Catalytic cracking and regeneration method for producing CO

Abstract

The invention relates to a catalytic cracking and regeneration method for producing CO, 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 and a carbon-deposited spent catalyst; (2) the spent catalyst is subjected to steam stripping and then sequentially enters a first regeneration area and a second regeneration area to be subjected to first regeneration and second regeneration respectively, and a regenerated catalyst and flue gas are obtained; h2O and optional CO2 are introduced into the lower part of the first regeneration area; oxygen-containing gas is introduced into the lower part of the second regeneration area; 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, the carbon deposit in the spent catalyst of the carbon deposit generated by catalytic cracking is subjected to flue gas conversion with higher CO selectivity, so that a CO product can be better obtained.

Description

Technical Field

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

[0002] The 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, the 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 combustion of coke produces a large amount of CO2 gas, making the catalytic cracking unit the largest source of CO2 emissions in the refinery. CO2 in the catalytic cracking flue gas accounts for 15% to 50% of the total emissions of the refinery. The catalytic cracking unit emits 211.7kgCO2 for processing each ton of raw materials. There are about 190 catalytic cracking units in China, with a total processing capacity of about 210 million tons / year, and at least 40 million tons of CO2 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] Catalytic cracking of hydrocarbon oil feedstock produces spent catalyst with carbon deposits. During the regeneration process of the spent catalyst, how to convert the carbon deposits on the spent catalyst into flue gas with high CO selectivity to reduce carbon emissions from the catalytic cracking unit while producing CO products is a technical problem that needs to be solved urgently. Summary of the invention

[0009] The present invention provides a catalytic cracking and regeneration method for producing CO, the purpose of which is to convert the carbon deposits in the spent catalyst produced by catalytic cracking into flue gas with higher CO selectivity to obtain a better CO product.

[0010] The present invention relates to a catalytic cracking and regeneration method for 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 includes a first regeneration zone and a second regeneration zone connected from top to bottom, so that the catalyst to be regenerated enters the first regeneration zone and the second regeneration zone in sequence after stripping to perform first regeneration and second regeneration respectively, thereby obtaining a regenerated catalyst and flue gas;

[0013] Wherein, H2O and optionally CO2 are introduced into the lower part of the first regeneration zone, so that the catalyst to be regenerated entering the first regeneration zone is contacted with H2O and optionally CO2 and the second flue gas from the second regeneration zone to perform the first regeneration;

[0014] 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;

[0015] The regeneration gas includes H2O and 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;

[0016] (3) returning at least a portion of the regenerated catalyst to the catalytic cracking reactor for recycling, and drawing the flue gas out from the top of the regenerator to obtain a CO product through separation.

[0017] Optionally, in step (2), the volume proportion of CO2 introduced into the lower part of the first regeneration zone in the regeneration gas is 0 to 50%, preferably 5 to 15%; the volume proportion of H2O introduced into the lower part of the first regeneration zone in the regeneration gas is 1 to 20%, preferably 2 to 10%.

[0018] Optionally, in step (2), the oxygen-containing gas introduced into the lower part of the second regeneration zone includes O2 and CO2.

[0019] Optionally, in step (2), the volume proportion of O2 introduced into the lower part of the second regeneration zone in the oxygen-containing gas is 22 to 100%, preferably 25 to 60%.

[0020] Optionally, in step (2), the temperature of the first regeneration and the second regeneration are independently 600 to 800° C., preferably 670 to 780° C.;

[0021] and / or,

[0022] The gas superficial velocity in the regenerator is 0.3 to 5 m / s, and the average residence time of the catalyst to be regenerated in the regenerator is 0.6 to 20 minutes.

[0023] Optionally, the volume ratio of the second regeneration zone to the first regeneration zone is 1:(1-10); and / or,

[0024] The first regeneration zone is provided with at least one orifice plate, the inclination angle of the orifice plate to the horizontal line is 1 to 50 degrees, the opening rate of the orifice plate is 1% to 90%, the opening diameter is 1 to 30 cm, and an overflow weir is arranged on the orifice plate.

[0025] Optionally, the second regeneration zone is a dense phase bed with a bed density of 100-700 kg / m3; and / or,

[0026] The catalytic cracking reactor is a riser reactor and / or a fluidized bed reactor.

[0027] Optionally, the catalytic cracking catalyst in step (1) is loaded with an oxide of an active metal;

[0028] The active metal is selected from one or more combinations of alkali metals, alkaline earth metals and transition metals, preferably one or more combinations of K, Ca, Na, Co, Mo, Ni and Fe;

[0029] The content of the active metal in the catalytic cracking catalyst is 0.1-5%, preferably 0.5-1%.

[0030] Optionally, the catalytic cracking catalyst in step (1) comprises 15 to 65 wt % of natural minerals, 10 to 30 wt % of inorganic oxides and 25 to 75 wt % of zeolite;

[0031] The inorganic oxide includes one or more combinations of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silicon aluminum, and the inorganic oxide also includes an oxide of the active metal;

[0032] The mass proportion of the active metal oxide in the inorganic oxide is 0.1% to 20%.

[0033] Optionally, the hydrocarbon oil feedstock in step (1) is selected from 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; and / or,

[0034] The conditions of the catalytic cracking reaction in step (1) include: a reaction temperature of 450 to 700° C., a reaction time of 1 to 10 seconds, and a catalyst to oil ratio of 1 to 100:1.

[0035] Beneficial effects:

[0036] (1) The present invention controls the combustion of coke during the catalyst regeneration process, causing it to undergo incomplete combustion to generate CO, and stores part of the energy in CO as chemical energy, which can reduce excess heat during the catalytic regeneration process, solve the problem of regenerator tail combustion, and significantly reduce CO2 emissions without affecting the catalyst regeneration effect.

[0037] (2) By introducing a small amount of H2O, the conversion of coke into CO is promoted, the reaction between CO2 and coke is strengthened, and the CO production is further increased.

[0038] (3) N2 is not introduced during the regeneration process, which is beneficial to the separation of CO and CO2 and reduces the separation energy consumption.

[0039] (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.

[0040] (5) In the context of carbon neutrality and carbon peak goals, the production of CO by catalytic cracking regeneration process can achieve waste recycling and energy conservation and emission reduction, which has huge economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] 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:

[0042] Figure 1 It is a schematic diagram of a specific implementation of the process of the catalytic cracking and regeneration method for producing CO of the present invention or the catalytic cracking and regeneration system for producing CO;

[0043] Figure 2 Schematic diagram of the catalytic cracking and regeneration system (single-stage regeneration) for producing CO used in Comparative Examples 2 and 4;

[0044] Description of Reference Numerals

[0045] 1 Hydrocarbon oil feedstock inlet 2 Catalytic cracking reaction 3 Settler 4 Reaction oil and gas outlet

[0046] 5 Waiting for regeneration slide valve 6 Regenerator 7 Inlet of O2 and CO2 8 Inlet of the second regeneration zone

[0047] 9First regeneration zone 10Flue gas outlet 11Energy recovery and separation 12CO product outlet unit

[0048] 13 Other flue gas components 14 Pipeline for H2O 15 Pipe for CO2 16 Regeneration slide valve outlet line

[0049] 21 Catalytic cracking feedstock 22 Riser reactor 23 Second settler 24 Reaction oil and gas

[0050] 25 second slide valve to be regenerated 26 second regenerator 27 regeneration flue gas 28 regeneration gas inlet

[0051] 29 Second regeneration slide valve DETAILED DESCRIPTION

[0052] 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.

[0053] 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.

[0054] 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.

[0055] The present invention relates to a catalytic cracking and regeneration method for producing CO, comprising the following steps:

[0056] (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;

[0057] (2) The regenerator includes a first regeneration zone and a second regeneration zone connected from top to bottom, so that the catalyst to be regenerated enters the first regeneration zone and the second regeneration zone in sequence after stripping to perform first regeneration and second regeneration respectively, thereby obtaining a regenerated catalyst and flue gas;

[0058] Wherein, H2O and optionally CO2 are introduced into the lower part of the first regeneration zone, so that the catalyst to be regenerated entering the first regeneration zone is contacted with H2O and optionally CO2 and the second flue gas from the second regeneration zone to perform the first regeneration;

[0059] 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 H2O and 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;

[0060] (3) returning at least a portion of the regenerated catalyst to the catalytic cracking reactor for recycling, and drawing the flue gas out from the top of the regenerator to obtain a CO product through separation.

[0061] It should be noted that the reaction oil and gas separated in step (1) can be sent to a subsequent separation system for separation to obtain a variety of gaseous or liquid catalytic cracking products. For example, the reaction oil and gas can be separated into dry gas, liquefied gas, stabilized gasoline and catalytic diesel fractions by a subsequent separation system. The specific separation method can be a conventional technical method in the field, and the present invention is not limited to this and will not be described in detail herein.

[0062] In step (2), H2O and optionally CO2 are introduced into the lower part of the first regeneration zone, which means that CO2 may be introduced into the lower part of the first regeneration zone at the same time as H2O is introduced into the lower part of the first regeneration zone, or CO2 may not be introduced.

[0063] In step (2), the catalyst to be regenerated entering the regenerator first enters the first regeneration zone and flows from top to bottom, the H2O and optional CO2 introduced into the lower part of the first regeneration zone flow from bottom to top, and the second flue gas from the second regeneration zone also flows from bottom to top, the catalyst to be regenerated is countercurrently contacted with the H2O and optional CO2 introduced into the lower part of the first regeneration zone and the second flue gas from the second regeneration zone in the first regeneration zone for a first regeneration, to obtain a semi-regenerated agent and flue gas; the semi-regenerated agent after the first regeneration is contacted with the oxygen-containing gas introduced into the lower part of the second regeneration zone for a second regeneration, to obtain a regenerated catalyst and a second flue gas; the second flue gas flows upward to the first regeneration zone, that is, the second flue gas is the reaction product of the semi-regenerated agent and the oxygen-containing gas introduced into the lower part of the second regeneration zone.

[0064] In step (3), in one embodiment, at least a portion of the catalytic cracking catalyst used in the catalytic cracking reaction is a regenerated catalyst, and preferably all of the regenerated catalyst is transported to the catalytic cracking reactor for recycling, or in other words, preferably all of the catalytic cracking catalyst is a regenerated catalyst.

[0065] Preferably, the method of the present invention further comprises: degassing the regenerated catalyst obtained by the first regeneration and the second regeneration and then returning it to the catalytic cracking reactor for recycling. An internal heat exchanger or an external heat exchanger can be provided in the regenerator, and the type, connection and operation of the heat exchanger are well known to those skilled in the art.

[0066] In step (3), the flue gas obtained by the regenerator is separated to obtain a CO product. The CO product can be obtained by separating the flue gas using chemical absorption, membrane separation, pressure swing adsorption, cryogenics, COSORB or other separation and purification methods known to those skilled in the art, preferably chemical absorption. Before separating the flue gas to obtain CO, the flue gas can be purified to remove impurities such as sulfides and nitrides.

[0067] The catalytic cracking and regeneration method for producing CO provided by the present invention introduces a small amount of H2O into the lower part of the first regeneration zone to promote the conversion of coke into CO in the presence of oxygen; more coke on the catalytic cracking catalyst to be spent is converted into carbon monoxide, which greatly reduces CO2 emissions and significantly improves CO selectivity; and carbon monoxide is produced by changing the regeneration coking method, which can effectively reduce tail combustion and slow down the catalyst deactivation rate.

[0068] According to a specific embodiment of the catalytic cracking and regeneration method of the present invention, in step (2), the volume proportion of CO2 introduced into the lower part of the first regeneration zone in the regeneration gas is 0-50%, preferably 5-15%; the volume proportion of H2O introduced into the lower part of the first regeneration zone in the regeneration gas is 1-20%, preferably 2-10%.

[0069] It should be noted that by controlling the volume proportion of H2O and CO2 introduced into the first regeneration zone in the regeneration gas as above, it is possible to better reduce combustion heat release through incomplete combustion, alleviate the problem of excess heat in the catalytic device, and better improve the selectivity of CO. The CO selectivity can reach more than 80%.

[0070] According to another specific embodiment of the catalytic cracking and regeneration method of the present invention, in step (2), the oxygen-containing gas introduced into the lower part of the second regeneration zone includes O2 and CO2.

[0071] It should be noted that the regeneration gas in the regenerator includes O2, CO2 and H2O, and the regeneration gas does not contain N2 and / or air.

[0072] According to another specific embodiment of the catalytic cracking and regeneration method of the present invention, in step (2), the volume proportion of O2 introduced into the lower part of the second regeneration zone in the oxygen-containing gas is 22-100%, preferably 25-60%.

[0073] It should be noted that the present invention uses oxygen, CO2 and a small amount of H2O as regeneration gas, and part of CO2 is converted into CO; without introducing nitrogen, a relatively simple method can be adopted to separate and obtain a CO product with higher purity, and at the same time, it plays a role in enriching CO2, which is beneficial to carbon capture and utilization, and a small amount of H2O plays a role in promoting the conversion of coke into CO. In particular, by controlling the volume ratio of O2 introduced into the second regeneration zone in the oxygen-containing gas as above, the semi-regenerated catalyst is completely regenerated in the second regeneration zone, without affecting the activity of the catalytic cracking reaction, and maintaining a high CO content in the flue gas, which is beneficial to the subsequent further purification and application of CO.

[0074] According to a specific embodiment of the catalytic cracking and regeneration method of the present invention, in step (2), the temperature of the first regeneration and the second regeneration are independently 600-800° C., preferably 670-780° C.;

[0075] and / or,

[0076] The gas superficial velocity in the regenerator is 0.3 to 5 m / s, and the average residence time of the catalyst to be regenerated in the regenerator is 0.6 to 20 minutes.

[0077] It should be noted that the temperature of the first regeneration and the second regeneration is preferably 680-740°C, specifically preferably 700°C, 740°C, 750°C, etc.; the superficial linear velocity of the gas in the regenerator is preferably 0.5-3.5 m / s, more preferably 0.8-2 m / s; the average residence time of the catalyst is preferably 0.6-15 minutes, more preferably 2-12 minutes, and further preferably 3-10 minutes.

[0078] It should be noted that by controlling the regeneration conditions in the regenerator as above, for example, controlling the regeneration temperature as above, under the above regeneration atmosphere, the coke on the catalyst to be regenerated can be converted into flue gas with higher CO selectivity, and more CO products can be obtained.

[0079] According to a specific embodiment of the catalytic cracking and regeneration method of the present invention, the volume ratio of the second regeneration zone to the first regeneration zone is 1:(1-10); and / or,

[0080] The first regeneration zone is provided with at least one orifice plate, the inclination angle of the orifice plate to the horizontal line is 1 to 50 degrees, the opening rate of the orifice plate is 1% to 90%, the opening diameter is 1 to 30 cm, and an overflow weir is arranged on the orifice plate.

[0081] It should be noted that the volume ratio of the second regeneration zone to the first regeneration zone is preferably 1:(2-5). Such a ratio is beneficial 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.

[0082] It should be noted that the orifice plate opening rate is preferably 5% to 80%, more preferably 20% to 70%; the opening diameter is preferably 5 to 20 cm, more preferably 10 to 15 cm. The number of orifice plates and their distribution in the first regeneration zone 9 can be set as needed. For example, the number of orifice plates can be 2 to 10, preferably 4 to 8, and can be distributed in the first regeneration zone 9 in a roughly uniform manner. The inclination angle of the orifice plate to the horizontal line is preferably 5 to 45°, more preferably 15 to 30°; setting the orifice plate to have a certain inclination angle is conducive to the semi-regenerated catalyst moving downward along the orifice plate in the first regeneration zone into the second regeneration zone. In one embodiment, an overflow weir is provided on the orifice plate.

[0083] By setting the perforated plate as above, the following effects can be achieved: under the premise of ensuring the fluidized state of the catalyst, the ratio of coke to oxygen can be increased, the catalyst residence time can be increased, and more coke can be promoted to be incompletely burned to produce CO, thereby reducing the combustion of coke to produce CO2 in the second regeneration zone.

[0084] It should be noted that in the catalytic cracking and regeneration method for producing CO of the present invention, by controlling the volume ratio of the two regeneration zones as above and designing the orifice plate as above, it is beneficial to convert the carbon deposits on the regenerated catalyst into flue gas with higher CO selectivity.

[0085] According to a specific embodiment of the catalytic cracking and regeneration method of the present invention, the second regeneration zone is a dense phase bed with a bed density of 100-700 kg / m3; and / or,

[0086] The catalytic cracking reactor is a riser reactor and / or a fluidized bed reactor.

[0087] It should be noted that the bed density is preferably 150 to 600 kg / m3, more preferably 180 to 500 kg / m3. 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] It should be noted that by making the second regeneration zone a dense phase bed and controlling the bed density as above, it is beneficial for more carbon deposits on the regenerated catalyst to be incompletely burned to generate CO under the above-mentioned regeneration atmosphere.

[0089] According to a specific embodiment of the catalytic cracking and regeneration method of the present invention, the catalytic cracking catalyst in step (1) is loaded with an oxide of an active metal;

[0090] The active metal is selected from one or more combinations of alkali metals, alkaline earth metals and transition metals, preferably one or more combinations of K, Ca, Na, Co, Mo, Ni and Fe;

[0091] The content of the active metal in the catalytic cracking catalyst is 0.1-5%, preferably 0.5-1%.

[0092] It should be noted that the inventors of the present application have discovered in many years of research and development experiments that when a catalytic cracking catalyst loaded with the above-mentioned active metal oxide is used and the content of the active metal in the catalytic cracking catalyst is controlled as above, when the carbon deposited catalyst to be regenerated produced by catalytic cracking enters a regenerator and is regenerated according to the regeneration method of the present application, the above-mentioned active metal contained in the catalyst plays a good activation or catalytic role, so that the carbon deposit is better incompletely oxidized and converted into CO in the above-mentioned regeneration atmosphere of the present application, so that the CO selectivity is further significantly improved.

[0093] According to a specific embodiment of the catalytic cracking and regeneration method of the present invention, the catalytic cracking catalyst in step (1) comprises 15 to 65 weight % of natural minerals, 10 to 30 weight % of inorganic oxides and 25 to 75 weight % of zeolite;

[0094] The inorganic oxide includes one or more combinations of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silicon aluminum, and the inorganic oxide also includes an oxide of the active metal;

[0095] The mass proportion of the active metal oxide in the inorganic oxide is 0.1% to 20%.

[0096] It should be noted that the zeolite as an active component is preferably one or more of Y zeolite, mordenite, beta zeolite, zeolite with MFI structure (such as ZSM series zeolite and / or ZRP zeolite). The natural mineral is selected from one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite.

[0097] It should be noted that, under the premise that the catalytic cracking catalyst of the present application includes the above-mentioned active metal, the catalyst adopts the above-mentioned substances and compositions so that the active metal in the catalyst can better play its role in the catalyst regeneration process, so that more carbon deposits can be converted into CO.

[0098] According to a specific embodiment of the catalytic cracking and regeneration method of the present invention, the hydrocarbon oil feedstock in step (1) is selected from 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; and / or,

[0099] The conditions of the catalytic cracking reaction in step (1) include: a reaction temperature of 450 to 700° C., a reaction time of 1 to 10 seconds, and a catalyst to oil ratio of 1 to 100:1.

[0100] It should be noted that the reaction temperature is preferably 500-650°C, more preferably 550-620°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.

[0101] In the present invention, 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.

[0102] It should be noted that the catalytic cracking and regeneration method for producing CO of the present application has a wide range of applicability. The spent catalyst produced by the above-mentioned hydrocarbon oil feedstock under the above-mentioned catalytic cracking reaction conditions can produce flue gas with high CO selectivity through the regeneration process of the present application, and at the same time, the regenerated catalyst can be well obtained.

[0103] The catalytic cracking and regeneration method for producing CO of the present invention can be implemented based on the catalytic cracking and regeneration system for producing CO, such as Figure 1 As shown, the catalytic cracking and regeneration system for producing CO includes a catalytic cracking reaction unit, a regenerator 6 and an energy recovery separation unit 11;

[0104] 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.

[0105] 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;

[0106] The regenerator 6 is provided with a first regeneration zone 9 and a second regeneration zone 8 connected from top to bottom, a pipeline 14 for introducing H2O and a pipeline 15 for introducing CO2 are provided at the lower part of the first regeneration zone 9, and an inlet 7 for introducing O2 and CO2 is provided at the lower part of the second regeneration zone 8;

[0107] 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 a regeneration slide valve 16 is provided on the regeneration agent pipeline;

[0108] 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 .

[0109] The catalytic cracking and regeneration method or system for producing CO provided by the present invention not only reduces the carbon dioxide emission of the catalytic device, but also produces CO, realizes the transformation of waste into treasure and the full utilization of resources, and improves the economic benefit of the catalytic cracking device; at the same time, CO is used as a raw material for subsequent chemical processes, 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.

[0110] 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.

[0111] The catalysts used in the following examples and comparative examples are catalytic cracking catalysts and modified catalysts thereof. The commercial brand of catalyst C is CDOS (Sinopec Catalyst Co., Ltd. Changling Branch). Catalyst A is loaded with Ni on catalyst C with a content of 1%, and catalyst B is loaded with K on catalyst C with a content of 0.5%.

[0112] The raw material oil used in the following examples and comparative examples is Anqing wax oil, and its properties are shown in Table 1.

[0113] Table 1

[0114]

[0115]

[0116] like Figure 1 As shown, the catalytic cracking feedstock oil enters the bottom of the catalytic cracking reactor 2 (riser reactor) through the hydrocarbon oil feedstock inlet 1, contacts with the regenerated catalyst for reaction, and the reaction oil gas and catalyst run upward to the settler 3 for gas-solid separation. The separated reaction oil gas flows out through the reaction oil gas outlet 4 to the subsequent absorption stabilization system, and the catalyst to be regenerated enters the first regeneration zone 9 of the regenerator 6 through the regeneration slide valve 5, and contacts with the second flue gas from the second regeneration zone 8 and H2O and CO2 (optional) introduced into the first regeneration zone 9 for the first regeneration to obtain a semi-regenerated catalyst; the semi-regenerated catalyst moves downward along the orifice plate of the first regeneration zone into the second regeneration zone 8, and contacts with the oxygen-containing gas introduced by the inlet 7 for O2 and CO2 for the second regeneration to obtain a regenerated catalyst; the regenerated catalyst returns to the bottom of the catalytic cracking reactor 2 (riser reactor) through the regeneration slide valve 16 to contact with the catalytic cracking feedstock oil entering from the hydrocarbon oil feedstock inlet 1 for reaction. The regenerated flue gas flowing out of the flue gas outlet 10 is led out of the regenerator 6 to the subsequent energy recovery separation unit 11 after gas-solid separation, and is separated to obtain carbon monoxide (CO product outlet 12) and other flue gas components (other flue gas components outlet 13).

[0117] Figure 1 The regenerator 6 used has the following structure:

[0118] The regenerator 6 includes a first regeneration zone 9 and a second regeneration zone 8, wherein four orifice plates are arranged in the first regeneration zone 9, the opening rate of the orifice plates is 70%, and the inclination angle of the orifice plates is 30°; the volume ratio of the first regeneration zone 9 to the second regeneration zone 8 is 4:1; and the second regeneration zone 8 is a dense phase bed.

[0119] In the following examples and comparative examples, the calculation method of CO selectivity is as follows:

[0120]

[0121] 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 deposited catalyst to be regenerated that enters the regenerator.

[0122] Examples 1-6

[0123] according to Figure 1 The relevant operating conditions and products are listed in Table 2.

[0124] Comparative Example 1, Example 7 and Comparative Example 3

[0125] according to Figure 1 The relevant operating conditions and products are listed in Table 3.

[0126] Comparative Examples 2 and 4

[0127] according to 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 to contact with the regeneration gas for regeneration, the regenerated flue gas 27 was led out of the second regenerator 26 to the subsequent energy recovery system, 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, and the regeneration gas inlet 28 at the lower part of the second regenerator 26 was fed with the regeneration gas. The relevant operating conditions and products are listed in Table 3.

[0128] Table 2

[0129]

[0130] Note: The volume of the regeneration gas is the total volume of H2O and CO2 introduced into the lower part of the first regeneration zone and the oxygen-containing gas (O2 and CO2) introduced into the lower part of the second regeneration zone.

[0131] Table 3

[0132]

[0133] It can be seen from the results of the examples that the method of the present invention has the advantages of greatly reducing carbon dioxide emissions and producing carbon monoxide, and CO selectivity is significantly improved.

[0134] 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.

[0135] 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.

[0136] 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 catalytic cracking and regeneration method for 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 includes a first regeneration zone and a second regeneration zone connected from top to bottom, so that the catalyst to be regenerated enters the first regeneration zone and the second regeneration zone in sequence after stripping to perform first regeneration and second regeneration respectively, thereby obtaining a regenerated catalyst and flue gas; Wherein, H2O and optionally CO2 are introduced into the lower part of the first regeneration zone, so that the catalyst to be regenerated entering the first regeneration zone is contacted with H2O and optionally 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 H2O and 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; (3) returning at least a portion of the regenerated catalyst to the catalytic cracking reactor for recycling, and drawing the flue gas out from the top of the regenerator to obtain a CO product through separation.

2. The catalytic cracking and regeneration method according to claim 1, characterized in that: In step (2), the volume proportion of CO2 introduced into the lower part of the first regeneration zone in the regeneration gas is 0-50%, preferably 5-15%; the volume proportion of H2O introduced into the lower part of the first regeneration zone in the regeneration gas is 1-20%, preferably 2-10%.

3. The catalytic cracking and regeneration method according to claim 1, characterized in that: In step (2), the oxygen-containing gas introduced into the lower part of the second regeneration zone includes O2 and CO2.

4. The catalytic cracking and regeneration method according to claim 3, characterized in that: In step (2), the volume proportion of O2 introduced into the lower part of the second regeneration zone in the oxygen-containing gas is 22 to 100%, preferably 25 to 60%.

5. The catalytic cracking and regeneration method according to claim 1, characterized in that: In step (2), the temperature of the first regeneration and the second regeneration are each independently 600 to 800° C., preferably 670 to 780° C.; and / or, The gas superficial velocity in the regenerator is 0.3 to 5 m / s, and the average residence time of the catalyst to be regenerated in the regenerator is 0.6 to 20 minutes.

6. The catalytic cracking and regeneration method according to claim 1, characterized in that: The volume ratio of the second regeneration zone to the first regeneration zone is 1:(1-10); and / or, The first regeneration zone is provided with at least one orifice plate, the inclination angle of the orifice plate to the horizontal line is 1 to 50 degrees, the opening rate of the orifice plate is 1% to 90%, the opening diameter is 1 to 30 cm, and an overflow weir is arranged on the orifice plate.

7. The catalytic cracking and regeneration method according to claim 1, characterized in that: The second regeneration zone is a dense phase bed with a bed density of 100-700 kg / m3; and / or, The catalytic cracking reactor is a riser reactor and / or a fluidized bed reactor.

8. The catalytic cracking and regeneration method according to claim 1, characterized in that: The catalytic cracking catalyst in step (1) is loaded with an oxide of an active metal; The active metal is selected from one or more combinations of alkali metals, alkaline earth metals and transition metals, preferably one or more combinations of K, Ca, Na, Co, Mo, Ni and Fe; The content of the active metal in the catalytic cracking catalyst is 0.1-5%, preferably 0.5-1%.

9. The catalytic cracking and regeneration method according to claim 8, characterized in that: The catalytic cracking catalyst in step (1) comprises 15-65 wt % of natural minerals, 10-30 wt % of inorganic oxides and 25-75 wt % of zeolite; The inorganic oxide includes one or more combinations of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silicon aluminum, and the inorganic oxide also includes an oxide of the active metal; The mass proportion of the active metal oxide in the inorganic oxide is 0.1% to 20%.

10. The catalytic cracking and regeneration method according to claim 1, characterized in that: The hydrocarbon oil feedstock in step (1) is selected from 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; and / or, The conditions of the catalytic cracking reaction in step (1) include: a reaction temperature of 450 to 700° C., a reaction time of 1 to 10 seconds, and a catalyst to oil ratio of 1 to 100:1.

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