CN106147828A - A kind of start-up method containing molecular sieve low boiling sulfide heaviness catalyst - Google Patents
A kind of start-up method containing molecular sieve low boiling sulfide heaviness catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of start-up method containing molecular sieve low boiling sulfide heaviness catalyst, in reactor after the first activated process of the sulphided state low boiling sulfide heaviness catalyst of filling, it is passivated again processing: reduce reactor inlet temperature, using the mixture of low alkene light-end products and catalytically cracked gasoline raw material as passivator, by swing type ladder-elevating temperature, make catalytically cracked gasoline ratio in passivated oil match with passivation temperature, complete to be passivated start-up process.The present invention uses catalytically cracked gasoline raw material 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 catalytically cracked 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 a kind of start-up method containing molecular sieve low boiling sulfide heaviness catalyst, mainly
By using the raw material oil product of low olefin-content to pass through swing type ladder-elevating temperature to through overactivation as passivator
The sulphided state catalyst processed is passivated processing, and reaches the purpose avoided temperature runaway, steadily go into operation, it is adaptable to
The start-up process of the low boiling sulfide heaviness catalyst containing molecular sieve, is particularly well-suited to catalytically cracked gasoline
Selective hydrogenation and removing alkadienes, mercaptan sulfur etherificate, the start-up process of thiophene alkylation catalyst.
Background technology
3 components can be divided into according to the sulfur of catalytic gasoline of whole fraction, mercaptan, alkene characteristic distributions:
(1) the light fraction LCN of low-sulfur high olefin content；(2) sulfur and the medium middle fraction MCN of olefin(e) centent；
(3) the heavy distillat HCN of high-sulfur low olefin-content.According to feedstock property and Production requirement, can be to entirely evaporating
Raw material is divided to carry out hydro-upgrading process, it is also possible to concentrate on low boiling range according to alkene in catalytically cracked gasoline
In LCN, sulfide concentrate on the feature in high boiling range HCN, full distillation gasoline is cut into LCN and
HCN, or LCN, MCN, HCN, only carry out hydrodesulfurization to the HCN that sulfur content is higher, favorably
In controlling degree of olefin saturation and keeping octane number.The hydrogen selective hydrocatalyst that faces containing molecular sieve can be by complete
Low boiling sulfide in fraction catalytically cracked gasoline is converted into heavier sulfide by heaviness, with
Being the function of monoolefine by part di-olefins, full feedstock after this treatment can pass through mercaptan sulfur
Most of sulfide of thiophene and following boiling point thereof is converted into higher than thiophene boiling point by etherificate, thiophene alkylation
Component, then carry out follow-up modifying process, owing to more alkene is retained in LCN, MCN through cutting
In and follow-up no longer carry out hydrodesulfurization process, thus solve alkene saturation factor than desulfurization degree increase faster,
The difficult problem that RON loss is bigger, to catalytically cracked gasoline ultra-deep hydrodesulfuration, especially for sour feedstock,
Can effectively keep octane number.
Owing to the acidity of catalyst containing molecular sieve is relatively strong, especially with the initial stage, molecular sieve pores road junction exposes
Acidic site is more, and does not has duct to limit, and on the one hand reactant and product is not had adsorption/desorption selectivity,
On the other hand there is stronger lytic activity and certain polymerization activity.If it is straight after catalyst reduction vulcanizes
Connect introducing raw material, owing to catalyst initial activity is too high, cause temperature rise relatively big, be likely to result in system temperature runaway, with
Time cracking can cause product liquid receive on the low side.Therefore, after catalyst vulcanization or activation terminate, need to be passivated
And after raw material hand-off process, could come into operation raw oil according to design data.
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 develop a kind of going into operation containing molecular sieve low boiling sulfide heaviness catalyst
Method, catalyst, after activation processing, uses the catalytically cracked gasoline after the dilution of low alkene light-end products former
Expect as passivator, by controlling catalytically cracked gasoline feedstock amount and using temperature swing, staged liter
The means of temperature control hydrogenation process, utilize on the coke covering catalyst produced in course of reaction superpower
Active sites, macromole sulfide covering catalyst opening of the channel, reach the purpose of catalyst structure.By controlling
Catalyst after passivation covers carbon amounts, obtains the catalyst that initial activity is suitable, activity stability is excellent, with can
Ensure that catalyst initial performance is stable, can be used for opening containing molecular sieve low boiling sulfide heaviness catalyst
Work process.
The technical problem to be solved is the catalytic cracking vapour only using low alkene light-end products to dilute
Oil raw material is as passivator, by catalyst activity position is passivated process, it is ensured that go into operation and operation process
Middle catalyst activity is suitable, stable.
A kind of start-up method containing molecular sieve low boiling sulfide heaviness catalyst, it is characterised in that reaction
The sulphided state low boiling sulfide heaviness catalyst elder generation activation processing of filling in device, then be passivated processing:
The inlet temperature of reactor is reduced to 100-130 DEG C, by the catalytically cracked gasoline raw material of 30-50wt% with
And the low alkene light-end products of surplus introduce response system as charging, according to the heating rate of 1-40 DEG C/h
Improve the inlet temperature of reactor, when inlet temperature reaches 130-160 DEG C, then by the entrance temperature of reactor
Degree reduces 10-15 DEG C；Then the ratio of catalytically cracked gasoline raw material in charging is improved to 50-70wt%,
When gradually stepping up the inlet temperature of reactor to 160-190 DEG C according to the heating rate of 1-40 DEG C/h, again will
The inlet temperature of reactor reduces 10-15 DEG C, then the ratio of catalytically cracked gasoline raw material in charging is improved
To 100wt%, gradually step up the inlet temperature of reactor to 190-200 according to the heating rate of 1-40 DEG C/h
DEG C, passivating process terminates, and proceeds to normal catalytically cracked gasoline sulfide weight after adjusting reactor inlet temperature
Matter process.In passivating process, preferably improve reactor inlet temperature with 1-20 DEG C/h heating rate.
Described sulphided state low boiling sulfide heaviness catalyst first contacts with hydrogen, low alkene light-end products,
Carrying out activation processing, activated process operating procedure condition is: reaction temperature 150-280 DEG C, reaction pressure
Power 0.5-4.0MPa, volume space velocity 1.5-3.5h-1, hydrogen to oil volume ratio 150-500:1, time of contact 8-48
Hour.
Described passivating process operating procedure condition is: reaction pressure 1.5-2.5MPa, volume space velocity
1.5-3.0h-1, hydrogen to oil volume ratio 3-14:1；Preferably operating procedure condition is: reaction pressure 2.0-2.5MPa,
Volume space velocity 2.5-3.0h-1, hydrogen to oil volume ratio 5-7:1.
Described catalytically cracked gasoline raw material be sulfur content 50-1500mg/kg, mercaptans content 10-500mg/kg,
Thiophene content 0-80mg/kg, olefin(e) centent 35-55v%, diene content 0-2.00gI/100g, arsenic content
Gasoline stocks less than 500 μ g/kg.
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.
The described low boiling sulfide heaviness catalyst containing molecular sieve is sulphided state catalyst, multiple with molecular sieve
Conjunction aluminium oxide is carrier, at supported on carriers vib, group VIII activity component metal, with catalysis
Agent weight is 100% meter, lives containing vib active component oxide 3.5-13.5wt%, group VIII
Property component oxide 9.5-19.0wt%, molecular sieve 5-15wt%, surplus is aluminium oxide, catalyst specific surface
Long-pending 100-150m2/g, aperture accounts for the 10-15% of total pore volume in the hole of 2.0-4.0nm, and aperture is at 9.0-12.0nm
Hole account for the 60-70% of total pore volume, the crystal formation of alumina support is γ type.Described vib activity group
Parting belongs to preferably Mo and/or W, and its oxide content is preferably 7.5-11.0wt%.Described VIII
Race's activity component metal is preferably Ni and/or Co, and its oxide content is preferably 13.0-17.0wt%.
Described molecular sieve is one or more in ZSM-5, β, SAPO-11, molecular sieve combined oxidation
The preparation process of alumina supporter can be preparation method commonly used in the art, such as: in carrier preparation process, and will
After alumina powder, molecular sieve, water etc. are mediated, extruded moulding, 40～120 DEG C of drying, 300～600 DEG C of roastings
Burn 4～6 hours.Described molecular sieve is preferably the compound of ZSM-5 and SAPO-11 or ZSM-5 and β,
Conventional mechanical mixture can be used, it would however also be possible to employ the composite molecular screen of In-situ reaction crystallization, wherein ZSM-5
Weight percentage be 40-60%.
In start-up method of the present invention, after passivating process terminates, the operating procedure condition of heaviness process
For: reaction pressure 1.5-2.5MPa, reaction temperature 90-190 DEG C, volume space velocity 1.5-3.0h-1, hydrogen oil body
Amass and compare 3-14:1；Preferably operating procedure condition is: reaction pressure 2.0-2.5MPa, reaction temperature 90-130
DEG C, volume space velocity 2.5-3.0h-1, hydrogen to oil volume ratio 5-7:1.
Low boiling sulfide heaviness catalyst containing molecular sieve is with thioetherification, alkylation and alkadienes
Selective hydrogenation function, according to this feature of catalyst, the present invention utilizes and proportionally switches catalytic cracking
Catalyst is passivated processing by the process of gasoline stocks, and passivated oil is that a certain proportion of catalytically cracked gasoline is former
Material and the mixture of lightweight low alkene oil product.In passivated oil, catalytically cracked gasoline ratio is relatively low, olefin(e) centent
Time the highest, carry out low-temperature passivation, utilize superpower active sites on the coke covering catalyst that side reaction produces to produce
Permanent passivation effect；In passivated oil, catalytically cracked gasoline ratio is higher, sulfide content height time, carry out
High temperature is passivated, and thioetherification and alkylated reaction now occur on catalyst simultaneously, and utilize that side reaction produces is big
Molecular sulfur compound covers abnormal activity position on molecular sieve pores road junction and produces reversibility passivation effect.
In start-up method of the present invention, make catalytically cracked gasoline ratio and passivation temperature phase in passivated oil
Coupling, to control in passivating process that catalyst covers carbon amounts is 2-5%, it is to avoid catalytically cracked gasoline ratio is higher
Time hold time the longer excessive carbon distribution causing catalyst at low temperature, thus avoid the irreversibility that carbon distribution reacts
The loss of catalyst activity caused.
Compared with prior art, the catalytically cracked gasoline raw material that the present invention uses low alkene light-end products to dilute is made
For passivator, passivating process has permanent passivation and reversibility passivation concurrently, utilizes molecular sieve catalyst opening of the channel
Place's active sites stronger feature more, active, uses carbon distribution, macromole sulfide to cover superpower active sites
Passivation mode is preferentially passivated does not has selective molecular sieve pore passage surface, reaches stably to go into operation, improve catalysis
The purpose of agent activity stability.Meanwhile, passivating process steps up the ratio of catalytically cracked gasoline raw material,
Passivating process terminates to complete the incision of raw oil simultaneously, eliminates the raw material after passivation terminates and introduces process.Adopt
With the start-up process reaction temperature rising of the present invention less than 40 DEG C.
Detailed description of the invention
The present invention relates to a kind of start-up method containing molecular sieve low boiling sulfide heaviness catalyst, specifically
Embodiment is as follows, and wherein, catalyst composition is shown in Table 1, catalytically cracked gasoline raw material and low alkene light-end products
Character is shown in Table 2.
Embodiment 1
By 5kg alumina powder, the composite molecular screen (composite molecular screen of 0.84kg ZSM-5 and SAPO-11
The weight percentage of middle ZSM-5 is 45%) and 0.3kg sesbania powder kneading 5min, by 0.2kg phosphoric acid
It is dissolved in 4L water, joins in mixed powder, extruded moulding after kneading, in atmosphere 100 DEG C of drying,
600 DEG C of roastings 5 hours, prepare the Al2O3 carrier containing molecular sieve.
Dissolving in 32L ammonia by 5.23kg ammonium molybdate, 18.66kg nickel acetate, stirring makes to be completely dissolved joins
Becoming impregnation liquid, impregnated on carrier, in atmosphere 120 DEG C of drying, 420 DEG C of roastings 5 hours, employing contains
The sulfide compound dipping 4h of sulfur 55%, prepares catalyst A.
Above-mentioned for 500ml catalyst A is filled in 500ml adiabatic reactor hydrogenation reactor, with hydrogen, stone
Cerebrol contact carries out activation processing, priming reaction temperature 270 DEG C, reaction pressure 2.0MPa, body for 40 hours
Long-pending air speed 3.0h-1, hydrogen to oil volume ratio 400:1.
After activation of catalyst terminates, the inlet temperature of reactor is down to 120 DEG C, according to catalytic cracking
Gasoline stocks A oil mass 430g/h, the feed rate of Petroleum oil mass 650g/h, by catalytically cracked gasoline and
Petroleum is simultaneously introduced response system；Heating rate according to 3 DEG C/h improves the inlet temperature of reactor, directly
Inlet temperature to reactor reaches 155 DEG C；
The inlet temperature of reactor is down to 140 DEG C, according to catalytically cracked gasoline raw material A oil mass 700g/h,
The feed rate of Petroleum oil mass 380g/h, is simultaneously introduced response system by catalytically cracked gasoline and Petroleum；
Heating rate according to 5 DEG C/h improves the inlet temperature of reactor, until the inlet temperature of reactor reaches
180℃；
The inlet temperature of reactor is down to 170 DEG C, according to catalytically cracked gasoline raw material A oil mass 1080g/h
Feed rate catalytically cracked gasoline is introduced response system；Reactor is improved according to the heating rate of 3 DEG C/h
Inlet temperature, until the inlet temperature of reactor reaches 195 DEG C, passivating process terminates.In passivating process,
The operating procedure condition of reactor is: reaction pressure 2.4MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio
6:1.Catalytically cracked gasoline raw material A is fully introduced into response system, and reactor inlet temperature is adjusted to 140
DEG C, reaction pressure, volume space velocity, hydrogen-oil ratio are constant, and catalytically cracked gasoline is carried out thioetherification, alkylation
And alkadienes selective hydrogenation.
Comparative example 2
Above-mentioned for 500ml catalyst A is filled in 500ml adiabatic reactor hydrogenation reactor, with hydrogen, stone
Cerebrol contact carries out activation processing, priming reaction temperature 270 DEG C, reaction pressure 2.0MPa, body for 40 hours
Long-pending air speed 3.0h-1, hydrogen to oil volume ratio 400:1.After activation of catalyst terminates, by the entrance temperature of reactor
Degree is down to 120 DEG C, according to catalytically cracked gasoline raw material A oil mass 430g/h, Petroleum oil mass 650g/h
Feed rate, is simultaneously introduced response system by catalytically cracked gasoline and Petroleum；Question response device temperature rise no longer increases
After adding, according to catalytically cracked gasoline raw material A oil mass 700g/h, the feed rate of Petroleum oil mass 380g/h,
Catalytically cracked gasoline and Petroleum are simultaneously introduced response system；After question response device temperature rise does not increases, according to urging
Catalytically cracked gasoline is introduced response system by the feed rate changing cracking gasoline feedstock A oil mass 1080g/h,
After reactor bed temperature rise is not further added by, reactor inlet temperature is adjusted to 140 DEG C, to catalytic cracking vapour
Oil carries out thioetherification, alkylation and alkadienes selective hydrogenation, and the operating procedure condition of reactor is:
Reaction pressure 2.4MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 6:1.
Embodiment 2
270g alumina powder, 15g ZSM-5,15g β and 15g sesbania powder are mediated 5min, by 15g
Glacial acetic acid is dissolved in 250ml water, joins in mixed powder, extruded moulding after kneading, in atmosphere
120 DEG C of drying, 540 DEG C of roastings 4 hours, prepare the Al2O3 carrier containing molecular sieve.
Dissolving in 140ml ammonia by 19.62g ammonium molybdate, 79.96g nickel acetate, stirring makes to be completely dissolved joins
Becoming impregnation liquid, impregnated on carrier, in atmosphere 120 DEG C of drying, 450 DEG C of roastings 4 hours, employing contains
The sulfide compound dipping 4h of sulfur 55%, prepares catalyst B.
Above-mentioned for 100ml catalyst B is filled in 100ml adiabatic reactor hydrogenation reactor, with hydrogen, stone
Cerebrol contact carries out activation processing, priming reaction temperature 240 DEG C, reaction pressure 2.4MPa, body for 35 hours
Long-pending air speed 2.0h-1, hydrogen to oil volume ratio 450:1.
After activation of catalyst terminates, the inlet temperature of reactor is down to 100 DEG C, according to catalytic cracking vapour
Oil raw material B oil mass 71g/h, the feed rate of catalytic reformate oil mass 131g/h by catalytically cracked gasoline and are urged
Change reformate and be simultaneously introduced response system；Heating rate according to 15 DEG C/h improves the inlet temperature of reactor,
Until the inlet temperature of reactor reaches 135 DEG C；
The inlet temperature of reactor is down to 125 DEG C, according to catalytically cracked gasoline raw material B oil mass 111g/h,
Catalytically cracked gasoline and catalytic reformate are simultaneously introduced instead by the feed rate of catalytic reformate oil mass 91g/h
Answer system；Heating rate according to 8 DEG C/h improves the inlet temperature of reactor, until the entrance temperature of reactor
Degree reaches 165 DEG C；
The inlet temperature of reactor is down to 150 DEG C, according to catalytically cracked gasoline raw material B oil mass 202g/h
Feed rate catalytically cracked gasoline is introduced response system；Reactor is improved according to the heating rate of 5 DEG C/h
Inlet temperature, until the inlet temperature of reactor reaches 190 DEG C；Passivating process terminates.In passivating process,
The operating procedure condition of reactor is: reaction pressure 2.0MPa, volume space velocity 2.8h-1, hydrogen to oil volume ratio
6.5:1.Catalytically cracked gasoline raw material B is fully introduced into response system, and reactor inlet temperature is adjusted to 95
DEG C, reaction pressure, volume space velocity, hydrogen-oil ratio are constant, and catalytically cracked gasoline is carried out thioetherification, alkylation
And alkadienes selective hydrogenation.
Comparative example 2
Above-mentioned for 100ml catalyst B is filled in 100ml adiabatic reactor hydrogenation reactor, with hydrogen, stone
Cerebrol contact carries out activation processing, priming reaction temperature 240 DEG C, reaction pressure 2.4MPa, body for 35 hours
Long-pending air speed 2.0h-1, hydrogen to oil volume ratio 450:1.After activation of catalyst terminates, by the inlet temperature of reactor
It is down to 100 DEG C, according to catalytically cracked gasoline raw material B oil mass 202g/h, catalytically cracked gasoline is introduced reaction
System, after reactor bed temperature rise is not further added by, is adjusted to 95 DEG C, to urging by reactor inlet temperature
Change cracking gasoline and carry out thioetherification, alkylation and alkadienes selective hydrogenation, the operating procedure of reactor
Condition is: reaction pressure 2.0MPa, volume space velocity 2.8h-1, hydrogen to oil volume ratio 6.5:1.
Embodiment 3
By 22.4kg alumina powder, the composite molecular screen (compound molecule of 1.6kg ZSM-5 and SAPO-11
In sieve, the weight percentage of ZSM-5 is 60%) and 1.2kg sesbania powder kneading 5min, by 1.12kg ice
Acetate dissolution, in 16.8L water, joins in mixed powder, extruded moulding after kneading, 110 DEG C in atmosphere
Dry, 490 DEG C of roastings 6 hours, prepare the Al2O3 carrier containing molecular sieve.
1.52kg ammonium molybdate, 0.36kg ammonium metatungstate are joined in 1.44L ammonia and stir to being completely dissolved
After, adding 4.42kg basic nickel carbonate, stirring, to being completely dissolved, adds 0.64kg cobalt nitrate, stirs
Mix to make to be completely dissolved and be made into impregnation liquid, impregnated on carrier, in atmosphere 110 DEG C of drying, 440 DEG C of roastings
6 hours, use the sulfide compound dipping 4h of sulfur-bearing 55%, prepare catalyst C.
Above-mentioned for 500ml catalyst C is filled in 500ml adiabatic reactor hydrogenation reactor, treats catalyst sulfur
Change after terminating, the inlet temperature of reactor is down to 105 DEG C, according to catalytically cracked gasoline raw material B oil mass
324g/h, the feed rate of Petroleum oil mass 396g/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 140 DEG C；
The inlet temperature of reactor is down to 130 DEG C, according to catalytically cracked gasoline raw material A oil mass 490g/h,
The feed rate of Petroleum oil mass 230g/h, is simultaneously introduced response system by catalytically cracked gasoline and Petroleum；
Heating rate according to 5 DEG C/h improves the inlet temperature of reactor, until the inlet temperature of reactor reaches
190℃；
The inlet temperature of reactor is down to 180 DEG C, according to catalytically cracked gasoline raw material A oil mass 720g/h
Feed rate catalytically cracked gasoline is introduced response system；Reactor is improved according to the heating rate of 3 DEG C/h
Inlet temperature, until the inlet temperature of reactor reaches 200 DEG C, passivating process terminates.In passivating process,
The operating procedure condition of reactor is: reaction pressure 1.8MPa, volume space velocity 2.0h-1, hydrogen to oil volume ratio
10:1.Catalytically cracked gasoline raw material A is fully introduced into response system, and reactor inlet temperature is adjusted to 110
DEG C, reaction pressure, volume space velocity, hydrogen-oil ratio are constant, and catalytically cracked gasoline is carried out thioetherification, alkylation
And alkadienes selective hydrogenation.
The physical property of table 1 catalyst A-C
Table 2 gasoline stocks and low alkene light-end products character
Table 3 embodiment 1-3 and comparative example 1-2 thereof go into operation operation properties of product
Claims (10)
1. the start-up method containing molecular sieve low boiling sulfide heaviness catalyst, it is characterised in that
The sulphided state low boiling sulfide heaviness catalyst elder generation activation processing of filling in reactor, then it is passivated place
Reason: the inlet temperature of reactor is reduced to 100-130 DEG C, by former for the catalytically cracked gasoline of 30-50wt%
The low alkene light-end products of material and surplus introduce reactor as charging, according to the intensification speed of 1-40 DEG C/h
Rate improves the inlet temperature of reactor, when inlet temperature reaches 130-160 DEG C, then by the entrance of reactor
Temperature reduces 10-15 DEG C；Then the ratio of catalytically cracked gasoline raw material in charging is improved to 50-70wt%,
When gradually stepping up the inlet temperature of reactor to 160-190 DEG C according to the heating rate of 1-40 DEG C/h, again will
The inlet temperature of reactor reduces 10-15 DEG C, then the ratio of catalytically cracked gasoline raw material in charging is improved
To 100wt%, gradually step up the inlet temperature of reactor to 190-200 according to the heating rate of 1-40 DEG C/h
DEG C, passivating process terminates；In passivating process, preferably improve reactor inlet with 1-20 DEG C/h heating rate
Temperature.
The side of going into operation containing molecular sieve low boiling sulfide heaviness catalyst the most according to claim 1
Method, it is characterised in that described sulphided state low boiling sulfide heaviness catalyst elder generation and hydrogen, low alkene
Light-end products contact, and carry out activation processing, and activated process 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.
The side of going into operation containing molecular sieve low boiling sulfide heaviness catalyst the most according to claim 1
Method, it is characterised in that in described passivating process, reactor operating procedure condition is: reaction pressure
1.5-2.5MPa, volume space velocity 1.5-3.0h-1, hydrogen to oil volume ratio 3-14:1；Preferably operating procedure condition is:
Reaction pressure 2.0-2.5MPa, volume space velocity 2.5-3.0h-1, hydrogen to oil volume ratio 5-7:1.
The side of going into operation containing molecular sieve low boiling sulfide heaviness catalyst the most according to claim 1
Method, it is characterised in that described catalytically cracked gasoline raw material is sulfur content 50-1500mg/kg, mercaptans content
10-500mg/kg, thiophene content 0-80mg/kg, olefin(e) centent 35-55v%, diene content
0-2.00gI/100g, the arsenic content gasoline stocks less than 500 μ g/kg.
The side of going into operation containing molecular sieve low boiling sulfide heaviness catalyst the most according to claim 1
Method, it is characterised in that described low alkene light-end products are that sulfur content is less than 50mg/kg, olefin(e) centent is less than
5v%, arsenic content are not more than the oil product of 240 DEG C less than 20 μ g/kg, the end point of distillation, preferably by Petroleum, urge
Change at least one in reformate and the constituted group of hydrofined oil.
The side of going into operation containing molecular sieve low boiling sulfide heaviness catalyst the most according to claim 1
Method, it is characterised in that described low boiling sulfide heaviness catalyst is sulphided state catalyst, with molecular sieve
Composite alumina is carrier, at supported on carriers vib, group VIII activity component metal, to urge
Agent weight is 100% meter, containing vib active component oxide 3.5-13.5wt%, group VIII
Active component oxide 9.5-19.0wt%, molecular sieve 5-15wt%, surplus is aluminium oxide, and catalyst compares table
Area is 100-150m2/ g, aperture accounts for the 10-15% of total pore volume in the hole of 2.0-4.0nm, and aperture exists
The hole of 9.0-12.0nm accounts for the 60-70% of total pore volume, and the crystal formation of alumina support is γ type.
The side of going into operation containing molecular sieve low boiling sulfide heaviness catalyst the most according to claim 6
Method, it is characterised in that in described low boiling sulfide heaviness catalyst, contained vib activity group
It is Mo and/or W that parting belongs to, and its oxide content is 7.5-11.0wt%, group VIII activity component metal
Ni and/or Co the most, its oxide content is 13.0-17.0wt%.
8. according to the opening containing molecular sieve low boiling sulfide heaviness catalyst described in claim 6 or 7
Work method, it is characterised in that the described molecular sieve containing molecular sieve low boiling sulfide heaviness catalyst is
One or more in ZSM-5, β, SAPO-11.
9. according to described in claim 6,7 or 8 containing molecular sieve low boiling sulfide heaviness catalyst
Start-up method, it is characterised in that the described molecular sieve containing molecular sieve low boiling sulfide heaviness catalyst
Compound for the compound of ZSM-5 and SAPO-11 or ZSM-5 and β, and the content of wherein ZSM-5
For 40-60wt%.
The side of going into operation containing molecular sieve low boiling sulfide heaviness catalyst the most according to claim 1
Method, it is characterised in that the operating procedure condition of sulfide heaviness process is: reaction pressure 1.5-2.5MPa,
Reaction temperature 90-190 DEG C, volume space velocity 1.5-3.0h-1, hydrogen to oil volume ratio 3-14:1；Preferably operative employee
Skill condition is: reaction pressure 2.0-2.5MPa, reaction temperature 90-130 DEG C, volume space velocity 2.5-3.0h-1,
Hydrogen to oil volume ratio 5-7:1.
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| CN109675643A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The preparation method and sulphided state catalyst of a kind of sulphided state catalyst and application |
| CN116396139A (en) * | 2023-06-08 | 2023-07-07 | 新疆天利石化股份有限公司 | Method for catalytic removal of thiophene aromatic heterocyclic sulfur compounds in styrene in fixed bed reactor |
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| CN101822985A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Pre-treatment method of nickel hydrogenation catalyst |
| CN103785482A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Olefin isomerization catalyst passivation treatment method |
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| US5688736A (en) * | 1991-07-30 | 1997-11-18 | Cri International, Inc. | Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst |
| CN101822985A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Pre-treatment method of nickel hydrogenation catalyst |
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| CN109675643A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The preparation method and sulphided state catalyst of a kind of sulphided state catalyst and application |
| CN116396139A (en) * | 2023-06-08 | 2023-07-07 | 新疆天利石化股份有限公司 | Method for catalytic removal of thiophene aromatic heterocyclic sulfur compounds in styrene in fixed bed reactor |
| CN116396139B (en) * | 2023-06-08 | 2023-08-18 | 新疆天利石化股份有限公司 | Method for catalytic removal of thiophene aromatic heterocyclic sulfur compounds in styrene in fixed bed reactor |
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