CN106147829A - Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst - Google Patents
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of start-up method containing molecular sieve gasoline hydrogenation modifying catalyst, after in gasoline hydrogenation modifying reactor, the sulphided state catalyst upon activation of filling processes, reduce reactor inlet temperature, using the mixture of low alkene light-end products and gasoline stocks as passivator, by swing type ladder-elevating temperature, make gasoline proportionality in passivated oil match with passivation temperature, complete start-up process.The present invention uses gasoline stocks that low alkene light-end products dilute as passivator, and passivating process has permanent passivation and reversibility passivation concurrently, the purpose of the catalyst activity stability that reaches stably to go into operation, improve.Meanwhile, stepping up the ratio of catalytic gasoline raw material in passivating process, passivating process terminates to complete the incision of raw oil simultaneously, eliminates the raw material after passivation terminates and introduces process.
Description
Technical field
The present invention relates to the start-up method containing molecular sieve gasoline hydrogenation modifying catalyst, mainly urge in sulphided state
After the activated process of agent, by using the raw material oil product of low olefin-content to pass through swing type rank as passivator
Ladder heats up and is passivated catalyst for hydro-upgrading, reaches to avoid the purpose of temperature runaway, it is adaptable to all kinds contain
The passivation start-up process of the gasoline hydrogenation modifying catalyst of molecular sieve, is particularly well-suited to produce high-octane rating cleaning
The hydro-upgrading of gasoline blend component.
Background technology
Catalytic gasoline, coker gasoline etc. all contain a large amount of sulfide, need to process could use through hydrodesulfurization
Make gasoline blend component.Wherein, catalytic gasoline and coker gasoline olefin(e) centent are in 30-50v%, hydrodesulfurization
Hydrocarbon fraction can be caused saturated and reduce octane number, the compound catalyst of preparing by metal Yu molecular sieve can
Reach hydrodesulfurization and isomerization, the purpose of aromatisation minimizing loss of octane number.Wherein, active metal is
Co, Mo, Ni etc., be supported on the alumina support containing molecular sieve, and hydrodesulfurization, different mainly occurs
Structure and aromatization, have certain reaction heat to release in course of reaction, needs to carry out reduced sulphur before using
Change processes；Catalyst for hydro-upgrading containing molecular sieve, while hydrodesulfurization, is reacted by isomery and aromatization
The octane number of product can be improved, but owing to the acidity of catalyst containing molecular sieve is relatively strong, particularly make
With the initial stage, the acidic site that molecular sieve pores road junction exposes is more, and does not has duct to limit, and one side is to reaction
Thing and product do not have adsorption/desorption selectivity, on the other hand have stronger lytic activity and certain polymerization is lived
Property.If being introduced directly into raw material after catalyst reduction vulcanizes, owing to catalyst initial activity is too high, cause temperature
Rising relatively big, be likely to result in system temperature runaway, it is on the low side that cracking simultaneously can cause product liquid to receive.Therefore, catalyst sulfur
After change or activation terminate, need to be passivated and after raw material hand-off process, could come into operation former according to design data
Material oil.
At present, hydrogenation plant is in order to solve the too high problem brought of catalyst initial activity, most by adjusting sulfur
Agent and the combination of sulfurized oil and use the method for sulfuration outside device to reduce the initial activity of catalyst, after sulfuration,
Commonly used low temperature, inertia naphthas raw material go into operation, by gradually cutting the side of raw material in inertia oil product
Method, reduces driving temperature runaway risk, or adds cold hydrogen by entrance in reactor design process, reach to fly
The purpose of temperature post-reactor fast cooling.
CN200510047487.X discloses the side of going into operation of a kind of FCC gasoline hydrodesulfurization Olefin decrease technology
Method.On the basis of conventional wet lay sulfidation, select reformed oil as sulfurized oil, vulcanize after terminating,
Strictly control reaction bed temperature, be stepped up FCC gasoline raw material in proportion.This inventive method is permissible
It is applicable to the various sulfidation containing molecular sieve gasoline reforming catalyst, is particularly well-suited to macromolecule sieve content
The sulfidation of gasoline reforming catalyst.Shortcoming is that sulfuration terminates the strict control of switching raw material process needs in proportion
Reaction bed temperature processed, prevents temperature runaway.
At present for the catalyst containing molecular sieve, anhydrous liquid ammonia is a kind of conventional catalyst initial activity passivation
Agent.In device start-up process, injecting a certain amount of anhydrous liquid ammonia, it is adsorbed by acidity of catalyst position after decomposing,
Along with raising and the continuity of the duration of runs of reaction temperature, adsorption potential occurs to resolve reaction, catalyst activity by
Step is recovered, thus reaches the purpose steadily driven.But owing to anhydrous liquid ammonia is that a kind of compressibility liquefaction is poisonous
Gas, has inflammable and explosive feature, needs special storage to transport.Meanwhile, ammonia is adsorbed as reversible reaction,
Therefore passivating process is reversible, although this passivating method is able to ensure that and goes into operation steadily, but cannot remove catalyst
The active sites that upper part is stronger is along with the recovery of catalyst activity, stronger at molecular sieve catalyst opening of the channel
Active sites easily causes the generation of side reaction because not having duct to limit, it is difficult to ensure the activity stabilized of catalyst
Property.
CN201110321354.2 discloses the Startup passivation method of a kind of hydrocracking catalyst, sulfuration knot
Shu Hou, introduces high nitrogen oil in response system, by the ammonia gas absorption of hydrodenitrogeneration reaction generation at catalyst
On complete passivating process.This method avoid the use of anhydrous liquid ammonia, simple to operate.
CN201210432673.5 discloses a kind of hydrocracking unit start-up method, at hydrocracking unit
Load sulfurized hydrogenation catalyst in reaction zone, start-up process: the activation oil that first goes into operation by heat exchange and/or
Heating reaches uniform temperature and passes through beds, is continuously heating to 230 ± 15 DEG C of constant temperature activation, and temperature is extremely
245 ± 15 DEG C introduce nitrogenous light distillates, temperature to 290 ± 15 DEG C or above time, change to nitrogenous heavy distillat
Oil, during temperature to 320 ± 15 DEG C, swap-in raw oil step by step, proceed to normally produce.The method is not injected into liquid
Nitrogen is passivated, but before substep cuts into raw oil, need to introduce respectively low olefin-content nitrogenous light,
Heavy distillate suppresses the initial activity of catalyst as passivator.
Passivating process in CN201110321354.2 and CN201210432673.5 is reversible process,
It is difficult to ensure that the activity stability of catalyst, and all employ the initial boiling point heavy oil product work more than 200 DEG C
For passivated oil, therefore it is not used to the passivation of the relatively low gasoline fraction of the end point of distillation.
Summary of the invention
It is an object of the invention to the exploitation start-up method containing molecular sieve gasoline hydrogenation modifying catalyst, catalyst
After activated process, the gasoline stocks after using low alkene light-end products to dilute is as passivator, by controlling
Gasoline stocks inlet amount and the means using temperature swing, staged to heat up control hydrogenation process, profit
With superpower active sites, macromole aromatic hydrocarbons covering catalyst hole on the coke covering catalyst produced in course of reaction
Road junction, reaches the purpose of catalyst structure.Catalyst after being passivated by control covers carbon amounts, obtains initial activity
Suitably, the excellent catalyst of activity stability, go into operation steadily ensure that, can be used for containing molecular sieve vapour
The start-up process of oil catalyst for hydro-upgrading.
The technical problem to be solved is that the catalytic gasoline only using low alkene light-end products to dilute is former
Expect as passivator, by catalyst activity position being passivated process, it is ensured that go into operation and operation process is urged
Agent activity is suitable, stable.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst, it is characterised in that gasoline hydrogenation modifying is anti-
Answer filling sulphided state catalyst in device first to contact with hydrogen, low alkene light-end products, carry out activation processing, it
After the inlet temperature of hydro-upgrading reactor is adjusted to 220-270 DEG C, by the gasoline stocks of 30-50wt%
And the low alkene light-end products of surplus introduce response system as charging, according to the intensification speed of 1-40 DEG C/h
Rate improves the inlet temperature of hydro-upgrading reactor, when inlet temperature reaches 300-320 DEG C, then will hydrogenation
The inlet temperature of reforming reactor reduces 10-30 DEG C；Then the ratio of gasoline stocks in charging is improved extremely
50-70wt%, gradually steps up the inlet temperature of hydro-upgrading reactor extremely according to the heating rate of 1-40 DEG C/h
When 320-350 DEG C, again the inlet temperature of hydro-upgrading reactor is reduced 10-30 DEG C, in then feeding
The ratio of gasoline stocks improves to 100wt%, gradually steps up reactor according to the heating rate of 1-40 DEG C/h
Inlet temperature is to 350-380 DEG C, and passivating process terminates, and proceeds to normal vapour after adjusting reactor inlet temperature
Oil upgrading processes.In passivating process, preferably improve reactor inlet temperature with 1-20 DEG C/h heating rate.
In described activated process, hydro-upgrading reactor operating procedure condition is: reaction temperature 150-280
DEG C, reaction pressure 0.5-4.0MPa, volume space velocity 1.5-3.5h-1, hydrogen to oil volume ratio 150-500:1, contact
8-48 hour time.
In described passivating process, hydro-upgrading reactor operating procedure condition is: reaction pressure 1.5-2.2MPa,
Volume space velocity 1.5-3.0h-1, hydrogen to oil volume ratio 150-500:1.
Described gasoline stocks is that sulfur content 50-1500mg/kg, olefin(e) centent 35-55v%, arsenic content are less than
The gasoline stocks of 500 μ g/kg, can be catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline, heat
Cracking gasoline or its mixture.
Described low alkene light-end products are that sulfur content is less than 50mg/kg, olefin(e) centent less than 5v%, arsenic content
It is not more than the oil product of 240 DEG C less than 20 μ g/kg, the end point of distillation, can be Petroleum, catalytic reformate, add
Hydrogen refined oil or its mixture.
Described can be regular price gasoline hydrodesulfurization isomerization virtue containing molecular sieve gasoline hydrogenation modifying catalyst
Structure sulphided state catalyst, generally with aluminium oxide or silicon-containing alumina as carrier, comprise vib and/or
Group VIII metal and molecular sieve, on the basis of the weight of catalyst, the content of molecular sieve is 5-70wt%,
In terms of sulfide, group vib tenor is 2-12wt%, and group VIII metal content is 1-7wt%.
Described containing molecular sieve gasoline hydrogenation modifying catalyst, its molecular sieve can be ZSM-5 and/or
SAPO-11, on the basis of catalyst weight, molecular sieve content is 5-70wt%, preferably 30-65wt%,
Tungsten and/or molybdenum count content as 2-12wt% with sulfide, and preferably 2-6wt%, nickel and/or cobalt contain in terms of sulfide
Amount is 1-7wt%, preferably 1-4wt%.
In start-up method of the present invention, after going into operation, the behaviour of hydro-upgrading process in hydro-upgrading reactor
As process conditions it is: reaction pressure 1.5-2.2MPa, reaction temperature 220-450 DEG C, volume space velocity
1.5-3.0h-1, hydrogen to oil volume ratio 150-500:1；Preferably operating procedure condition is: reaction pressure
1.6-2.0MPa, reaction temperature 220-400 DEG C, volume space velocity 1.7-2.2h-1, hydrogen to oil volume ratio 300-400:1.
Containing molecular sieve gasoline hydrogenation modifying catalyst with isomerization and aromatisation function, according to catalyst
This feature, the present invention utilizes and proportionally switches the process of gasoline stocks and carry out the catalyst after activation
Passivation Treatment, passivated oil is a certain proportion of gasoline stocks and the mixture of lightweight low alkene oil product.In passivation
When in oil gasoline proportionality is relatively low, olefin(e) centent is the highest, carries out low-temperature passivation, utilize the coke that side reaction produces
On covering catalyst, superpower active sites produces permanent passivation effect；In passivated oil, catalytic gasoline ratio is relatively
When height, alkene, arene content height, carry out high temperature passivation, aromatisation and different now occurs on catalyst simultaneously
Structureization is reacted, and the macromole aromatic hydrocarbons utilizing side reaction to produce covers abnormal activity position on molecular sieve pores road junction and produces
Reversibility passivation effect.
In start-up method of the present invention, gasoline proportionality in passivated oil is made to match with passivation temperature, control
In passivating process processed, catalyst covers carbon amounts is 2-5%, it is to avoid maintain at low temperature when catalytic gasoline ratio is higher
The time longer excessive carbon distribution causing catalyst, thus the catalyst that the irreversibility avoiding carbon distribution to react causes
Loss of activity.
Compared with prior art, the present invention uses gasoline stocks that low alkene light-end products dilute as passivation
Agent, passivating process has permanent passivation and reversibility passivation concurrently, utilizes activity at molecular sieve catalyst opening of the channel
Position stronger feature more, active, uses carbon distribution, macromole aromatic hydrocarbons to cover the passivation mode of superpower active sites
Preferential passivation does not have selective molecular sieve pore passage surface, reaches stably to go into operation, to improve catalyst activity steady
Purpose qualitatively.Meanwhile, stepping up the ratio of catalytic gasoline raw material in passivating process, passivating process terminates
Complete the incision of raw oil simultaneously, eliminate the raw material after passivation terminates and introduce process.The employing present invention's is blunt
When changing start-up method, passivating process reaction temperature rising is less than 50 DEG C.
Detailed description of the invention
The present invention relates to a kind of start-up method containing molecular sieve gasoline hydrogenation modifying catalyst, specific embodiment
As follows, wherein, containing molecular sieve gasoline hydrogenation modifying catalyst for using technology system as well known to those skilled in the art
Standby load hydrogenation modification sulphided state catalyst, its composition is shown in Table 3, gasoline stocks and low alkene light oil
Moral character matter is shown in Table 4, table 5.
Embodiment 1
500ml gasoline hydrogenation modifying catalyst A is filled in 500ml adiabatic reactor hydrogenation reactor, with
The contact of hydrogen, Petroleum carries out activation processing, priming reaction temperature 270 DEG C, reaction pressure for 40 hours
2.0MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 400:1.
After activation of catalyst terminates, the inlet temperature of reactor is down to 250 DEG C, according to catalytic cracking vapour
Oil raw material oil mass 252g/h, Petroleum oil mass 468g/h, be simultaneously introduced catalytically cracked gasoline and Petroleum
Response system；Heating rate according to 3 DEG C/h improves the inlet temperature of reactor, until the entrance of reactor
Temperature reaches 315 DEG C；
The inlet temperature of reactor is down to 300 DEG C, according to catalytically cracked gasoline raw material oil mass 468g/h, stone brain
Oil oil mass 252g/h, is simultaneously introduced response system by catalytically cracked gasoline and Petroleum；Improve according to 3 DEG C/h
The inlet temperature of reactor, until the inlet temperature of reactor reaches 340 DEG C；
The inlet temperature of reactor is down to 320 DEG C, will according to catalytically cracked gasoline raw material oil mass 720g/h
Catalytically cracked gasoline introduces response system；The inlet temperature of reactor is improved according to 3 DEG C/h, until reactor
Inlet temperature reach 370 DEG C, passivating process terminates.In passivating process, the operating procedure condition of reactor
For: reaction pressure 1.7MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 300:1.Catalytically cracked gasoline is former
Material be fully introduced into response system, reactor inlet temperature is adjusted to 320 DEG C, reaction pressure, volume space velocity,
Hydrogen-oil ratio is constant, and catalytically cracked gasoline is carried out hydro-upgrading.
500ml gasoline hydrogenation modifying catalyst B is filled in 500ml adiabatic reactor hydrogenation reactor, weight
Multiple above-mentioned start-up process.
Comparative example 1
500ml gasoline hydrogenation modifying catalyst A is filled in 500ml adiabatic reactor hydrogenation reactor, with
The contact of hydrogen, Petroleum carries out activation processing, priming reaction temperature 270 DEG C, reaction pressure for 40 hours
2.0MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 400:1.After activation of catalyst terminates, by reactor
Inlet temperature be down to 320 DEG C, according to catalytically cracked gasoline raw material oil mass 720g/h by catalytically cracked gasoline
Introduce response system；The operating procedure condition of reactor is: reaction pressure 1.7MPa, volume space velocity 2.0h-1,
Hydrogen to oil volume ratio 300:1.
500ml gasoline hydrogenation modifying catalyst B is filled in 500ml adiabatic reactor hydrogenation reactor, weight
Multiple above-mentioned hydro-upgrading course of reaction.
Table 1 embodiment 1 and comparative example thereof go into operation operation properties of product
Embodiment 2
500ml gasoline hydrogenation modifying catalyst C is filled in 500ml adiabatic reactor hydrogenation reactor, with
The contact of hydrogen, Petroleum carries out activation processing, priming reaction temperature 240 DEG C, reaction pressure for 35 hours
2.4MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 450:1.
After activation of catalyst terminates, the inlet temperature of reactor is down to 230 DEG C, according to coker gasoline raw material
Oil mass 230g/h, catalytic reformate oil mass 346g/h, be simultaneously introduced coker gasoline and catalytic reformate instead
Answer system；The inlet temperature of reactor is improved, until the inlet temperature of reactor reaches 310 according to 10 DEG C/h
℃；
The inlet temperature of reactor is down to 285 DEG C, according to coker gasoline raw material oil mass 346g/h, catalysis weight
Whole oil oil mass 230g/h, is simultaneously introduced response system by coker gasoline and catalytic reformate；Carry according to 5 DEG C/h
The inlet temperature of high reactor, until the inlet temperature of reactor reaches 340 DEG C；
The inlet temperature of reactor is down to 315 DEG C, according to coker gasoline raw material oil mass 576g/h by coking
Gasoline introduces response system；The inlet temperature of reactor is improved according to 5 DEG C/h, until the entrance temperature of reactor
Degree reaches 360 DEG C；Passivating process terminates.In passivating process, the operating procedure condition of reactor is: reaction
Pressure 2.0MPa, volume space velocity 1.6h-1, hydrogen to oil volume ratio 400:1.Coker gasoline raw material is fully introduced into instead
Answering system, reactor inlet temperature is adjusted to 340 DEG C, reaction pressure, volume space velocity, hydrogen-oil ratio are constant,
Coker gasoline is carried out hydro-upgrading.
500ml gasoline hydrogenation modifying catalyst D is filled in 500ml adiabatic reactor hydrogenation reactor, weight
Multiple above-mentioned start-up process.
Comparative example 2
500ml gasoline hydrogenation modifying catalyst C is filled in 500ml adiabatic reactor hydrogenation reactor, with
The contact of hydrogen, Petroleum carries out activation processing, priming reaction temperature 240 DEG C, reaction pressure for 35 hours
2.4MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio 450:1.After activation of catalyst terminates, by reactor
Inlet temperature rise to 320 DEG C, according to coker gasoline raw material oil mass 230g/h, catalytic reformate oil mass
346g/h, is simultaneously introduced response system by coker gasoline and catalytic reformate；In reactor bed temperature rise no longer
After increase, according to coker gasoline raw material oil mass 346g/h, catalytic reformate oil mass 230g/h, by coking vapour
Oil and catalytic reformate are simultaneously introduced response system；After reactor bed temperature rise is not further added by, according to coking
Coker gasoline is introduced response system by gasoline stocks oil mass 576g/h；It is not further added by reactor bed temperature rise
After, reactor inlet temperature is adjusted to 340 DEG C, coker gasoline is carried out hydro-upgrading.The behaviour of reactor
As process conditions it is: reaction pressure 2.0MPa, volume space velocity 1.6h-1, hydrogen to oil volume ratio 400:1.
500ml gasoline hydrogenation modifying catalyst D is filled in 500ml adiabatic reactor hydrogenation reactor, weight
Multiple above-mentioned start-up process.
Table 2 embodiment 2 and comparative example thereof go into operation operation properties of product
Embodiment 3
Gasoline hydrogenation modifying catalyst A is applied to the catalytic gasoline hydrogenation device of 1,200,000 tons/year.
Contact with hydrogen, Petroleum 48 hours and carry out activation processing, priming reaction temperature 260 DEG C, reaction pressure
1.9MPa, volume space velocity 1.8h-1, hydrogen to oil volume ratio 260:1.After activation terminates, according to catalytic cracking vapour
Oil material flow 64t/h, hydrofined oil oil product flow 78t/h, by catalytically cracked gasoline and hydrofined oil
Being simultaneously introduced response system, simultaneity factor sends product 142t/h outside；Entering of reactor is improved according to 20 DEG C/h
Mouth temperature, until the inlet temperature of reactor reaches 310 DEG C；
The inlet temperature of hydro-upgrading reactor is down to 300 DEG C, according to catalytically cracked gasoline material flow
100t/h, hydrofined oil oil product flow 42t/h, be simultaneously introduced catalytically cracked gasoline and hydrofined oil instead
System, simultaneity factor is answered to send product 142t/h outside；The inlet temperature of reactor is improved according to 8 DEG C/h, until
The inlet temperature of reactor reaches 340 DEG C；
The inlet temperature of hydro-upgrading reactor is down to 330 DEG C, according to catalytically cracked gasoline material flow
142t/h introduces response system, and simultaneity factor sends product 142t/h outside；Entering of reactor is improved according to 8 DEG C/h
Mouth temperature, until the inlet temperature of reactor reaches 370 DEG C；Passivating process terminates.Catalytically cracked gasoline is former
Material is fully introduced into response system, passivating process reactor bed maximum temperaturerise 48 DEG C.
In passivating process, the operating procedure condition of hydro-upgrading reactor is: reaction pressure 1.9MPa, body
Long-pending air speed 1.8h-1, hydrogen to oil volume ratio 260:1.
At the catalyst runs initial stage, the sulfur content of hydrogenated products is 9mg/kg, 0.5 unit of loss of octane number.
After catalyst runs three months, the sulfur content of hydrogenated products is 9mg/kg, 0.3 unit of loss of octane number.
Table 3 gasoline hydrogenation modifying catalyst and composition thereof
| Composition, wt% | Catalyst A | Catalyst B | Catalyst C | Catalyst D |
| Nickel sulfide | - | - | - | 3.6 |
| Magnesium sulfide | - | - | - | 0.7 |
| Molybdenum sulfide | 3.8 | 8.8 | 5.0 | - |
| Cobalt sulfide | 2.2 | 7.0 | 4.1 | - |
| ZSM-5 | 45 | 55 | 35 | 40 |
| SAPO-11 | 15 | 15 | - | 30 |
| Aluminium oxide | Surplus | Surplus | Surplus | Surplus |
Table 4 gasoline stocks and character thereof
| Analysis project | Unit | Catalytically cracked gasoline | Coker gasoline | Analysis method |
| Boiling range FBP | ℃ | 200 | 205 | GB/T 6536 |
| Alkene | Vol% | 40.0 | 35 | GB/T 11132 |
| Sulfur content | mg/kg | 150 | 3000 | SH/T 0689-2000 |
| Arsenic content | μg/kg | 100 | 150 | SH/T 0629-1996 |
Table 5 low alkene light-end products and character thereof
| Analysis project | Unit | Petroleum | Catalytic reformate | Hydrofined oil | Analysis method |
| Boiling range FBP | ℃ | 200 | 198 | 199 | GB/T 6536 |
| Alkene | Vol% | 1.0 | 2.0 | 1.0 | GB/T 11132 |
| Sulfur content | mg/kg | 50 | 10 | 5 | SH/T 0689-2000 |
| Arsenic content | μg/kg | 5 | 2 | 1 | SH/T 0629-1996 |
Claims (10)
1. the start-up method containing molecular sieve gasoline hydrogenation modifying catalyst, it is characterised in that gasoline adds
In hydrogen reforming reactor, the sulphided state catalyst of filling first contacts with hydrogen, low alkene light-end products, lives
Change process, afterwards be passivated process: reduce hydro-upgrading reactor inlet temperature to 220-270 DEG C,
The gasoline stocks of 30-50wt% and the low alkene light-end products of surplus are introduced reactor as charging, presses
Heating rate according to 1-40 DEG C/h improves the inlet temperature of hydro-upgrading reactor, when inlet temperature reaches
When 300-320 DEG C, then the inlet temperature of hydro-upgrading reactor is reduced 10-30 DEG C；Then vapour in feeding
The ratio of oil raw material improves to 50-70wt%, gradually steps up hydro-upgrading according to the heating rate of 1-40 DEG C/h
When the inlet temperature of reactor is to 320-350 DEG C, again the inlet temperature of hydro-upgrading reactor is reduced
10-30 DEG C, then the ratio of gasoline stocks in charging is improved to 100wt%, according to the liter of 1-40 DEG C/h
Temperature speed gradually steps up the inlet temperature of reactor to 350-380 DEG C, and passivating process terminates；In passivating process,
Preferably improve reactor inlet temperature with 1-20 DEG C/h heating rate.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 1, its
Being characterised by, in described activation process, hydro-upgrading reactor operating procedure condition is: reaction temperature
150-280 DEG C, reaction pressure 0.5-4.0MPa, volume space velocity 1.5-3.5h-1, hydrogen to oil volume ratio 150-500:1,
8-48 hour time of contact；In described passivating process, hydro-upgrading reactor operating procedure condition is: anti-
Answer pressure 1.5-2.2MPa, volume space velocity 1.5-3.0h-1, hydrogen to oil volume ratio 150-500:1.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 1, its
Being characterised by, described gasoline stocks is that sulfur content 50-1500mg/kg, olefin(e) centent 35-55v%, arsenic contain
The amount gasoline stocks less than 500 μ g/kg.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 3, its
Being characterised by, described gasoline stocks selects free catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline and heat
At least one in the group that cracking gasoline is constituted.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 1, its
Be characterised by, described low alkene light-end products be sulfur content be less than 50mg/kg, olefin(e) centent less than 5v%,
Arsenic content is not more than the oil product of 240 DEG C less than 20 μ g/kg, the end point of distillation.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 5, its
Being characterised by, described low alkene light-end products select free Petroleum, catalytic reformate and hydrofined oil institute structure
At least one in the group become.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 1, its
Be characterised by, described containing molecular sieve gasoline hydrogenation modifying catalyst with aluminium oxide or silicon-containing alumina as carrier,
Comprise vib and/or group VIII metal and molecular sieve, on the basis of the weight of catalyst, molecule
The content of sieve is 5-70wt%, and in terms of the weight of sulfide, group vib tenor is 2-12wt%, VIII
Race's tenor is 1-7wt%.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 1, its
Be characterised by, described containing molecular sieve gasoline hydrogenation modifying catalyst, its molecular sieve be ZSM-5 and/or
SAPO-11, on the basis of the weight of catalyst, molecular sieve content is 30-65wt%.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 1, its
Be characterised by, described containing in molecular sieve gasoline hydrogenation modifying catalyst, in terms of the weight of sulfide, tungsten and
/ or molybdenum content be 2-12wt%, preferably 2-6wt%, nickel and/or cobalt content be 1-7wt%, preferably 1-4wt%.
Start-up method containing molecular sieve gasoline hydrogenation modifying catalyst the most according to claim 1, its
Being characterised by, in hydro-upgrading reactor, the operating procedure condition of hydro-upgrading process is: reaction pressure
1.5-2.2MPa, reaction temperature 220-450 DEG C, volume space velocity 1.5-3.0h-1, hydrogen to oil volume ratio 150-500:1,
Preferred processing condition is: reaction pressure 1.6-2.0MPa, reaction temperature 220-400 DEG C, volume space velocity
1.7-2.2h-1, hydrogen to oil volume ratio 300-400:1.
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| CN111100688A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for improving stable operation of hydrocracking device |
| CN111100689A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for improving operation safety of hydrocracking device |
| CN112694912A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Naphtha modification method |
| CN116064116A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Method for starting low-activity hydrocracking catalyst |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109777477A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of stable start-up method of hydrocracking catalyst |
| CN111100688A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for improving stable operation of hydrocracking device |
| CN111100689A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for improving operation safety of hydrocracking device |
| CN111100689B (en) * | 2018-10-29 | 2022-04-05 | 中国石油化工股份有限公司 | Method for improving operation safety of hydrocracking device |
| CN111100688B (en) * | 2018-10-29 | 2022-04-08 | 中国石油化工股份有限公司 | Method for improving stable operation of hydrocracking device |
| CN112694912A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Naphtha modification method |
| CN112694912B (en) * | 2019-10-22 | 2022-12-13 | 中国石油化工股份有限公司 | Naphtha modification method |
| CN116064116A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Method for starting low-activity hydrocracking catalyst |
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| CN106147829B (en) | 2018-08-10 |
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