Catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas and operation method thereof

Abstract

The present invention discloses a method for oxygen-enriched regeneration of catalytic cracking with co-production of syngas, comprising the following steps: (1) Reacting a micro-oxygen carrier with air to obtain an oxygen-enriched carrier, and the oxygen-enriched carrier releases oxygen under the action of high-temperature regeneration flue gas to obtain oxygen-enriched flue gas, which enters the regenerator to participate in the regeneration of the catalyst; (2) Part of the regeneration flue gas successively enters a CO2 conversion reactor and an H2O conversion reactor to react with the oxygen carrier under different conditions, and part of the CO2 and H2O in the flue gas are converted into syngas. The present invention adopts the chemical looping oxygen production technology to realize the oxygen-enriched regeneration of the catalyst, and at the same time uses the heat released by the oxygen-enriched regeneration of the catalyst to produce syngas, thereby improving the coking capacity and processing capacity of the catalytic cracking unit, increasing the product yield, and solving the problems of low coking capacity, large amount of regeneration flue gas and complex subsequent treatment process in the conventional air regeneration catalytic cracking technology.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic cracking, and in particular relates to a catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas and an operation method thereof. Background Art

[0002] At present, the catalytic cracking unit of the refinery adopts conventional air regeneration technology, which has the disadvantages of low coking capacity, large regeneration flue gas volume, and complex subsequent treatment process. In order to further improve the processing capacity of the catalytic cracking unit, increase product yield, reduce pollutant emissions and simplify the subsequent regeneration flue gas treatment process, oxygen-enriched regeneration catalytic cracking technology has a very broad prospect. The high cost of conventional oxygen production technologies such as cryogenic distillation technology, membrane separation technology and pressure swing adsorption technology has restricted the development of oxygen-enriched regeneration catalytic cracking technology.

[0003] Chemical chain air separation technology is a new air separation technology. Its principle is to use oxygen-rich oxygen carriers to produce oxygen in oxygen release reactors, convert oxygen-rich oxygen carriers into oxygen-poor oxygen carriers, and then the oxygen-poor oxygen carriers react with air in oxygen absorption reactors to oxidize and regenerate oxygen-rich oxygen carriers, and produce oxygen-rich gas through the circulation of oxygen carriers. Compared with conventional oxygen production technology, it has the advantages of low energy consumption, fast startup, low cost, and convenient operation, which provides conditions for the development and application of oxygen-rich regenerative catalytic cracking technology.

[0004] Under certain conditions, CO2 reacts with reduced oxygen carriers (M x O y-1 ) can generate CO, and H2O can generate H2 by reacting with reduced oxygen carriers under certain conditions. The reaction equation is:

[0005]

[0006]

[0007] The flue gas CO2 and H2O produced by catalytic cracking oxygen-enriched regeneration account for more than 95%. Under different conditions, they can react with reduced oxygen carriers to produce synthesis gas, thereby significantly reducing flue gas emissions. Summary of the invention

[0008] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a catalytic cracking oxygen-enriched regeneration system and an operating method for co-producing synthesis gas, which adopts chemical chain oxygen production technology to achieve oxygen-enriched regeneration of the catalyst, and at the same time utilizes the heat released by the oxygen-enriched regeneration of the catalyst to produce synthesis gas, thereby improving the charring capacity and processing capacity of the catalytic cracking unit, increasing product yield, reducing pollutant emissions, and solving the problems of low charring capacity, large regeneration flue gas volume, and complex subsequent treatment process in conventional air regeneration catalytic cracking technology.

[0009] To achieve the above object, the present invention provides the following technical solutions:

[0010] A catalytic cracking oxygen-enriched regeneration method for co-producing synthesis gas comprises the following steps:

[0011] (1) In an oxygen absorption reactor, a micro-oxygen oxygen carrier is reacted with air to obtain an oxygen-rich oxygen carrier and high-temperature oxygen-depleted air; the oxygen-rich oxygen carrier enters an oxygen release reactor and releases oxygen under the action of high-temperature flue gas to obtain oxygen-rich flue gas and oxygen-depleted oxygen carrier; the oxygen-rich flue gas enters a regenerator to participate in a catalyst regeneration reaction to obtain a regenerated catalyst and regenerated flue gas;

[0012] (2) the regenerated catalyst obtained in step (1) enters a catalytic reactor to react with crude oil to obtain an oil-gas mixture and a catalyst to be regenerated; a portion of the regenerated flue gas obtained in step (1) enters an oxygen release reactor to fluidize the oxygen carrier and provide heat for the oxygen release reaction, and another portion enters a CO2 conversion reactor to react with the oxygen-depleted oxygen carrier to obtain a slightly oxygen-depleted oxygen carrier and flue gas containing CO; the slightly oxygen-depleted oxygen carrier and the flue gas containing CO enter an H2O conversion reactor to react, and the H2O in the flue gas is converted into H2 to obtain a slightly oxygen-depleted oxygen carrier and a flue gas rich in synthesis gas, the slightly oxygen-depleted oxygen carrier enters an oxygen absorption reactor, and the flue gas containing synthesis gas enters a synthesis gas separator to separate and obtain synthesis gas.

[0013] Preferably, the high-temperature oxygen-depleted air in step (1) enters the gas turbine to perform work, and then exchanges heat with the air in the third heat exchanger to obtain high-temperature air and low-temperature oxygen-depleted air; the oxygen-depleted oxygen carrier in step (2) exchanges heat with the low-temperature heat medium through the first heat exchanger before entering the CO2 conversion reactor to obtain a low-temperature oxygen-depleted oxygen carrier; the slightly oxygen-depleted oxygen carrier exchanges heat with the high-temperature heat medium through the second heat exchanger before entering the H2O conversion reactor to obtain a high-temperature slightly oxygen-depleted oxygen carrier.

[0014] Preferably, the process of the oxygen absorption reactor in step (1) is a low-pressure oxygen absorption process or a high-pressure oxygen absorption process; the reaction temperature of the low-pressure oxygen absorption process is 530-800°C, and the reaction pressure is 0.1-0.5MPa; the reaction temperature of the high-pressure oxygen absorption process is 800-1000°C, and the reaction pressure is 0.5-5MPa; the reaction temperature of the oxygen release reactor is 600-750°C, and the reaction pressure is 0.1-0.5MPa; the reaction temperature of the regenerator is 600-750°C, and the reaction pressure is 0.1-0.5MPa.

[0015] Preferably, the reaction temperature of the catalytic reactor in step (2) is 500-650°C, and the reaction pressure is 0.1-0.5MPa; the reaction temperature of the CO2 conversion reactor is 150-230°C, and the reaction pressure is 0.1-0.5MPa; the reaction temperature of the H2O conversion reactor is 550-700°C, and the reaction pressure is 0.1-0.5MPa.

[0016] Preferably, the micro-oxygen oxygen carrier is one or more of an iron-indium-based oxygen carrier, a cobalt-indium-based oxygen carrier, and a perovskite oxygen carrier; and the heat medium is one of heat transfer oil, water vapor, and molten salt.

[0017] Preferably, the oxygen concentration of the oxygen-enriched flue gas in step (1) is 22-70%, and the oxygen-enriched concentration can be adjusted by controlling the flue gas volume of the oxygen release reactor and the circulation volume of the oxygen carrier, preferably 25-40%; the H / C in the synthesis gas in step (2) is 0.1-10.

[0018] The present invention also protects a catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas for implementing the above method, comprising: an oxygen absorption reactor, wherein a fifth inlet and a fourth inlet for an oxygen carrier are provided at the bottom of the oxygen absorption reactor, wherein the fifth inlet is connected to a third heat exchanger through a pipeline, and the oxygen absorption reactor is connected to a fourth cyclone separator; the upper outlet of the fourth cyclone separator is connected to a gas turbine, and the lower outlet of the fourth cyclone separator is connected to the first inlet for the oxygen carrier below the oxygen release reactor;

[0019] A second inlet is provided at the bottom of the oxygen release reactor, and the oxygen release reactor is connected to a first cyclone separator; an upper outlet of the first cyclone separator is connected to a first inlet at the bottom of the regenerator, and a lower outlet of the first cyclone separator is connected to an upper inlet of the first heat exchanger;

[0020] The bottom outlet of the first heat exchanger is connected to the second inlet of the oxygen carrier below the CO2 conversion reactor, the bottom of the CO2 conversion reactor is provided with a third inlet, the CO2 conversion reactor is connected to a second cyclone separator, the upper outlet of the second cyclone separator is connected to the fourth inlet at the bottom of the H2O conversion reactor, and the lower outlet of the second cyclone separator is connected to the upper inlet of the second heat exchanger;

[0021] The regenerator is provided with a regeneration flue gas outlet at the top, and a return inclined pipe and a regeneration inclined pipe connected to the catalytic reactor are provided on the side, and the regeneration flue gas outlet is connected to the second inlet and the third inlet;

[0022] The bottom outlet of the second heat exchanger is connected to the third inlet of the oxygen carrier below the H2O conversion reactor, the H2O conversion reactor is connected to the third cyclone separator, the upper outlet of the third cyclone separator is connected to the synthesis gas separator, and the lower outlet of the third cyclone separator is connected to the fourth inlet of the oxygen carrier of the oxygen absorption reactor.

[0023] Preferably, the first heat exchanger and the second heat exchanger are both provided with a heat medium inlet and a heat medium outlet, the heat medium inlet of the first heat exchanger and the heat medium outlet of the second heat exchanger are connected to each other through a pipeline, the heat medium outlet of the first heat exchanger and the heat medium inlet of the second heat exchanger are connected to each other through a pipeline, and the heat medium circulates between the first heat exchanger and the second heat exchanger.

[0024] Preferably, the synthesis gas separator is provided with a waste gas outlet and a synthesis gas outlet; the separation method in the synthesis gas separator is one or more of membrane separation, pressure swing adsorption, solvent absorption, low temperature separation, and distillation tower separation.

[0025] Preferably, a gas-solid separator is provided at the top of the regenerator; a water vapor inlet and a crude oil inlet are provided at the bottom of the catalytic reactor, and an oil-gas mixture outlet is provided at the top; a gas-solid separator is provided at the top of the catalytic reactor.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The preferred embodiment of the present invention can improve the processing capacity of the catalytic cracking unit, change the product distribution, and improve the product yield. The chemical chain oxygen production technology is used to realize the oxygen-enriched regeneration of the catalyst in the catalytic cracking reaction unit. The oxygen-enriched regeneration catalytic cracking can greatly improve the regenerator's charring capacity, further reduce the catalyst carbon content, improve the catalyst reaction activity, and improve the processing capacity of the catalytic cracking unit; at the same time, the product distribution is optimized, the total liquid yield can be increased by 1-2%, and the emission of pollutants is reduced, solving the problems of low charring capacity, large regeneration flue gas volume, and complex subsequent treatment process in conventional air regeneration catalytic cracking technology.

[0028] (2) The preferred embodiment of the present invention can use the regenerated flue gas to produce synthesis gas, which has significant economic benefits. The preferred embodiment of the present invention uses the heat of the oxygen-enriched regeneration of the catalyst to produce synthesis gas with a H / C ratio of 0.1 to 10 by reacting the regenerated flue gas under different conditions, which has significant economic benefits.

[0029] (3) The preferred embodiment of the present invention can significantly reduce the emission of pollutants and achieve efficient capture of regeneration flue gas. In conventional processes, the amount of catalytic cracking regeneration flue gas is large, and the CO2 therein cannot be collected and sealed, and is directly discharged into the atmosphere. The present invention utilizes the generated regeneration flue gas to produce synthesis gas, with a CO2 conversion rate of 20-35%, an H2O conversion rate of more than 70%, and a significant reduction in flue gas emissions. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a schematic diagram of the structure of the catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas of the present invention.

[0031] Among them, 1. regenerator; 2. oxygen release reactor; 3. CO2 conversion reactor; 4. H2O conversion reactor; 5. oxygen absorption reactor; 6. synthesis gas separator; 7. catalytic reactor; E1, first heat exchanger; E2, second heat exchanger; E3, third heat exchanger; T, gas turbine; 11, first inlet; 12, return inclined pipe; 13, regeneration inclined pipe; 21, second inlet; 22, first inlet of oxygen carrier; 23, first cyclone separator; 31, third inlet; 32, second inlet of oxygen carrier; 33, second cyclone separator; 41, fourth inlet; 42, third inlet of oxygen carrier; 43, third cyclone separator; 51, fifth inlet; 52, fourth inlet of oxygen carrier; 53, fourth cyclone separator; 71, water vapor inlet; 72, crude oil inlet. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. The described embodiments are part of the embodiments of the present invention, rather than all the embodiments.

[0033] A catalytic cracking oxygen-enriched regeneration method for co-producing synthesis gas specifically comprises the following steps:

[0034] (1) Air enters the oxygen absorption reactor and reacts with a micro-oxygen carrier at 550-700°C in the oxygen absorption reactor. After the reaction is completed, the generated gas-solid mixture is subjected to solid-gas separation to obtain high-temperature oxygen-depleted air at 650-800°C and an oxygen-rich oxygen carrier;

[0035] Preferably, air at normal temperature may first enter the third heat exchanger for heat exchange with oxygen-depleted air at 550-700°C, and then enter the oxygen absorption reactor after the temperature rises to 530-630°C; the high-temperature oxygen-depleted air enters the gas turbine to perform work, and the temperature drops to 550-700°C before entering the third heat exchanger for heat exchange to form low-temperature oxygen-depleted air below 50°C and then is directly discharged.

[0036] In some embodiments, the process of the oxygen absorption reactor is one of a low-pressure oxygen absorption process or a high-pressure oxygen absorption process; the reaction temperature of the low-pressure oxygen absorption process is 530-800°C, which can be 530°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C; the reaction pressure is 0.1-0.5MPa, which can be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa; the reaction temperature of the high-pressure oxygen absorption process is 800-1000°C, which can be 800°C, 850°C, 900°C, 950°C, 1000°C; the reaction pressure is 0.5-5MPa, which can be 0.5MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa.

[0037] (2) The oxygen-rich oxygen carrier in step (1) enters an oxygen release reactor to perform an oxygen release reaction, releases oxygen under the fluidization of 600-750°C regeneration flue gas, and then performs solid-gas separation to obtain a high-temperature oxygen-depleted oxygen carrier and oxygen-rich flue gas at 550-700°C; the high-temperature oxygen-depleted oxygen carrier at 550-700°C enters a CO2 conversion reactor;

[0038] Preferably, the 550-700℃ high-temperature oxygen-depleted oxygen carrier can first enter the first heat exchanger to exchange heat with the low-temperature heat medium, and then enter the CO2 conversion reactor after the temperature of the low-temperature oxygen-depleted oxygen carrier drops to 150-230℃. The high-temperature heat medium obtained after the temperature of the low-temperature heat medium is increased enters the second heat exchanger.

[0039] In some embodiments, the reaction temperature of the oxygen release reactor is 600-750°C, which may be 600°C, 650°C, 700°C, or 750°C; the reaction pressure is 0.1-0.5MPa, which may be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, or 0.5MPa.

[0040] (3) The 550-700° C. oxygen-enriched flue gas in step (2) undergoes an oxygen-enriched regeneration reaction with the catalyst to be regenerated in the regenerator to generate a regenerated catalyst at 600-750° C. and a regenerated flue gas at 600-750° C., with one portion of the regenerated flue gas entering the oxygen release reactor and the other portion entering the CO2 conversion reactor;

[0041] In some embodiments, the reaction temperature of the regenerator is 600-750°C, which may be 600°C, 650°C, 700°C, or 750°C; the reaction pressure is 0.1-0.5MPa, which may be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, or 0.5MPa.

[0042] (4) The 600-750° C. regenerated catalyst in step (3) enters the catalytic reactor and reacts with the feedstock oil in the catalytic reactor. After the reaction is completed, solid-gas separation is performed, and the obtained oil-gas mixture enters the next process. The obtained catalyst to be regenerated enters the regenerator for oxygen-enriched regeneration reaction, completing the catalyst cycle;

[0043] In some embodiments, the reaction temperature of the catalytic reactor is 500-650°C, which can be 500°C, 550°C, 600°C, or 650°C; the reaction pressure is 0.1-0.5MPa, which can be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, or 0.5MPa.

[0044] (5) The oxygen-poor oxygen carrier entering the CO2 conversion reactor reacts with the regenerated flue gas, followed by solid-gas separation to obtain a low-temperature slightly oxygen-poor oxygen carrier at 250-300°C and flue gas containing CO. The slightly oxygen-poor oxygen carrier enters the H2O conversion reactor, and the flue gas containing CO at 250-300°C enters the H2O conversion reactor;

[0045] Preferably, the low-temperature slightly oxygen-depleted oxygen carrier at 250-300°C can first enter the second heat exchanger for heat exchange with the high-temperature heat medium, and then enter the H2O conversion reactor after the high-temperature slightly oxygen-depleted oxygen carrier with a temperature increased to 550-650°C. The low-temperature heat medium obtained after the temperature of the high-temperature heat medium is reduced enters the first heat exchanger.

[0046] In some embodiments, the reaction temperature of the CO2 conversion reactor is 150-230°C, which can be 150°C, 170°C, 190°C, 210°C, or 230°C; the reaction pressure is 0.1-0.5MPa, which can be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, or 0.5MPa.

[0047] Specifically, the first heat exchanger and the second heat exchanger are connected to each other through a pipeline, and the heat medium circulates between the two to transfer heat.

[0048] (6) The slightly oxygen-poor oxygen carrier entering the H2O conversion reactor reacts with the flue gas containing CO at 250-300°C, and most of the H2O in the flue gas is converted into H2, followed by solid-gas separation to obtain a slightly oxygen-poor oxygen carrier at 550-700°C and a flue gas rich in synthesis gas; the slightly oxygen-poor oxygen carrier at 550-700°C enters the oxygen absorption reactor, and the flue gas rich in synthesis gas enters the synthesis gas separator. After the synthesis gas is separated, the waste gas is directly discharged after treatment.

[0049] In some embodiments, the reaction temperature of the H2O conversion reactor is 550-700°C, which can be 550°C, 600°C, 650°C, or 700°C; the reaction pressure is 0.1-0.5MPa, which can be 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, or 0.5MPa.

[0050] Preferably, a portion of the exhaust gas can be returned to the CO2 conversion reactor and the H2O conversion reactor to adjust the H / C ratio of the synthesis gas.

[0051] Specifically, the oxygen carrier circulates and reacts between reactors to provide oxygen-rich gas for catalyst regeneration, and the regenerated flue gas is used to produce synthesis gas. The additional energy consumption of the reaction is provided by the heat released by the oxygen-rich regeneration of the catalyst.

[0052] In some embodiments, the micro-oxygen oxygen carrier is one or more of an iron-indium-based oxygen carrier, a cobalt-indium-based oxygen carrier, and a perovskite oxygen carrier; and the heat medium is one of heat transfer oil, water vapor, and molten salt.

[0053] Preferably, the preparation method of the oxygen carrier can adopt mechanical synthesis, hydrothermal synthesis, combustion synthesis, etc., and iron-based, indium-based, and cobalt-based oxygen carriers can be synthesized separately and then blended to obtain iron-indium-based oxygen carriers and cobalt-indium-based oxygen carriers.

[0054] Preferably, the oxygen carrier is an iron-indium based oxygen carrier, wherein the molar ratio of iron to indium is 8:2-4:6; more preferably, the molar ratio of iron to indium is 1:1.

[0055] In some embodiments, the oxygen concentration of the oxygen-enriched flue gas is 22-70%, preferably 25-40%; and the H / C in the synthesis gas is 0.1-10.

[0056] like Figure 1 As shown, a catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas provided by the present invention comprises: an oxygen absorption reactor 5, wherein a fifth inlet 51 and a fourth inlet 52 for oxygen carrier are provided at the bottom of the oxygen absorption reactor 5, wherein the fifth inlet 51 is connected to a third heat exchanger E3 through a pipeline, and the oxygen absorption reactor 5 is connected to a fourth cyclone separator 53; an upper outlet of the fourth cyclone separator 53 is connected to a gas turbine T, and a lower outlet of the fourth cyclone separator 53 is connected to a first inlet 22 for oxygen carrier below the oxygen release reactor 2;

[0057] The bottom of the oxygen release reactor 2 is provided with a second inlet 21, and the oxygen release reactor 2 is connected to a first cyclone separator 23; the upper outlet of the first cyclone separator 23 is connected to the first inlet 11 at the bottom of the regenerator 1, and the lower outlet of the first cyclone separator 23 is connected to the upper inlet of the first heat exchanger E1;

[0058] The bottom outlet of the first heat exchanger E1 is connected to the second inlet 32 ​​of the oxygen carrier below the CO2 conversion reactor 3. The bottom of the CO2 conversion reactor 3 is provided with a third inlet 31. The CO2 conversion reactor 3 is connected to a second cyclone separator 33. The upper outlet of the second cyclone separator 33 is connected to the fourth inlet 41 at the bottom of the H2O conversion reactor 4. The lower outlet of the second cyclone separator 33 is connected to the upper inlet of the second heat exchanger E2.

[0059] The regenerator 1 is provided with a regeneration flue gas outlet at the top, and a return inclined pipe 12 and a regeneration inclined pipe 13 connected to the catalytic reactor 7 are provided on the side, and the regeneration flue gas outlet is connected to the second inlet 21 and the third inlet 31;

[0060] The bottom outlet of the second heat exchanger E2 is connected to the third inlet 42 of the oxygen carrier below the H2O conversion reactor 4, the H2O conversion reactor 4 is connected to the third cyclone separator 43, the upper outlet of the third cyclone separator 43 is connected to the synthesis gas separator 6, and the lower outlet of the third cyclone separator 43 is connected to the fourth inlet 52 of the oxygen carrier of the oxygen absorption reactor 5.

[0061] Preferably, the first heat exchanger E1 and the second heat exchanger E2 are both provided with a heat medium inlet and a heat medium outlet, the heat medium inlet of the first heat exchanger E1 and the heat medium outlet of the second heat exchanger E2 are connected to each other through a pipeline, the heat medium outlet of the first heat exchanger E1 and the heat medium inlet of the second heat exchanger E2 are connected to each other through a pipeline, and the heat medium circulates between the first heat exchanger E1 and the second heat exchanger E2.

[0062] Preferably, the synthesis gas separator 6 is provided with a waste gas outlet and a synthesis gas outlet; the synthesis gas separator 6 is also provided with a waste gas reflux port (not shown in the figure), which can return the first-step waste gas to the CO2 conversion reactor 3 and the H2O conversion reactor 4 to adjust the H / C ratio of the synthesis gas; the separation method in the synthesis gas separator 6 is one or more of membrane separation, pressure swing adsorption, solvent absorption, low-temperature separation, and distillation tower separation.

[0063] Preferably, a gas-solid separator is provided at the top of the regenerator 1; a water vapor inlet 71 and a crude oil inlet 72 are provided at the bottom of the catalytic reactor 7, and an oil-gas mixture outlet is provided at the top; a gas-solid separator is provided at the top of the catalytic reactor 7.

[0064] Example 1

[0065] A catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas, comprising: an oxygen absorption reactor 5, wherein a fifth inlet 51 and a fourth inlet 52 for oxygen carrier are provided at the bottom of the oxygen absorption reactor 5, wherein the fifth inlet 51 is connected to a third heat exchanger E3 through a pipeline, and the oxygen absorption reactor 5 is connected to a fourth cyclone separator 53; an upper outlet of the fourth cyclone separator 53 is connected to a gas turbine T, and a lower outlet of the fourth cyclone separator 53 is connected to a first inlet 22 for oxygen carrier below the oxygen release reactor 2;

[0066] The bottom of the oxygen release reactor 2 is provided with a second inlet 21, and the oxygen release reactor 2 is connected to a first cyclone separator 23; the upper outlet of the first cyclone separator 23 is connected to the first inlet 11 at the bottom of the regenerator 1, and the lower outlet of the first cyclone separator 23 is connected to the upper inlet of the first heat exchanger E1;

[0067] The bottom outlet of the first heat exchanger E1 is connected to the second inlet 32 ​​of the oxygen carrier below the CO2 conversion reactor 3. The bottom of the CO2 conversion reactor 3 is provided with a third inlet 31. The CO2 conversion reactor 3 is connected to a second cyclone separator 33. The upper outlet of the second cyclone separator 33 is connected to the fourth inlet 41 at the bottom of the H2O conversion reactor 4. The lower outlet of the second cyclone separator 33 is connected to the upper inlet of the second heat exchanger E2.

[0068] The regenerator 1 is provided with a regeneration flue gas outlet at the top, and a return inclined pipe 12 and a regeneration inclined pipe 13 connected to the catalytic reactor 7 are provided on the side, and the regeneration flue gas outlet is connected to the second inlet 21 and the third inlet 31;

[0069] The bottom outlet of the second heat exchanger E2 is connected to the third inlet 42 of the oxygen carrier below the H2O conversion reactor 4, the H2O conversion reactor 4 is connected to the third cyclone separator 43, the upper outlet of the third cyclone separator 43 is connected to the synthesis gas separator 6, and the lower outlet of the third cyclone separator 43 is connected to the fourth inlet 52 of the oxygen carrier of the oxygen absorption reactor 5.

[0070] In this embodiment, the first heat exchanger E1 and the second heat exchanger E2 are both provided with a heat medium inlet and a heat medium outlet. The heat medium inlet of the first heat exchanger E1 and the heat medium outlet of the second heat exchanger E2 are connected to each other through a pipeline, and the heat medium outlet of the first heat exchanger E1 and the heat medium inlet of the second heat exchanger E2 are connected to each other through a pipeline, and the heat medium circulates between the first heat exchanger E1 and the second heat exchanger E2.

[0071] In this embodiment, the synthesis gas separator 6 is provided with a waste gas outlet and a synthesis gas outlet; the synthesis gas separator 6 is also provided with a waste gas reflux port (not shown in the figure), which can return the first-step waste gas to the CO2 conversion reactor 3 and the H2O conversion reactor 4 to adjust the H / C ratio of the synthesis gas; the separation method in the synthesis gas separator 6 is distillation tower separation.

[0072] In this embodiment, a gas-solid separator is provided at the top of the regenerator 1; a water vapor inlet 71 and a crude oil inlet 72 are provided at the bottom of the catalytic reactor 7, and an oil-gas mixture outlet is provided at the top; a gas-solid separator is provided at the top of the catalytic reactor 7.

[0073] Example 2

[0074] A method for catalytic cracking oxygen-enriched regeneration for co-producing synthesis gas using the system described in Example 1, the specific steps are as follows:

[0075] (1) Normal temperature air enters the third heat exchanger E3 and exchanges heat with oxygen-depleted air at 600-650°C. After the temperature rises to 550-600°C, the air enters the oxygen absorption reactor 5 from the fifth inlet 51. In the oxygen absorption reactor 5, the air reacts with the micro-oxygen carrier (Fe3O4 / lnO) at 550-600°C to generate a gas-solid mixture of high-temperature oxygen-depleted air and oxygen-rich oxygen carrier (Fe2O3 / ln2O3) at 700-750°C. The gas-solid mixture enters the fourth cyclone separator 53 for solid-gas separation. The high-temperature oxygen-depleted air at 700-750°C enters the gas turbine T to perform work. The temperature drops to 600-650°C and the air enters the third heat exchanger E3 for heat exchange to form low-temperature oxygen-depleted air below 50°C, which is then directly discharged.

[0076] (2) The oxygen-rich oxygen carrier (Fe2O3 / ln2O3) generated in step (1) enters the oxygen release reactor 2 from the first oxygen carrier inlet 22 through the lower outlet of the fourth cyclone separator 53, releases oxygen under the fluidization of the regenerated flue gas at 650-700°C, generates a high-temperature oxygen-depleted oxygen carrier (FeO / ln2O) at 600-650°C and the oxygen-rich flue gas enters the first cyclone separator 23 for solid-gas separation, and the oxygen-rich flue gas enters the regenerator 1 from the first inlet 11, and the high-temperature oxygen-depleted oxygen carrier (FeO / ln2O) enters the first heat exchanger E1 through the first cyclone separator 23;

[0077] (3) The 600-650°C oxygen-enriched flue gas in step (2) participates in the oxygen-enriched regeneration reaction of the catalyst in the regenerator 1 to generate a regenerated catalyst at 650-700°C and a regenerated flue gas at 650-700°C. The regenerated flue gas is drawn out from the top of the regenerator 1, a portion of which enters the oxygen release reactor 2 through the second inlet 21, and the other portion enters the CO2 conversion reactor 3 through the third inlet 31; the 600-650°C high-temperature oxygen-poor oxygen carrier (FeO / ln2O) in step (2) exchanges heat with the low-temperature heat medium in the first heat exchanger E1 to obtain a low-temperature oxygen-poor oxygen carrier (FeO / ln2O) with a temperature reduced to 170-210°C, which enters the CO2 conversion reactor 3 from the second inlet 32 ​​of the oxygen carrier, and the obtained high-temperature heat medium enters the second heat exchanger E2;

[0078] (4) The 650-700° C. regenerated catalyst in step (3) enters the catalytic reactor 7 through the return inclined pipe 12, reacts with the crude oil entering from the crude oil inlet 72, and reacts while rising under the fluidization of the water vapor entering from the water vapor inlet 71. After the reaction is completed, the oil-gas mixture and the catalyst to be regenerated enter the cyclone separator at the top of the catalytic reactor 7 for solid-gas separation. The oil-gas mixture is discharged from the outlet at the top of the reactor and enters the next process. The catalyst to be regenerated returns to the regenerator 1 from the regeneration inclined pipe 13 for oxygen-enriched regeneration reaction, completing the catalyst cycle;

[0079] (5) The 170-210°C low-temperature oxygen-poor oxygen carrier (FeO / ln2O) entering the CO2 conversion reactor 3 reacts with the regenerated flue gas to generate a 260-290°C low-temperature slightly oxygen-poor oxygen carrier (Fe3O4 / ln2O) and CO-containing flue gas, which are separated into solid and gas by the second cyclone separator 33. The 260-290°C low-temperature slightly oxygen-poor oxygen carrier enters the second heat exchanger E2 for heat exchange with the high-temperature heat medium to obtain a high-temperature slightly oxygen-poor oxygen carrier (Fe3O4 / ln2O) with a temperature increased to 580-620°C. The oxygen carrier enters the H2O conversion reactor 4 from the third oxygen carrier inlet 42, and the obtained low-temperature heat medium enters the first heat exchanger E1; the 260-290°C CO-containing flue gas enters the H2O conversion reactor 4 through the fourth inlet 41;

[0080] (6) The 580-620°C high-temperature slightly oxygen-poor oxygen carrier (Fe3O4 / ln2O) entering the H2O conversion reactor 4 reacts with the 260-290°C flue gas containing CO, and most of the H2O in the flue gas is converted into H2, generating 550-600°C slightly oxygen carrier (Fe3O4 / lnO) and flue gas rich in synthesis gas, which are separated into solid and gas through the third cyclone separator 43. The 550-600°C slightly oxygen carrier (Fe3O4 / lnO) enters the oxygen absorption reactor 5 through the fourth oxygen carrier inlet 52, and the flue gas rich in synthesis gas enters the synthesis gas separator 6. After the synthesis gas is separated, part of the exhaust gas is discharged after treatment, and part of it is returned to the CO2 conversion reactor 3 and the H2O conversion reactor 4.

[0081] Wherein, the process of the oxygen absorption reactor is a low-pressure oxygen absorption process; the reaction temperature of the low-pressure oxygen absorption process is 600-800°C; and the reaction pressure is 0.2-0.4MPa.

[0082] The reaction temperature of the oxygen release reactor is 650-700° C.; the reaction pressure is 0.2-0.4 MPa.

[0083] The reaction temperature of the regenerator is 650-700°C; the reaction pressure is 0.2-0.4MPa.

[0084] The reaction temperature of the catalytic reactor is 550-600° C.; the reaction pressure is 0.2-0.4 MPa.

[0085] The reaction temperature of the CO2 conversion reactor is 170-210°C; the reaction pressure is 0.2-0.4MPa.

[0086] The reaction temperature of the H2O conversion reactor is 580-620°C; the reaction pressure is 0.2-0.4MPa.

[0087] The oxygen concentration in the oxygen-enriched flue gas is 25%-40%, the heat medium is water vapor; the oxygen carrier is Fe3O4 / lnO oxygen carrier, and the molar ratio of iron to indium is 1:1.

[0088] In this embodiment, the CO2 conversion rate is 25%-35%, the H2O conversion rate is higher than 75%, the H / C ratio in the synthesis gas is 2-8, and the carbon content in the regenerated catalyst is 0.02-0.04%.

[0089] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A catalytic cracking oxygen-enriched regeneration method for co-producing synthesis gas, characterized in that: The following steps are involved: (1) In an oxygen absorption reactor, a micro-oxygen oxygen carrier is reacted with air to obtain an oxygen-rich oxygen carrier and high-temperature oxygen-depleted air. The oxygen-rich oxygen carrier enters an oxygen release reactor and releases oxygen under the action of high-temperature flue gas to obtain oxygen-rich flue gas and oxygen-depleted oxygen carrier. The oxygen-rich flue gas enters a regenerator to participate in the regeneration of the catalyst, thereby generating regenerated flue gas and a regenerated catalyst. (2) the regenerated catalyst obtained in step (1) enters a catalytic reactor to react with crude oil; a portion of the regenerated flue gas obtained in step (1) enters an oxygen release reactor to participate in an oxygen release reaction, and another portion enters a CO2 conversion reactor to react with the oxygen-depleted oxygen carrier to obtain a slightly oxygen-depleted oxygen carrier and flue gas containing CO; the slightly oxygen-depleted oxygen carrier and the flue gas containing CO enter an H2O conversion reactor to react to obtain a slightly oxygen-depleted oxygen carrier and a flue gas rich in synthesis gas, the slightly oxygen-depleted oxygen carrier enters an oxygen absorption reactor, and the flue gas containing synthesis gas enters a synthesis gas separator to separate and obtain synthesis gas; The high-temperature oxygen-depleted air in step (1) enters the gas turbine to perform work, and then exchanges heat with the air in the third heat exchanger to obtain high-temperature air and low-temperature oxygen-depleted air; the oxygen-depleted oxygen carrier in step (2) exchanges heat with the low-temperature heat medium through the first heat exchanger before entering the CO2 conversion reactor to obtain a low-temperature oxygen-depleted oxygen carrier; the slightly oxygen-depleted oxygen carrier exchanges heat with the high-temperature heat medium through the second heat exchanger before entering the H2O conversion reactor to obtain a high-temperature slightly oxygen-depleted oxygen carrier; The reaction temperature of the CO2 conversion reactor is 150-230°C, and the reaction pressure is 0.1-0.5MPa; the reaction temperature of the H2O conversion reactor is 550-700°C, and the reaction pressure is 0.1-0.5MPa; The micro-oxygen oxygen carrier is one or more of an iron-indium-based oxygen carrier, a cobalt-indium-based oxygen carrier, and a perovskite oxygen carrier; the heat medium is one of heat transfer oil, water vapor, and molten salt.

2. The catalytic cracking oxygen-enriched regeneration method for co-producing synthesis gas according to claim 1, characterized in that: The process of the oxygen absorption reactor in step (1) is a low-pressure oxygen absorption process or a high-pressure oxygen absorption process; the reaction temperature of the low-pressure oxygen absorption process is 530-800°C, and the reaction pressure is 0.1-0.5MPa; the reaction temperature of the high-pressure oxygen absorption process is 800-1000°C, and the reaction pressure is 0.5-5MPa; the reaction temperature of the oxygen release reactor is 600-750°C, and the reaction pressure is 0.1-0.5MPa; the reaction temperature of the regenerator is 600-750°C, and the reaction pressure is 0.1-0.5MPa.

3. The catalytic cracking oxygen-enriched regeneration method for co-producing synthesis gas according to claim 1, characterized in that: The reaction temperature of the catalytic reactor in step (2) is 500-650° C., and the reaction pressure is 0.1-0.5 MPa.

4. The catalytic cracking oxygen-enriched regeneration method for co-producing synthesis gas according to claim 1, characterized in that: The oxygen concentration of the oxygen-enriched flue gas in step (1) is 22-70%; the H / C in the synthesis gas in step (2) is 0.1-10.

5. A catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas for implementing the method according to any one of claims 1 to 4, characterized in that: include: An oxygen absorption reactor (5), wherein a fifth inlet (51) and a fourth inlet (52) for an oxygen carrier are provided at the bottom of the oxygen absorption reactor (5); the fifth inlet (51) is connected to the third heat exchanger (E3) through a pipeline; the oxygen absorption reactor (5) is connected to a fourth cyclone separator (53); the upper outlet of the fourth cyclone separator (53) is connected to the gas turbine (T); the lower outlet of the fourth cyclone separator (53) is connected to the first inlet (22) for the oxygen carrier below the oxygen release reactor (2); A second inlet (21) is provided at the bottom of the oxygen release reactor (2), and the oxygen release reactor (2) is connected to a first cyclone separator (23); an upper outlet of the first cyclone separator (23) is connected to a first inlet (11) at the bottom of the regenerator (1), and a lower outlet of the first cyclone separator (23) is connected to an upper inlet of the first heat exchanger (E1); The bottom outlet of the first heat exchanger (E1) is connected to the second inlet (32) of the oxygen carrier below the CO2 conversion reactor (3), the bottom of the CO2 conversion reactor (3) is provided with a third inlet (31), the CO2 conversion reactor (3) is connected to a second cyclone separator (33), the upper outlet of the second cyclone separator (33) is connected to the fourth inlet (41) at the bottom of the H2O conversion reactor (4), and the lower outlet of the second cyclone separator (33) is connected to the upper inlet of the second heat exchanger (E2); The regenerator (1) is provided with a regeneration flue gas outlet at the top, and a return inclined pipe (12) and a regeneration inclined pipe (13) connected to the catalytic reactor (7) are provided on the side, and the regeneration flue gas outlet is connected to the second inlet (21) and the third inlet (31); The bottom outlet of the second heat exchanger (E2) is connected to the third inlet (42) of the oxygen carrier below the H2O conversion reactor (4), the H2O conversion reactor (4) is connected to the third cyclone separator (43), the upper outlet of the third cyclone separator (43) is connected to the synthesis gas separator (6), and the lower outlet of the third cyclone separator (43) is connected to the fourth inlet (52) of the oxygen carrier of the oxygen absorption reactor (5).

6. A catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas according to claim 5, characterized in that: The first heat exchanger (E1) and the second heat exchanger (E2) are both provided with a heat medium inlet and a heat medium outlet. The heat medium inlet of the first heat exchanger (E1) and the heat medium outlet of the second heat exchanger (E2) are connected to each other through a pipeline, and the heat medium outlet of the first heat exchanger (E1) and the heat medium inlet of the second heat exchanger (E2) are connected to each other through a pipeline, and the heat medium circulates between the first heat exchanger (E1) and the second heat exchanger (E2).

7. A catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas according to claim 5, characterized in that: The synthesis gas separator (6) is provided with a waste gas outlet and a synthesis gas outlet; the separation method in the synthesis gas separator (6) is one or more of membrane separation, pressure swing adsorption, solvent absorption, low temperature separation, and fractionation tower separation.

8. The catalytic cracking oxygen-enriched regeneration system for co-producing synthesis gas according to claim 5, characterized in that: A gas-solid separator is provided at the top of the regenerator (1); a water vapor inlet (71) and a crude oil inlet (72) are provided at the bottom of the catalytic reactor (7), and an oil-gas mixture outlet is provided at the top; a gas-solid separator is provided at the top of the catalytic reactor (7).

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