Method for regenerating and producing CO based on catalytic cracking spent catalyst

Abstract

The invention relates to a method for regenerating and producing CO based on a catalytic cracking spent catalyst, which comprises the following steps: (1) contacting a hydrocarbon oil raw material with a catalytic cracking catalyst in a catalytic cracking reactor, carrying out catalytic cracking reaction, and separating reaction oil gas from the carbon-deposited spent catalyst; (2) carrying out steam stripping on the spent catalyst, and sequentially carrying out first regeneration and second regeneration to obtain a regenerated catalyst and flue gas; the first regeneration zone is a bubbling bed, and the second regeneration zone is a rapid bed; cO2 is introduced into the lower part of the first regeneration area, and oxygen-containing gas with the volume ratio of oxygen greater than or equal to 22% is introduced into the lower part of the second regeneration area; the regeneration temperature of the first regeneration is 700-800 DEG C; and (3) returning at least part of the regenerated catalyst to the catalytic cracking reactor for recycling, leading out the flue gas from the top of the regenerator, and separating to obtain a CO product. According to the invention, in the regeneration process of the spent catalyst with carbon deposit, the carbon deposit is converted into flue gas with higher CO selectivity.

Description

Technical Field

[0001] The invention relates to the technical field of catalytic cracking of petroleum hydrocarbons, and in particular to a method for regenerating a spent catalyst of catalytic cracking and producing CO. Background Art

[0002] Catalytic cracking of petroleum raw materials is an important petroleum refining process. The catalytic cracking unit mainly includes a catalytic cracking reactor and a catalyst regenerator. In the catalyst regenerator, regeneration gas is used to regenerate the carbonized catalyst, and regeneration flue gas is generated at the same time. During the regeneration process of the catalyst, the coke burns to produce a large amount of CO 2 Gas, making the catalytic cracking unit the largest CO 2 Emission source, CO in catalytic cracking flue gas 2 It accounts for 15% to 50% of the total emissions from refineries. The catalytic cracking unit emits 211.7 kg CO per ton of raw material processed. 2 China has more than 190 catalytic cracking units with a total processing capacity of about 210 million tons / year, and at least 40 million tons of CO 2 Emissions.

[0003] During the regeneration process of the catalyst, a large amount of heat is generated, which makes the catalytic device have excess heat. An external heat extraction device is required to convert the heat generated by the catalyst regeneration into steam energy and recover the energy of the high-temperature flue gas, but this is all low-quality energy utilization. In addition, the regenerated flue gas contains carbon monoxide, which often causes tail combustion, causing local overheating of the regenerator and aggravated catalyst deactivation. Tail combustion can be reduced by controlling the oxygen content in the flue gas, but it will reduce the burning rate and burning intensity. At the same time, there is a problem of tail gas emissions, resulting in the loss of chemical energy in carbon monoxide. Refineries often use carbon monoxide combustion aids or flue gas boilers to reduce carbon monoxide in flue gas and recover energy, but the problem of carbon monoxide in flue gas has never been properly solved.

[0004] CN1400159A discloses a method for producing hydrogen using catalytic cracking regeneration flue gas, which can make reasonable use of CO in the regeneration flue gas and alleviate the problem of excess heat in the FCC device. However, the CO content obtained by this method is low, at about 14% by volume, while the nitrogen content is above 70% by volume.

[0005] CN102698817A discloses a fluidized catalytic cracking catalyst pure oxygen regeneration process and hydrogen production method, which can significantly improve the quality and efficiency of energy utilization, reduce the energy consumption and pollutant emissions of the FCC regeneration system, and at the same time enable the generated CO to produce hydrogen through a water-gas shift reaction.

[0006] CN101457152A discloses a hydrocarbon oil conversion method, in which, during the regeneration process, the catalyst to be regenerated contacts water vapor and oxygen-containing gas in a gasifier to obtain synthesis gas and semi-regenerated catalyst. The method can increase the production of carbon monoxide and hydrogen, and carbon monoxide can also be converted into hydrogen in the subsequent processing process, thereby obtaining a higher hydrogen yield.

[0007] However, the existing technology produces hydrogen by incompletely regenerating flue gas. Although coke is used, carbon is still mainly emitted in the form of carbon dioxide; and the method of directly contacting the regenerated catalyst with water vapor to produce synthesis gas will accelerate the deactivation of the catalyst.

[0008] During the regeneration process of the spent catalyst with carbon deposits produced by the catalytic cracking reaction, how to convert the carbon deposits on the spent catalyst into flue gas with higher CO selectivity, reduce the carbon emissions of the catalytic cracking unit, and produce CO at the same time is a technical problem that needs to be solved urgently. Summary of the invention

[0009] The present invention provides a method for regenerating a spent catalyst of catalytic cracking and producing CO, the purpose of which is to convert the deposited carbon into flue gas with higher CO selectivity during the regeneration of the spent catalyst of carbon deposition.

[0010] The present invention relates to a method for regenerating a spent catalyst for catalytic cracking and producing CO, comprising the following steps:

[0011] (1) contacting a hydrocarbon oil feedstock with a catalytic cracking catalyst in a catalytic cracking reactor to carry out a catalytic cracking reaction, and separating the reaction oil gas and the spent catalyst with carbon deposition;

[0012] (2) The regenerator is provided with a first regeneration zone and a second regeneration zone connected from top to bottom, so that the catalyst to be regenerated passes through the first regeneration zone and the second regeneration zone in sequence after stripping to perform the first regeneration and the second regeneration respectively, thereby obtaining a regenerated catalyst and flue gas;

[0013] Wherein, the first regeneration zone is a bubbling bed, and the second regeneration zone is a fast bed;

[0014] The lower part of the first regeneration zone is fed with CO 2 , so that the catalyst to be regenerated entering the first regeneration zone is reacted with CO 2 Contacting with the second flue gas from the second regeneration zone to perform the first regeneration;

[0015] The oxygen-containing gas is introduced into the lower part of the second regeneration zone to contact with the semi-regenerated agent after the first regeneration to perform the second regeneration;

[0016] The regeneration gas includes CO introduced into the lower part of the first regeneration zone. 2and the oxygen-containing gas introduced into the lower part of the second regeneration zone;

[0017] The volume proportion of oxygen in the oxygen-containing gas introduced into the lower part of the second regeneration zone is greater than or equal to 22%; the regeneration temperature of the first regeneration is 700-800°C;

[0018] (3) returning at least a portion of the regenerated catalyst to the catalytic cracking reactor for recycling, and allowing the flue gas to be drawn out from the top of the regenerator and then separated to obtain a CO product.

[0019] Optionally, the bed density of the bubbling bed is 300-700 kg / m 3 and / or,

[0020] The bed density of the fast bed is 120-300 kg / m 3 .

[0021] Optionally, the conditions for the first regeneration include: a gas superficial linear velocity of 0.1 to 1 m / s, and an average catalyst residence time of 0.6 to 20 minutes.

[0022] Optionally, the CO introduced into the lower part of the first regeneration zone 2 The volume proportion of the regeneration gas is 1 to 50%, preferably 2 to 15%.

[0023] Optionally, the conditions for the second regeneration include: a regeneration temperature of 600-700° C., a gas superficial velocity of 0.8-4 m / s, and an average catalyst residence time of 0.6-15 minutes.

[0024] Optionally, the oxygen-containing gas introduced into the lower part of the second regeneration zone is CO 2 and O 2 Mixed gas;

[0025] The CO introduced into the lower part of the first regeneration zone 2 The CO introduced into the lower part of the second regeneration zone 2 The total amount of the regeneration gas accounts for 1 to 89% by volume, preferably 60 to 80% by volume.

[0026] Optionally, the volume ratio of the second regeneration zone to the first regeneration zone is 1:(1-10).

[0027] Optionally, in step (1), the hydrocarbon oil feedstock includes petroleum hydrocarbons and / or other mineral oils, the petroleum hydrocarbons are selected from a combination of one or more of gasoline, diesel, vacuum wax oil, atmospheric wax oil, coker wax oil, deasphalted oil, vacuum residue oil, atmospheric residue oil, extracted oil and inferior recycled oil, and the other mineral oils are selected from a combination of one or more of coal liquefaction oil, oil sand oil and shale oil.

[0028] Optionally, in step (1), the conditions of the catalytic cracking reaction include: a reaction temperature of 450 to 700° C., a reaction time of 1 to 10 seconds, and a catalyst-oil ratio of (1 to 100):1.

[0029] Optionally, the catalytic cracking reactor is a riser reactor, a fluidized bed reactor or a combination of the two.

[0030] Beneficial effects:

[0031] (1) The present invention controls the combustion of coke during the catalyst regeneration process, causing incomplete combustion to generate CO, and stores part of the energy in CO as chemical energy, which can reduce the excess heat in the catalytic regeneration process, solve the problem of regenerator tail combustion, and significantly reduce CO 2 Emissions and does not affect the catalyst regeneration effect.

[0032] (2) Strengthening CO 2 The reaction with coke further increases CO production.

[0033] (3) No N is introduced during the regeneration process 2 , which is beneficial to CO and CO 2 separation and reduce separation energy consumption.

[0034] (4) The generated CO can be used as a raw material for subsequent chemical and metallurgical industries, which can save raw materials such as coal and methane for producing CO, save resources and energy consumption, and further reduce emissions.

[0035] (5) Using the catalytic cracking regeneration process to produce CO can turn waste into treasure and save energy and reduce emissions, which has huge economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] 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:

[0037] Figure 1 It is a schematic diagram of a process of a method for regenerating a spent catalytic cracking catalyst and producing CO according to the present invention or a specific embodiment of a system for regenerating a spent catalytic cracking catalyst and producing CO;

[0038] Figure 2 It is a schematic diagram of the catalytic cracking process of the single-stage regeneration method in Comparative Examples 3 and 5 of the present invention;

[0039] Description of reference numerals:

[0040] 1 Hydrocarbon oil feedstock inlet 2 Catalytic cracking reaction 3 Settler 4 Reaction oil and gas outlet

[0041] 5 Waiting for regeneration slide valve 6 Regenerator 7 Oxygen-containing gas inlet 8 Second regeneration zone 9 First regeneration zone 10 Flue gas outlet 11 Energy recovery separation 12 CO product outlet unit

[0042] 13 Other flue gas components 14 Regeneration slide valve 15 CO 2 Entrance

[0043] exit

[0044] 21 Catalytic cracking feedstock 22 Riser reactor 23 Second settler 24 Reaction oil and gas

[0045] 25 second regeneration slide valve 26 second regenerator 27 regeneration flue gas 28 regeneration gas inlet 29 second regeneration slide valve DETAILED DESCRIPTION

[0046] The present application is further described in detail below through the accompanying drawings and embodiments. Through these descriptions, the characteristics and advantages of the present application will become clearer and more specific.

[0047] The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are shown in the drawings, the drawings are not necessarily drawn to scale unless otherwise noted.

[0048] In addition, the technical features involved in different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0049] The present invention relates to a method for regenerating a spent catalyst for catalytic cracking and producing CO, comprising the following steps:

[0050] (1) contacting a hydrocarbon oil feedstock with a catalytic cracking catalyst in a catalytic cracking reactor to carry out a catalytic cracking reaction, and separating the reaction oil gas and the spent catalyst with carbon deposition;

[0051] (2) The regenerator is provided with a first regeneration zone and a second regeneration zone connected from top to bottom, so that the catalyst to be regenerated passes through the first regeneration zone and the second regeneration zone in sequence after stripping to perform the first regeneration and the second regeneration respectively, thereby obtaining a regenerated catalyst and flue gas;

[0052] Wherein, the first regeneration zone is a bubbling bed, and the second regeneration zone is a fast bed;

[0053] The lower part of the first regeneration zone is fed with CO 2 , so that the catalyst to be regenerated entering the first regeneration zone is reacted with CO 2 Contacting with the second flue gas from the second regeneration zone to perform the first regeneration;

[0054] The oxygen-containing gas is introduced into the lower part of the second regeneration zone to contact with the semi-regenerated agent after the first regeneration to perform the second regeneration;

[0055] The regeneration gas includes CO introduced into the lower part of the first regeneration zone. 2 and the oxygen-containing gas introduced into the lower part of the second regeneration zone;

[0056] The volume proportion of oxygen in the oxygen-containing gas introduced into the lower part of the second regeneration zone is greater than or equal to 22%; the regeneration temperature of the first regeneration is 700-800°C;

[0057] (3) returning at least a portion of the regenerated catalyst to the catalytic cracking reactor for recycling, and allowing the flue gas to be drawn out from the top of the regenerator and then separated to obtain a CO product.

[0058] It should be noted that in step (1), the reaction oil and gas obtained by separation can be sent to a subsequent separation system to obtain a variety of catalytic cracking products after separation. The reaction oil and gas can be separated by the subsequent separation system to obtain dry gas, liquefied gas, stable gasoline and catalytic diesel fractions. The separation method can be a conventional technical method in the field, and the present invention is not limited to this and is not described in detail here. The catalyst to be produced is derived from a catalytic cracking reactor of a hydrocarbon oil feedstock.

[0059] In step (2), the catalyst to be regenerated first enters the first regeneration zone and flows downward, and the CO introduced into the lower part of the first regeneration zone 2 The first regeneration is carried out by countercurrent contact with the second flue gas from the second regeneration zone to obtain flue gas and semi-regeneration agent; the obtained semi-regeneration agent continues to flow downward to the second regeneration zone and countercurrently contacts with the oxygen-containing gas introduced into the lower part of the second regeneration zone to carry out the second regeneration to obtain regenerated catalyst and second flue gas. The second flue gas entering the first regeneration zone is the gas after the reaction of the oxygen-containing gas and the semi-regeneration agent. The CO introduced into the lower part of the first regeneration zone 2 The oxygen-containing gas introduced into the lower part of the second regeneration zone forms the regeneration gas or regeneration atmosphere of the regenerator.

[0060] In step (3), the regenerated regenerated catalyst can be transported to the catalytic cracking reactor for recycling. At least a portion of the catalytic cracking catalyst used for the catalytic cracking reaction is a regenerated catalyst, preferably all of it is a regenerated catalyst. Preferably, the method of the present invention also includes degassing the regenerated catalyst obtained by the second regeneration and returning it to the catalytic cracking reactor for recycling. An internal heat exchanger or an external heat exchanger can be set in the regenerator, and the type, connection and operation of the heat exchanger are well known to those skilled in the art. The flue gas obtained by the regenerator is separated to obtain a CO product. The separation method for separating the flue gas to obtain the CO product can adopt chemical absorption method, membrane separation method, pressure swing adsorption method, deep cooling method, COSORB method or other separation and purification methods well known to those skilled in the art, preferably chemical absorption method. Before separating the flue gas to obtain CO, the flue gas can be purified to remove impurities such as sulfides and nitrides.

[0061] It should be noted that the bubbling bed in the first regeneration zone can achieve the following effects: on the premise of ensuring the fluidization state of the catalyst, the ratio of coke to oxygen can be increased, the residence time of the catalyst can be increased, and more coke can be incompletely burned to generate CO, thereby reducing the generation of CO by the combustion of coke in the second regeneration zone. 2 The second regeneration zone adopts a fast bed, which can improve the coke burning efficiency and quickly convert the coke on the semi-regenerated catalyst under oxygen-rich conditions, thus restoring the activity of the catalyst.

[0062] More importantly, the inventors of the present application have found in the process of many years of research and development that in the method of the present application, oxygen-containing gas is introduced into the lower part of the second regeneration zone, and CO is introduced into the lower part of the first regeneration zone. 2 , and at the same time, the first regeneration zone is a bubbling bed and the second regeneration zone is a fast bed, so that the CO selectivity is significantly improved.

[0063] It should be noted that in the method for regenerating a spent catalyst based on catalytic cracking and producing CO of the present invention, on the premise that gas is introduced into the lower part of the first regeneration zone and the second regeneration zone as above, and the bed types of the first regeneration zone and the second regeneration zone are simultaneously controlled as above, the regeneration temperature of the first regeneration is 700-800°C, so that the carbon deposits on the spent catalyst are converted into flue gas with higher CO selectivity; the regeneration temperature of the first regeneration is preferably 740-780°C, which can further improve the CO selectivity.

[0064] According to a specific embodiment of the method for regenerating spent catalytic cracking catalyst and producing CO according to the present invention, the bed density of the bubbling bed is 300-700 kg / m 3 and / or,

[0065] The bed density of the fast bed is 120-300 kg / m 3 .

[0066] It should be noted that the bed density of the bubbling bed is preferably 450-650 kg / m 3 The bed density of the fast bed is preferably 180 to 250 kg / m 3 .

[0067] It should be noted that in the method for regenerating and producing CO based on the spent catalytic cracking catalyst of the present invention, by controlling the bed density of the bubbling bed and the bed density of the fast bed as above, the coke on the spent catalytic cracking catalyst can be better converted into carbon monoxide, so that the coke can be converted into flue gas with higher CO selectivity, thereby greatly reducing CO. 2 By changing the regeneration burning method to produce carbon monoxide, it can effectively reduce tail combustion and slow down the catalyst deactivation rate.

[0068] According to a specific embodiment of the method for regenerating a spent catalyst based on catalytic cracking and producing CO according to the present invention, the conditions for the first regeneration include: a gas superficial linear velocity of 0.1 to 1 m / s and an average catalyst residence time of 0.6 to 20 minutes.

[0069] It should be noted that in the first regeneration zone, the average residence time of the catalyst is preferably 5 to 15 minutes.

[0070] According to a specific embodiment of the method for regenerating spent catalytic cracking catalyst and producing CO according to the present invention, the CO introduced into the lower part of the first regeneration zone 2 The volume proportion of the regeneration gas is 1 to 50%, preferably 2 to 15%.

[0071] It should be noted that the present invention controls the conditions of the first regeneration as above and controls the CO introduced into the lower part of the first regeneration zone as above. 2 The amount is beneficial to convert the carbon deposits on the spent catalyst into flue gas with higher CO selectivity.

[0072] According to a specific embodiment of the method for regenerating a spent catalyst for catalytic cracking and producing CO according to the present invention, the conditions for the second regeneration include: a regeneration temperature of 600 to 700°C, a gas superficial velocity of 0.8 to 4 m / s, and an average catalyst residence time of 0.6 to 15 minutes.

[0073] It should be noted that, in the second regeneration, the regeneration temperature is preferably 650 to 690° C., and the average catalyst residence time is preferably 2 to 10 minutes.

[0074] According to a specific embodiment of the method for regenerating spent catalytic cracking catalyst and producing CO according to the present invention, the oxygen-containing gas introduced into the lower part of the second regeneration zone is CO 2 and O2 Mixed gas;

[0075] The CO introduced into the lower part of the first regeneration zone 2 The CO introduced into the lower part of the second regeneration zone 2 The total amount of the regeneration gas accounts for 1 to 89% by volume, preferably 60 to 80% by volume.

[0076] It should be noted that the regeneration gas in the regenerator does not contain N 2 and / or air, with oxygen and CO 2 As regeneration gas, part of CO 2 Converted into CO; without introducing nitrogen, a simpler method can be used to separate and obtain a higher purity CO product, while enriching CO 2 It is beneficial to carbon capture and utilization.

[0077] It should be noted that by controlling the conditions of the second regeneration as above, the CO introduced into the two regeneration zones is controlled as above. 2 The proportion of the total amount in the regeneration gas (which also controls the oxygen content in the regeneration gas), as well as the CO introduced into the first regeneration zone 2 The proportion of semi-regenerated agent in the regeneration gas can make the semi-regenerated agent completely regenerated in the second regeneration zone without affecting the activity of catalytic cracking reaction; and it is conducive to better incomplete combustion, reducing combustion heat release, alleviating the problem of excess heat in the catalytic device, and significantly increasing the CO content in the flue gas, which is beneficial to the subsequent further purification and application of CO. The CO selectivity can reach more than 81%.

[0078] According to a specific embodiment of the method for regenerating spent catalyst based on catalytic cracking and producing CO according to the present invention, the volume ratio of the second regeneration zone to the first regeneration zone is 1:(1-10).

[0079] It should be noted that the volume ratio of the second regeneration zone to the first regeneration zone is preferably 1:2-6. Such a ratio is conducive to prolonging the residence time of the regenerated catalyst in the first regeneration zone, so that more coke is burned to generate CO and the carbon content on the semi-regenerated catalyst is reduced.

[0080] According to a specific embodiment of the method for regenerating spent catalysts based on catalytic cracking and producing CO according to the present invention, in step (1), the hydrocarbon oil feedstock includes petroleum hydrocarbons and / or other mineral oils, the petroleum hydrocarbons are selected from a combination of one or more of gasoline, diesel, vacuum wax oil, atmospheric wax oil, coker wax oil, deasphalted oil, vacuum residue oil, atmospheric residue oil, extracted oil and inferior recycled oil, and the other mineral oils are selected from a combination of one or more of coal liquefaction oil, oil sand oil and shale oil.

[0081] It should be noted that the method of the present invention for regenerating spent catalysts based on catalytic cracking and producing CO has a wide range of applicability. The spent catalysts with carbon deposits produced by catalytic cracking of the above-mentioned various hydrocarbon oil feedstocks can be converted into flue gas with high CO selectivity through the above-mentioned regeneration process.

[0082] According to a specific embodiment of the method for regenerating a spent catalytic cracking catalyst and producing CO according to the present invention, in step (1), the conditions of the catalytic cracking reaction include: a reaction temperature of 450 to 700° C., a reaction time of 1 to 10 seconds, and a catalyst-oil ratio of (1 to 100):1.

[0083] It should be noted that the reaction temperature is preferably 500-650°C, more preferably 550-630°C; the reaction time is preferably 2-5 seconds, and the catalyst-oil ratio (weight ratio of catalytic cracking catalyst to hydrocarbon oil feedstock) is preferably 5-30:1.

[0084] In the present invention, as a variation of the embodiment, water vapor may be injected into the catalytic cracking reactor. The water vapor is preferably injected in the form of atomized steam. The weight ratio of the injected water vapor to the hydrocarbon oil feedstock may be 0.01 to 1:1, preferably 0.05 to 0.5:1.

[0085] The catalytic cracking catalyst used in the catalytic cracking reaction may include 15 to 65% by weight of natural minerals, 10 to 30% by weight of inorganic oxides, and 25 to 75% by weight of zeolite. The zeolite is used as an active component, preferably one or more mixtures of Y zeolite, mordenite, beta zeolite, and zeolite with MFI structure (e.g., ZSM series zeolite and / or ZRP zeolite). The natural mineral is selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite. The inorganic oxide is selected from one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and amorphous silicon aluminum.

[0086] According to a specific embodiment of the method for regenerating spent catalytic cracking catalyst and producing CO according to the present invention, the catalytic cracking reactor is a riser reactor, a fluidized bed reactor or a combination of the two.

[0087] It should be noted that the catalytic cracking reactor can be a conventional catalytic cracking riser reactor, a fluidized bed reactor or a combination thereof known to those skilled in the art, for example, a catalytic cracking riser reactor connected in series with a fluidized bed reactor. The riser reactor can be selected from an equal diameter riser reactor and / or an equal linear velocity riser reactor, preferably an equal diameter riser. The fluidized bed reactor is located downstream of the riser reactor and is connected to the outlet of the riser reactor. The riser reactor includes a pre-lifting section and at least one reaction zone from bottom to top. In order to allow the crude oil to react fully and according to different quality requirements of the target product, the reaction zones can be 2 to 8, preferably 1 to 3.

[0088] The method for regenerating a spent catalytic cracking catalyst and producing CO according to the present invention can be implemented based on a system for regenerating a spent catalytic cracking catalyst and producing CO, and the system for regenerating a spent catalytic cracking catalyst and producing CO comprises a catalytic cracking reaction unit, a regenerator 6 and an energy recovery and separation unit 11;

[0089] The catalytic cracking reaction unit comprises a catalytic cracking reactor 2 and a settler 3. The catalytic cracking reactor 2 is provided with a hydrocarbon oil feedstock inlet 1, a catalyst inlet and an oil agent outlet. The oil agent outlet of the catalytic cracking reactor 2 is connected to the inlet of the settler 3. The settler 3 is provided with a catalyst outlet to be produced and a reaction oil and gas outlet 4.

[0090] The catalyst outlet of the settler 3 is connected to the catalyst inlet of the regenerator 6 through a catalyst pipeline, and the catalyst pipeline is provided with a slide valve 5;

[0091] The regenerator 6 is provided with a first regeneration zone 9 and a second regeneration zone 8 connected from top to bottom. The lower part of the first regeneration zone 9 is provided with a CO 2 Inlet 15, the lower part of the second regeneration zone 8 is provided with an oxygen-containing gas inlet 7;

[0092] The first regeneration zone 9 is a bubbling bed, and the second regeneration zone 8 is a fast bed;

[0093] The second regeneration zone 8 is provided with a regeneration agent outlet, which is connected to the catalyst inlet of the catalytic cracking reactor 2 through a regeneration agent pipeline, and the regeneration agent pipeline is provided with a regeneration slide valve 14;

[0094] The top of the regenerator 6 is provided with a flue gas outlet 10 , which is communicated with the inlet of the energy recovery and separation unit 11 . The energy recovery and separation unit 11 is also provided with a CO product outlet 12 and other flue gas component outlets 13 .

[0095] It should be noted that the method for regenerating a spent catalytic cracking catalyst and producing CO, or the system for regenerating a spent catalytic cracking catalyst and producing CO, not only reduces the carbon dioxide emission of the catalytic device and produces CO, but also realizes the transformation of waste into treasure and full utilization of resources, thereby improving the economic benefits of the catalytic cracking device; at the same time, CO is used as a raw material for subsequent chemical processes, thereby saving fossil resources such as coal, oil and methane used to produce CO, reducing energy consumption and investment, reducing pollution, and improving the economic and social benefits of the petrochemical industry.

[0096] The present invention is further described in detail by way of examples below, but the present invention is not limited thereto. In the following examples, unless otherwise specified, the experimental instruments and raw materials involved are all commercially available products.

[0097] The raw material oil used in the embodiments and comparative examples is Anqing wax oil, and its properties are shown in Table 1.

[0098] The catalytic cracking catalyst used in the examples and comparative examples has a trade name of CDOS (Sinopec Catalyst Co., Ltd. Changling Branch).

[0099] Table 1

[0100]

[0101] As attached Figure 1 As shown in the figure, the catalytic cracking feedstock oil enters from the hydrocarbon oil feedstock inlet 1 at the bottom of the catalytic cracking reactor 2 (riser reactor), contacts with the regenerated catalyst for reaction, and the reaction oil gas and catalyst move upward to the settler 3 for gas-solid separation. The separated reaction oil gas goes to the subsequent absorption stabilization system through the reaction oil gas outlet 4. The catalyst to be regenerated enters the first regeneration zone 9 of the regenerator 6 through the slide valve 5 to be regenerated, and the second flue gas from the second regeneration zone 8 and the lower part of the first regeneration zone 9 are regenerated by CO 2 CO introduced at inlet 15 2 The semi-regenerated catalyst moves downward into the second regeneration zone 8 and contacts the oxygen-containing gas (CO 2 and O 2 The regenerated catalyst is returned to the bottom of the catalytic cracking reactor 2 (riser reactor) through the regeneration slide valve 14 to contact with the crude oil for reaction. The regenerated flue gas flows out from the flue gas outlet 10, and is separated from the gas and solid before being led out of the regenerator 6 to the subsequent energy recovery and separation unit 11, where carbon monoxide (CO product outlet 12) and other flue gas components (other flue gas components outlet 13) are separated. The first regeneration zone 9 is a bubbling bed, and the second regeneration zone 8 is a fast bed.

[0102] Examples 1-5

[0103] According to the attached Figure 1 The relevant operating conditions and products are listed in Table 2.

[0104] Comparative Examples 1, 2 and 4

[0105] According to the attached Figure 1 The relevant operating conditions and products are listed in Table 3.

[0106] Comparative Examples 3 and 5

[0107] According to the attached Figure 2 The process was tested, the catalytic cracking feedstock oil 21 entered from the bottom of the riser reactor 22, contacted with the regenerated catalyst for reaction, the reaction oil gas and catalyst moved upward to the second settler 23 for gas-solid separation, the separated reaction oil gas 24 went to the subsequent separation system, the catalyst to be regenerated entered the second regenerator 26 through the second regenerated slide valve 25 and contacted with the regeneration gas for regeneration, the regeneration gas entered the second regenerator 26 through the regeneration gas inlet 28, the regeneration flue gas 27 was led out of the second regenerator 26 to the subsequent energy recovery system, and the regenerated catalyst returned to the bottom of the riser reactor 22 through the second regeneration slide valve 29 to contact with the catalytic cracking feedstock oil 21 for reaction. The relevant operating conditions and products are listed in Table 3.

[0108] In the following examples and comparative examples, the calculation method of CO selectivity is as follows:

[0109]

[0110] In the CO selectivity calculation formula, the amount of CO substance generated represents the amount of CO substance in the flue gas obtained by the regenerator, and the amount of carbon substance in the coke represents the amount of carbon substance in the coke or carbon deposits on the carbon deposited catalyst entering the regenerator.

[0111] Table 2

[0112]

[0113] Note: The regeneration gas includes the CO introduced into the first regeneration zone. 2 and the O introduced into the second regeneration zone 2 and CO 2 , supplement CO 2 The volume percentage in the regeneration gas indicates the CO introduced into the first regeneration zone. 2 Volume share in the regeneration gas.

[0114] Table 3

[0115]

[0116]

[0117] It can be seen from the results of the examples that the method of the present invention has the advantages of significantly reducing carbon dioxide emissions and producing carbon monoxide.

[0118] In the description of the present application, it should be noted that the terms "upper", "lower", "inside", "outside", "front", "back", "left", "right", etc. indicate directions or positional relationships based on the directions or positional relationships in the working state of the present application. They are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific direction, be constructed and operated in a specific direction. Therefore, they should not be understood as limitations on the present application.

[0119] In the description of this application, it should be noted that, unless otherwise clearly specified and limited, the terms "install", "connect" and "connect" should be understood in a broad sense. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0120] The present application has been described above in conjunction with preferred embodiments, but these embodiments are only exemplary and serve only as an illustration. On this basis, various replacements and improvements may be made to the present application, all of which fall within the scope of protection of the present application.

Claims

1. A method for regenerating spent catalytic cracking catalyst and producing CO, characterized in that: The steps include: (1) contacting a hydrocarbon oil feedstock with a catalytic cracking catalyst in a catalytic cracking reactor to carry out a catalytic cracking reaction, and separating the reaction oil gas and the spent catalyst with carbon deposition; (2) The regenerator is provided with a first regeneration zone and a second regeneration zone connected from top to bottom, so that the catalyst to be regenerated passes through the first regeneration zone and the second regeneration zone in sequence after stripping to perform the first regeneration and the second regeneration respectively, thereby obtaining a regenerated catalyst and flue gas; Wherein, the first regeneration zone is a bubbling bed, and the second regeneration zone is a fast bed; CO2 is introduced into the lower part of the first regeneration zone, so that the catalyst to be regenerated entering the first regeneration zone contacts with CO2 and the second flue gas from the second regeneration zone to perform the first regeneration; The oxygen-containing gas is introduced into the lower part of the second regeneration zone to contact with the semi-regenerated agent after the first regeneration to perform the second regeneration; The regeneration gas includes CO2 introduced into the lower part of the first regeneration zone and the oxygen-containing gas introduced into the lower part of the second regeneration zone; The volume proportion of oxygen in the oxygen-containing gas introduced into the lower part of the second regeneration zone is greater than or equal to 22%; the regeneration temperature of the first regeneration is 700-800°C; (3) returning at least a portion of the regenerated catalyst to the catalytic cracking reactor for recycling, and allowing the flue gas to be drawn out from the top of the regenerator and then separated to obtain a CO product.

2. The method for regenerating a spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: The bed density of the bubbling bed is 300-700 kg / m 3 and / or, The bed density of the fast bed is 120-300 kg / m 3 .

3. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: The conditions for the first regeneration include: a gas superficial linear velocity of 0.1 to 1 m / s, and an average catalyst residence time of 0.6 to 20 minutes.

4. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: The volume proportion of CO2 introduced into the lower part of the first regeneration zone in the regeneration gas is 1 to 50%, preferably 2 to 15%.

5. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: The conditions for the second regeneration include: a regeneration temperature of 600-700° C., a gas superficial velocity of 0.8-4 m / s, and an average catalyst residence time of 0.6-15 minutes.

6. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: The oxygen-containing gas introduced into the lower part of the second regeneration zone is a mixed gas of CO2 and O2; The total amount of CO2 introduced into the lower part of the first regeneration zone and the CO2 introduced into the lower part of the second regeneration zone accounts for 1 to 89% by volume in the regeneration gas, preferably 60 to 80% by volume.

7. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: The volume ratio of the second regeneration zone to the first regeneration zone is 1:(1-10).

8. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: In step (1), the hydrocarbon oil feedstock includes petroleum hydrocarbons and / or other mineral oils, the petroleum hydrocarbons are selected from one or more combinations of gasoline, diesel, vacuum wax oil, atmospheric wax oil, coker wax oil, deasphalted oil, vacuum residue oil, atmospheric residue oil, extracted oil and inferior recycled oil, and the other mineral oils are selected from one or more combinations of coal liquefaction oil, oil sand oil and shale oil.

9. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: In step (1), the conditions of the catalytic cracking reaction include: reaction temperature of 450-700° C., reaction time of 1-10 seconds, and catalyst-oil ratio of (1-100):

1.

10. The method for regenerating spent catalytic cracking catalyst and producing CO according to claim 1, characterized in that: The catalytic cracking reactor is a riser reactor, a fluidized bed reactor or a combination of the two.

Images