the hydrosulfurization transfer reactor (7) through a pipeline, and the outlet of the desulfurization adsorbent to be restored of the hydrosulfurization transfer reactor (7) is connected to the desulfurization adsorbent inlet of the non-hydrodesulfurization reactor (2) through a pipeline; wherein the pipeline (6, 20) is provided with a device (not shown) for respectively pressing the desulfurization adsorbent to be regenerated and the desulfurization adsorbent that has at least partially restored its activity into the hydrosulfurization transfer reactor (7) and the non-hydrodesulfurization reactor (2) and / or a device (not shown) for preventing gas from flowing between the non-hydrodesulfurization reactor (2) and the hydrosulfurization transfer reactor (7).

[0082] According to a preferred embodiment, as shown in FIG1 , the system according to the present invention comprises a non-hydrodesulfurization reactor 2, a hydrosulfur transfer reactor 7, a first receiver 5 and a second receiver 19, wherein the bottom of the non-hydrodesulfurization reactor 2 is provided with a hydrocarbon oil inlet for supplying hydrocarbon oil, a desulfurization adsorbent inlet is provided at the bottom, a desulfurized oil and gas outlet is provided at the top and a desulfurized adsorbent outlet to be regenerated is provided at the top; the hydrosulfur transfer reactor 7 is provided with a hydrogen donor inlet at the bottom, a desulfurized adsorbent inlet to be regenerated, a regenerated desulfurized adsorbent inlet, an outlet for at least partially recovering the activity of the desulfurized adsorbent at the top and a gas outlet is provided at the top, the first receiver 5 is provided with a first material inlet and a first material outlet, and the second receiver 19 is provided with a second material inlet and a second material outlet; the desulfurized adsorbent outlet to be regenerated of the non-hydrodesulfurization reactor 2 is provided with a hydrogen donor inlet, a desulfurized adsorbent inlet to be regenerated, a regenerated desulfurized adsorbent inlet, an outlet for at least partially recovering the activity of the desulfurized adsorbent, and a gas outlet at the top, the first receiver 5 is provided with a first material inlet and a first material outlet, and the second receiver 19 is provided with a second material inlet and a second material outlet; The first material inlet of the first receiver 5 is communicated with the first material outlet of the first receiver 5 through a pipeline 6 and the desulfurization adsorbent inlet to be regenerated of the hydrosulfurization transfer reactor 7; and the desulfurization adsorbent outlet of the hydrosulfurization transfer reactor 7 is communicated with the second material inlet of the second receiver 19, and the second material outlet of the second receiver 19 is switchably communicated with the desulfurization adsorbent inlet of the non-hydrodesulfurization reactor 2 through a pipeline 20; wherein the pipelines (6, 20) are provided with a device (not shown) for respectively pressing the desulfurization adsorbent to be regenerated and the desulfurization adsorbent that has at least partially recovered its activity into the non-hydrodesulfurization reactor (2) and the hydrosulfurization transfer reactor (7) and / or a device (not shown) for preventing gas from flowing between the non-hydrodesulfurization reactor (2) and the hydrosulfurization transfer reactor (7).

[0083] According to one specific embodiment, the method for treating hydrocarbon oil according to the present invention can be implemented in the system shown in FIG1 as follows: preheated hydrocarbon oil containing sulfides and olefins in gaseous form enters the non-hydrodesulfurization reactor 2 through hydrocarbon oil inlet 1 at the bottom of the non-hydrodesulfurization reactor 2. It then passes through the non-hydrodesulfurization reactor 2 from bottom to top and comes into contact with a desulfurization adsorbent A in the form of a fluidized bed. A desulfurization reaction occurs under non-hydrogen conditions, producing desulfurized hydrocarbon oil gas and a regenerated desulfurization adsorbent with reduced desulfurization activity. The desulfurized hydrocarbon oil gas and the regenerated desulfurization adsorbent are separated at the top of the non-hydrodesulfurization reactor 2 and then sent to a stabilization system through a desulfurized hydrocarbon oil gas outlet 3 for subsequent treatment. The regenerated desulfurization adsorbent is sent to the first receiver 5 through the regenerated desulfurization adsorbent outlet 4, and then transported to the hydrosulfurization transfer reactor 7 through pipeline 6. It contacts hydrogen entering from the bottom of the hydrosulfurization transfer reactor 7 through hydrogen inlet 8 to undergo a sulfur transfer reaction, thereby obtaining a desulfurization adsorbent B with at least partial activity restored and hydrogen-containing gas. The hydrogen-containing gas is sent to the hydrogen circulation system through the circulating hydrogen outlet 9. The desulfurization adsorbent B with at least partial activity restored enters the second receiver 19 through the reactivated desulfurization adsorbent outlet 18, and then all of the desulfurization adsorbent B with at least partial activity restored is returned to the non-hydrosulfurization reactor 2 through pipeline 20 to continue participating in the desulfurization reaction.

[0084] According to a preferred embodiment, as shown in Figure 2, the system for processing hydrocarbon oil of the present invention also includes a lock hopper 11 and a regenerator 14; wherein the regenerator 14 is provided with an oxygen-containing gas inlet at the bottom, a regenerated desulfurization adsorbent outlet at the lower part, a desulfurization adsorbent inlet at the upper part, and a flue gas outlet at the top; the lock hopper 11 is provided with a third material inlet, a third material outlet and a regenerated desulfurization adsorbent inlet; the second material outlet of the second receiver 19 can also be switchably connected to the third material inlet of the lock hopper 11, the third material outlet of the lock hopper 11 can be switchably connected to the desulfurization adsorbent inlet of the regenerator 14, the regenerated desulfurization adsorbent outlet of the regenerator 14 is connected to the regenerated desulfurization adsorbent inlet of the lock hopper 11, and the third material outlet of the lock hopper 11 can also be switchably connected to the regenerated desulfurization adsorbent inlet of the hydrogen sulfur transfer reactor 7.

[0085] According to one specific embodiment, the method for treating hydrocarbon oil according to the present invention can be implemented in the system according to the present invention as follows: As shown in Figure 2, the preheated hydrocarbon oil containing sulfides and olefins in gaseous form enters the non-hydrodesulfurization reactor 2 through the hydrocarbon oil inlet 1 at the bottom of the non-hydrodesulfurization reactor 2. It then passes through the non-hydrodesulfurization reactor 2 from bottom to top and comes into contact with a desulfurization adsorbent A in the form of a fluidized bed. A desulfurization reaction occurs under non-hydrogen conditions, resulting in desulfurized hydrocarbon oil gas and a regenerated desulfurization adsorbent with reduced desulfurization activity. The desulfurized hydrocarbon oil gas and the regenerated desulfurization adsorbent are separated at the top of the non-hydrodesulfurization reactor 2 and then sent to a stabilization system through the desulfurized hydrocarbon oil gas outlet 3 for subsequent treatment. The regenerated desulfurization adsorbent is sent to the first receiver 5 through the regenerated desulfurization adsorbent outlet 4, and then transported to the hydrosulfurization transfer reactor 7 through pipeline 6. It contacts hydrogen entering from the bottom of the hydrosulfurization transfer reactor 7 through hydrogen inlet 8 to undergo a sulfur transfer reaction, thereby obtaining a desulfurization adsorbent B with at least partial activity restored and hydrogen-containing gas. The hydrogen-containing gas is sent to the hydrogen circulation system through the circulating hydrogen outlet 9. The desulfurization adsorbent B with at least partial activity restored enters the second receiver 19 through the reactivated desulfurization adsorbent outlet 18, and then a portion of the at least partially reactivated desulfurization adsorbent B is returned to the non-hydrosulfurization reactor 2 through pipeline 20 to continue participating in the desulfurization reaction.

[0086] The remaining desulfurization adsorbent B is conveyed via pipeline 10 to a lock hopper 11 for pressure adjustment and a conversion from a hydrogen atmosphere to a nitrogen atmosphere. The remaining desulfurization adsorbent B is then conveyed via pipeline 13 to a regenerator 14, where it undergoes an oxygen-containing charring reaction with oxygen-containing gas entering from the bottom of the regenerator 14 via gas inlet 15 to burn off the sulfur and carbon loaded on the desulfurization adsorbent B, yielding a regenerated desulfurization adsorbent with deep activity recovery. The regenerated desulfurization adsorbent is conveyed via pipeline 17 to a lock hopper 11 for pressure adjustment and a conversion from an oxygen atmosphere to a hydrogen atmosphere. The regenerated desulfurization adsorbent is then conveyed via pipeline 12 to a hydrogen-based sulfur transfer reactor 7, where it comes into contact with hydrogen in the hydrogen-based sulfur transfer reactor 7 for reduction, yielding a reduced desulfurization adsorbent. The reduced desulfurization adsorbent enters a second receiver 19 via the reactivated desulfurization adsorbent outlet 18, and then returns to the non-hydrogen-based desulfurization reactor 2 via pipeline 20 to continue the reaction.

[0087] In the above method, the sulfur transfer reaction of the regenerated desulfurization adsorbent in the hydrosulfurization reactor 7 and the reduction reaction of the regenerated desulfurization adsorbent in the hydrosulfurization reactor 7 are preferably carried out in a continuous manner.

[0088] Figures 1 and 2 merely schematically illustrate the components and connections of systems for treating hydrocarbon oil according to two preferred embodiments of the present invention. It should be noted that the systems shown in the figures can be used to implement a method for treating hydrocarbon oil according to the present invention, and this does not mean that the method according to the present invention cannot be implemented using other systems or devices.

[0089] Example

[0090] The following examples are provided to further illustrate the technical solution of the present invention. The raw materials used in the examples and comparative examples can be obtained by commercial means or by conventional techniques in the art. Wherein, the liquefied gas raw material A used in the examples and comparative examples comes from the 2 million tons / year catalytic cracking unit (Cangzhou LPG) of Sinopec Cangzhou Refining and Chemical Co., Ltd., and the liquefied gas raw material B comes from the 3 million tons / year catalytic cracking unit (Shijiazhuang LPG) of Sinopec Shijiazhuang Refining and Chemical Co., Ltd. The compositions of liquefied gas raw material A and liquefied gas raw material B are shown in Table 1-1, and the compositions of the sulfides in liquefied gas raw material A and liquefied gas raw material B are shown in Table 1-2. The measurements performed in the examples are carried out according to the most conventional methods in the art, for example, the metal sulfides on the adsorbent surface are measured by X-ray photoelectron spectroscopy (XPS).

[0091] The preparation of the desulfurization adsorbent used in the examples and comparative examples of the present invention was carried out in Examples 1-4.

[0092] Table 1-1. Composition of liquefied gas raw materials

[0093] Table 1-2. Composition of sulfides in liquefied gas raw materials

[0094] The following examples 1-4 illustrate the preparation of desulfurization adsorbents according to conventional methods in the art:

[0095] Example 1

[0096] 40g of perlite and 200g of zinc oxide were mixed and ground for 30 minutes to obtain mixture A1. Simultaneously, 100g of dispersed aluminum sol, 230g of deionized water, and 120g of 5% dilute nitric acid were mixed with mixture A1 to obtain mixture A2. After stirring, the mixture was dried using a CCX130AT spray drying system to obtain carrier A3 with an average particle size of 60-80μm. Carrier A3 was calcined at 650°C for 90 minutes. 93.24g of nickel nitrate hexahydrate was dissolved in 110g of deionized water to obtain an impregnation solution, which was used to impregnate 100g of carrier A3. The resulting product was dried at 120°C for 60 minutes and calcined at 650°C for 90 minutes to obtain desulfurization adsorbent A.

[0097] Example 2

[0098] 40g of perlite and 200g of zinc oxide were mixed and ground for 30 minutes to obtain mixture A1. Simultaneously, 100g of dispersed aluminum sol, 230g of deionized water, and 120g of 5% dilute nitric acid were mixed with mixture A1 to obtain mixture A2. After stirring, the mixture was dried using a CCX130AT spray drying system to obtain carrier A3 with an average particle size of 60-80μm. Carrier A3 was calcined at 650°C for 90 minutes. Carrier A3 was impregnated with an impregnation solution obtained by dissolving 93.24g of nickel nitrate hexahydrate, 12.8g of copper nitrate trihydrate, and 110g of deionized water. The resulting product was dried at 120°C for 60 minutes and calcined at 650°C for 90 minutes to obtain desulfurization adsorbent B.

[0099] Example 3

[0100] The operation of this embodiment is the same as that of Example 1, except that the impregnation solution used is a mixture of 57.54 g of cobalt nitrate and 110 g of deionized water.

[0101] Example 4

[0102] The operation of this embodiment is the same as that of Example 1, except that the impregnation solution used is a mixture of 73.50 g of molybdenum nitrate and 110 g of deionized water.

[0103] The following Examples 5-10 illustrate the desulfurization of liquefied gas feedstock under non-hydrogen conditions using the desulfurization adsorbent of the present invention. Prior to carrying out the following Examples and Comparative Examples, the desulfurization adsorbent was reduced under a hydrogen atmosphere using techniques known to those skilled in the art.

[0104] Example 5

[0105] In this embodiment, the liquefied gas raw material A is subjected to desulfurization treatment under non-hydrogen conditions, specifically comprising the following steps:

[0106] (1) 800 g of desulfurization adsorbent a and liquefied gas raw material A were subjected to a desulfurization reaction in a fluidized bed desulfurization reactor 2 of a medium-sized device, wherein the reaction pressure was 1.5 MPa, the reaction temperature was 350° C., the liquefied gas feed was 4 kg / h, and the reaction was carried out for 1 hour to obtain desulfurized liquefied gas and a desulfurization adsorbent to be regenerated. The desulfurized liquefied gas was discharged from the desulfurized hydrocarbon oil and gas outlet 3; and the sulfur content and hydrocarbon component content contained therein were measured by chromatography (the results are shown in Table 2); the desulfurization adsorbent to be regenerated was discharged from the reactor and the metal sulfide content in the desulfurization adsorbent to be regenerated was measured. After sampling, analysis and calculation, it was found that more than 15% of the nickel in the desulfurization adsorbent to be regenerated was converted into nickel sulfide, and a trace amount of zinc sulfide was contained (less than 0.01% of the zinc oxide was converted into zinc sulfide relative to the total weight of the zinc oxide on the surface).

[0107] Example 6

[0108] This embodiment performs desulfurization treatment on the liquefied gas raw material A under non-hydrogen conditions and performs sulfur transfer and oxidation regeneration on the regenerated desulfurization adsorbent under hydrogen conditions, specifically comprising the following steps:

[0109] (1) 800 g of desulfurization adsorbent a and liquefied gas raw material A were subjected to a desulfurization reaction in a fluidized bed desulfurization reactor 2 of a medium-sized device, wherein the reaction pressure was 1.5 MPa, the reaction temperature was 350° C., the liquefied gas feed was 4 kg / h, and the reaction was carried out for 1 hour to obtain desulfurized liquefied gas and a desulfurization adsorbent to be regenerated. The desulfurized liquefied gas was discharged from the desulfurized hydrocarbon oil and gas outlet 3; and the sulfur content and hydrocarbon component content thereof were measured by chromatography (the results are shown in Table 2); by sampling and measuring the metal sulfide content in the desulfurization adsorbent to be regenerated, it was calculated and analyzed that more than 10% of the nickel on the surface of the desulfurization adsorbent to be regenerated was converted into nickel sulfide, and a trace amount of zinc sulfide was contained (less than 0.01% of the zinc oxide was converted into zinc sulfide relative to the total weight of zinc oxide on the surface);

[0110] (2) transferring the desulfurization adsorbent to be regenerated from the desulfurization adsorbent outlet 4 to the medium-sized fluidized bed sulfur transfer reactor 7 via the first receiver 5 and the pipeline 6 at a rate of 10 g / min, wherein the desulfurization adsorbent is contacted with hydrogen to perform a sulfur transfer reaction, wherein the temperature of the sulfur transfer reaction is 350° C., the pressure is 1.5 MPa, the volume ratio of hydrogen to the desulfurization adsorbent in the reactor is 500, and the average sulfur transfer reaction time is about 0.5 h, thereby obtaining a desulfurization adsorbent with at least partially restored activity; sampling, analysis and calculation show that the nickel sulfide on the surface of the desulfurization adsorbent with at least partially restored activity is almost completely reduced to nickel, and at the same time, more than 1% of the zinc oxide on the surface of the desulfurization adsorbent is converted into zinc sulfide;

[0111] (3) sending a portion of the desulfurization adsorbent that has at least partially recovered its activity from the desulfurization adsorbent outlet 18 via the second receiver 19 and the pipeline 20 to the fluidized bed desulfurization reactor 2 to continue the desulfurization reaction, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity sent to the fluidized bed desulfurization reactor 2 accounts for 90% of the total desulfurization adsorbent circulation amount;

[0112] (4) feeding the remaining portion of the desulfurization adsorbent that has at least partially recovered its activity into the regenerator 14 via the pipeline 10, the lock hopper 11 and the pipeline 13 to contact with air for regeneration to obtain a regenerated desulfurization adsorbent, wherein the regeneration is performed at a temperature of 500° C. and a pressure of atmospheric pressure, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity fed into the fluidized bed regenerator accounts for 10% of the total desulfurization adsorbent circulation amount;

[0113] (5) The regenerated desulfurization sorbent is fed into the fluidized bed sulfur transfer reactor 7 of step (1) via pipeline 17, lock hopper 11, and pipeline 12, where it is contacted with hydrogen for reduction treatment. The reduced regenerated desulfurization sorbent, along with a portion of the at least partially reactivated desulfurization sorbent obtained in step 3, is returned to step (1) to continue the desulfurization reaction under non-hydrogen conditions. The product properties are shown in Table 2.

[0114] Example 7

[0115] This embodiment performs desulfurization treatment on the liquefied gas raw material B under non-hydrogen conditions and performs sulfur transfer and oxidation regeneration on the regenerated desulfurization adsorbent under hydrogen conditions, specifically comprising the following steps:

[0116] (1) 800 g of desulfurization adsorbent b and liquefied gas feed B were subjected to a desulfurization reaction in a fluidized bed desulfurization reactor 2 of a medium-sized device, wherein the reaction pressure was 1.5 MPa, the reaction temperature was 430° C., and the liquefied gas feed was 2 kg / h, to obtain desulfurized liquefied gas and a desulfurization adsorbent to be regenerated. The desulfurized liquefied gas was discharged from a desulfurized hydrocarbon oil and gas outlet 3, and the sulfur content and hydrocarbon component content in the desulfurized liquefied gas were measured by chromatography (the results are shown in Table 2); the metal sulfide content in the desulfurization adsorbent to be regenerated was measured, and after sampling and analysis, it was found that more than 6% of the nickel and more than 5% of the copper on the surface of the desulfurization adsorbent to be regenerated were converted into nickel sulfide and copper sulfide, and contained a trace amount of zinc sulfide;

[0117] (2) transferring the desulfurization adsorbent to be regenerated from the desulfurization adsorbent outlet 4 to the medium-sized fluidized bed sulfur transfer reactor 7 via the first receiver 5 and the pipeline 6 at a rate of 40 g / min, wherein the desulfurization adsorbent is contacted with hydrogen to perform a sulfur transfer reaction, wherein the temperature of the sulfur transfer reaction is 400° C., the pressure is 1.5 MPa, the volume ratio of hydrogen to the desulfurization adsorbent to be regenerated in the reactor is 300, and the average sulfur transfer reaction time is about 2.0 h, thereby obtaining a desulfurization adsorbent with at least partially restored activity; sampling and analysis of the desulfurization adsorbent with at least partially restored activity show that the nickel sulfide in the desulfurization adsorbent with at least partially restored activity is almost completely reduced to nickel, the copper sulfide is almost completely reduced to copper, and at the same time, more than 0.6% of the zinc oxide on the surface of the desulfurization adsorbent is converted into zinc sulfide;

[0118] (3) sending a portion of the desulfurization adsorbent that has at least partially recovered its activity from the desulfurization adsorbent outlet 18 via the second receiver 19 and the pipeline 20 to the fluidized bed desulfurization reactor 2 to continue the desulfurization reaction, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity sent to the fluidized bed desulfurization reactor 2 accounts for 80% of the total desulfurization adsorbent circulation amount;

[0119] (4) feeding the remaining portion of the desulfurization adsorbent that has at least partially recovered its activity into the regenerator 14 via the pipeline 10, the lock hopper 11 and the pipeline 13 to contact with air for regeneration to obtain a regenerated desulfurization adsorbent, wherein the regeneration is performed at a temperature of 500° C. and a pressure of atmospheric pressure, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity fed into the fluidized bed regenerator accounts for 20% of the total desulfurization adsorbent circulation amount;

[0120] (5) The regenerated desulfurization sorbent is fed into the fluidized bed sulfur transfer reactor 7 of step (1) via pipeline 17, lock hopper 11, and pipeline 12, where it is contacted with hydrogen for reduction treatment. The reduced regenerated desulfurization sorbent, along with a portion of the at least partially reactivated desulfurization sorbent obtained in step 3, is returned to step (1) to continue the desulfurization reaction under non-hydrogen conditions. The product properties are shown in Table 2.

[0121] Example 8

[0122] This embodiment performs desulfurization treatment on the liquefied gas raw material B under non-hydrogen conditions and performs sulfur transfer and oxidation regeneration on the regenerated desulfurization adsorbent under hydrogen conditions, specifically comprising the following steps:

[0123] (1) 800 g of desulfurization adsorbent c and liquefied gas feed B were subjected to a desulfurization reaction in a fluidized bed desulfurization reactor of a medium-sized device, wherein the reaction pressure was 2.5 MPa, the reaction temperature was 430° C., and the liquefied gas feed was 2 kg / h, to obtain desulfurized liquefied gas and a desulfurized adsorbent to be regenerated. The desulfurized liquefied gas was discharged from the desulfurized hydrocarbon oil and gas outlet 3; the sulfur content and hydrocarbon component content thereof were measured by chromatography (the results are shown in Table 2); the metal sulfide content in the desulfurized adsorbent to be regenerated was measured; sampling, analysis and calculation showed that more than 6% of the cobalt on the surface of the desulfurized adsorbent to be regenerated was converted into cobalt sulfide and contained a trace amount of zinc sulfide;

[0124] (2) transferring the desulfurization adsorbent to be regenerated from the desulfurization adsorbent outlet 4 to the medium-sized fluidized bed sulfur transfer reactor 7 at a rate of 30 g / min via the first receiver 5 and the pipeline 6, wherein the desulfurization adsorbent is contacted with hydrogen to perform a sulfur transfer reaction, wherein the temperature of the sulfur transfer reaction is 410° C., the pressure is 2.5 MPa, the volume ratio of hydrogen to the desulfurization adsorbent to be regenerated in the reactor is 500, and the average sulfur transfer reaction time is about 0.5 h, thereby obtaining a desulfurization adsorbent with at least partially restored activity. After sampling, analysis and calculation, it is found that almost all of the cobalt sulfide in the desulfurization adsorbent with at least partially restored activity is reduced to cobalt, and at the same time, more than 0.6% of the zinc oxide on the surface of the desulfurization adsorbent is converted into zinc sulfide;

[0125] (3) sending a portion of the desulfurization adsorbent that has at least partially recovered its activity from the desulfurization adsorbent outlet 18 via the second receiver 19 and the pipeline 20 to the fluidized bed desulfurization reactor to continue the desulfurization reaction, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity sent to the fluidized bed desulfurization reactor 2 accounts for 70% of the total desulfurization adsorbent circulation amount;

[0126] (4) feeding the remaining portion of the desulfurization adsorbent that has at least partially recovered its activity into the regenerator 14 via the pipeline 10, the lock hopper 11 and the pipeline 13 to contact with air for regeneration to obtain a regenerated desulfurization adsorbent, wherein the regeneration is performed at a temperature of 500° C. and a pressure of atmospheric pressure, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity fed into the fluidized bed regenerator accounts for 30% of the total desulfurization adsorbent circulation amount;

[0127] (5) The regenerated desulfurization sorbent is fed into the fluidized bed sulfur transfer reactor 7 of step (1) via pipeline 17, lock hopper 11, and pipeline 12, where it is contacted with hydrogen for reduction treatment. The reduced regenerated desulfurization sorbent, along with a portion of the at least partially reactivated desulfurization sorbent obtained in step 3, is returned to step (1) to continue the desulfurization reaction under non-hydrogen conditions. The product properties are shown in Table 2.

[0128] Example 9

[0129] This embodiment performs desulfurization treatment on the liquefied gas raw material A under non-hydrogen conditions and performs sulfur transfer and oxidation regeneration on the regenerated desulfurization adsorbent under hydrogen conditions, specifically comprising the following steps:

[0130] (1) 800 g of desulfurization adsorbent d and liquefied gas raw material A were subjected to a desulfurization reaction in a fluidized bed desulfurization reactor of a medium-sized device, wherein the reaction pressure was 2.5 MPa, the reaction temperature was 400° C., and the liquefied gas feed was 3 kg / h, to obtain desulfurized liquefied gas and a desulfurization adsorbent to be regenerated, and the desulfurized liquefied gas was discharged from the desulfurized hydrocarbon oil and gas outlet 3; the sulfur content and hydrocarbon component content thereof were measured by chromatography (the results are shown in Table 2); the metal sulfide content in the desulfurization adsorbent to be regenerated was measured; sampling analysis and calculation showed that more than 9% of the molybdenum on the surface of the desulfurization adsorbent to be regenerated was converted into molybdenum sulfide and contained a trace amount of zinc sulfide;

[0131] (2) transferring the desulfurization adsorbent to be regenerated from the desulfurization adsorbent outlet 4 to the medium-sized fluidized bed sulfur transfer reactor 7 at a rate of 5 g / min via the first receiver 5 and the pipeline 6, wherein the desulfurization adsorbent is contacted with hydrogen to carry out a sulfur transfer reaction, wherein the temperature of the sulfur transfer reaction is 430° C., the pressure is 2.5 MPa, the volume ratio of hydrogen to the desulfurization adsorbent to be regenerated in the reactor is 500, and the average sulfur transfer reaction time is about 0.5 h, thereby obtaining a desulfurization adsorbent with at least partially restored activity. After sampling, analysis and calculation, it is found that almost all of the molybdenum sulfide in the desulfurization adsorbent with at least partially restored activity is reduced to molybdenum, and at the same time, more than 0.8% of the zinc oxide on the surface of the desulfurization adsorbent is converted into zinc sulfide;

[0132] (3) sending a portion of the desulfurization adsorbent that has at least partially recovered its activity from the desulfurization adsorbent outlet 18 via the second receiver 19 and the pipeline 20 to the fluidized bed desulfurization reactor to continue the desulfurization reaction, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity sent to the fluidized bed desulfurization reactor 2 accounts for 50% of the total desulfurization adsorbent circulation amount;

[0133] (4) feeding the remaining portion of the desulfurization adsorbent that has at least partially recovered its activity into the regenerator 14 via the pipeline 10, the lock hopper 11 and the pipeline 13 to contact with air for regeneration to obtain a regenerated desulfurization adsorbent, wherein the regeneration is performed at a temperature of 500° C. and a pressure of atmospheric pressure, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity fed into the fluidized bed regenerator accounts for 50% of the total desulfurization adsorbent circulation amount;

[0134] (5) The regenerated desulfurization sorbent is fed into the fluidized bed sulfur transfer reactor 7 of step (1) via pipeline 17, lock hopper 11, and pipeline 12, where it is contacted with hydrogen for reduction treatment. The reduced regenerated desulfurization sorbent, along with a portion of the at least partially reactivated desulfurization sorbent obtained in step 3, is returned to step (1) to continue the desulfurization reaction under non-hydrogen conditions. The composition of the product is shown in Table 2.

[0135] Table 2. Product composition

[0136] Example 10

[0137] This embodiment performs desulfurization treatment on the liquefied gas raw material A under non-hydrogen conditions and performs sulfur transfer and oxidation regeneration on the regenerated desulfurization adsorbent under hydrogen conditions, specifically comprising the following steps:

[0138] (1) 800 g of desulfurization adsorbent a and liquefied gas raw material A were subjected to a desulfurization reaction in a fluidized bed desulfurization reactor of a medium-sized device at a reaction pressure of 2.5 MPa, a reaction temperature of 400° C., and a liquefied gas feed rate of 4 kg / h to obtain desulfurized liquefied gas and a desulfurized adsorbent to be regenerated. The desulfurized liquefied gas was discharged from the desulfurized hydrocarbon oil and gas outlet 3; the sulfur content and hydrocarbon component content in the desulfurized liquefied gas were measured by chromatography (the results are shown in Table 2); the metal sulfide content in the desulfurized adsorbent to be regenerated was measured; sampling, analysis and calculation showed that more than 10% of the nickel on the surface of the desulfurized adsorbent to be regenerated was converted into nickel sulfide and contained a trace amount of zinc sulfide;

[0139] (2) transferring the desulfurization adsorbent to be regenerated from the desulfurization adsorbent outlet 4 to the medium-sized fluidized bed sulfur transfer reactor 7 at a rate of 10 g / min via the first receiver 5 and the pipeline 6, wherein the desulfurization adsorbent is contacted with hydrogen to perform a sulfur transfer reaction, wherein the temperature of the sulfur transfer reaction is 430° C., the pressure is 2.5 MPa, the volume ratio of hydrogen to the desulfurization adsorbent to be regenerated in the reactor is 500, and the average sulfur transfer reaction time is about 0.5 h, thereby obtaining a desulfurization adsorbent with at least partially restored activity;

[0140] (3) A portion of the desulfurization adsorbent that has at least partially recovered its activity is sent from the desulfurization adsorbent outlet 18 via the second receiver 19 and the pipeline 20 to the fluidized bed desulfurization reactor to continue the desulfurization reaction, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity sent to the fluidized bed desulfurization reactor 2 accounts for 70% of the total desulfurization adsorbent circulation amount.

[0141] (4) The remaining portion of the desulfurization adsorbent that has at least partially recovered its activity is sent to the regenerator 14 via pipeline 10, the lock hopper 11 and the pipeline 13 to contact with the air for regeneration to obtain a regenerated desulfurization adsorbent, wherein the regeneration temperature is 500°C and the pressure is atmospheric pressure, wherein the portion of the desulfurization adsorbent that has at least partially recovered its activity sent to the fluidized bed regenerator accounts for 30% of the total desulfurization adsorbent circulation amount.

[0142] (5) The regenerated desulfurization sorbent is fed into the fluidized bed sulfur transfer reactor 7 of step (1) via pipeline 17, lock hopper 11, and pipeline 12, where it is contacted with hydrogen for reduction treatment. The reduced regenerated desulfurization sorbent, along with a portion of the at least partially reactivated desulfurization sorbent obtained in step 3, is returned to step (1) to continue the desulfurization reaction under non-hydrogen conditions. The relationship between the product sulfur content and the reaction time is shown in Table 3.

[0143] Comparative Example 1

[0144] In this comparative example, liquefied gas raw material A is subjected to desulfurization treatment under non-hydrogen conditions, specifically comprising the following steps:

[0145] 16 g of desulfurization adsorbent a was reacted with liquefied gas feed A in a small fixed-bed reactor for desulfurization. The reaction pressure was 2.5 MPa, the reaction temperature was 400°C, and the liquefied gas feed was 80 g / h. The relationship between the product sulfur content and the reaction time is shown in Table 3.

[0146] Table 3 Sulfur content of desulfurized liquefied gas in fluidized bed and fixed bed reactors versus reaction time

[0147] Comparative Example 2

[0148] In this comparative example, liquefied gas raw material A is subjected to desulfurization treatment under hydrogen conditions, specifically comprising the following steps:

[0149] This comparative example was carried out according to step (1) described in Example 5, except that the desulfurization adsorbent a and the liquefied gas raw material A were subjected to a desulfurization reaction under hydrogen conditions in a medium-sized fluidized bed reactor, and the molar ratio of hydrogen to liquefied gas in the reducing gas was 0.10:1.

[0150] Comparative Example 3

[0151] In this comparative example, liquefied gas raw material A is subjected to desulfurization treatment under hydrogen conditions, specifically comprising the following steps:

[0152] This comparative example was carried out according to step (1) described in Example 5, except that the desulfurization adsorbent b and the liquefied gas feedstock A were subjected to a desulfurization reaction under hydrogen conditions in a medium-sized fluidized bed reactor, and the molar ratio of hydrogen to liquefied gas was 0.05:1.

[0153] Table 4. Reaction conditions and product properties of comparative examples

[0154] By comparing the data in Table 2 and Table 4, it can be seen that the present invention not only achieves deep desulfurization of liquefied gas by contacting sulfide- and olefin-containing liquefied gas with a desulfurization adsorbent under non-hydrogenation conditions to carry out a desulfurization reaction, but also avoids the loss of olefins caused by hydrogenation saturation of unsaturated olefins under hydrodesulfurization reaction conditions.

[0155] When the above method is used for desulfurization of light gasoline fractions, the octane number loss caused by the traditional hydrodesulfurization process can be avoided.

[0156] Comparative Example 4

[0157] This comparative example was carried out according to the method of Example 5, except that a catalytic gasoline feedstock A that had been subjected to selective hydrodesulfurization (total sulfur content of 93 mg / kg) was used as the feedstock, wherein the sulfides were primarily thiophene sulfides. The operating conditions in step (1) were: pressure 2.0 MPa, temperature 300°C, and weight hourly space velocity 5 h -1;

[0158] The sulfur content of the desulfurized gasoline obtained in step (1) was measured by chromatography and was about 80 mg / kg. The desulfurized adsorbent obtained in step (2) was measured and showed that only a small amount of nickel was converted into nickel sulfide.

[0159] Comparing Example 5 with Comparative Example 4 reveals that no sulfur chemically reacts with nickel to form nickel sulfide, indicating that the thiophenic sulfides in the FG gasoline feedstock A after selective hydrodesulfurization are physically adsorbed onto the desulfurization adsorbent rather than chemically reacting with nickel. Due to the weak physical adsorption of thiophenic sulfides on the adsorbent, under the high-temperature and high-gas-flow conditions of the fluidized bed, most of the thiophenic sulfides are not firmly adsorbed on the adsorbent and are desorbed. Consequently, the desulfurization efficiency of the fluidized bed in Comparative Example 4 is significantly lower than that of the fixed bed. Consequently, hydrocarbon oils containing only thiophenic sulfides cannot be efficiently desulfurized in a fluidized bed desulfurization reactor operating under non-hydrogenation conditions.

[0160] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

[0161] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0162] In addition, the various embodiments of the present invention may be arbitrarily combined, as long as they do not violate the concept of the present invention, and they should also be regarded as the contents disclosed by the present invention.

Claims

1. A method for treating a hydrocarbon oil containing sulfides and optionally olefins, characterized in that The method comprises the following steps (1): contacting hydrocarbon oil, preferably gaseous hydrocarbon oil, with a desulfurization adsorbent containing a metal active component M under non-hydrogen conditions in a desulfurization reactor to carry out a selective desulfurization reaction and generate a metal active component sulfide called a metal sulfur compound, thereby obtaining at least partially desulfurized hydrocarbon oil and a desulfurization adsorbent to be produced containing the metal sulfide; wherein at least a portion of the sulfides in the hydrocarbon oil, preferably all of them, are non-thiophene sulfides, and the metal active component M is selected from one or more of cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin and vanadium; preferably, step (1) is carried out continuously.

2. The method according to claim 1, wherein the desulfurization sorbent further comprises a carrier, wherein the carrier contains a sulfur-carrying component in the form of an oxide, and the metal active component M is supported on the carrier.

3. The method according to claim 2, wherein the method further comprises the following step (2): transferring the desulfurization adsorbent to be produced to a sulfur transfer reactor and contacting it with a hydrogen donor to carry out a sulfur transfer reaction to reduce the metal sulfide to a metal active component M, and converting the sulfur-carrying component in the form of an oxide into a sulfide to obtain a desulfurization adsorbent with at least partial activity restored, and optionally returning at least a portion of the desulfurization adsorbent with at least partial activity restored to the desulfurization reactor of step (1), preferably, step (2) is carried out in a continuous manner.

4. The method according to claim 3, wherein: The desulfurization reactor is a fluidized bed reactor and / or the sulfur transfer reactor is a fluidized bed reactor.

5. The method according to any one of claims 1 to 4, wherein: The conditions of the selective desulfurization reaction in step (1) include: a temperature of 150-550°C, preferably 300-450°C; a pressure of 0.1-5 MPa, preferably 1.5-4 MPa; and / or a weight hourly space velocity of 0.1-30 h / min of the hydrocarbon oil containing sulfides and olefins. -1 , preferably 1-20h -1 .

6. The method according to any one of claims 1 to 5, wherein: The sulfur content in the hydrocarbon oil containing sulfide is 10-5000 μg / g, preferably 30-3000 μg / g, and the mass percentage of olefins is 2-100%, preferably 5-85%.

7. The method according to any one of claims 1 to 6, wherein: The hydrocarbon oil containing sulfides is selected from one or more of dry gas, liquefied gas and catalytic gasoline; preferably, the hydrocarbon oil containing sulfides is selected from one or more of catalytic cracking dry gas, catalytic cracking liquefied gas, catalytic cracking dry gas, catalytic cracking liquefied gas, steam cracking ethylene and / or propylene products.

8. The method according to any one of claims 3 to 7, wherein: In step (2), the conditions for the sulfur transfer reaction include: a temperature of 300-550° C., preferably 350-450° C.; and a pressure of 0.1-5 MPa, preferably 1.5-4 MPa.

9. The method according to any one of claims 3 to 8, wherein: The hydrogen donor is selected from one or more of hydrogen, a mixed gas containing hydrogen and a hydrogen donor. Preferably, the volume fraction of hydrogen in the mixed gas containing hydrogen is 10-99%, preferably 30-90%; preferably, the hydrogen donor is selected from one or more of cyclohexane, methylcyclohexane, tetralin and decalin. Preferably, the volume ratio of hydrogen in the hydrogen donor to the desulfurization adsorbent to be generated is (10-3000):

1.

10. The method according to any one of claims 3 to 9, wherein: The sulfur content of the at least partially restored desulfurization sorbent in terms of sulfur element is 0.5-12%, preferably 1-10%, relative to the total weight of the desulfurization sorbent.

11. The method according to any one of claims 3 to 10, wherein: The method also includes the following step (3): subjecting the remaining portion of the at least partially restored desulfurization adsorbent to oxygen-containing char regeneration to obtain a regenerated desulfurization adsorbent, and subjecting the regenerated desulfurization adsorbent to a reduction treatment in a reducing gas atmosphere to obtain a reduced desulfurization adsorbent, and then returning the reduced desulfurization adsorbent to the desulfurization reactor of step (1).

12. The method according to claim 11, in step (3), the oxygen-containing coke regeneration is carried out in the presence of an oxygen-containing gas, the volume fraction of oxygen in the oxygen-containing gas is 5-50 volume %; preferably, the oxygen-containing gas is selected from one of air, a mixture of oxygen and nitrogen, and a mixture of air and nitrogen; preferably, the reaction conditions of the oxygen-containing coke regeneration include: The temperature is 300-800°C, preferably 350-600°C; the pressure is 0.1-3.0 MPa, preferably 0.1-1.0 MPa.

13. The method according to claim 11, in step (3), the conditions for the reduction treatment of the regenerated desulfurization adsorbent include: The temperature is 300-550°C, preferably 350-450°C; the pressure is 0.1-5MPa, preferably 1.5-4MPa; the volume space velocity of hydrogen in the reducing gas is 10-3000h -1 ; Preferably, the reducing gas is selected from one or more of hydrogen, a mixed gas containing hydrogen and a precursor compound capable of generating hydrogen; Preferably, the volume fraction of hydrogen in the mixed gas containing hydrogen is 10-99%, preferably 30-90%.

14. The method according to any one of claims 1 to 13, wherein: The metal active component is selected from cobalt, copper and nickel, and / or the sulfur-carrying component is selected from ZnO, TiO2, ZrO2, MnO2, Fe2O3, CuO, MgO, CaO, SrO, GeO, SnO, PbO; preferably, the sulfur-carrying component is selected from ZnO; based on the total weight of the desulfurization adsorbent, the content of the metal active component is 2-30wt%, and the total content of the carrier containing the sulfur-carrying component is 70-98wt%.

15. The method according to any one of claims 2 to 14, wherein: The carrier containing the sulfur-carrying component comprises 20-85wt%, preferably 25-75wt% of the sulfur-carrying component, 10-75wt%, preferably 15-60wt% of alumina, and 5-70wt%, preferably 15-60wt% of silica, based on the total weight of the carrier containing the sulfur-carrying component.

16. The method according to any one of claims 1 to 15, wherein: The sulfide is selected from one or more of mercaptans, sulfides, carbonyl sulfide and hydrogen sulfide.

17. A system for treating hydrocarbon oil, characterized in that: The system comprises a non-hydrogen desulfurization reactor (2) and a hydrosulfur transfer reactor (7), wherein the non-hydrogen desulfurization reactor (2) is provided with a hydrocarbon oil inlet for hydrocarbon oil at the bottom, a desulfurization adsorbent inlet at the bottom, a desulfurization oil gas outlet at the top and an outlet for a regenerated desulfurization adsorbent at the top; the hydrosulfur transfer reactor (7) is provided with a hydrogen donor inlet at the bottom, a desulfurization adsorbent inlet for regenerated desulfurization adsorbent and an optional regenerated desulfurization adsorbent inlet at the bottom, an outlet for a desulfurization adsorbent for at least partially recovering its activity at the top, a gas outlet at the top, and the desulfurization adsorbent to be regenerated at the non-hydrogen desulfurization reactor (2) is provided with a hydrogen donor inlet at the bottom, a desulfurization adsorbent inlet for regenerated desulfurization adsorbent and an optional regenerated desulfurization adsorbent inlet at the bottom, an outlet for a desulfurization adsorbent for at least partially recovering its activity at the top, and a gas outlet at the top. The adsorbent outlet is connected to the inlet of the desulfurization adsorbent to be generated of the hydrosulfurization transfer reactor (7) through a pipeline, and the outlet of the desulfurization adsorbent for recovering activity of the hydrosulfurization transfer reactor (7) is connected to the desulfurization adsorbent inlet of the non-hydrosulfurization desulfurization reactor (2) through a pipeline; wherein the pipeline (6, 20) is provided with a device for respectively pressing the desulfurization adsorbent to be generated and the desulfurization adsorbent with at least part of its activity recovered into the hydrosulfurization transfer reactor (7) and the non-hydrosulfurization desulfurization reactor (2) and a device for preventing gas from flowing between the non-hydrosulfurization desulfurization reactor (2) and the hydrosulfurization transfer reactor (7).

18. The system according to claim 17, characterized in that The system further comprises a first receiver (5) and a second receiver (19), wherein the first receiver (5) is provided with a first material inlet and a first material outlet, and the second receiver (19) is provided with a second material inlet and a second material outlet; wherein the outlet of the desulfurization adsorbent to be generated of the non-hydrodesulfurization reactor (2) is connected to the first material inlet of the first receiver (5), and the first material outlet of the first receiver (5) is connected to the inlet of the desulfurization adsorbent to be generated of the hydrosulfurization transfer reactor (7); and the outlet of the desulfurization adsorbent for reactivation of the hydrosulfurization transfer reactor (7) is connected to the second material inlet of the second receiver (19), and the second material outlet of the second receiver (19) is switchably connected to the desulfurization adsorbent inlet of the non-hydrodesulfurization reactor (2).

19. The system according to claim 18, characterized in that The system further comprises a lock hopper (11) and a regenerator (14); wherein the regenerator (14) is provided with an oxygen-containing gas inlet at the bottom, a regenerated desulfurization adsorbent outlet at the lower part, a desulfurization adsorbent inlet at the upper part, and a flue gas outlet at the top; the lock hopper (11) is provided with a third material inlet, a third material outlet and a regenerated desulfurization adsorbent inlet; the second material outlet of the second receiver (19) can also be switchably connected to the third material inlet of the lock hopper (11), the third material outlet of the lock hopper (11) can be switchably connected to the desulfurization adsorbent inlet of the regenerator (14), the regenerated desulfurization adsorbent outlet of the regenerator (14) is connected to the regenerated desulfurization adsorbent inlet of the lock hopper (11), and the third material outlet of the lock hopper (11) can also be switchably connected to the regenerated desulfurization adsorbent inlet of the hydrogen sulfur transfer reactor (7).

20. The system according to any one of claims 18-19, characterized in that The desulfurization reactor is a fluidized bed reactor and / or the sulfur transfer reactor is a fluidized bed reactor.

21. The system according to any one of claims 19-20, characterized in that The regenerator (14) is a fluidized bed reactor.

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