CN103666528A - Work starting method for catalytic cracking unit - Google Patents
Work starting method for catalytic cracking unit Download PDFInfo
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- CN103666528A CN103666528A CN201210352775.6A CN201210352775A CN103666528A CN 103666528 A CN103666528 A CN 103666528A CN 201210352775 A CN201210352775 A CN 201210352775A CN 103666528 A CN103666528 A CN 103666528A
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Abstract
The invention relates to a work starting method for a catalytic cracking unit. The method comprises the steps of infusing a hot fluidizing medium to a regenerator and a reactor, so as to heat the regenerator and the reactor, shutting off valves between the regenerator and the reactor, and loading a fresh catalyst into the regenerator; when the regenerator reaches a certain temperature, infusing water vapor to a degassing tank, so as to increase the pressure of the regenerator; after the activity of the catalyst in the regenerator is lowered by 10-50%, stopping infusing the water vapor, recovering the pressure of the regenerator, and conveying the catalyst to the reactor; enabling the catalyst in the reactor to enter a precipitator for gas-solid separation, and returning the separated catalyst to the regenerator; spraying a hydrocarbon oil raw material into the reactor for catalytic cracking reaction. According to the method, the activity of the fresh catalyst can be rapidly lowered to an equilibrium catalyst level before oil spraying by making full use of the existing devices and conditions, so that the catalyst replacement link in the conventional methods is avoided, and the unit is put into normal operation in shorter time.
Description
Technical field
The present invention relates to the start-up method of catalytic cracking unit, more particularly, is a kind of method that industrial catalyticing cracking device reactor and regenerator system adopt live catalyst to go into operation.
Background technology
Fluid catalytic cracking (FCC) is most important heavy oil lighting process in current petroleum refining industry, along with oils demand progressively increases, constantly has the operation that goes into operation of newly-built catalytic cracking unit in global range.
The start-up process of catalytic cracking full scale plant reactor and regenerator system is generally followed following basic step: first air is injected to revivifier and reactor after by the combustion heating of inflammable gas and/or liquid successively aid burning is indoor, make two devices be warming up to 350 ℃ of-550 ℃ of left and right; Then close the valve in catalyst recycle line between two devices, warm air continues to inject revivifier, and passes into water vapor in reactor; Subsequently catalyzer is injected to revivifier and make catalyzer under the effect of warm air, in revivifier, carry out single device fluidisation; At suitable temperature, in revivifier, spray into combustion oil, make revivifier inner catalyst continue to be warming up to 600 ℃ of left and right; Normal and set up after suitable catalyzer material level until revivifier inner catalyst fluidisation, slowly open the valve on regenerated catalyst line between revivifier and reactor, the part high temperature catalyst in revivifier is transferred in reactor under fluidized state; In turning agent process, need to supplement a certain amount of catalyzer in revivifier, to maintain the material level of revivifier inner catalyst; Question response device inner catalyst there is certain reserve and under the effect of water vapor fluidisation normal after, slowly open the valve on reclaimable catalyst line of pipes between reactor and revivifier, make the catalyzer in reactor be back to revivifier under fluidized state, set up two devices of catalyzer between revivifier and reactor ciculation fluidized; Temperature, pressure and catalyst inventory until two devices reach after set(ting)value, to spraying into hydrocarbon oil crude material in reactor, carry out catalytic cracking reaction and obtain product, complete the start-up process of catalytic cracking full scale plant reactor and regenerator system.
The catalyzer that catalytic cracking full scale plant adopts in start-up process is generally the industrial equilibrium catalyst of taking from allied equipment, also has minority device to adopt the low activity of the special development catalyzer that goes into operation to go into operation.Why in start-up process, do not adopt live catalyst, mainly because the activity of live catalyst is very high, the reaction of hydrocarbon oil crude material on live catalyst will produce a large amount of coke, causes coke a large amount of " accumulation " on catalyzer, and then causes device to turn round.In most cases, even if the feedstock property between similar catalytic cracking unit and product requirement also all exist certain difference, so the catalyzer that the normal operation stage adopts is also incomplete same.In order to reach the products distribution of expection, no matter adopt above-mentioned which kind of scheme that goes into operation, after device smooth running, all must use as this installs custom-designed live catalyst and slowly replace the catalyzer that start-up process adopts.
With adopt the go into operation start-up process of special-purpose catalyst of other device equilibrium catalyst and low activity and compare, directly adopt fresh running catalyzer to go into operation and can avoid catalyzer displacement link, make device within the shorter time, drop into normal operation, thereby save the expense of refinery in start-up process, drop into; But the problem need solving be how before oil spout by the active fast reducing of live catalyst the level to equilibrium catalyst.
The activity that adopts the mode of hydrothermal treatment consists to reduce catalyzer in laboratory is very ripe method.Result of study shows, under catalytic cracking unit routine operation pressure, conventionally need to, under the hot conditions of 730 ℃-830 ℃, adopt 100% water vapor to process and could obtain the catalyzer close with equilibrium catalyst activity catalytic cracking live catalyst.In the stage of going into operation, catalytic cracking full scale plant reaction-regeneration system relies on the type of heating that sprays into fuel combustion to provide system required heat, and owing to being subject to the restriction of device materials and catalyzer tolerable temperature, the temperature of two devices generally will be controlled at below 700 ℃.Visible catalytic cracking unit cannot reach the required temperature condition of laboratory hydrothermal treatment consists in the stage of going into operation.
CN1124899C discloses a kind of catalytic cracking catalyst cyclic polluting, aging method of making, will be dissolved with in metal-organic hydrocarbon oil crude material injecting reactor to contact, react with regenerated catalyst, oil gas after separating reaction and catalyzer, oil gas is sent into subsequent separation system, after reacted catalyzer is aging through stripping, water vapor and flue gas, oxygen-containing gas is regenerated, is delivered to reactor cycles and uses.Live catalyst is after the method is processed, and its every physico-chemical property is all close to industrial equilibrium catalyst.The method is implemented on small-sized, medium-sized experimental installation, and is not suitable for catalytic cracking full scale plant.
CN101927198A and CN101927199A disclose a kind of optionally treatment process of catalytic cracking catalyst of improving, pack live catalyst into dense phase fluidized bed, contact with water vapor, under certain thermal and hydric environment, carry out after aging obtaining aging catalyst, described aging catalyst is joined in industrial catalyticing cracking device.It is more even that the method can make the activity and selectivity of catalytic cracking unit inner catalyst distribute, and the catalytic cracking unit that its enforcement need to turned round provides necessary external conditions, and the catalytic cracking unit in the stage of going into operation cannot adopt the method.
Summary of the invention
The object of the invention is on the basis of existing catalytic cracking full scale plant start-up method, propose a kind of method that catalytic cracking unit adopts live catalyst to go into operation.
Catalytic cracking unit start-up method provided by the invention comprises the following steps:
(1) hot gas phase fluidization medium being injected to For Fcc Regenerator and reactor makes after its intensification, close the valve on regenerated catalyst line and reclaimable catalyst line of pipes between revivifier and reactor, continuation passes into hot gas phase fluidization medium in revivifier and reactor, and live catalyst is packed in revivifier, make catalyzer in revivifier in fluidized state, wherein revivifier is provided with catalyzer degassing vessel;
(2) water vapor is injected in the degassing vessel with revivifier UNICOM and contact with catalyzer, and improve the pressure of regeneration system rapidly, now the catalyzer in degassing vessel is in pressurizeing and the fluidized state of water vapor atmosphere, catalyst activity fast reducing;
(3) increase degassing vessel middle part water vapor injection rate, catalyzer is promoted through the pipeline of degassing vessel top and revivifier dilute phase UNICOM and carries and return to revivifier, the catalyst make-up in revivifier enters degassing vessel, continues steam treatment;
(4) after the activity decline 10%-50% of regeneration system rapidly inner catalyst, stop to injected water steam in degassing vessel, by revivifier Pressure Drop to normal level, open subsequently the valve on regenerated catalyst line, the catalyzer after the active decline of part is delivered to reactor by regenerated catalyst line;
(5) catalyzer in reactor carries out gas solid separation enter settling vessel under the promotion of gas phase fluidization medium in, and isolated catalyzer enters reclaimable catalyst line of pipes;
(6) open the valve on reclaimable catalyst line of pipes, make catalyzer be back to revivifier, set up ciculation fluidized between revivifier and reactor of catalyzer;
(7) to spraying into hydrocarbon oil crude material in reactor, carry out catalytic cracking reaction and obtain reaction product.
Method provided by the invention is to implement like this:
Hot gas phase fluidization medium is injected to For Fcc Regenerator bottom, and introduce in reactor by regenerated catalyst line between revivifier and reactor and reclaimable catalyst line of pipes.Revivifier is provided with catalyzer degassing vessel.One or more among gas after the described fluidizing medium of step (1) is selected from gas, flammable liquid after air, oxygen, inflammable gas burn in air or oxygen and burns in air or oxygen.
Until revivifier and inside reactor temperature, at least reach after 300 ℃, close the valve on regenerated catalyst line and reclaimable catalyst line of pipes.The gas phase fluidization medium of heat continues to inject revivifier, at reactor bottom, injects another strand of gas phase fluidization medium.Fluidizing medium in reactor can be identical with the fluidizing medium in step (1) revivifier, can be also water vapor, preferably water steam.
Live catalyst is packed in revivifier, make catalyzer under the effect of fluidizing medium in fluidized state.Any catalyzer that described catalyzer is used for being applicable to catalytic cracking unit.
When the internal temperature of revivifier reaches more than 350 ℃, can to spray in revivifier at this temperature can spontaneous combustion combustion oil contact with live catalyst and burn,, with the intensification of accelerator activator.
The pressure that improves revivifier, is the preferred 0.5MPa-1.0MPa of 0.5MPa-3.0MPa at pressure, injects superheated vapour in the degassing vessel of Xiang Yu revivifier UNICOM.Maintain fluidized state 1-90 minute in degassing vessel, preferably 15-30 minute; Increase degassing vessel middle part water vapor injection rate, catalyzer is promoted through the pipeline of degassing vessel top and revivifier dilute phase UNICOM and carries and return to revivifier.Meanwhile, the catalyst make-up in revivifier enters degassing vessel, continues steam treatment.Pressure of the present invention all refers to absolute pressure.
Micro-activity decline 10%-50% when revivifier inner catalyst, preferably after decline 15%-30%, stop to degassing vessel injected water steam, by revivifier Pressure Drop to normal level (generally lower than 0.3MPa), open subsequently the valve on regenerated catalyst line, the catalyzer after the active decline of part is delivered to reactor by regenerated catalyst line.Described catalyst activity adopts ASTM D3907 or its to improve one's methods and measures.
Catalyzer in reactor carries out gas solid separation enter settling vessel under the promotion of gas phase fluidization medium in, and isolated catalyzer enters into reclaimable catalyst line of pipes.Open the valve on reclaimable catalyst line of pipes, make catalyzer be back to revivifier, set up ciculation fluidized between revivifier and reactor of catalyzer.Afterwards, to spraying into hydrocarbon oil crude material in reactor, carry out catalytic cracking reaction and obtain reaction product, completing the start-up process of catalytic cracking unit.
The beneficial effect of method provided by the invention is:
Method provided by the invention takes full advantage of the catalytic cracking unit condition that the stage itself can provide that goes into operation, and does not need to change and can implement installing inside, therefore can not affect the normal operation of catalytic cracking unit.
Method provided by the invention can be before oil spout by the active fast reducing of live catalyst the method to the level of equilibrium catalyst, thereby avoided adopting conventional start-up method catalyzer displacement link afterwards, make device within the shorter time, drop into normal operation, thereby save the expense of refinery in start-up process, drop into.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that catalytic cracking unit provided by the invention adopts live catalyst start-up method, and the For Fcc Regenerator shown in Fig. 1 is provided with catalyzer degassing vessel.
Embodiment
Below in conjunction with accompanying drawing, describe method provided by the invention in detail, but the present invention is not therefore subject to any restriction.
As shown in Figure 1, the gas phase fluidization medium of heat is injected the bottom of For Fcc Regenerator 10 by pipeline 1, and by entering degassing vessel 16 communicating pipe 15, entering in reactor 6 and settling vessel 7 by regenerated catalyst 2 again, by reclaimable catalyst transfer lime 8, enter in revivifier 10 simultaneously.Until revivifier 10, reactor 6 and settling vessel 7 internal temperatures, at least reach after 300 ℃, close respectively valve 3 and valve 9 on regenerated catalyst line 2 and reclaimable catalyst line of pipes 8.The gas phase fluidization medium of heat continues to inject revivifier 10 by pipeline 1, in the bottom of reactor 6, through pipeline 4, injects another strand of gas phase fluidization medium.Live catalyst is packed in revivifier 10, make catalyzer under the effect of fluidizing medium in fluidized state.Catalyzer entered in degassing vessel 16 by communicating pipe 15, and the fluidizing medium that contains oxygen injects degassing vessels 16 by pipeline 13, made catalyzer in degassing vessel 16 in fluidized state.When the internal temperature of revivifier 10 reaches more than 350 ℃, can to spray in revivifier 10 at this temperature can spontaneous combustion combustion oil, with the intensification of accelerator activator.By the fluidizing medium that contains oxygen, change pipeline 13 injecting gas into water vapor, water vapour contacts with catalyzer in degassing vessel 16.After contacting with catalyzer, water vapour is by managing 17 tops that enter revivifier 10.By the variable valve 12 on flue gas pipeline 11, the pressure of revivifier 10 is increased to 0.5MPa-3.0Mpa.Now the catalyzer in degassing vessel carries out fluidization treatment under pressure 0.5MPa-3.0MPa, 550 ℃-700 ℃ of temperature, 100% water vapor atmosphere, maintains this state 1-90 minute.By pipeline 14, to the interior injection fluidizing medium of degassing vessel 16 or water vapor, the catalyzer of degassing vessel middle and upper part is delivered to revivifier 10 tops through pipeline 17.Meanwhile, the catalyst make-up in revivifier enters degassing vessel, continues steam treatment.After being so repeated to the micro-activity decline 10%-50% of revivifier inner catalyst, stop injected water steam, by the variable valve 12 on flue gas pipeline 11 by the Pressure Drop of revivifier 10 to normal level, open subsequently the valve 3 on regenerated catalyst line 2, the catalyzer after activity is declined is delivered to reactor 6 by regenerated catalyst line 2.Catalyzer in reactor 6 carries out gas solid separation enter settling vessel 7 under the promotion of the gas phase fluidization medium from pipeline 4 in, and isolated catalyzer enters into reclaimable catalyst line of pipes 8.Open the valve 9 on reclaimable catalyst line of pipes 8, make catalyzer be back to revivifier 10, set up ciculation fluidized between revivifier 10 and reactor 6 of catalyzer.Afterwards, by pipeline 5, to spraying into hydrocarbon oil crude material in reactor 6, carry out catalytic cracking reaction and obtain reaction product, completing the start-up process of catalytic cracking unit.
Below by embodiment, further illustrate method provided by the invention, but the present invention is not therefore subject to any restriction.
The catalyzer using in embodiment is by catalyzer asphalt in Shenli Refinery of Sinopec Group industrial production, and trade names are MMC-2.This catalyzer contains the ZSP zeolite that ultrastable Y－type zeolite and mean pore size are less than 0.7 nanometer.The main physico-chemical property of MMC-2 live catalyst is in Table 1.In embodiment, the micro-activity of catalyzer all adopts ASTMD3907 method to measure.
Embodiment 1
Embodiment 1 explanation adopts method provided by the invention, live catalyst is carried out the effect of hydrothermal treatment consists under pressurized conditions.
Adopt the go into operation condition in stage of the fixed fluidized bed experimental installation simulation of pressurization For Fcc Regenerator to test.By MMC-2 live catalyst pack into fixed fluidized bed in, simultaneously using air as fluidizing medium, after preheating oven is heated to 350 ℃ of left and right, pass into fluidized-bed bottom, the automatic pressure regulating valve by fixed fluidized bed outlet by fixed fluidized bed pressure-controlling at 0.5MPa.Adopt electrically heated mode fixed fluidized bed inner catalyst is heated and be stabilized in 650 ℃.Adopt two-step heating stove by water vapor and after being superheated to 400 ℃, pass into fluidized-bed bottom.Under these conditions catalyzer is carried out to hydrothermal treatment consists 12 hours.The micro-activity of the underlying condition of processing and processing rear catalyst is listed in table 2.
Experiment basic skills with embodiment 1, difference be by fixed fluidized bed pressure-controlling at 0.7MPa, catalyst temperature is controlled at 600 ℃.Under these conditions catalyzer is carried out to hydrothermal treatment consists 9 hours.The micro-activity of the underlying condition of processing and processing rear catalyst is listed in table 2.
Comparative example 1
The effect of hydrothermal treatment consists is carried out in comparative example 1 explanation under the low pressure conditions of comparing with embodiment 1 to live catalyst.
The basic skills of experiment and most of hydrothermal treatment consists condition are with embodiment 1, and difference is at 0.3MPa by fixed fluidized bed pressure-controlling.Main operational condition and the results are shown in table 2.
Comparative example 2
Comparative example 2 explanations, comparing under low pressure conditions with embodiment 1, are carried out the effect of long period hydrothermal treatment consists to live catalyst.
Experiment basic skills and most of hydrothermal treatment consists condition with embodiment 1, difference be by fixed fluidized bed pressure-controlling at 0.3MPa, will extend to 72 hours the treatment time.Main operational condition and the results are shown in table 2.
In table 2, the experimental result of embodiment 1 and embodiment 2 shows, adopt method provided by the invention, under the condition that live catalyst can provide in the catalytic cracking unit stage of going into operation, only by 12 hours hydrothermal treatment consists just can be by activity decreased the level to equilibrium catalyst, illustrate that industrial catalyticing cracking device adopts method provided by the invention to realize and adopts live catalyst to go into operation.Embodiment 1 and comparative example 1 are compared known with comparative example 2, adopted method provided by the invention can significantly accelerate the decay of activity speed of live catalyst, even if under low pressure significantly extend the hydrothermal treatment consists time, also cannot effectively reduce the activity of live catalyst.
Table 1
| Catalyzer | MMC-2 |
| Zeolite content, heavy % | |
| Y | 16 |
| |
12 |
| Physical properties | |
| Specific surface, rice 2/ gram | 258 |
| Pore volume, centimetre 3/ gram | 0.19 |
| Apparent density, gram per centimeter 3 | 0.75 |
| Screening, heavy % | |
| 0-20 micron | 0.8 |
| 0-40 micron | 10.4 |
| 0-80 micron | 70.8 |
| 0-110 micron | 88.5 |
| 0-149 micron | 97.8 |
| > 149 microns | 2.2 |
| Micro-activity | 91 |
Table 2
| Project | Embodiment 1 | |
Comparative example 1 | Comparative example 2 |
| Treatment condition | ||||
| Fluidized-bed temperature, ℃ | 650 | 600 | 650 | 650 |
| Fluidized-bed pressure, MPa | 0.5 | 0.7 | 0.3 | 0.3 |
| The actual treatment time, hour | 24 | 18 | 24 | 72 |
| Process rear catalyst micro-activity | 69 | 65 | 85 | 84 |
Claims (9)
1. a catalytic cracking unit start-up method, is characterized in that the method comprises the following steps:
(1) hot gas phase fluidization medium being injected to For Fcc Regenerator and reactor makes after its intensification, close the valve on regenerated catalyst line and reclaimable catalyst line of pipes between revivifier and reactor, continuation passes into hot gas phase fluidization medium in revivifier and reactor, and live catalyst is packed in revivifier, make catalyzer in revivifier in fluidized state, wherein revivifier is provided with catalyzer degassing vessel;
(2) water vapor is injected in the degassing vessel with revivifier UNICOM and contact with catalyzer, and improve the pressure of regeneration system rapidly, now the catalyzer in degassing vessel is in pressurizeing and the fluidized state of water vapor atmosphere, catalyst activity fast reducing;
(3) increase degassing vessel middle part water vapor injection rate, catalyzer is promoted through the pipeline of degassing vessel top and revivifier dilute phase UNICOM and carries and return to revivifier, the catalyst make-up in revivifier enters degassing vessel, continues steam treatment;
(4) after the activity decline 10%-50% of regeneration system rapidly inner catalyst, stop to injected water steam in degassing vessel, by revivifier Pressure Drop to normal level, open subsequently the valve on regenerated catalyst line, the catalyzer after the active decline of part is delivered to reactor by regenerated catalyst line;
(5) catalyzer in reactor carries out gas solid separation enter settling vessel under the promotion of gas phase fluidization medium in, and isolated catalyzer enters reclaimable catalyst line of pipes;
(6) open the valve on reclaimable catalyst line of pipes, make catalyzer be back to revivifier, set up ciculation fluidized between revivifier and reactor of catalyzer;
(7) to spraying into hydrocarbon oil crude material in reactor, carry out catalytic cracking reaction and obtain reaction product.
2. method according to claim 1, is characterized in that the described pressure of step (2) is 0.5MPa-3.0MPa.
3. method according to claim 2, is characterized in that the described pressure of step (2) is 0.5MPa-1.0MPa.
4. method according to claim 1, the temperature that it is characterized in that revivifier is 550 ℃-700 ℃.
5. method according to claim 4, the temperature that it is characterized in that revivifier is 600 ℃-680 ℃.
6. method according to claim 1, is characterized in that the activity decline 15%-30% of the described catalyzer of step (4).
7. method according to claim 1, is characterized in that one or more among the gas after the described fluidizing medium of step (1) is selected from gas, flammable liquid after air, oxygen, inflammable gas burn in air or oxygen and burns in air or oxygen.
8. method according to claim 1, is characterized in that the degassing vessel inner catalyst fluidisation time is 1-90 minute.
9. method according to claim 8, is characterized in that the degassing vessel inner catalyst stream fluidisation time is 15-30 minute.
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| CN109135801A (en) * | 2017-06-16 | 2019-01-04 | 中国石油化工股份有限公司 | Catalyst cracking method and device |
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| CN110724553B (en) | 2018-07-16 | 2021-04-06 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting dilute phase conveying bed and rapid fluidized bed |
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