A hydrocarbon catalytic cracking process method with balanced agent activity promotion function
By combining gas-phase aluminum replenishment and carbon burning regeneration in the catalytic cracking process, the problem of catalyst deactivation due to hydrothermal reaction was solved, thereby improving catalyst activity and recycling, and enhancing the conversion rate and economy of the unit.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- THE NORTHWEST RES INST OF CHEM IND
- Filing Date
- 2023-12-13
- Publication Date
- 2026-06-30
AI Technical Summary
In existing hydrocarbon catalytic cracking processes, catalyst deactivation due to hydrothermal reactions leads to reduced catalyst activity, making it impossible to effectively utilize the balance agent, resulting in resource waste and environmental pollution.
By performing gas-phase aluminum replenishment in the regenerator, combined with carbon burning regeneration, the activity of the balancing agent is enhanced. Furthermore, by performing fluidized or boiling fluidized aluminum replenishment in the activity enhancement reactor, the recycling and activity enhancement of the catalyst are achieved.
It improves the conversion rate and diolefin yield of the catalytic cracking unit, reduces the consumption of fresh catalyst, reduces energy consumption, improves the economic efficiency of the unit, and reduces environmental pollution.
Smart Images
Figure CN117720945B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of hydrocarbon catalytic cracking technology, specifically relating to a hydrocarbon catalytic cracking process method with a balancer activity enhancement function. Background Technology
[0002] Hydrocarbon catalytic cracking catalysts are molecular sieve-type catalytic materials, whose main component is a molecular sieve with a unique pore structure, strong acidity, and good shape selectivity. These molecular sieves are widely used in petrochemical fields such as catalytic cracking and catalytic pyrolysis. Under high-temperature hydrothermal reaction conditions, SiO2 in the molecular sieve is easily oxidized. OH Al-bridged hydroxyl groups undergo dehydration, and skeletal aluminum detaches, clogging micropores. This leads to a significant loss of active sites and a reduction in pore properties, resulting in decreased catalyst activity. Some of this deactivated catalyst is collected in the downstream cyclone separator after being discharged with the oil and gas due to particle breakage. The remaining intact particles (i.e., the balancer) are replaced by fresh catalyst and discharged outside the separator, treated as waste catalyst and disposed of in landfills, causing a certain degree of resource waste. At the same time, improper disposal of spent hydrocarbon catalytic cracking catalysts will also cause serious environmental pollution.
[0003] CN116731742A provides an oxygen-enriched regeneration device for light hydrocarbon cracking catalysts. The regeneration device includes a premixing zone, a combustion regeneration zone, and a catalyst storage section. One end of the premixing zone is equipped with an atomizing steam nozzle, a fuel oil nozzle, and a fuel gas nozzle, and a gas distributor communicating with the atomizing steam nozzle is installed inside. The other end communicates with the combustion regeneration zone. One end of the catalyst storage section extends to the center of the premixing zone and is equipped with a plunger valve. The catalyst storage section located above the premixing zone is fitted with a deflector plate or a distributor. One end of the combustion regeneration zone is equipped with an oxygen-enriched gas inlet, a fuel oil nozzle, a fuel gas nozzle, and a gas distributor, and the other end is equipped with a cyclone separator. The side of the regeneration device is equipped with a catalyst sampling port, a temperature sampling point, a catalyst outlet, and a steam inlet.
[0004] CN1626623A provides a multi-effect coupled fluidized catalytic reaction process method for a dual-reaction regeneration system. A secondary regenerator for regenerating a dedicated catalyst for a novel fluidized catalytic reaction process is established next to the main regenerator of the original catalytic cracking unit. High-temperature flue gas from the main regenerator is introduced into the bottom of the regenerator via a flue gas duct to supplement heat to the novel fluidized catalytic reaction regeneration system. Simultaneously, air is introduced into the bottom of the regenerator to fluidize the dedicated catalyst and regenerate it under specific reaction conditions. The regenerated dedicated catalyst then enters the reactor of the novel fluidized catalytic reaction process and contacts, vaporizes, mixes, and reacts with catalytic cracked gasoline, liquefied petroleum gas, or C4 hydrocarbons under specific reaction conditions.
[0005] The drawback of both existing technologies is that they are traditional reaction-regeneration systems. Prolonged hydrothermal reactions lead to a decrease in the activity of the equilibrium agent due to dealuminization, resulting in a decline in the reactivity of the catalytic cracking system. The only way to maintain the reaction system's activity is by adding fresh equilibrium agent after removing it from the reactor; the device cannot regenerate the equilibrium agent by replenishing it with aluminum. (That is, traditional devices can only solve the problem of carbon buildup deactivation, not dealuminization deactivation. This patent solves the problem of dealuminization deactivation by using a gas-phase aluminum replenishment method after the reaction-regeneration system.)
[0006] In summary, most current catalytic cracking / cracking processes are reaction-regeneration systems. Since the regeneration systems are all high-temperature carbonization devices, they cannot improve the activity of the balance agent. Therefore, the optimization of existing technologies mainly focuses on how to optimize and improve the carbonization effect of the existing balance agent. It is necessary to discharge the balance agent outside the device and then regenerate it through external regeneration to achieve the regeneration and utilization of the balance agent. Summary of the Invention
[0007] To overcome the shortcomings of the existing technology, the present invention aims to provide a hydrocarbon catalytic cracking process with a function of enhancing the activity of the balancer. By supplementing the balancer with aluminum in the regenerator in the gas phase, the activity of the balancer is enhanced and it is recycled, reducing the unit's reagent consumption. Simultaneously, the yield of diolefins is increased and product distribution is controlled, thereby improving the economic efficiency of the unit. This process has the advantages of flexible unit operation, low reagent consumption, high system catalytic activity, mild conditions, and high diolefin yield.
[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0009] A hydrocarbon catalytic cracking process with a balancer activity enhancement function includes the following steps;
[0010] Step 1: Preheated feedstock and steam enter from the bottom of the riser reactor and react with high-temperature carbonization regeneration balance agent from the regenerator, active boosting balance agent from the active boosting balance agent storage tank, and fresh catalyst in the riser reactor to form an oil-gas and balance agent mixture;
[0011] Step 2: The oil and gas mixture and the balance agent pass through the riser reactor together. The oil and gas are rapidly separated from the balance agent by gravity and the reactor settling tank located above the riser reactor and the top cyclone separator set at the top of the reactor settling tank. The oil and gas enter the oil and gas fractionation system from the top of the reactor settling tank. The balance agent enters the stripping section and is stripped. After being stripped, it enters the bottom of the reactor settling tank through the bottom of the reactor settling tank and the bottom of the coking tank through the inclined pipe at the bottom of the coking tank and into the bottom of the coking tank of the regenerator.
[0012] After charring in the coke oven, the flue gas and the char regeneration balance agent mixture are separated by the top cyclone separator of the regenerator. The flue gas enters the flue gas system, and part of the char regeneration balance agent returns to the bottom of the riser reactor to participate in the catalytic cracking reaction. The other part passes through the bottom of the regenerator and enters the active booster reactor through the inlet inclined tube of the active booster reactor.
[0013] Step 3: The charcoal regeneration balancing agent and aluminum supplement agent mixture enter the activated booster reactor through the inclined tube at the bottom of the regenerator and come into contact with each other to fluidize and supplement aluminum, forming a mixture of aluminum supplement agent mixture and aluminum balancing agent (the mixture generated after the charcoal regeneration balancing agent and aluminum supplement agent mixture gaseous reaction). This mixture is separated by a multi-stage cyclone separator at the top of the activated booster reactor. The aluminum supplement agent mixture (the gas phase separated by the cyclone separator from the mixture of aluminum supplement agent mixture and aluminum balancing agent mixture) is then fed with aluminum supplement agent and reintroduced into the bottom of the activated booster reactor. The aluminum balancing agent then enters the activated booster balancing agent stripping tower through the inclined tube at the bottom of the activated booster reactor and the inlet of the stripping tower.
[0014] Step 4: Nitrogen stripping gas is introduced into the bottom of the activity-enhancing balance agent stripping tower to strip the aluminum supplementation balance agent. After stripping, the activity-enhancing balance agent enters the bottom of the riser reactor through the activity-enhancing balance agent storage tank to participate in the catalytic cracking reaction. The stripping gas containing the aluminum supplementation agent is cooled and recycled back to the bottom of the activity-enhancing balance agent stripping tower after recovering the aluminum supplementation agent. After recovery, the aluminum supplementation agent is condensed and added to the aluminum supplementation agent mixture, realizing the recycling of the aluminum supplementation agent, improving the utilization rate of the aluminum supplementation agent, and realizing efficient gas-phase aluminum supplementation of the carbon regeneration balance agent.
[0015] In step 1, the reaction is carried out in the riser reactor at a reaction temperature of 550~700℃, with the total amount of fresh catalyst, char regeneration balancing agent and activity enhancement balancing agent being 10~30 times the mass ratio of the preheated raw material (raw material oil), and the residence time being 1.0~7.0s.
[0016] The ratio of the total amount of fresh catalyst, char regeneration balancing agent, and activity enhancement balancing agent to the mass of feedstock oil is 10-30, which refers to the commonly used catalyst-to-oil ratio in petrochemicals, i.e., the ratio of the total amount of catalyst used to the feedstock oil. The amount of fresh catalyst used is the catalyst consumption, and the current addition amount is 1-3 kg / ton of oil. This value is a reduction indicator. By using the activity enhancement balancing agent to replace part of the fresh catalyst, the amount of fresh catalyst used is reduced, thus reducing catalyst consumption. The specific doping ratio will be shown later.
[0017] In step 2, air is introduced into the bottom of the coking tank to fluidize the char under the conditions of a reaction temperature of 650~850℃ and a gas flow rate of 0.1~5m / s.
[0018] The bottom of the activity-enhancing reactor introduces an aluminum-supplementing mixture to fluidize the charcoal regeneration balancing agent under reaction temperatures of 150-300℃ and contact times of 30-240 minutes. (The contact time is limited because it is a key factor affecting the activity enhancement effect of the balancing agent. 30-240 minutes is a relatively long contact time within the fluidization range, ensuring that the aluminum-supplementing agent can fully contact the charcoal regeneration balancing agent to achieve a better regeneration effect; at the same time, the contact time is also one of the main means of control and a key parameter for controlling the activity of the balancing agent.)
[0019] Nitrogen gas is introduced into the bottom of the stripping tower to strip the aluminum supplementation agent. After stripping, the active enhancement agent enters the bottom of the riser reactor through the active enhancement agent storage tank to participate in the catalytic cracking reaction. The stripping gas containing the aluminum supplementation agent is cooled and recovered, and then circulated back to the bottom of the active enhancement agent stripping tower through the stripping gas circulation path.
[0020] The regenerator bottom is connected to the activation enhancement reactor via an inclined tube leading to the inlet of the activation enhancement reactor. Heat exchange occurs between the bottom of the stripping tower (connected to the riser reactor) and the bottom of the activation enhancement balance agent storage tank (connected to the riser reactor). The temperature of the balance agent at the inlet of the activation enhancement reactor is 100~300℃. (The balance agent exiting the regenerator is at a higher temperature and needs to be cooled to the suitable temperature for the activation enhancement reaction (i.e., 100~300℃). The activation enhancement balance agent entering the riser reactor requires a higher temperature, necessitating insulation or heating of its inclined tubes and storage tank. Therefore, heat exchange through these two pipelines achieves efficient heat utilization.)
[0021] The activity enhancement reactor is a fluidized bed reactor with a multi-stage gas distribution plate at the bottom, and the charcoal regeneration balancing agent is kept in a stable fluidized state inside the reactor.
[0022] The activity enhancement reactor is introduced with a mixture of gaseous aluminum supplement and nitrogen, wherein the volume percentage of the gaseous aluminum supplement in the mixture is 20% to 100%, and the inlet temperature of the mixture is 150 to 300°C. The ratio of aluminum supplement to nitrogen in the mixture is a key factor affecting the activity enhancement balancing agent; the activity of the balancing agent is adjusted by regulating the proportion of aluminum supplement in the mixture.
[0023] The inlet and outlet gas circulation pipelines of the activation enhancement reactor (both the inlet gas pipeline connected to the bottom of the reactor and the outlet gas pipeline connected to the bottom are insulated to maintain a certain temperature) are maintained at a constant temperature of 150℃~300℃. Recovered aluminum supplementer and fresh aluminum supplementer are added to the inlet pipeline of the activation enhancement reactor at a certain dosage. The proportion of aluminum supplementer in the aluminum supplementer mixture is maintained (i.e., a fixed value within the range of 20%~100% mentioned above).
[0024] The stripping medium in the stripping tower for the activity-enhancing balancing agent is hot nitrogen. After stripping, the mixed gas undergoes aluminum replenishment agent condensation and recovery in a condensation recovery tank. After recovery, the aluminum replenishment agent enters the gas in the activity-enhancing reactor to participate in the aluminum replenishment reaction.
[0025] The mass ratio of the activity-enhancing balancing agent to the fresh catalyst at the inlet below the riser reactor (this is the feed at the riser, the mass ratio of the activity-enhancing balancing agent to the fresh catalyst, that is, how much activity-enhancing balancing agent is used to replace the fresh catalyst to achieve the recycling of the balancing agent) is (0.5~4):1. The ratio is adjusted according to the system activity and product distribution requirements.
[0026] The feed method of the activity enhancement reactor is intermittent feeding. The feed rate is adjusted according to the material height of the activity enhancement balancer tank to keep the material level of the activity enhancement balancer tank between 30% and 70%. The activity enhancement reactor bed can be switched between two modes: circulating fluidized aluminum supplementation and boiling fluidized aluminum supplementation. The sample is fed with aluminum gas.
[0027] A hydrocarbon catalytic cracking device with a balancer activity enhancement function includes a riser reactor. The top inlet of the riser reactor is connected to the bottom outlet of the regenerator settling tank and the bottom outlet of the activity enhancement balancer storage tank via a regenerator bottom-reactor inlet inclined pipe and an activity enhancement balancer storage tank bottom-to-riser reactor inclined pipe, respectively.
[0028] The bottom of the reactor settling tank above the riser reactor is connected to the coking tank of the regenerator via an inclined pipe from the bottom of the settling tank to the bottom of the coking tank. The other outlet of the bottom of the regenerator settling tank above the coking tank is connected to the inlet of the fluidized bed at the bottom of the active booster reactor via an inclined pipe from the bottom of the regenerator to the inlet of the active booster reactor.
[0029] A cyclone separator is installed at the top of the reactor settling tank, and the reaction products are discharged from the top; the lower part of the reactor settling tank is the reactor stripping section;
[0030] The top of the regenerator settling tank is the regenerator top vortex, and the flue gas is output from the top.
[0031] The bottom outlet of the settling tank at the top of the activity enhancement reactor is connected to the activity enhancement balance agent stripping tower via an inclined pipe from the bottom of the activity enhancement reactor to the stripping tower inlet.
[0032] The top of the settling tank of the activated booster reactor is a multi-stage cyclone separator. The output activated booster reaction gas enters the bottom of the activated booster fluidized bed through the aluminum supplement gas circulation path and the aluminum supplement gas mixture. The bottom of the activated booster fluidized bed is also equipped with gas distribution plate I and gas distribution plate II.
[0033] One outlet at the bottom of the stripping tower for the active boosting balancing agent is connected to the top inlet of the active boosting balancing agent storage tank via an inclined pipe from the bottom of the stripping tower to the bottom inlet of the boosting reactor. The other outlet is connected to the bottom inlet of the active boosting reactor via an inclined pipe from the bottom of the stripping tower to the active boosting circulation. The gas pipeline at the top of the settling tank of the active boosting reactor is circulated and then connected to the bottom gas inlet of the active boosting reactor. The stripping mixed gas output from the top of the stripping tower for the active boosting balancing agent is connected to the condensation recovery tank via a gas pipeline in the stripping gas circulation path. The gas phase outlet of the condensation recovery tank is connected to the gas inlet of the stripping section of the active boosting balancing agent stripping tower, and the solid phase outlet of the condensation recovery tank is connected to the aluminum supplement gas circulation pipeline.
[0034] The bottom of the stripping tower for the active boosting balancing agent is the stripping section, the area above the stripping section is the settling zone, and the top is the top vortex separator.
[0035] The beneficial effects of this invention are:
[0036] (1) This invention utilizes a combination of “carbon burning regeneration” and “gas phase aluminum replenishment regeneration” of the catalytic cracking balance agent to specifically address the problem of reduced catalyst activity caused by carbon deposition and hydrothermal dealuminization during the reaction process, thereby improving the catalyst activity of the reaction system, increasing the conversion rate and diolefin yield of the hydrocarbon catalytic cracking unit. At the same time, the activity-enhancing balance agent replaces part of the fresh catalyst, thereby reducing the consumption of fresh catalyst, thus reducing the procurement cost of fresh catalyst and improving the technical economy of the hydrocarbon catalytic cracking unit.
[0037] (2) The present invention includes a reaction-regeneration system, an activity enhancement reaction system and a post-treatment system. The activity enhancement reaction system can realize the gas phase aluminum replenishment process of the balance agent by means of circulating fluidization or boiling fluidization. The aluminum replenishment effect of the balance agent can be controlled by adjusting the amount of aluminum replenishing agent, fluidization time and other conditions of the device.
[0038] (3) The propylene yield of the activity-enhancing balancing agent is significantly higher than that of the carbon-burning regeneration balancing agent. The activity and product distribution of the catalytic cracking reaction system can be adjusted by regulating the ratio of the activity-enhancing balancing agent to the carbon-burning regeneration balancing agent.
[0039] (4) The present invention can comprehensively improve the overall activity of the catalyst in the reaction system, thereby reducing the reaction temperature of the process system, reducing the severity and energy consumption of the hydrocarbon catalytic cracking process, and further improving the technical economy of the device. Attached Figure Description
[0040] Figure 1 This is a schematic diagram of the overall structure of the present invention.
[0041] Figure labels: 1-Steam, 2-Preheated raw material, 3-Steam stripping gas, 4-Riser reactor, 5-Reactor stripping section, 6-Reactor settling tank, 7-Cyclone separator, 8-Reaction product, 9-Inclined tube from bottom of reactor settling tank to bottom of coke burner, 10-Control valve I, 11-Air, 12-Coke burner, 13-Regenerator settling tank, 14-Regenerator top cyclone, 15-Flue gas, 16-Regenerator bottom to reactor inlet inclined tube, 17-Control valve II, 18-Regenerator bottom to activated booster reactor inlet inclined tube, 19-Control valve III, 20-Gas distribution plate I, 21-Gas distribution plate II, 22-Activated booster fluidized bed, 23-Activated booster reactor settling tank, 24-Multi-stage cyclone separator, 25-Activated booster reaction gas, 26-Aluminum supplementation agent mixture, 27- 28-Control valve IV, 29-Control valve V, 30-Circulation inclined pipe from the bottom of the stripper to the active enhancement reactor, 31-Control valve VI, 32-Inlet inclined pipe from the bottom of the stripper to the bottom of the riser reactor, 33-Stripping section of the stripper, 34-Settling zone of the stripper, 35-Top vortex separator of the stripper, 36-Stripping mixed gas, 37-Condensation recovery tank, 38-Nitrogen stripping gas, 39-Recovered aluminum replenishing agent, 40-Stripping gas circulation path, 41-Aluminum replenishing agent gas circulation path, 42-Active enhancement balancing agent storage tank, 43-Control valve VII, 44-Regenerator, 45-Active enhancement reactor, 46-Active enhancement balancing agent stripper, 47-Inlet inclined pipe from the bottom of the active enhancement balancing agent storage tank to the bottom of the riser reactor, 48-Fresh catalyst. Detailed Implementation
[0042] The present invention will now be described in further detail with reference to the accompanying drawings.
[0043] like Figure 1 As shown, a hydrocarbon catalytic cracking device with a balancer activity enhancement function includes a riser reactor 4. The top inlet of the riser reactor 4 is connected to the bottom outlet of the regenerator settling tank 13 and the bottom outlet of the activity enhancement balancer storage tank 42 via a regenerator bottom-reactor inlet inclined pipe 16 and an activity enhancement balancer storage tank bottom-riser reactor bottom inclined pipe 47.
[0044] A control valve II 17 is installed on the inclined tube 16 at the bottom of the regenerator-reactor inlet;
[0045] A control valve VII43 is installed on the inclined pipe 47 from the bottom of the active enhancement balancing agent storage tank to the bottom of the riser reactor.
[0046] The bottom of the reactor settling tank 6 above the riser reactor 4 is connected to the regenerator coke burner 12 via an inclined pipe 9 from the bottom of the settling tank to the bottom of the coke burner. The other outlet of the bottom of the regenerator settling tank 13 above the regenerator coke burner 12 is connected to the bottom fluidized bed inlet of the active riser reactor 45 via an inclined pipe 18 from the bottom of the regenerator to the inlet of the active riser reactor.
[0047] A control valve Ⅲ19 is installed on the inclined tube 18 from the bottom of the regenerator to the inlet of the activity enhancement reactor;
[0048] A cyclone separator 7 is installed at the top of the settling tank 6 of the reactor, and the reaction products 8 are discharged from the top; the lower part of the settling tank 6 of the reactor is the stripping section 5 of the reactor;
[0049] The top of the regenerator settling tank 13 is the regenerator top vortex 14, and the top output flue gas 15;
[0050] The bottom outlet of the settling tank 23 of the active booster reactor at the top of the active booster reactor 45 is connected to the active booster balancing agent stripping tower 46 through the inclined pipe 27 from the bottom of the active booster reactor to the stripping tower inlet.
[0051] The top of the settling tank 23 of the activated booster reactor is a multi-stage cyclone separator 24. The output activated booster reaction gas 25 enters the bottom of the activated booster fluidized bed 22 through the aluminum supplement gas circulation path 41 and the aluminum supplement mixed gas 26. The bottom of the activated booster fluidized bed 22 is also equipped with gas distribution plate I 20 and gas distribution plate II 21.
[0052] The activity-enhancing fluidized bed 22, the gas distribution plate I 20 and the gas distribution plate II 21 are located in the activity-enhancing reactor 45;
[0053] A control valve Ⅳ28 is installed on the inclined pipe 27 from the bottom of the activity enhancement reactor to the inlet of the stripping tower.
[0054] One outlet at the bottom of the stripping tower 46 is connected to the top inlet of the stripping agent storage tank 42 via the inclined pipe 32 from the bottom of the stripping tower to the bottom inlet of the riser reactor. The other outlet is connected to the bottom inlet of the active boosting reactor 45 via the inclined pipe 30 from the bottom of the stripping tower to the active boosting circulation pipe. The gas pipeline at the top of the settling tank 23 of the active boosting reactor is connected to the bottom gas inlet of the active boosting reactor 45 after circulation. The stripping mixed gas 36 output from the top of the stripping tower 46 is connected to the condensation recovery tank 37 via the gas pipeline of the stripping gas circulation path 40. The gas phase outlet of the condensation recovery tank 37 is connected to the gas inlet of the stripping section of the stripping tower 46. The solid phase outlet of the condensation recovery tank 37 is connected to the aluminum supplement gas circulation path 41.
[0055] A control valve V29 is installed at the bottom of the stripping tower and on the active boosting circulation inclined tube 30.
[0056] A control valve VI31 is installed on the inclined pipe 32 at the bottom inlet of the riser reactor, which leads from the bottom of the stripping tower.
[0057] The bottom of the active balancing agent stripping tower 46 is the stripping section 33, the top of the stripping section 33 is the settling zone 34, and the top is the top swirl divider 35.
[0058] Example 1: Fluidized Bed Activation Enhancement Reactor (Stable Fluidized Bed State)
[0059] Preheated raw material 2 and steam 1 enter the bottom of riser reactor 4, where they react with high-temperature carbonization regeneration balancing agent from regenerator 44 and activity enhancing balancing agent from activity enhancing balancing agent storage tank 42 in riser reactor 4 at a reaction temperature of 650°C, a catalyst to raw material oil mass ratio of 26, a residence time of 7s, and an activity enhancing balancing agent and fresh catalyst added in a mass ratio of 1:1.
[0060] The oil and gas mixture and the balance agent are passed together through the riser reactor 4. The oil and gas are rapidly separated from the balance agent by gravity and the cyclone separator 7 at the top of the reactor settling tank 6. The oil and gas enter the oil and gas fractionation system from the top of the reactor settling tank 6. The balance agent enters the stripping section 5 for stripping and then enters the bottom of the coking tank 12 of the regenerator 44 through the inclined pipe 9 at the bottom of the reactor settling tank.
[0061] At the bottom of the coking tank 12, air 11 is introduced to fluidize the char-burning agent under the conditions of a reaction temperature of 720℃ and a gas flow rate of 0.5m / s. After char-burning, the flue gas and the mixture of char-burning regeneration char-burning ...
[0062] At the bottom of the activation enhancement reactor 45, an aluminum supplement mixture gas 25 containing 80% aluminum supplement agent is introduced to fluidize the charcoal regeneration balance agent under the conditions of reaction temperature 250℃ and fluidized aluminum supplementation for 180 min. The reactor bed is in a stable fluidized state. After fluidization, the gas velocity is increased to carry the aluminum supplement balance agent out of the bed. The mixture gas and the aluminum supplement balance agent are separated by the multi-stage cyclone separator 24 at the top of the activation enhancement reactor 45. The activation enhancement reaction gas 25 (aluminum supplement mixture gas) is reintroduced into the bottom of the activation enhancement reactor 45 after adding the recovered aluminum supplement agent 39. The aluminum supplement balance agent enters the activation enhancement balance agent stripping tower 46 through the inclined pipe 27 at the bottom of the activation enhancement reactor to the stripping tower.
[0063] Nitrogen stripping gas 38 is introduced into the bottom of the activity-enhancing balancing agent stripping tower 46 to strip the aluminum supplementing balancing agent. After stripping, the activity-enhancing balancing agent enters the bottom of the riser reactor 4 through the activity-enhancing balancing agent storage tank 42 to participate in the catalytic cracking reaction. The pipeline temperature is maintained at 250℃ throughout the process. The stripping mixture 36 containing the aluminum supplementing agent is cooled and recycled back to the bottom of the activity-enhancing balancing agent stripping tower 46 after recovering the aluminum supplementing agent. After recovery, the aluminum supplementing agent 39 is condensed and added to the aluminum supplementing agent mixture 26.
[0064] Example 2: Fluidized bed activity enhancement reactor (stable fluidized bed state)
[0065] Preheated raw material 2 and steam 1 enter the bottom of riser reactor 4, where they react with high-temperature carbonization regeneration balancing agent from regenerator 44 and active balancing agent from active balancing agent storage tank 42 in riser reactor 4 at a reaction temperature of 635°C, a balancing agent to raw material oil mass ratio of 2:4, a residence time of 7s, and an active balancing agent and fresh catalyst added at a mass ratio of 1:1.
[0066] The oil and gas mixture and the balance agent are passed together through the riser reactor 4. The oil and gas are rapidly separated from the balance agent by gravity and the cyclone separator 7 at the top of the reactor settling tank 6. The oil and gas enter the oil and gas fractionation system from the top of the reactor settling tank 6. The balance agent enters the reactor stripping section 5 for stripping and then enters the bottom of the coking tank 12 of the regenerator 44 through the inclined pipe 9 from the bottom of the reactor settling tank to the bottom of the coking tank.
[0067] At the bottom of the coking tank 12, air 11 is introduced to fluidize the char-burning agent under the conditions of a reaction temperature of 720℃ and a gas flow rate of 0.5m / s. After char-burning, the flue gas and the mixture of char-burning regeneration char-burning ...
[0068] At the bottom of the activation enhancement reactor 45, an activation enhancement reaction gas 25 containing 80% aluminum supplementation agent (aluminum supplementation agent mixed gas) is introduced to fluidize and supplement the charcoal regeneration balance agent under the conditions of reaction temperature 250℃ and fluidized aluminum supplementation for 240 min. The reactor bed is in a stable fluidized state. After fluidization, the gas velocity is increased to carry the aluminum supplementation balance agent out of the bed. The mixed gas and the aluminum supplementation balance agent are separated by the multi-stage cyclone separator 24 at the top of the activation enhancement reactor 45. The activation enhancement reaction gas 25 is then reintroduced into the bottom of the activation enhancement reactor 45 after adding the recovered aluminum supplementation agent 39. The aluminum supplementation balance agent enters the activation enhancement balance agent stripping tower 46 through the inclined pipe 27 at the bottom of the activation enhancement reactor.
[0069] Nitrogen stripping gas 38 is introduced into the bottom of the activity-enhancing balancer stripping tower 46 to strip the aluminum supplementation balancer. After stripping, the activity-enhancing balancer enters the bottom of the riser reactor 4 through the activity-enhancing balancer storage tank 42 to participate in the catalytic cracking reaction. The pipeline temperature is maintained at 250℃ throughout the process. The stripping mixed gas 36 (stripping gas containing aluminum supplementation agent) is cooled and the aluminum supplementation agent 39 is recovered and then circulated back to the bottom of the activity-enhancing balancer stripping tower 46. After recovery, the aluminum supplementation agent is condensed and added to the aluminum supplementation agent mixed gas 26.
[0070] Example 3: Fluidized bed activity enhancement reactor (stable fluidized bed state)
[0071] Preheated raw material 2 and steam 1 enter the bottom of riser reactor 4, where they react with high-temperature carbonization regeneration balancing agent from regenerator 44 and activity enhancement balancing agent from activity enhancement balancing agent storage tank 42 in riser reactor 4 at a reaction temperature of 640℃, a balancing agent to raw material oil mass ratio of 26, a residence time of 7s, and an activity enhancement balancing agent and fresh catalyst added at a mass ratio of 0.5:1.
[0072] The oil and gas mixture and the balance agent are passed together through the riser reactor 4. The oil and gas are rapidly separated from the balance agent by gravity and the cyclone separator 7 at the top of the reactor settling tank 6. The oil and gas enter the oil and gas fractionation system from the top of the reactor settling tank 6. The balance agent enters the stripping section 5 and is stripped. After being stripped, it enters the bottom of the coking tank 12 of the regenerator 44 through the inclined pipe 9 from the bottom of the reactor settling tank 6 to the bottom of the coking tank.
[0073] At the bottom of the coking tank 12, air 11 is introduced to fluidize the char-burning agent under the conditions of a reaction temperature of 720℃ and a gas flow rate of 0.5m / s. After char-burning, the flue gas and the mixture of char-burning regeneration char-burning ...
[0074] At the bottom of the activation enhancement reactor 45, an activation enhancement reaction gas 25 containing 80% aluminum supplement is introduced to fluidize and supplement the charcoal regeneration balance agent under the conditions of reaction temperature 250℃ and fluidized aluminum supplementation for 180 min. The reactor bed is in a stable fluidized state. After fluidization, the gas velocity is increased to carry the aluminum supplement balance agent out of the bed. The mixed gas and the aluminum supplement balance agent are separated by the multi-stage cyclone separator 24 at the top of the activation enhancement reactor 45. The activation enhancement reaction gas 25 is reintroduced into the bottom of the activation enhancement reactor 45 after adding the recovered aluminum supplement agent. The aluminum supplement balance agent enters the activation enhancement balance agent stripping tower 46 through the inclined pipe 27 at the bottom of the activation enhancement reactor.
[0075] Nitrogen stripping gas 38 is introduced into the bottom of the activity-enhancing balancing agent stripping tower 46 to strip the aluminum supplementing balancing agent. After stripping, the activity-enhancing balancing agent enters the bottom of the riser reactor 4 through the activity-enhancing balancing agent storage tank 42 to participate in the catalytic cracking reaction. The pipeline temperature is maintained at 250℃ throughout the process. The stripping mixture 36 containing the aluminum supplementing agent is cooled and the aluminum supplementing agent 39 is recovered and then circulated back to the bottom of the activity-enhancing balancing agent stripping tower 46. After recovery, the aluminum supplementing agent 39 is condensed and added to the aluminum supplementing agent mixture 26.
[0076] Example 4: Circulating fluidized bed activity enhancement reactor (rapid fluidization state of the bed)
[0077] Preheated raw material 2 and steam 1 enter the bottom of riser reactor 4, where they react with high-temperature carbonization regeneration balancing agent from regenerator 44 and activity enhancing balancing agent from activity enhancing balancing agent storage tank 42 in riser reactor 4 at a reaction temperature of 650°C, a catalyst to raw material oil mass ratio of 26, a residence time of 7s, and an activity enhancing balancing agent and fresh catalyst added in a mass ratio of 1:1.
[0078] The oil and gas mixture and the balance agent are passed together through the riser reactor 4. The oil and gas are rapidly separated from the balance agent by gravity and the top cyclone separator 7 of the reactor settling tank 6. The oil and gas enter the oil and gas fractionation system from the top of the reactor settling tank 6. The balance agent enters the reactor stripping section 5 for stripping and then enters the bottom of the coking tank 12 of the regenerator 44 through the inclined pipe 9 at the bottom of the reactor settling tank.
[0079] At the bottom of the coking tank 12, air 11 is introduced to fluidize the char-burning agent under the conditions of a reaction temperature of 720℃ and a gas flow rate of 0.5m / s. After char-burning, the flue gas and the mixture of char-burning regeneration char-burning ...
[0080] At the bottom of the activation enhancement reactor 45, an activation enhancement reaction gas 25 containing 80% aluminum supplement is introduced to fluidize the charcoal regeneration balancing agent under the conditions of reaction temperature 250℃ and gas flow rate 0.2m / s. The reactor bed is in a rapid circulating fluidized state. The mixed gas and the aluminum supplement balancing agent are separated by a multi-stage cyclone separator 24 at the top of the activation enhancement reactor 45. The activation enhancement reaction gas 25 is reintroduced into the bottom of the activation enhancement reactor 45 after the aluminum supplement 39 is recovered. The aluminum supplement balancing agent enters the stripping section 33 of the stripping tower through the inclined pipe 27 at the bottom of the activation enhancement reactor.
[0081] Nitrogen is not introduced into the bottom of the active boosting balance agent stripping tower 46 initially, so that the balance agent is circulated and fluidized in the gas phase to replenish aluminum. When the circulation fluidization time reaches 120 min, nitrogen stripping gas 38 is introduced to strip the aluminum replenishing balance agent. Control valve V29 is closed, and the pipeline temperature is maintained at 260℃ throughout the process. After stripping, the active boosting balance agent enters the bottom of the riser reactor 4 through the active boosting balance agent storage tank 42 to participate in the catalytic cracking reaction. The stripping mixture 36 containing the aluminum replenishing agent is cooled and the aluminum replenishing agent is recovered and then circulated back to the bottom of the active boosting balance agent stripping tower 46. After recovery, the aluminum replenishing agent 39 is condensed and replenished to the aluminum replenishing agent mixture 26.
[0082] Comparative Example 1
[0083] The comparative example selected was a conventional reaction-regeneration system under the process conditions of Example 1, using 100% fresh catalyst feed.
[0084] The specific implementation results are shown in the table below.
[0085] Riser reactor temperature (°C) Diolefin yield (%) propylene / ethylene Conversion rate (%) Example 1 650 44.58 0.91 77.45 Example 2 635 45.87 0.95 79.48 Example 3 640 42.95 0.83 75.50 Example 4 650 43.46 0.93 78.24 Comparative Example 1 650 42.36 0.72 73.63
[0086] Based on the comparative evaluation results, it can be seen that, compared with the comparative example, this invention can comprehensively improve the key technical indicators of the unit, such as the yield of diolefins, conversion rate and propylene / ethylene ratio, while replacing the freshener. This improves the overall activity of the unit's reaction system, reduces the temperature of the riser reactor, enhances the unit's technical and economic indicators, and effectively reduces agent consumption and the emission of balancing agent, thus having good environmental benefits.
Claims
1. A hydrocarbon catalytic cracking process with a balancer activity enhancement function, characterized in that, Includes the following steps; Step 1: Preheated feedstock and steam enter from the bottom of the riser reactor and react with high-temperature carbonization regeneration balance agent from the regenerator, active boosting balance agent from the active boosting balance agent storage tank, and fresh catalyst in the riser reactor to form an oil-gas and balance agent mixture; Step 2: The oil and gas mixture and the balance agent are passed together through the riser reactor. The oil and gas are quickly separated from the balance agent by gravity and the reactor settling tank located above the riser reactor and the cyclone separator set on the top of the reactor settling tank. The oil and gas enter the oil and gas fractionation system from the top of the reactor settling tank, and the balance agent enters the stripping section and is stripped. After being stripped, it enters the bottom of the coking tank of the regenerator through the inclined pipe at the bottom of the reactor settling tank to the bottom of the coking tank. After charring in the coke burner, the flue gas and the char regeneration balance agent mixture are separated by the top vortex of the regenerator. The flue gas enters the flue gas system, and part of the char regeneration balance agent returns to the bottom of the riser reactor to participate in the catalytic cracking reaction. The other part enters the active booster reactor through the inclined tube at the bottom of the regenerator. Step 3: The carbon regeneration balancing agent and aluminum supplement agent mixture gas enter the activated booster reactor through the inclined tube at the bottom of the regenerator and the inlet of the activated booster reactor, and are fluidized to supplement aluminum, forming a mixture of aluminum supplement agent mixture gas and aluminum balancing agent mixture after reaction. This mixture is separated by a multi-stage cyclone separator at the top of the activated booster reactor. After adding aluminum supplement agent, the mixture gas is reintroduced into the bottom of the activated booster reactor. The aluminum balancing agent enters the activated booster balancing agent stripping tower through the inclined tube at the bottom of the activated booster reactor and the inlet of the stripping tower. Step 4: Nitrogen stripping gas is introduced into the bottom of the activity-enhancing balance agent stripping tower to strip the aluminum supplementation balance agent. After stripping, the activity-enhancing balance agent enters the bottom of the riser reactor through the activity-enhancing balance agent storage tank to participate in the catalytic cracking reaction. The stripping mixture containing the aluminum supplementation agent is cooled and recycled back to the bottom of the activity-enhancing balance agent stripping tower after recovering the aluminum supplementation agent. The recovered aluminum supplementation agent is condensed and added to the aluminum supplementation agent mixture, realizing the recycling of the aluminum supplementation agent, improving the utilization rate of the aluminum supplementation agent, and realizing efficient gas-phase aluminum supplementation of the carbon regeneration balance agent.
2. The hydrocarbon catalytic cracking process with balancer activity enhancement function according to claim 1, characterized in that, In step 1, the reaction is carried out under the following conditions: the reaction temperature of the riser reactor is 550~700℃, the total amount of fresh catalyst, char regeneration balancing agent and activity enhancement balancing agent is 10~30 times the mass ratio of preheated raw material, and the residence time is 1.0~7.0s.
3. The hydrocarbon catalytic cracking process with balancer activity enhancement function according to claim 1, characterized in that, In step 2, air is introduced into the bottom of the coking tank to fluidize the char under the conditions of a reaction temperature of 650~850℃ and a gas flow rate of 0.1~5m / s.
4. The hydrocarbon catalytic cracking process with balancer activity enhancement function according to claim 1, characterized in that, The bottom of the activity enhancement reactor is used to fluidize and supplement aluminum to the charcoal regeneration balancing agent by introducing a mixture of aluminum supplementing agent and gas at a reaction temperature of 150~300℃ and a contact time of 30min~240min.
5. A hydrocarbon catalytic cracking process with a balancer activity enhancement function according to claim 1, characterized in that, The temperature of the balancing agent at the inlet of the activity-enhancing reactor is 100~300℃.
6. A hydrocarbon catalytic cracking process with a balancer activity enhancement function according to claim 5, characterized in that, The activity enhancement reactor is a fluidized bed or a boiling bed reactor. The bottom of the reactor is equipped with a multi-stage gas distribution plate, and the char regeneration balancing agent is kept in a stable fluidized state in the reactor. The activity enhancement reactor is introduced with a mixture of gaseous aluminum supplement and nitrogen, and the inlet temperature of the mixture is 150~300℃. The inlet and outlet gas circulation pipelines of the activation enhancement reactor are maintained at a constant temperature of 150℃~300℃, and the recovered aluminum supplement and fresh aluminum supplement are added to the inlet pipeline of the activation enhancement reactor.
7. A hydrocarbon catalytic cracking process with a balancer activity enhancement function according to claim 5, characterized in that, The stripping medium in the stripping tower for the activity-enhancing balancing agent is hot nitrogen. After stripping, the mixed gas undergoes aluminum replenishment agent condensation and recovery in a condensation recovery tank. After recovery, the aluminum replenishment agent enters the gas in the activity-enhancing reactor to participate in the aluminum replenishment reaction.
8. The hydrocarbon catalytic cracking process with balancer activity enhancement function according to claim 1, characterized in that, The mass ratio of the active boosting balancing agent to the fresh catalyst at the lower inlet of the riser reactor is (0.5~4):1; The feed method of the activity enhancement reactor is intermittent feeding. The feed rate is adjusted according to the material height of the activity enhancement balancer tank to keep the material level of the activity enhancement balancer tank between 30% and 70%. The activity enhancement reactor bed switches between two modes: circulating fluidized aluminum supplementation and boiling fluidized aluminum supplementation.
9. A hydrocarbon catalytic cracking device with a balancer activity enhancement function according to any one of claims 1-8, characterized in that, The riser reactor is connected to the bottom outlet of the regenerator settling tank and the bottom outlet of the active boosting balancer storage tank via the bottom-reactor inlet inclined pipe of the regenerator and the bottom outlet of the active boosting balancer storage tank, respectively. The bottom of the settling tank above the riser reactor is connected to the coking tank of the regenerator via an inclined pipe from the bottom of the settling tank to the bottom of the coking tank. The other outlet of the bottom of the settling tank above the coking tank is connected to the inlet of the fluidized bed at the bottom of the active booster reactor via an inclined pipe from the bottom of the regenerator to the inlet of the active booster reactor. A cyclone separator is installed at the top of the reactor settling tank, and the reaction products are discharged from the top. The lower part of the reactor settling tank is the reactor stripping section; The top of the regenerator settling tank is the regenerator top vortex, and the flue gas is output from the top. The bottom outlet of the settling tank at the top of the activity enhancement reactor is connected to the activity enhancement balance agent stripping tower via an inclined pipe from the bottom of the activity enhancement reactor to the stripping tower inlet. The top of the settling tank of the activation enhancement reactor is a multi-stage cyclone separator. The output activation enhancement reaction gas enters the bottom of the fluidized bed of the activation enhancement reactor through the aluminum supplement gas circulation path and the aluminum supplement gas mixture. The bottom of the fluidized bed of the activation enhancement reactor is also equipped with gas distribution plate I and gas distribution plate II. One outlet at the bottom of the stripping tower for the active boosting balancing agent is connected to the top inlet of the active boosting balancing agent storage tank via an inclined pipe from the bottom of the stripping tower to the bottom inlet of the boosting reactor. The other outlet is connected to the bottom inlet of the active boosting reactor via an inclined pipe from the bottom of the stripping tower to the circulation of the active boosting reactor. The gas pipeline at the top of the settling tank of the active boosting reactor is circulated and then connected to the bottom gas inlet of the active boosting reactor. The stripping mixed gas output from the top of the stripping tower for the active boosting balancing agent is connected to the condensation recovery tank via a gas pipeline in the stripping gas circulation path. The gas phase outlet of the condensation recovery tank is connected to the gas inlet of the stripping section of the active boosting balancing agent stripping tower, and the solid phase outlet of the condensation recovery tank is connected to the aluminum supplement gas circulation path. The bottom of the stripping tower for the active boosting balancing agent is the stripping section, the area above the stripping section is the settling zone, and the top is the top vortex separator.