CN103666534A - Work starting method for catalytic cracking unit - Google Patents

Work starting method for catalytic cracking unit Download PDF

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Publication number
CN103666534A
CN103666534A CN201210352971.3A CN201210352971A CN103666534A CN 103666534 A CN103666534 A CN 103666534A CN 201210352971 A CN201210352971 A CN 201210352971A CN 103666534 A CN103666534 A CN 103666534A
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catalyst
revivifier
reactor
catalyzer
regenerator
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CN103666534B (en
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李正
孙益群
谢朝钢
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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, loading a fresh catalyst into the regenerator, opening a valve on a catalyst external-circulation pipe, infusing water vapor to the external-circulation pipe, and increasing 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, opening a valve on a regenerated catalyst conveying pipeline, 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, thereby obtaining a reaction product. 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

A kind of catalytic cracking unit start-up method
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 regenerator, 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 outer circulating tube;
(2) open the valve on catalyzer outer circulating tube, in loosening wind entrance injection outer circulating tube by water vapor by outer circulation pipeline, contact with live catalyst, and improve the pressure of revivifier, under the condition of pressurization, use water vapor in outer circulating tube, to process the live catalyst in fluidized state;
(3) after the micro-activity decline 10%-50% of revivifier inner catalyst, change the water vapor that injects outer circulating tube into loosening wind, by revivifier Pressure Drop to normal level, open the valve on regenerated catalyst line, the catalyzer after micro-activity is declined is delivered to reactor by regenerated catalyst line;
(4) catalyzer in reactor carries out gas solid separation enter settling vessel under the promotion of another strand of gas phase fluidization medium in, and isolated catalyzer enters into reclaimable catalyst line of pipes;
(5) 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;
(6) 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 outer circulating tube.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, with the intensification of accelerator activator.
Open the valve on outer circulating tube, in the loosening wind entrance injection outer circulating tube by water vapor by outer circulating tube, contact with live catalyst.Controlling the apparent linear speed of water vapour in outer circulating tube is 0.1 meter per second-0.7 meter per second, preferably 0.1 meter per second-0.5 meter per second.
The pressure that improves revivifier, is the preferred 0.3MPa-1.0MPa of 0.3MPa-3.0MPa at pressure, and temperature is 550 ℃-700 ℃ and preferably under the condition of 600 ℃-680 ℃, processes the live catalyst in fluidized state.Described water vapor is superheat state under the pressure of revivifier.Pressure of the present invention all refers to absolute pressure.
Micro-activity decline 10%-50% when revivifier inner catalyst, preferably after decline 15%-30%, change the water vapor that injects outer circulating tube into loosening wind, 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.
Method provided by the invention is applicable to all fluidizing reactor, fluidization revivifier, catalytic cracking catalysts.Wherein said fluidizing reactor includes but not limited to a kind of or its combination in various forms of riser tubes, various forms of fluidized-bed, various forms of transfer limes, structure and the quantity of described fluidization revivifier are not all limit, and the composition of described catalytic cracking catalyst is not limit.
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 outer circulating tube.
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 introduces in reactor 6 and settling vessel 7 by regenerated catalyst line 2 between revivifier 10 and reactor 6 and reclaimable catalyst line of pipes 8.Until revivifier 10, reactor 6 and settling vessel 7 internal temperatures, at least reach after 300 ℃, close 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 line 4 of reactor 6, 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.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.Open the valve 14 on outer circulating tube 13, in the loosening wind entrance 15 injection outer circulating tubes 13 by water vapor by outer circulating tube 13, contact with live catalyst, controlling the apparent linear speed of water vapour in outer circulating tube 13 is 0.1 meter per second-0.7 meter per second.By the variable valve 12 on flue gas pipeline 11, the pressure of revivifier 10 is increased to 0.3MPa-1.0MPa, at the temperature of 550 ℃-700 ℃, use water vapor in the interior processing of outer circulating tube 13 live catalyst in fluidized state.Described water vapor is superheat state under the pressure of revivifier 10.After the micro-activity decline 10%-50% of revivifier 10 inner catalysts, change the water vapor that injects outer circulating tube 13 into loosening wind, and 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 the active decline of part 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, using air as fluidizing medium, pass into fluidized-bed bottom simultaneously, adopt electrically heated mode fixed fluidized bed inner catalyst is heated and be stabilized in 660 ℃, by water vapor and after being superheated to 400 ℃, pass into fluidized-bed bottom, and stop injecting air in fluidized-bed, controlling the apparent linear speed of water vapour in fluidized-bed is 0.3 meter per second.Automatic pressure regulating valve by fixed fluidized bed outlet by fixed fluidized bed pressure-controlling at 0.4MPa.Under these conditions catalyzer is carried out to hydrothermal treatment consists 24 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 0.2MPa by fixed fluidized bed pressure-controlling.Main operational condition and the results are shown in table 2.
Embodiment 2
Embodiment 2 explanation adopts method provided by the invention, further improves the effect of under the condition of temperature and pressure, live catalyst being carried out hydrothermal treatment consists.
Experiment basic skills with embodiment 1, difference be by fixed fluidized bed pressure-controlling at 2.5MPa, catalyst temperature is controlled at 680 ℃, the apparent linear speed of water vapour in fluidized-bed is 0.6 meter per second.Under these conditions catalyzer is carried out to hydrothermal treatment consists 6 hours.The micro-activity of the underlying condition of processing and processing rear catalyst is listed 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 0.2MPa, 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 24 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
ZSP 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 Embodiment 2 Comparative example 1 Comparative example 2
Treatment condition
Fluidized-bed temperature, ℃ 660 680 660 660
Fluidized-bed pressure, MPa 0.4 2.5 0.2 0.2
The apparent linear speed of water vapor, meter per second 0.3 0.6 0.3 0.3
Treatment time, hour 24 6 24 72
Process rear catalyst micro-activity 69 60 85 84

Claims (11)

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 outer circulating tube;
(2) open the valve on catalyzer outer circulating tube, in loosening wind entrance injection outer circulating tube by water vapor by outer circulation pipeline, contact with live catalyst, and improve the pressure of revivifier, under the condition of pressurization, use water vapor in outer circulating tube, to process the live catalyst in fluidized state;
(3) after the micro-activity decline 10%-50% of revivifier inner catalyst, change the water vapor that injects outer circulating tube into loosening wind, by revivifier Pressure Drop to normal level, open the valve on regenerated catalyst line, the catalyzer after micro-activity is declined is delivered to reactor by regenerated catalyst line;
(4) catalyzer in reactor carries out gas solid separation enter settling vessel under the promotion of another strand of gas phase fluidization medium in, and isolated catalyzer enters into reclaimable catalyst line of pipes;
(5) 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;
(6) 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 0.3MPa-3.0MPa.
3. method according to claim 2, is characterized in that the described pressure of step (2) is 0.3MPa-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 micro-activity decline 15%-30% of the described catalyzer of step (3).
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 described another strand of fluidizing medium of step (4) is identical with the described fluidizing medium of step (1).
9. method according to claim 1, is characterized in that described another strand of fluidizing medium of step (4) is water vapor.
10. method according to claim 1, is characterized in that the apparent linear speed of water vapour in described outer circulating tube is 0.1 meter per second-0.7 meter per second.
11. methods according to claim 10, is characterized in that the apparent linear speed of water vapour in described outer circulating tube is 0.3 meter per second-0.5 meter per second.
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