CN102989519B - Catalytic cracking catalyst continuous aging method - Google Patents
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- CN102989519B CN102989519B CN201110272645.7A CN201110272645A CN102989519B CN 102989519 B CN102989519 B CN 102989519B CN 201110272645 A CN201110272645 A CN 201110272645A CN 102989519 B CN102989519 B CN 102989519B
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Abstract
The invention relates to a catalytic cracking catalyst continuous aging method and a catalytic cracking catalyst continuous aging device. The method comprises the steps that: a catalyst enters a bottom of a dilute-phase combustion tube, and then mixed with oxygen-containing gas and a fuel; the mixture is combusted and flows upward; gas-solid separation is carried out at the port of the dilute-phase combustion tube; catalyst obtained by separation enters a fluidized-bed reactor; the catalyst is subjected to a reaction with steam, such that activity is reduced; gas-solid separation is carried out at the top of the fluidized-bed reactor, and gas is discharged out of the device; the catalyst enters a catalyst buffering tank from the bottom of fluidized-bed reactor, and is circulated back to the bottom of the dilute-phase combustion tube through a control valve; when aging is finished, the catalyst is unloaded; material level in the catalyst buffering tank is maintained, and the catalyst continues to participate in circulation reaction in the dilute-phase combustion tube and the fluidized-bed reactor. The invention also relates to a device used for realizing the aging method. With the aging method and device provided by the invention, combustion reaction and hydro-thermal reaction operation conditions can be respectively controlled; and activity of aged catalyst is uniformly distributed. When the catalyst is used in hydrocarbon oil catalytic cracking reactions, product distribution can be improved.
Description
Technical field
The present invention relates to the pretreated method and apparatus of catalyst in a kind of catalytic cracking process, more particularly, relate to a kind of method and apparatus of the active fast reducing of catalytic cracking catalyst to certain maintenance level that make.
Background technology
Catalytic cracking technology is the main secondary operations technique of oil refining enterprise.This technology is converted into heavy hydrocarbon oil raw material the products such as gasoline, diesel oil, propylene and liquefied gas.In catalytic cracking unit operation process, in device, the activity of catalyst need to remain on maintenance level, and catalyst activity is too high, can cause dry gas and coke yield too high, and product selectivity is very poor; Catalyst activity is too low low, for example, lower than 55, can cause conversion ratio to decline, and clean or white yield reduces.The activity of catalyst can be measured by the micro-activity experiment method of catalytic cracking " Petrochemical Engineering Analysis method (RIPP test method) ", and in unit normal run process, the activity of catalytic cracking catalyst is generally 60-70.
Catalytic cracking is the general stable equilibrium catalyst of catalytic activity that uses in the time going into operation, and equilibrium catalyst refers to the regenerated catalyst in regenerator when catalytic cracking unit runs well.In there is no equilibrium catalyst, water vapour can not passed in regenerator and fuel oil re-uses the activity decreased of fresh catalyst to a certain extent yet.
In device running, because the average grain diameter of catalyst granules is 40-80 μ m, microspheric catalyst constantly runs and damages from device, needs timely fresh makeup catalyst.In addition, in some catalytic cracking heavy charges, tenor is higher, and in processing when these heavy charges, the metals such as metallic iron in raw material, nickel, vanadium, calcium can pollute catalyst, and catalyst is lost activity.In this case, in catalytic cracking unit, need to draw off partially catalyzed agent, supplement part fresh catalyst to alleviate metal contamination level and to maintain suitable catalyst activity simultaneously.Supplementary fresh catalyst activity is very high, and activity is generally greater than 80, is even greater than 90.This part high activity fresh catalyst can recover rapidly catalytic cracking system catalyst activity, but this part high activated catalyst also brings negative effect to catalytic cracking unit simultaneously.Test shows, this part high activated catalyst can obviously increase coke yield, reduces octane number, and meanwhile, the activity decreased of high activated catalyst is also very fast, and activity stability is poor.Therefore in catalytic cracking unit operation process, also need the activity decreased of fresh highly active catalytic cracking catalyst to maintenance level, and constantly add in device.
Before fresh catalyst adding apparatus, must be by fresh catalyst activity decreased to maintenance level, carry out aging to catalyst, the aging method of the catalyst of available technology adopting, generally that fresh catalyst is placed in to For Fcc Regenerator, in regenerator, pass into water vapour, fuel oil and oxygen-containing gas, make catalyst at high temperature reduce active with steam reaction.Because fuel oil sprays into inhomogeneously, the distribution of catalyst in regenerator is also inhomogeneous, causes catalyst activity to reduce inhomogeneous, and some catalyst spray into the serious inactivation of position hyperthermal environments at combustion oil, and some catalyst activities are also very high.In addition, the aging method of conventional catalytic cracking catalyst, before entering regenerator, catalyst need to use fuel gas and oxygen-containing gas and catalyst mix to burn catalyzer temperature-elevating after uniform temperature, spray into again the heavy oil burning of entering heat is provided, after a collection of catalyst ageing draws off to suitable activity, regenerator lowers the temperature, and above-mentioned intermittence, aging flow process was more loaded down with trivial details.
In order to improve catalyst ageing effect and efficiency, improve catalytic cracking process product and distribute, need to develop new catalyst ageing method and apparatus.
Summary of the invention
The object of this invention is to provide a kind of catalytic cracking catalyst aging method efficiently, catalytic cracking catalyst reduces the continued operation method of initial activity to maintenance level.
Another object of the present invention is to provide that a kind of volume is little, efficiency is high, saves the catalyst ageing equipment of energy consumption.
Catalyst ageing method provided by the invention, comprising:
(1) catalyst ageing device comprises fluidized-bed reactor and dilute phase combustion tube, catalyst enters dilute phase combustion tube bottom, with oxygen-containing gas, fuel mix after-combustion upwards mobile, the gas reacting completely and catalyst are in dilute phase combustion tube outlet gas solid separation, and isolated catalyst enters in fluidized-bed reactor;
(2) injected water steam in fluidized-bed reactor, contact with high temperature catalyst and carry out hydro-thermal reaction, reduce the activity of catalyst, catalyst and gas are in catalyst ageing device top gas solid separation, gas exhausting device, isolated catalyst returns to fluidized-bed reactor;
(3) fluidized-bed reactor bottom arranges catalyst surge tank, and catalyst is entered in catalyst surge tank by fluidized-bed reactor bottom, and the catalyst in catalyst surge tank enters dilute phase combustion tube bottom through control valve;
(4) catalyst activity is reduced to after proper level, draw off most of aging catalyst completing by fluidized-bed reactor bottom, maintain material level in catalyst surge tank, catalyst continues circular response in dilute phase combustion tube and fluidized-bed reactor, until it is aging to add fresh catalyst to continue.
The beneficial effect of catalyst ageing method provided by the invention is:
(1) reaction of catalyst hydrothermal aging and fuel oil combustion exothermic reaction are separated, can control respectively the two operating condition and reaction speed.
(2) dilute phase combustion tube size is little, is conducive to catalyst, oxygen-containing gas and fuel mix evenly and the heat release rear catalyst that is conducive to burn evenly absorbs heat, avoids local temperature too high.
(3) in dilute phase combustion tube, reacted gas is drawn catalyst ageing device, does not enter fluidized-bed reactor, can increase the steam partial pressure in fluidized-bed reactor, makes catalyst activity be reduced to the speed of maintenance level faster, thereby reduces energy consumption.
(4) owing to drawing off after most of aging catalyst completing, a small amount of catalyst still circulates in catalyst ageing device, maintain the temperature of catalyst ageing device, when again aging, fresh catalyst does not need to use gas phase fuel to heat up in advance before entering ager, can improve ageing efficiency and reduce energy consumption.
(5) catalyst activity after using method provided by the invention aging is evenly distributed, and catalytic cracking product distributes and obviously improves.
Catalytic cracking catalyst ager provided by the invention, comprise fluidized-bed reactor and dilute phase combustion tube, the top of dilute phase combustion tube arranges gas-solid separator, the gaseous phase outlet of described gas-solid separation equipment is drawn catalyst ageing device, fluid bed reactor catalysis agent dense-phase bed is introduced in solid phase outlet, fluidized-bed reactor top is gas-solid separation equipment, the gas-solid separation equipment top at described fluid bed top is communicated with gas discharge outlet, fluidized-bed reactor bottom is communicated with catalyst surge tank, and catalyst surge tank bottom is communicated with dilute phase combustion tube bottom by control valve.
The beneficial effect of catalyst ageing equipment provided by the invention is:
Catalyst ageing equipment provided by the invention can be used for aging catalytic cracking catalyst, and the catalyst ageing time is short, and efficiency is high, reduces energy consumption; Can reduce equipment size and the investment of ager; Convenient operating condition and the reaction speed of controlling respectively the reaction of catalyst hydrothermal aging and fuel oil combustion exothermic reaction when use; Catalyst activity after using this catalyst ageing device aging is evenly distributed, and catalytic cracking product distributes and obviously improves.
Accompanying drawing explanation
Fig. 1 is catalytic cracking catalyst aging method schematic flow sheet provided by the invention;
Fig. 2 is the conventional catalyst aging method schematic flow sheet adopting in comparative example.
The specific embodiment
Catalytic cracking catalyst aging method provided by the invention, specifically implement like this:
(1) catalyst ageing device comprises fluidized-bed reactor and dilute phase combustion tube, it is outside or inner that dilute phase combustion tube can be arranged on fluidized-bed reactor, preferably be arranged on fluidized-bed reactor inside, described dilute phase combustion tube is dilute phase reactor, catalyst enters in dilute phase combustion tube through pipeline and control valve, dilute phase combustion tube bottom passes into oxygen-containing gas, on oxygen-containing gas entrance, introduce fuel, catalyst, oxygen-containing gas and fuel mix after-combustion, gas after burning completely and catalyst are through dilute phase combustion tube outlet gas solid separation, isolated gas is discharged catalyst ageing device from top, isolated catalyst enters in fluidized-bed reactor,
(2) at fluidized-bed reactor bottom injected water steam, water vapour contacts and carries out hydro-thermal reaction with pyrolytic cracking catalyst, reduce catalyst activity, gas upwards flows simultaneously, catalyst is in back-mixing bed fluidized state, gas in fluidized-bed reactor and entrained catalyst thereof carry out gas solid separation at ager top, and isolated gas is discharged catalyst ageing device from top; Isolated catalyst returns to fluidized-bed reactor bottom;
(3) fluidized-bed reactor bottom arranges the catalyst surge tank that cross-sectional area is less, catalyst is entered in catalyst surge tank by fluidized-bed reactor bottom, catalyst in catalyst surge tank enters dilute phase combustion tube bottom through control valve, because the area of section of described catalyst surge tank is less than fluidized-bed reactor, in the time that the storage of catalyst in fluidized-bed reactor is less, also can in catalyst surge tank, keep stable material level;
(4) catalyst activity is reduced to after proper level, draw off most of aging catalyst completing by fluidized-bed reactor bottom, preferably draw off the 80%-95% of whole catalyst, catalyst after aging completing is introduced in the reactor of catalytic cracking unit, the catalyst of remaining 5%-20% continues to circulate in the dilute phase combustion tube of catalyst ageing device and fluidized-bed reactor; To maintain the temperature of catalyst ageing device, until it is aging to add fresh catalyst to continue.
In method provided by the invention, described catalyst refers to catalytic cracking catalyst, refers in particular to the catalytic cracking catalyst that contains molecular sieve.Described catalyst ageing refers at high temperature, with the molecular sieve reaction in water vapour and catalytic cracking catalyst, reduces the activity of catalyst.The object of catalyst ageing is to reduce the activity of fresh catalyst, because fresh catalyst activity is very high, after joining in catalytic cracking unit, can obviously increase the coke yield in the distribution of catalytic cracking product, and reduce octane number.Therefore, catalytic cracking catalyst initial activity need to be reduced to maintenance level.
In method provided by the invention, the catalyst ageing device fluidized-bed reactor bottom injected water steam described in step (1), by controlling the flow of water vapour, controls the gas void tower linear speed of fluidized-bed reactor.The gas void tower linear speed of described catalyst ageing device fluidized-bed reactor is 0.05-1.5m/s, preferred 0.1-0.9m/s, and mean temperature is 500-790 ℃, preferred 550-720 ℃.Apparent pressure is normal pressure-10kgf/cm
2, preferred 1-5kgf/cm
2.
In method provided by the invention, the dilute phase combustion tube described in step (2) is dilute phase reactor, and gas void tower linear speed is 1.2-20m/s, be preferably 1.5-15m/s.Inject oxygen-containing gas in dilute phase combustion tube bottom, by controlling the gas void tower linear speed of flow-control dilute phase combustion tube of oxygen-containing gas.
In method provided by the invention, oxygen in described dilute phase combustion tube in oxygen-containing gas and fuel and catalyst carry out combustion reaction, generate water and carbon dioxide, and heatable catalytic Cracking catalyst, control oxygen-containing gas flow and make in combustion reaction process oxygen excessive.Preferably controlling oxygen volume content in dilute phase combustion tube exit gas is 0.1-10v%, more preferably 1-5v%, and the oxygen content in dilute phase combustion tube exit gas can be measured by gas Orsat flue gas analyzer.
Gas residence time in dilute phase combustion tube is 0.2-20 second, preferred 0.4-15 second, and mean temperature is 600-800 ℃, preferred 650-750 ℃.Wherein gas residence time is that oxygen-containing gas mixes after touch with fuel joint, to the logarithmic mean time of staying of dilute phase burner outlet.Wherein dilute phase combustion tube top exit temperature can be by controlling fuel flow rate control and adjustment.
In method provided by the invention, in described oxygen-containing gas, the content of oxygen is greater than 5v%, preferably air.
In method provided by the invention, the fuel injecting in dilute phase combustion tube in step (2), for combustible gas or liquid fuel, wherein gaseous fuel is dry gas, the device in Gas etc. of natural gas, liquefied gas, various oil refining apparatus, and liquid fuel is gasoline, diesel oil or mink cell focus.The preferred diesel oil of fuel and mink cell focus.
In method provided by the invention, at dilute phase combustion tube top, gas-solid separation equipment is set, the catalyst after reaction after gas and heating by ignition is in dilute phase combustion tube top gas solid separation, and isolated gas is directly drawn catalyst ageing device; Isolated high temperature catalyst is guided to the middle and lower part of fluidized-bed reactor through solid phase material pipe.Described fluidized-bed reactor middle and lower part preferred streams fluidized bed reactor inner catalyst dense-phase bed 0-80% place from bottom to up, is preferably 0-40% place.Gas after combustion reaction is directly drawn to reactor, can increase the dividing potential drop of water vapour in fluidized-bed reactor, be conducive to the quick aging of catalyst in fluidized-bed reactor.In addition, by guide to the middle and lower part of fluidized-bed reactor from the high temperature catalyst of dilute phase combustion tube, can promote the back-mixing between catalyst, promote exchange heat, improve catalyst ageing reaction efficiency.
In method provided by the invention, the reaction temperature of described fluidized-bed reactor can be by controlling the catalyst circulation rate exchanging in fluidized-bed reactor and dilute phase combustion tube, and to introduce dilute phase be so that fuel flow rate in pipe regulates.Can control by the control valve on the pipeline of fluidized-bed reactor bottom and dilute phase combustion tube bottom UNICOM the circular flow of catalyst, and further regulate dilute phase combustion tube outlet temperature by adjusting fuel flow rate, thereby control and regulate the temperature of catalyst ageing device fluidized-bed reactor.
In method provided by the invention, in step (4), catalyst activity is reduced to after suitable level, shut-down draws off most of catalyst, and the activity decreased that described suitable level refers generally to catalyst during to 60-78, can need to be determined and stop the aging time according to subsequent reactions.
In method provided by the invention, described shut-down does not need whole catalyst all to draw off, but draw off most of aging catalyst completing, preferably draw off the 80-95% of whole catalyst total amounts in catalyst ageing device, more preferably 90%-95%, and remaining a small amount of catalyst can maintain stable material level in catalyst surge tank, continues to circulate in the fluidized-bed reactor of catalyst ageing device and dilute phase combustion tube, the reaction temperature that holdout device is higher, reaction temperature is 500-790 ℃.If catalyst surge tank is not set, after catalyst ageing completes, the 20-40% that at least will retain whole catalyst just can maintain catalyst middle circulation in fluidized-bed reactor and dilute phase combustion tube, maintains the temperature in catalyst ageing device.Retain too many catalyst, the problem causing is that this part catalyst carries out once again aging inactivation, causes partially catalyzed agent activity too low, a part of hyperactivity.Adopt method provided by the invention, can retain the catalyst of little amount to maintain the temperature of ageing system, do not affect catalyst overall activity.
Catalyst ageing device provided by the invention, comprise fluidized-bed reactor and dilute phase combustion tube, the top of dilute phase combustion tube arranges gas-solid separation equipment, the gaseous phase outlet of the gas-solid separation equipment at described dilute phase combustion tube top is arranged at outside catalyst ageing device, its solid phase outlet is arranged in fluid bed reactor catalysis agent dense-phase bed, fluidized-bed reactor top is gas-solid separation equipment, the gaseous phase outlet of described fluidized-bed reactor top gas-solid separation equipment is positioned at outside catalyst tiger rises, its solid phase outlet is positioned at fluidized-bed reactor inside, fluidized-bed reactor bottom is communicated with dilute phase combustion tube bottom through catalyst surge tank and control valve.
In catalyst ageing device provided by the invention, described dilute phase combustion tube is riser reactor, and fluidized-bed reactor bottom is communicated with catalyst surge tank, and catalyst surge tank bottom is communicated with burner bottom through valve.Fresh catalyst entrance is set on catalyst ageing device, and fresh catalyst entrance can be located at fluidized-bed reactor wall or direct UNICOM dilute phase combustion tube.In fluidized-bed reactor bottom, catalyst outlet is set, for drawing off the catalyst after aging completing.Oxygen-containing gas entrance is arranged on dilute phase combustion tube bottom, steam entry and is positioned at that fluidized-bed reactor bottom, fuel inlet are positioned on dilute phase combustion tube, oxygen-containing gas entrance top.
In catalyst ageing device provided by the invention, described dilute phase combustion tube top arranges gas-solid separation equipment, and the isolated gas of gas-solid separation equipment is directly drawn catalyst ageing device; Gas-solid separation equipment solid-phase catalyst outlet be arranged at the middle and lower part of fluidized-bed reactor.The place of 0-80% from bottom to up of the described close phase material level of the preferred ager in fluidized-bed reactor middle and lower part, is preferably 0-40% place.So that the high temperature catalyst of dilute phase combustion tube outlet enters the middle and lower part of fluid bed in fluidized-bed reactor, carry out effective back-mixing with the catalyst in fluidized-bed reactor.
In catalyst ageing device provided by the invention, described gas-solid separation equipment is the various separation equipments that gas phase can be separated with solid phase, the present invention is not limited in this respect, it can be cyclone separator, or filter plant, gas is drawn from catalyst ageing device top, and catalyst turns back to catalyst ageing device bottom.Described filter plant can be metal or ceramic chimney filter, can be also high temperature filter bag.
In method provided by the invention, dilute phase combustion tube is 1 with the caliber ratio of fluidized-bed reactor: 40-300.The draw ratio of dilute phase combustion tube is 100-500: 1.
In method provided by the invention, the 5%-20% of the sectional area that the sectional area of described catalyst surge tank is fluidized-bed reactor.
With reference to the accompanying drawings, illustrate catalytic cracking catalyst aging method provided by the invention, but the present invention is not therefore subject to any restriction.
In the fluidized-bed reactor 5 of catalyst ageing device, water vapour by pipeline 7 injects fluidized-bed reactor 5 bottoms, catalyst and steam carry out hydro-thermal reaction and reduce catalyst initial activity, water vapour mixes with the high temperature catalyst from separating after dilute phase combustion tube 4 combustion reactions completely with catalyst, to keep aging temperature, the gas of dilute phase combustion tube outlet is isolated and direct ejector, can at utmost keep the steam partial pressure in fluid bed reactor catalysis agent bed, increase catalyst ageing speed.Fluidized-bed reactor 5 bottoms arrange catalyst surge tank 22, and catalyst is entered in catalyst surge tank 22 by fluidized-bed reactor bottom, and the catalyst in catalyst surge tank 22 enters dilute phase combustion tube 4 bottoms through pipeline 9 and control valve 10; Catalyst flows out the circular flow of the control valve 10 adjustable catalyst on pipeline, can regulate the temperature in fluidized-bed reactor by controlling the circular flow of catalyst and adjusting dilute phase combustion tube outlet temperature.
Gas in fluidized-bed reactor 5 and entrained catalyst thereof are after fluidized-bed reactor top is by gas-solid separation equipment 6 gas solid separation, and gas enters subsequent treatment system through pipeline 8, and catalyst returns to fluidized-bed reactor bottom.Described gas-solid separation equipment 6 can be cyclone separator or filter.
When catalyst ageing reaches after required activity, most of catalyst draws off through pipeline 23, and residue fraction maintains material level in catalyst surge tank 22, and continues liking being to circulate in that combustion tube and fluidized-bed reactor.After most of catalyst draws off, can immediately fresh catalyst be joined in fluidized-bed reactor 5 by pipeline 7, now strengthen flow and the catalyst circulation amount of fuel oil, make the catalyst adding be raised to rapidly required aging temperature; After whole catalyst add, adjust flow and the required aging temperature of catalyst circulation amount control of fuel.
Further illustrate method provided by the invention below by embodiment, but therefore the present invention is not subject to any restriction.
Comparative example 1
Comparative example 1 illustrates the effect of conventional catalyst aging method.
As shown in Figure 2, catalyst ageing device 15 is fluidized-bed reactor, first fresh catalytic cracking catalyst CTZ-1 aging needs is packed in catalyst ageing device 15, water vapour is entered in catalyst ageing device through pipeline 17 by reactor bottom, air and fuel from middle part through pipeline 11, 13 enter catalyst ageing device, fuel and oxygen-containing gas reactive combustion heat up, high-temperature catalytic Cracking catalyst under vapor action activity decreased to maintenance level, at catalyst ageing device 15 tops, catalyst and reacted gas gas solid separation after filter 16, isolated gas is through pipeline 18 dischargers.After catalyst activity meets the demands, stop work and draw off catalyst.
Fresh catalyst CTZ-1 is produced by Chang Ling catalyst branch company of Sinopec Co., Ltd, and character is in table 1.Fuel is diesel oil, and character is in table 2.Operating condition is in table 3, and aging rear catalyst character is in table 1.
Comparative example 2
Comparative example 2 illustrates the effect for cracking reaction by the aging catalyst of conventional catalyst aging method.
To on catalyst medium-sized tester aging in comparative example 1, test, the height of riser reactor is 5.5 meters, and caliber is 16 millimeters.Daqing atmospheric residue (character is in table 4) is preheating to 260 ℃ of bottoms that enter riser reactor, under water vapour exists, with the catalyst haptoreaction after heat aging by comparative example 1.The oil gas generating rises to separator together with reclaimable catalyst, and after gas solid separation, reclaimable catalyst enters coke burning regeneration in regenerator after stripping, recycles.Isolated reaction oil gas enters fractionating column, is further separated into dry gas, liquefied gas, gasoline, diesel oil.The products such as heavy oil.Main reaction condition, product distribute in table 5.
As shown in Figure 1, fresh catalyst enters the bottom of dilute phase combustion tube 4 upwards to flow along dilute phase combustion tube after mixing with from the air of pipeline 1, then with diesel oil mixing after-combustion from pipeline 2 for catalyst ageing device structure and flow process.Gas after combustion reaction completely and catalyst export gas solid separation at dilute phase combustion tube, isolated gas exhausting device, and isolated catalyst is incorporated into fluidized-bed reactor dense bed 50% place from bottom to top through solid phase material pipe 25.By the steam injection fluidized-bed reactor bottom of pipeline 7, catalyst reacts with high-temperature steam and reduces activity.Gas upwards flows, after the ceramic chimney filter at fluidized-bed reactor top filters through pipeline 8 dischargers.Fluidized-bed reactor 5 bottoms arrange catalyst surge tank 22, and catalyst is entered in catalyst surge tank 22 by fluidized-bed reactor bottom, and the catalyst in catalyst surge tank 22 enters dilute phase combustion tube 4 bottoms through pipeline 9 and control valve 10.When catalyst ageing is after required activity, most of catalyst draws off through pipeline 23, and residue fraction is stayed in catalyst surge tank 22.After most of catalyst draws off, fresh catalyst is added in fluidized-bed reactor 5 by pipeline 7, now strengthen flow and the catalyst circulation amount of fuel, the catalyst adding is heated up rapidly; After whole catalyst add, adjust flow and the required aging temperature of catalyst circulation amount control of fuel.Wherein, dilute phase combustion tube is 1: 80 with fluidized-bed reactor diameter ratio, and the draw ratio of dilute phase combustion tube is 100: 1, and the cross-sectional area of catalyst surge tank is fluidized-bed reactor 5%.Fresh catalyst CTZ-1 character is in table 1, and diesel oil character is in table 2, and catalyst ageing operating condition is in table 3, and aging rear catalyst character is in table 1.
Embodiment 2
Embodiment 2 illustrates catalyst that method provided by the invention the is aging effect for catalytic cracking reaction.
Adopt middle-scale device, feedstock oil in comparative example 2, operating procedure and reaction condition are with comparative example 2, and difference is the catalyst that catalyst adopts the aging activity decreased obtaining in embodiment 1.Feedstock oil character is in table 4, reaction condition and the results are shown in Table 5.
Table 1
2 fuel oil bavin oil properties
| Density (20 ℃)/(kg/m 3) | 911.1 |
| Viscosity (50 ℃)/(mm 2/s) | 2.902 |
| Viscosity (20 ℃)/(mm 2/s) | 6.191 |
| Freezing point/℃ | -8 |
| Quality elements composition/% | |
| C | 88.95 |
| H | 10.98 |
| S | 0.50 |
| N/(mg/L) | 993 |
| Boiling range/℃ | |
| Initial boiling point | 181 |
| 5％ | 230 |
| 10％ | 244 |
| 30％ | 264 |
| 50％ | 289 |
| 70％ | 323 |
| 90％ | 354 |
| 95％ | 364 |
| The end point of distillation | 367 |
Table 3
| Project | Comparative example 1 | |
| Catalyst weight/kg | 100 | 100 |
| Fluidized-bed reaction actuator temperature/℃ | 700 | 700 |
| Fluidized-bed reactor gauge pressure/KPa | 300 | 300 |
| Fluidized-bed reactor void tower linear speed/m/s | 0.7 | 0.7 |
| Dilute phase combustion tube reaction temperature/℃ | 750 | |
| Dilute phase combustion tube gas residence time/s | 5.0 | |
| Dilute phase combustion tube void tower linear speed/m/s | 2.0 | |
| Steam flow/kg/h | 4 | 4 |
| Air mass flow/Nm3/h | 17 | 13 |
| Diesel oil flow/kg/h | 1.03 | 1.01 |
| Catalyst circulation amount/kg/h | 20 | |
| Catalyst ageing vapor partial pressure/KPa | 66 | 300 |
| Catalyst ageing time/h | 30 | 10 |
Table 4 catalytic cracking reaction raw produce distributes
| Feedstock oil | Daqing atmospheric residue |
| Density (20 ℃)/(g/cm 3) | 915.8 |
| Kinematic viscosity (80 ℃)/(mm 2/s) | 41.13 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 21.81 |
| Condensation point/℃ | 32 |
| Carbon residue/% | 4.32 |
| Element quality composition/% | |
| C | 86.95 |
| H | 12.57 |
| S | 0.19 |
| N | 0.37 |
| Boiling range/℃ | 300 |
| Initial boiling point | 384 |
| 0.05 | 403 |
| 10％ | 446 |
| 30％ | 482 |
| 50％ | 531 |
Table 5 catalytic cracking reaction condition and result
| Comparative example 2 | Embodiment 2 | |
| Reaction temperature/℃ | 515 | 515 |
| |
5 | 5 |
| Air speed/ |
25 | 25 |
| Product distributes, w% | ||
| Dry gas | 2.5 | 2.4 |
| Liquefied gas | 15.2 | 15.1 |
| Gasoline | 43.9 | 44.9 |
| Diesel oil | 20.2 | 20.7 |
| Heavy oil | 9.5 | 8.9 |
| Coke | 8.7 | 8.2 |
From table 1, method provided by the invention is compared with conventional catalyst aging method, and the catalyst physical property after aging is suitable.From table 3, in the situation that catalyst ageing temperature is identical, method provided by the invention shortened to 10 hour to the ageing time of suitable activity by 30 hours by catalyst ageing, had improved ageing efficiency, had reduced energy consumption.From table 5, compared with comparative example 2, the product of embodiment 2 distributes and obviously improves, and gasoline yield increases by 1.0 percentage points, and diesel yield increases by 0.5 percentage point, and dry gas yied reduces by 0.1 percentage point, and coke yield reduces by 0.5 percentage point.Compared with conventional aging method, adopt the catalyst that catalyst ageing method provided by the invention is aging seasonable for Catalytic Cracking Unit of Measure, can improve product and distribute.
Claims (14)
1. a catalytic cracking catalyst continuous ageing method, is characterized in that, comprises the following steps:
(1) catalyst ageing device comprises fluidized-bed reactor and dilute phase combustion tube, catalyst enters dilute phase combustion tube bottom, with oxygen-containing gas, fuel mix after-combustion upwards mobile, the gas reacting completely and catalyst are in dilute phase combustion tube outlet gas solid separation, and isolated catalyst enters the middle and lower part of dense-phase bed in fluidized-bed reactor;
(2) injected water steam in fluidized-bed reactor, contact with high temperature catalyst and carry out hydro-thermal reaction, reduce the activity of catalyst, catalyst and gas are in catalyst ageing device top gas solid separation, gas exhausting device, isolated catalyst returns to fluidized-bed reactor;
(3) fluidized-bed reactor bottom arranges catalyst surge tank, and catalyst is entered in catalyst surge tank by fluidized-bed reactor bottom, and the catalyst in catalyst surge tank enters dilute phase combustion tube bottom through control valve;
(4) catalyst activity is reduced to proper level, draw off most of aging catalyst completing by fluidized-bed reactor bottom, maintain material level in catalyst surge tank, catalyst continues circular response in dilute phase combustion tube and fluidized-bed reactor, until it is aging to add fresh catalyst to continue.
2. according to the method for claim 1, it is characterized in that the middle and lower part of described fluidized-bed reactor dense-phase bed is the close phase material level of fluidized-bed reactor 0-80% place from bottom to up.
3. according to the method for claim 2, it is characterized in that the middle and lower part of described fluidized-bed reactor is the close phase material level of fluidized-bed reactor device 0-40% place from bottom to up.
4. according to any method in claim 1～3, it is characterized in that, the gas void tower linear speed of described catalyst ageing device fluidized-bed reactor is 0.05-1.5m/s, and mean temperature is 500-790 ℃, and apparent pressure is normal pressure-10kgf/cm
2.
5. according to the method for claim 4, it is characterized in that, the gas void tower linear speed of described catalyst ageing device fluidized-bed reactor is 0.1-0.9m/s, and mean temperature is 550-720 ℃, and apparent pressure is 1-5kgf/cm
2.
6. according to any method in claim 1-3, it is characterized in that, the gas void tower linear speed of described dilute phase combustion tube is 1.2-20m/s.
7. according to the method for claim 6, it is characterized in that, the gas void tower linear speed of described dilute phase combustion tube is 1.5-15m/s.
8. according to any method in claim 1-3, it is characterized in that, the reaction temperature of described dilute phase combustion tube is 600-800 ℃.
9. according to the method for claim 8, it is characterized in that, the reaction temperature of described dilute phase combustion tube is 650-750 ℃.
10. according to any method in claim 1-3, it is characterized in that, the gas residence time of described dilute phase combustion tube is 0.2-20 second.
11. according to the method for claim 10, it is characterized in that, the time of staying of described dilute phase combustion tube is 0.4-15 second.
12. according to any method in claim 1-3, it is characterized in that, in step (4), catalyst activity is aged to after proper level, is drawn off the 80-95% of whole catalyst by fluidized-bed reactor bottom.
13. according to any method in claim 1-3, it is characterized in that, in described dilute phase combustion tube top exit gas, the volume content of oxygen is 0.1-10v%.
14. according to the method for claim 13, it is characterized in that, in described dilute phase combustion tube top exit gas, the volume content of oxygen is 1-5v%.
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| CN105562121B (en) * | 2014-10-16 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of metallic pollution and hydrothermal aging method of catalytic cracking catalyst |
| CN105562120B (en) * | 2014-10-16 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of Cracking catalyst in batches plus agent, continuous ageing method |
| CN117282472B (en) * | 2023-11-27 | 2024-02-09 | 中科益天环境工程(北京)有限公司 | Catalytic cracking catalyst aging method and equipment |
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| JP3736021B2 (en) * | 1997-04-17 | 2006-01-18 | Ｊｆｅスチール株式会社 | Method for separating and analyzing silicon and phosphorus |
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