CN107446616A - One kind is hydrocracked start-up method - Google Patents
One kind is hydrocracked start-up method Download PDFInfo
- Publication number
- CN107446616A CN107446616A CN201610365747.6A CN201610365747A CN107446616A CN 107446616 A CN107446616 A CN 107446616A CN 201610365747 A CN201610365747 A CN 201610365747A CN 107446616 A CN107446616 A CN 107446616A
- Authority
- CN
- China
- Prior art keywords
- vulcanizing agent
- hydrocracking catalyst
- catalyst
- temperature
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
- B01J2229/123—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to deactivate outer surface
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses one kind and is hydrocracked start-up method, including following content：Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then constant temperature vulcanization is carried out to hydrocracking catalyst under the conditions of 220~260 DEG C, hydrogen sulfide content in hydrogen to be recycled reduces the addition speed of vulcanizing agent after reaching 3000~5000ppm and lifts hydrocracking catalyst bed temperature, the addition speed of vulcanizing agent is improved when hydrocracking catalyst bed temperature reaches 310 DEG C 330 DEG C, continue to lift temperature to 340 DEG C 350 DEG C and be passed through feedstock oil after constant temperature vulcanization to be reacted, wherein described hydrocracking catalyst contains 0.5% 8% by weight percentage.This method is with short the time required to going into operation, switching raw material and enter steady production state, avoid the consumption of passivator in start-up process and note potential danger existing for ammonia process, energy consumption has not only been saved, and has reduced pollution of the passivator to environment and the harm to human body.
Description
Technical field
The present invention relates to a kind of start-up method being hydrocracked, relate in particular to a kind of without using outer note passivator
The working process method being hydrocracked.
Background technology
Hydrocracking process is in the presence of hydrogen, high temperature, condition of high voltage and catalyst is faced, and makes heavy distillate（VGO、
CGO、DAO）Hydrodesulfurization, hydrodenitrogeneration, polycyclic aromatic hydrocarbon hydrogenation saturation and open loop cracking, are converted into light oil and intermediate oil etc.
The process of purpose product.The hydrocracking catalyst of current domestic industry production is substantially oxidized form.It is industrial new
Catalyst or regenerated catalyst, the active metal component contained by it（Mo、Ni、Co、W）, all it is with oxidation state（MoO3、NiO、
CoO、WO3）Form exist.Basic research and commercial Application practice have shown that, the active metal of most hydrogenation catalysts
Component, its sulphided state have higher hydrogenation activity and activity stability, so before catalyst use, generally to include urging
Several links such as the drying of agent, vulcanization, passivation, swap-in feedstock oil.
Hydrocracking catalyst containing molecular sieve after curing, has very high hydrocracking activity, therefore former in switching
Before material oil, it must take appropriate measures and catalyst is passivated, to suppress its too high initial activity, prevent and avoid oil-feed
During the temperature that is likely to occur ascend to heaven phenomenon, it is ensured that catalyst, equipment and personal safety.Wherein, it is nitrogenous to note anhydrous liquid ammonia etc.
Compound is exactly a kind of passivating method that can effectively suppress catalyst initial activity, is inhaled after the anhydrous liquid ammonia decomposition of injection by catalyst
It is attached, it can effectively suppress the initial activity of catalyst, and with the rise of reaction temperature and the continuity of the duration of runs, acidity of catalyst
Ammonia is adsorbed at center can little by little desorb loss, and catalyst and can recovers its normal activity.But selected passivator without
Aqueous ammonia be compressibility liquefaction toxic gas, be under a certain pressure colourless liquid, have high pressure, inflammable, explosive characteristic, one
As using steel cylinder, automobile, train tank car transport preserve.Not only industrially there is certain danger using anhydrous liquid ammonia, and it is right
The injury of human body is also larger, does not meet safe and healthy environmentally friendly theory.
In addition, hydrocracking unit is typically all to carry out vulcanization under hyperbaric environment to go into operation, and in the prior art, catalyst
Going into operation can select to inject ammonia and be not injected into the two ways of ammonia, but respectively have its pros and cons.
The mode canonical process of injection ammonia is generally：Reactor inlet temperature is controlled at 160 DEG C, introduced to reaction system
Low nitrogen oil, lifting reactor inlet temperature note vulcanizing agent to 180 DEG C, to reaction system.Concentration of hydrogen sulfide reaches in recycle hydrogen
After 0.1v%, for lifting reactor inlet temperature to 230 DEG C, constant temperature vulcanizes at least 8h.After 230 DEG C of constant temperature vulcanize 4 hours, start note
Ammonia pump, start to note ammonia passivation, after note ammonia starts 2 hours, start to note washings before air cooler.After water filling 2 hours, start to analyze
Ammonia content in high score acid water.230 DEG C of constant temperature vulcanizations steady lifting reactor inlet temperature after terminating.When ammonia in high score acid water
When content reaches 0.1w%, it is believed that ammonia has penetrated.Before ammonia penetrates, Cracking catalyst bed inlet temperatures ≯ 250 DEG C are controlled, and
Any bed temperature rise ≯ 5 DEG C.After ammonia penetrates, adjust anhydrous liquid ammonia charge velocity and steadily lift reactor inlet temperature extremely
320 DEG C, constant temperature 8h.
The mode canonical process for being not injected into ammonia is generally：Reactor inlet temperature is controlled at 160 DEG C.Draw to reaction system
Enter low nitrogen oil, lifting reactor inlet temperature notes vulcanizing agent to 180 DEG C, to reaction system.Concentration of hydrogen sulfide reaches in recycle hydrogen
To after 0.1v%, for lifting reactor inlet temperature to 230 DEG C, constant temperature vulcanizes at least 8h.After constant temperature vulcanization terminates, steady lifting is anti-
Answer device inlet temperature.During temperature raising, after Cracking catalyst bed temperature rise reaches 5 DEG C, stop heating, constant temperature 8h.
The passivator such as the anhydrous liquid ammonia injected outside device can make the steady safety of start-up process but need to use compression pump to carry out
Conveying, this not only adds the one-time investment of device, also wastes floor space, simultaneously because the pump belongs to cyclical intermission
The equipment of unlatching, frequent breaks down, and influences the progress that goes into operation, while danger of anhydrous liquid ammonia etc. had described in front,
Its controlling is self-evident；If being injected when Cracking catalyst vulcanizes without passivator outside device, then start-up process
Steady security certainly will reduce, while sulfidation also can shorten or terminate, and have a great impact to the activity of catalyst, from
And the stable operation of catalyst long period may be had influence on.
CN101492613A and CN101492607A discloses the start-up method of hydrocracking process, has certain peace
Quan Xing, convenience, but still fall within and use the mode for forcing note ammonia outside device to inject certain passivator to reaction system to suppress
The activity of cracking agent, there certainly will be the drawbacks of present in the above-mentioned mentioned ammonia of injection in the prior art, can bring certain hidden
Suffer from and endanger.
CN101003749A describes a kind of start-up method of oxidation state hydrocracking catalyst, is related to a kind of catalyst,
More particularly, to one kind in oil refining process relevant oxidation state hydrocracking catalyst.One kind is provided to split using existing hydrogenation
Change under catalysts conditions, the start-up method of the oxidation state hydrocracking catalyst of the presulfurization without carrying out catalyst.This process
Presulfurization is carried out to the catalyst of oxidation state without additional vulcanizing agent again, the problem of avoiding being brought by presulfurization, and partial reduction
Catalyst there is higher hydrogenation cracking activity.This is that a kind of overall process is hydrocracked the side of going into operation without using passivator
Method, there is safety and environmental protection, the characteristics of process is steady, although simple to operate, process is easy, it can be difficult to ensureing oxidation state and list
The lytic activity and activity stability of matter metallic catalyst.
CN103059961A and CN103059969A discloses a kind of Startup passivation method of hydrocracking catalyst.Urging
Agent is passivated the stage toward the high nitrogen naphtha of refining stage introducing, and the ammonia being hydrogenated to by it is used as the progress of passivator counterincision agent
Passivation, so as to reach the purpose without using passivator.Although the work that initial activity is killed to cracking catalyst structure can be played
With, but extra other liquid components of introducing are needed, its control process is comparatively laborious, and effect is not easy to realize, it is difficult to plays
Reduce the purpose of on-stream time.
CN103789023A describes a kind of hydrocracking unit start-up method.In the blunt of hydrocracking unit start-up process
Change the passivation that step carries out catalyst by introducing nitrogenous distillate step by step, anhydrous liquid ammonia can be replaced with nitrogenous distillate,
Start-up process is steady.But still the other liquid components additionally introduced being present, control control is difficult to realize, and during start-up process
Between it is longer.
CN102284299A and CN1602999A is related to a kind of hydrogenation catalyst in hydrogenation reaction ex situ presulfiding-in hydrogenation reaction
The method of activation in device, it completes the vulcanizing agent passivating process of catalyst outside reactor under specific operating mode, but introduce
It is " poisonous substance " and relatively simple containing catalyst in gas, the passivating process of catalyst can not be thoroughly completed, is being transported in addition
And absorption and the excess of passivation gas are difficult to ensure that in sulfidation, easily cause passivation gas not in start-up process
Foot.
CN102921441A describes a kind of preparation method of tungsten phosphide catalyst, and it is passed through nitrogen in preparation process
Stream is passivated to catalyst, although the effect of passivation can be played to a certain extent, the passivation effect of inert gas
It is very poor, hydrocracking process can not be applied to.
CN104593051A and CN104593050A discloses a kind of start-up method of sulfurized hydrogenation catalyst, using adding
The oil film of the chemical substance generation entered is passivated to the exothermic process of sulfide type catalyst, although can thoroughly solve to vulcanize
Process sulphur concentrates the heat management problems of release, but can not be applied to be hydrocracked field, and its oil film generated splits in hydrogenation
It can react or decompose during change, passivation can not be played a part of.
CN102310006A discloses a kind of hydrogenation catalyst regeneration and method for pre-sulphuration, is mainly urged in the hydrogenation of inactivation
Ex situ presulfiding and Passivation Treatment are directly carried out in agent coke combustion.Although the process side of the outer pre-sulfide catalyst of its preparing device
It can go, Power dissipation reductions, but its passivating process, which is still heat release for ex situ presulfiding catalyst, to be played certain suppression and makees
With, can not be applied to be hydrocracked field.
CN104342200A discloses a kind of method of reformed oil selective hydrogenation, and its core is to utilize
" poisonous substance " is passivated to the active metal in catalyst, although significant effect, be not particularly suited for hydrocracking process for
The passivating process of molecular sieve.
Document《Hydrogenation catalyst presulfurizing passivation technology is studied》In detailed describe the blunt of presulfurization hydrogenation catalyst
The reaction mechanism of change process, although catalyst ex situ presulfiding and in-situ presulfurization process can be instructed, it is only applicable to not
It is different from our PASSIVATION MECHANISMs of conventional hydrocracking catalyst in the hydrogenation process that cracking reaction be present, it can not be applied to
Hydrocracking process.
The content of the invention
For the existing problem present in technology that goes into operation, the present invention provides one kind and is hydrocracked start-up method.This method has
Have go into operation, switch raw material and enter steady production state the time required to it is short, avoid consumption and the note ammonia of passivator in start-up process
Potential danger existing for process, energy consumption is not only saved, and reduced pollution of the passivator to environment and the harm to human body.
One kind of the present invention is hydrocracked start-up method, including following content：Low nitrogen is introduced into hydrocracking unit first
Go into operation oil, hydrogen and vulcanizing agent, then carries out constant temperature vulcanization to hydrocracking catalyst under the conditions of 220~260 DEG C, to be recycled
Hydrogen sulfide content in hydrogen reduces the addition speed of vulcanizing agent after reaching 3000~5000ppm and lifts hydrocracking catalyst bed
Layer temperature, the addition speed of vulcanizing agent is improved when hydrocracking catalyst bed temperature reaches 310 DEG C -330 DEG C, continues constant temperature
340 DEG C -350 DEG C are lifted temperature to after vulcanization it is passed through feedstock oil and reacted, wherein described hydrocracking catalyst percentage by weight
Contain 0.5%-8%, preferably 1%-6% nitrogen than meter, the nitrogen comes from low molecule nitride, the nitridation of described low molecule
Thing is the one or more in propylamine, butylamine, amylamine, hexylamine and their various derivatives.
In above-mentioned start-up method, described hydrocracking catalyst content meter by weight contains 10% ~ 45%, preferably 15% ~
35% reactive metal oxides, 45%~70% molecular sieve, the active metal include the one or more in Wo, Mo, Co, Ni,
The molecular sieve includes but is not limited to Y types or USY molecular sieve.
In above-mentioned start-up method, the time of constant temperature vulcanization is carried out under the conditions of described 220~260 DEG C to hydrocracking catalyst
For 5-12h, preferably 6-10h, the addition speed of vulcanizing agent is sulphur per hour during constant temperature vulcanization under the conditions of described 220~260 DEG C
The 2.5-6% of agent theoretical amount.
In above-mentioned start-up method, lifting hydrocracking catalyst bed after constant temperature vulcanization terminates under the conditions of described 220~260 DEG C
Layer temperature is to 310 DEG C -330 DEG C, and the time used is 5-20h, preferably 10-15h, and the addition speed of vulcanizing agent is vulcanizing agent per hour
The 0.5-2% of theoretical amount.
In above-mentioned start-up method, constant temperature vulcanizes 2- when the hydrocracking catalyst bed temperature reaches 310 DEG C -330 DEG C
4h, the addition speed of vulcanizing agent are the 2.5-4% of vulcanizing agent theoretical amount per hour.
In above-mentioned start-up method, the vulcanizing agent theoretical amount is defined as all active metals in catalyst and turned by oxidation state
It is changed into the total amount of vulcanizing agent consumed during sulphided state（In mass）.
In above-mentioned start-up method, described vulcanizing agent is generally one or both of DMDS or carbon disulfide
Mixing.Vulcanizing agent introduces when reactor inlet temperature is 160~200 DEG C.Described low nitrogen go into operation oil be generally nitrogen content it is small
In 100 μ gg-1Straight-run diesel oil or hydrogenation after diesel oil.
In above-mentioned start-up method, the MPa of operating pressure 6.0~16.0, hydrogen to oil volume ratio 300: 1~1500: 1, volume space velocity
For 0.1~5.0 h-1；The MPa of preferred operations pressure 8.0~15.0, hydrogen to oil volume ratio 800: 1~1000: 1.
In above-mentioned start-up method, described hydrocracking catalyst is prepared one of with the following method：First in routine
Low molecular nitride is loaded on hydrocracking catalyst, is then made or is loaded on component is hydrocracked low after drying
The nitride of molecule, dry back loading active metal component and hydrocracking catalyst or the mistake in catalyst kneading and compacting is made
Low molecular nitride is added in journey.Load low molecule nitride can use infusion process or be passed through low molecule nitride steaming process
It is made.It is 50~150 DEG C to load the drying temperature after low molecule nitride, and drying time is 2~8h.Described low molecule nitridation
Thing is the one or more in propylamine, butylamine, amylamine, hexylamine and their various derivatives.Described be hydrocracked in component loads
Low molecular nitride preferably omits roasting process after drying, supported active metals.
In above-mentioned start-up method, drying process preferably carries out stage drying after loading low molecule nitride, dries first extremely
Water content is that 10%-50% stops drying（Water content is counted using water contained before drying as 100%）, normal temperature aging 1-2h is down to, so
After continue drying.Above-mentioned drying process is advantageous to improve nitride with the interaction of Cracking Component internal gutter, makes nitride
It is dispersed in acidic components.
In above-mentioned start-up method, the Cracking Component involved by catalyst preparation includes but is not limited to Y types or USY molecular sieve.
Described conventional hydrocracking catalyst includes hydrogenation active metals, molecular sieve component and alumina support.Hydrogenation active metals
Including the one or more mixing in Wo, Mo, Co, Ni, molecular sieve component includes Y types or USY molecular sieve.The conventional hydro splits
Changing catalyst includes carrier and the hydrogenation metal loaded.On the basis of the weight of catalyst, hydrogenation metal generally includes element
Metal component of group VIB in periodic table, as tungsten and/or molybdenum are calculated as 10% ~ 35%, preferably 15% ~ 30% with oxide；VIIIth race gold
Category such as nickel and/or cobalt is calculated as 1% ~ 7%, preferably 1.5% ~ 6% with oxide, and carrier is molecular sieve and aluminum oxide, mainly emphasizes point
The content of son sieve, generally 45%~70%.
Compared with prior art, start-up process has been carried out great innovation by the present invention, in existing start-up process, one
As need it is outer filling ammonia pump carry out catalyst Passivation Treatment, both have lost resource and wasted the time, if compulsory cancellation
Passivating process, then due to the initial activity that Cracking catalyst is too high, in order to avoid temperature runaway or overtemperature, switching occur for catalyst
The temperature spot of raw material will certainly significantly shift to an earlier date, and can so cause the poisoning of catalyst to a certain extent, on the other hand, sulphur
The insufficient reduction for also resulting in catalyst activity changed, it is unfavorable for the long period steady production of device.The present invention is in order to make up
The deficiency of existing process technology, hydrocracking catalyst transformation innovation is subjected to according to the requirement of technical process, will have been gone into operation blunt
Change process is upgraded, and the characteristic of nitrogen substance can be made full use of to obtain preferable comprehensive process effect, do not influenceing to urge
The vulcanization work of catalyst is completed on the basis of agent activity, reduces the consumption for even cancelling outer note passivator to greatest extent,
Human and material resources not only can be largely saved, while it also avoid the murder by poisoning of the pollution and passivator of environment to human body, were both dropped
Low operation difficulty with it is dangerous, investment overall in start-up process can be reduced again.
In technical process, the inventive method is applied to wet in hydrocracking unit by the catalyst containing passivation component
In method start-up process, it can avoid noting in the device invested and extend catalyst as requested of ammonia equipment and strengthen sulfidation,
Catalyst activity is improved, in addition to greatest extent using compound decomposition/ammonia caused by release/subtractive process to Cracking catalyst
It is passivated, solves the discharge or subsequent treatment work of toxicant, reached the purpose of resource rational utilization, had simultaneously
Have the advantages that the saving energy, technological process are simple, operation is convenient, environmentally friendly low-carbon.
Additionally due to the inventive method is good for the passivation effect of catalyst, sulfidation is abundant, and process conditions are suitable,
Can further accelerator activator initial activity stabilization process, make enterprise earlier produce qualified products.
Embodiment
Further illustrate that a kind of wet method of hydrocracking catalyst of the present invention goes into operation with reference to embodiment and comparative example
The functions and effects of method.Oily and feedstock oil the property that goes into operation used in following embodiments and comparative example is shown in Table 1, wherein opening
Work oil is less than 100 μ gg for nitrogen content-1Straight-run diesel oil, vulcanizing agent uses DMDS.
Table 1 go into operation oil and feedstock oil main character
Embodiment 1
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 220 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 8h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 4% of amount, the hydrogen sulfide content in hydrogen to be recycled reach that the addition speed of vulcanizing agent is reduced after 4000ppm is vulcanizing agent per hour
Theoretical amount 1% and lift 320 DEG C of hydrocracking catalyst bed temperature, the time used is 15h, works as hydrocracking catalyst
Bed temperature improves vulcanizing agent addition speed when reaching 320 DEG C is the 3% of vulcanizing agent theoretical amount per hour, continues constant temperature sulphur
Change to lift temperature to 345 DEG C and be passed through feedstock oil after 3h and reacted, wherein described hydrocracking catalyst contains by weight percentage
There is 5% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen comes from tri-n-amyl amine.Institute
The preparation process for stating catalyst is that load tri-n-amyl amine is made on the catalyst of routine, and drying temperature is 130 DEG C after load, is done
The dry time is 5h.Sulfidation operating condition is operating pressure 15MPa, and hydrogen to oil volume ratio 1000: 1, volume space velocity is 0.8 h-1。
Embodiment 2
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 230 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 8h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 5% of amount, the hydrogen sulfide content in hydrogen to be recycled reach that the addition speed of vulcanizing agent is reduced after 5000ppm is vulcanizing agent per hour
Theoretical amount 1.5% and lift 325 DEG C of hydrocracking catalyst bed temperature, the time used is 13h, works as hydrocracking catalyst
Agent bed temperature improves vulcanizing agent addition speed when reaching 325 DEG C is the 4% of vulcanizing agent theoretical amount per hour, continues constant temperature
Lift temperature to 345 DEG C after vulcanization 2h and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst is by weight percentage
Tri-n-amyl amine is come from containing 5% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen.
The preparation process of the catalyst is that load tri-n-amyl amine is made on the catalyst of routine, and drying temperature is 150 DEG C after load,
Drying time is 6h.Sulfidation operating condition is operating pressure 15MPa, hydrogen to oil volume ratio 1000: 1, volume space velocity 0.8
h-1。
Embodiment 3
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 240 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 10h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 3% of amount, the hydrogen sulfide content in hydrogen to be recycled reach that the addition speed of vulcanizing agent is reduced after 3000ppm is vulcanizing agent per hour
Theoretical amount 0.8% and lift 330 DEG C of hydrocracking catalyst bed temperature, the time used is 10h, works as hydrocracking catalyst
Agent bed temperature improves vulcanizing agent addition speed when reaching 330 DEG C is the 3% of vulcanizing agent theoretical amount per hour, continues constant temperature
Lift temperature to 340 DEG C after vulcanization 4h and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst is by weight percentage
Tri-n-amyl amine is come from containing 4% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen.
The preparation process of the catalyst is to load tri-n-amyl amine on component is hydrocracked to be made, and drying temperature is 100 DEG C after load,
Drying time is 8h.Sulfidation operating condition is operating pressure 15MPa, hydrogen to oil volume ratio 1000: 1, volume space velocity 0.8
h-1。
Embodiment 4
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 230 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 6h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 4% of amount, the hydrogen sulfide content in hydrogen to be recycled reach that the addition speed of vulcanizing agent is reduced after 4000ppm is vulcanizing agent per hour
Theoretical amount 1.2% and lift 325 DEG C of hydrocracking catalyst bed temperature, the time used is 11h, works as hydrocracking catalyst
Agent bed temperature improves vulcanizing agent addition speed when reaching 325 DEG C is the 3.5% of vulcanizing agent theoretical amount per hour, is continued permanent
Lift temperature to 345 DEG C after temperature vulcanization 4h and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst is by weight percentage
Meter comes from three positive penta containing 3.5% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen
Amine.The preparation process of the catalyst is that load tri-n-amyl amine is made on the catalyst of routine, and drying temperature is 120 after load
DEG C, drying time 4h, it is 30% stopping drying drying to water content（Water content is counted using water contained before drying as 100%）,
Normal temperature aging 2h is down to, then proceedes to lift temperature to 120 DEG C of dry 4h.Sulfidation operating condition is operating pressure 15MPa, and hydrogen is oily
Volume ratio 1000: 1, volume space velocity are 0.8 h-1。
Embodiment 5
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 230 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 6h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 3.5% of amount, the hydrogen sulfide content in hydrogen to be recycled, which reaches, reduces the addition speed of vulcanizing agent after 4000ppm to vulcanize per hour
Agent theoretical amount 2% and lift 325 DEG C of hydrocracking catalyst bed temperature, the time used is 15h, works as hydrocracking catalyst
Agent bed temperature improves vulcanizing agent addition speed when reaching 325 DEG C is the 3.5% of vulcanizing agent theoretical amount per hour, is continued permanent
Lift temperature to 340 DEG C after temperature vulcanization 4h and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst is by weight percentage
Meter comes from three positive fourths containing 3% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen
Amine.The preparation process of the catalyst is that load tri-n-butylamine is made on the catalyst of routine, and drying temperature is 140 after load
DEG C, drying time 6h.Sulfidation operating condition is operating pressure 15MPa, hydrogen to oil volume ratio 1000: 1, and volume space velocity is
0.8 h-1。
Embodiment 6
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 220 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 12h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 4% of amount, the hydrogen sulfide content in hydrogen to be recycled reach that the addition speed of vulcanizing agent is reduced after 5000ppm is vulcanizing agent per hour
Theoretical amount 1.8% and lift 320 DEG C of hydrocracking catalyst bed temperature, the time used is 11h, works as hydrocracking catalyst
Agent bed temperature improves vulcanizing agent addition speed when reaching 320 DEG C is the 3.5% of vulcanizing agent theoretical amount per hour, is continued permanent
Lift temperature to 345 DEG C after temperature vulcanization 2h and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst is by weight percentage
Meter comes from three positive fourths containing 4% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen
Amine.The preparation process of the catalyst is that load tri-n-butylamine is made on the catalyst of routine, and drying temperature is 120 after load
DEG C, drying time 8h.Sulfidation operating condition is operating pressure 15MPa, hydrogen to oil volume ratio 1000: 1, and volume space velocity is
0.8 h-1。
Embodiment 7
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 240 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 8h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 5% of amount, the hydrogen sulfide content in hydrogen to be recycled reach that the addition speed of vulcanizing agent is reduced after 5000ppm is vulcanizing agent per hour
Theoretical amount 1% and lift 325 DEG C of hydrocracking catalyst bed temperature, the time used is 10h, works as hydrocracking catalyst
Bed temperature improves vulcanizing agent addition speed when reaching 325 DEG C is the 4% of vulcanizing agent theoretical amount per hour, continues constant temperature sulphur
Change to lift temperature to 345 DEG C and be passed through feedstock oil after 4h and reacted, wherein described hydrocracking catalyst contains by weight percentage
There is 5.5% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen comes from tri-n-butylamine.
The preparation process of the catalyst is to load tri-n-butylamine on component is hydrocracked to be made, and drying temperature is 110 DEG C after load,
Drying time is 4h, and it is 50% stopping drying drying to water content（Water content is counted using water contained before drying as 100%）, it is down to
Normal temperature aging 2h, then proceed to lift temperature to 110 DEG C of dry 2h.Sulfidation operating condition is operating pressure 15MPa, hydrogen oil volume
Than 1000: 1, volume space velocity is 0.8 h-1。
Embodiment 8
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 220 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 8h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 3% of amount, the hydrogen sulfide content in hydrogen to be recycled reach that the addition speed of vulcanizing agent is reduced after 3000ppm is vulcanizing agent per hour
Theoretical amount 0.8% and lift 320 DEG C of hydrocracking catalyst bed temperature, the time used is 14h, works as hydrocracking catalyst
Agent bed temperature improves vulcanizing agent addition speed when reaching 320 DEG C is the 2.5% of vulcanizing agent theoretical amount per hour, is continued permanent
Lift temperature to 350 DEG C after temperature vulcanization 2h and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst is by weight percentage
Meter has come from three just containing 2% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen
Amine.The preparation process of the catalyst is to load three n-hexylamines on the catalyst of routine to be made, and drying temperature is 150 after load
DEG C, drying time 8h.Sulfidation operating condition is operating pressure 15MPa, hydrogen to oil volume ratio 1000: 1, and volume space velocity is
0.8 h-1。
Embodiment 9
Low nitrogen is introduced into hydrocracking unit first to go into operation oil, hydrogen and vulcanizing agent, then hydrogenation is split under the conditions of 230 DEG C
Change catalyst and carry out constant temperature vulcanization, the time of constant temperature vulcanization is 10h, and the addition speed of vulcanizing agent is used for vulcanizing agent per hour is theoretical
The 4.5% of amount, the hydrogen sulfide content in hydrogen to be recycled, which reaches, reduces the addition speed of vulcanizing agent after 4500ppm to vulcanize per hour
Agent theoretical amount 1.2% and lift 325 DEG C of hydrocracking catalyst bed temperature, the time used is 10h, is urged when being hydrocracked
Agent bed temperature improves vulcanizing agent addition speed when reaching 325 DEG C is the 2.9% of vulcanizing agent theoretical amount per hour, is continued
Lift temperature to 345 DEG C after constant temperature vulcanization 4h and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst percentage by weight
Than meter three are being come from containing 2.5% nitrogen, 5% nickel oxide, 16% molybdenum oxide, 55% Y type molecular sieve, the nitrogen just
Hexylamine.The preparation process of the catalyst is made to load three n-hexylamines on component is hydrocracked, and drying temperature is after load
150 DEG C, drying time 3h, it is 20% stopping drying drying to water content（Water content is using water contained before drying as 100%
Meter）, normal temperature aging 2h is down to, then proceedes to lift temperature to 150 DEG C of dry 3h.Sulfidation operating condition is operating pressure 15MPa,
Hydrogen to oil volume ratio 1000: 1, volume space velocity are 0.8 h-1。
Comparative example 1
Start-up process according to conventional hydrocracking device is gone into operation, and reactor inlet temperature is controlled at 160 DEG C, to reaction
The low nitrogen oil of system import, lifting reactor inlet temperature note vulcanizing agent to 180 DEG C, to reaction system.The hydrogen sulfide in recycle hydrogen
After concentration reaches 0.1v%, for lifting reactor inlet temperature to 230 DEG C, constant temperature vulcanizes at least 8h.230 DEG C of constant temperature vulcanize 4 hours
Afterwards, start note ammonia pump, start to note ammonia passivation, after note ammonia starts 2 hours, start to note washings before air cooler.Water filling 2 hours
Afterwards, start to analyze ammonia content in high score acid water.230 DEG C of constant temperature vulcanizations steady lifting reactor inlet temperature after terminating.Work as height
When ammonia content reaches 0.1w% in point acid water, it is believed that ammonia has penetrated.Before ammonia penetrates, Cracking catalyst bed inlet temperature is controlled
≯ 250 DEG C of degree, and any bed temperature rise ≯ 5 DEG C.After ammonia penetrates, adjust anhydrous liquid ammonia charge velocity and steadily lift reactor
Inlet temperature then slowly lifts temperature and progressively switching feedstock oil is transferred to normal production to 320 DEG C, constant temperature 8h.What is used urges
The composition that agent does not carry out nitrogen-containing compound dipping with the catalyst in embodiment 1~9 is consistent.
Comparative example 2
Reactor inlet temperature is controlled at 160 DEG C.Low nitrogen oil, lifting reactor inlet temperature to 180 are introduced to reaction system
DEG C, note vulcanizing agent to reaction system.After concentration of hydrogen sulfide reaches 0.1v% in recycle hydrogen, lifting reactor inlet temperature to 230
DEG C, constant temperature vulcanization at least 8h.After constant temperature vulcanization terminates, reactor inlet temperature is steadily lifted.During temperature raising, when cracking is urged
After agent bed temperature rise reaches 5 DEG C, stop heating, constant temperature 8h, then slowly lift temperature and progressively switching feedstock oil is transferred to just
Often production.The composition that the catalyst used does not carry out nitrogen-containing compound dipping with the catalyst in embodiment 1~9 is consistent.
The effect of above-described embodiment and comparative example is contrasted, the results are shown in Table 2.
Table 2
The maximum feature that embodiment and comparative example above can be seen that the start-up method is lived not influenceing catalyst vulcanization
On the basis of property, for some drawbacks present in existing start-up method, in particular for produced problem in passivating process,
Processing is passivated using the optimization improvement of enterprise's catalyst, it is possible thereby to largely save the consumption of passivator in start-up process
Measure and go into operation, switch raw material, the time of Initial stability process, while also eliminate the potential safety hazard of passivator poisoning, save
Investment, there is very big advantage on human and material resources.
Claims (12)
1. one kind is hydrocracked start-up method, it is characterised in that：Including following content：Introduced first into hydrocracking unit low
Nitrogen goes into operation oil, hydrogen and vulcanizing agent, then carries out constant temperature vulcanization to hydrocracking catalyst under the conditions of 220~260 DEG C, waits to follow
Hydrogen sulfide content in ring hydrogen reduces the addition speed of vulcanizing agent after reaching 3000~5000ppm and lifts hydrocracking catalyst
Bed temperature, the addition speed of vulcanizing agent is improved when hydrocracking catalyst bed temperature reaches 310 DEG C -330 DEG C, continued permanent
Lift temperature to 340 DEG C -350 DEG C after temperature vulcanization and be passed through feedstock oil and reacted, wherein described hydrocracking catalyst by weight hundred
Divide and contain 0.5%-8%, preferably 1%-6% nitrogen than meter, the nitrogen comes from low molecule nitride, described low molecule nitrogen
Compound is the one or more in propylamine, butylamine, amylamine, hexylamine and their various derivatives.
2. according to the method for claim 1, it is characterised in that：Described hydrocracking catalyst content meter by weight contains
10% ~ 45% reactive metal oxides, 45%~70% molecular sieve, the active metal include one kind in Wo, Mo, Co, Ni
Or it is several, the molecular sieve includes but is not limited to Y types or USY molecular sieve.
3. according to the method for claim 1, it is characterised in that：To hydrocracking catalyst under the conditions of described 220~260 DEG C
The time for carrying out constant temperature vulcanization be 5-12h, preferably 6-10h, vulcanizing agent during constant temperature vulcanizes under the conditions of described 220~260 DEG C
Add 2.5-6% of the speed for vulcanizing agent theoretical amount per hour.
4. according to the method for claim 1, it is characterised in that：Constant temperature vulcanization carries after terminating under the conditions of described 220~260 DEG C
Hydrocracking catalyst bed temperature is risen to 310 DEG C -330 DEG C, the time used is 5-20h, preferably 10-15h, the addition of vulcanizing agent
Speed is the 0.5-2% of vulcanizing agent theoretical amount per hour.
5. according to the method for claim 1, it is characterised in that：The hydrocracking catalyst bed temperature reach 310 DEG C-
Constant temperature vulcanizes 2-4h at 330 DEG C, and the addition speed of vulcanizing agent is the 2.5-4% of vulcanizing agent theoretical amount per hour.
6. according to the method for claim 1, it is characterised in that：Described vulcanizing agent is DMDS or carbon disulfide
One or both of mixing.
7. according to the method for claim 1, it is characterised in that：The MPa of operating pressure 6.0~16.0 in start-up process, hydrogen oil
Volume ratio 300: 1~1500: 1, volume space velocity are 0.1~5.0 h-1。
8. according to the method for claim 7, it is characterised in that：The MPa of operating pressure 8.0~15.0 in start-up process, hydrogen oil
Volume ratio 800: 1~1000: 1.
9. according to the method for claim 1, it is characterised in that：Described hydrocracking catalyst is one of with the following method
Prepare：Low molecular nitride is loaded on the hydrocracking catalyst of routine first, is then made or is adding after drying
Load low molecular nitride on hydrogen Cracking Component, dry back loading active metal component be made hydrocracking catalyst or
Low molecular nitride is added during catalyst kneading and compacting.
10. according to the method for claim 9, it is characterised in that：Load low molecule nitride is using infusion process or is passed through low
Molecule nitride steaming process is made.
11. according to the method for claim 9, it is characterised in that：Load the drying temperature after low molecule nitride for 50~
150 DEG C, drying time is 2~8h.
12. according to the method for claim 11, it is characterised in that：Drying process is preferably carried out after load low molecule nitride
Stage drying, it is that 10%-50% stops drying drying first to water content, is down to normal temperature aging 1-2h, then proceedes to drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610365747.6A CN107446616B (en) | 2016-05-30 | 2016-05-30 | One kind being hydrocracked start-up method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610365747.6A CN107446616B (en) | 2016-05-30 | 2016-05-30 | One kind being hydrocracked start-up method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107446616A true CN107446616A (en) | 2017-12-08 |
| CN107446616B CN107446616B (en) | 2019-08-06 |
Family
ID=60484624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610365747.6A Active CN107446616B (en) | 2016-05-30 | 2016-05-30 | One kind being hydrocracked start-up method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107446616B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111729690A (en) * | 2019-03-25 | 2020-10-02 | 中国石油化工股份有限公司 | Method for passivating sulfuration type hydrocracking catalyst by using ammonia outside reactor and passivated catalyst |
| CN113083376A (en) * | 2019-12-23 | 2021-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | Passivation method of hydrocracking catalyst |
| CN113117762A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Hydrocracking catalyst pretreatment method |
| CN113122317A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Hydrogen introduction method after shutdown of hydrocracking device |
| CN116064079A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Start-up method of diesel hydrogenation device |
| CN116064134A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Start-up method of coal synthetic oil hydrocracking device |
| CN116064133A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Method for starting coal tar hydrogenation device |
| CN116064134B (en) * | 2021-10-29 | 2024-05-31 | 中国石油化工股份有限公司 | Start-up method of coal synthetic oil hydrocracking device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417299A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Pre-sulfurizing process of hydrogenating catalyst |
| CN1611577A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Prevulcanizing method for hydrogenating catalyst |
| CN1861256A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Treatment method before application of hydrogenation catalyst |
| CN101088615A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Process of treating hydrogenation catalyst before application |
| CN102465008A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Sulfuration method of catalyst for hydrocracking technology |
| CN103059940A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Startup method of hydrocracking device |
-
2016
- 2016-05-30 CN CN201610365747.6A patent/CN107446616B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417299A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Pre-sulfurizing process of hydrogenating catalyst |
| CN1611577A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Prevulcanizing method for hydrogenating catalyst |
| CN1861256A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Treatment method before application of hydrogenation catalyst |
| CN101088615A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Process of treating hydrogenation catalyst before application |
| CN102465008A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Sulfuration method of catalyst for hydrocracking technology |
| CN103059940A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Startup method of hydrocracking device |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111729690A (en) * | 2019-03-25 | 2020-10-02 | 中国石油化工股份有限公司 | Method for passivating sulfuration type hydrocracking catalyst by using ammonia outside reactor and passivated catalyst |
| CN113083376A (en) * | 2019-12-23 | 2021-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | Passivation method of hydrocracking catalyst |
| CN113117762A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Hydrocracking catalyst pretreatment method |
| CN113122317A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Hydrogen introduction method after shutdown of hydrocracking device |
| CN113117762B (en) * | 2019-12-31 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrocracking catalyst pretreatment method |
| CN113122317B (en) * | 2019-12-31 | 2022-08-12 | 中国石油化工股份有限公司 | Hydrogen introduction method after shutdown of hydrocracking device |
| CN116064079A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Start-up method of diesel hydrogenation device |
| CN116064134A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Start-up method of coal synthetic oil hydrocracking device |
| CN116064133A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Method for starting coal tar hydrogenation device |
| CN116064134B (en) * | 2021-10-29 | 2024-05-31 | 中国石油化工股份有限公司 | Start-up method of coal synthetic oil hydrocracking device |
| CN116064133B (en) * | 2021-10-29 | 2024-05-31 | 中国石油化工股份有限公司 | Method for starting coal tar hydrogenation device |
| CN116064079B (en) * | 2021-10-29 | 2024-05-31 | 中国石油化工股份有限公司 | Start-up method of diesel hydrogenation device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107446616B (en) | 2019-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107446616B (en) | One kind being hydrocracked start-up method | |
| CN106947522B (en) | A kind of start-up method of the hydrocracking unit containing two class site catalysts | |
| CN103801335B (en) | The preparation method of sulfurized hydrogenation catalyst | |
| CN102311766B (en) | Class II active center hydrogenation catalyst start-up vulcanization method | |
| CN107456974A (en) | A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved | |
| CN102051204B (en) | Work starting method for hydrogenation process | |
| CN100525912C (en) | Treatment method before application of hydrogenation catalyst | |
| CN107457006A (en) | A kind of hydrogenation catalyst and its preprocess method methods and applications desulphurizing activated with hydrogenation catalyst is improved | |
| CN102443412B (en) | Start-up method for ex-situ prevulcanization secondary activity center hydrogenation catalysts | |
| CN103801334A (en) | Preparation method of sulfuration-type hydrogenation catalyst | |
| CN103059940B (en) | The start-up method of hydroeracking unit | |
| CN109777486A (en) | It is hydrocracked start-up method | |
| CN114471631A (en) | Hydrodesulfurization catalyst and preparation method and application thereof | |
| CN100360231C (en) | Hydrogenating catalyst composition and preparation process thereof | |
| CN103100444A (en) | Preparation method of prevulcanization type catalyst | |
| CN109777474A (en) | A kind of wet process start-up method being hydrocracked | |
| CN103100395A (en) | Preparation method of vulcanization type catalyst | |
| CN109777480A (en) | A kind of efficient start-up method of hydrocracking catalyst | |
| CN109777472A (en) | One kind plus hydrogen start-up method | |
| CN103769243B (en) | The ex situ presulfiding method of hydrogenation catalyst | |
| CN106925356B (en) | Pre-sulfurizing method of hydrogenation catalyst | |
| CN109777476A (en) | A kind of start-up method of hydrocracking catalyst safety | |
| CN106179522B (en) | A kind of ex situ presulfiding method of hydrogenation catalyst | |
| CN109777475A (en) | A kind of quick start-up method of hydrocracking catalyst | |
| CN109777477A (en) | A kind of stable start-up method of hydrocracking catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |