CN109705916A - The method of process residual oils raw material - Google Patents
The method of process residual oils raw material Download PDFInfo
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- CN109705916A CN109705916A CN201711012670.5A CN201711012670A CN109705916A CN 109705916 A CN109705916 A CN 109705916A CN 201711012670 A CN201711012670 A CN 201711012670A CN 109705916 A CN109705916 A CN 109705916A
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Abstract
The present invention relates to residual hydrogenation fields; disclose the method for process residual oils raw material; it include: that the first material containing feed residue is introduced in the fixed bed hydrogenation device for successively taking off carbon residue reaction zone containing the protection reaction zone, hydrodemetallization reaction zone and desulfurization being connected in series to carry out hydrogenation reaction; after the fixed bed hydrogenation device runs a period of time; any one in reactor A and reactor B is cut out, and introduces the second material containing hydrogen and cleaning oil into the reactor cut out to carry out adding hydrogen cleaning treatment wherein；And switches the material from the reactor A upstream and go out device to be concomitantly introduced into the reactor not cut out into the reactor A and the reactor B after progress hydrogenation reaction with the reaction effluent in the reactor cut out.Method of the invention can online elimination desulfurization take off carbon residue reactor catalyst on carbon deposit, to extend operation cycle.
Description
Technical field
The present invention relates to residual hydrogenation fields, and in particular to a kind of method of process residual oils raw material.
Background technique
As the heaviness of crude oil is got worse, oil variety is increasing, and the requirement to heavy oil product lighting is also got over
Come higher.
" heavy oil product ", which refers to, to be obtained by topped crude, petroleum residual oil, oil-sand, pitch, shale oil, liquefaction coal or reclaimed oil
The hydro carbons of high asphalt content.
The hydrogenation technique of heavy oil product is a kind of heavy oil deep processing technology, which is the presence in hydrogen and catalyst
Under, hydrodesulfurization, hydrodenitrogeneration, hydrodemetallization and carbon residue conversion and hydrocracking reaction, institute are carried out to heavy oil such as residual oil
Residual oil after obtain plus hydrogen can be used as the charging of fine quality catalytic cracking to produce light-end products, maximum to reach residual oil
Sludgeless oil refinery is realized in lighting.
Up to the present, residual hydrogenation has developed four kinds of technology types: fixed bed, ebullated bed, slurry bubble bed and moving bed.
In four kinds of technology types, fixed-bed process is mature, and easy to operate, plant investment is relatively low；The increase of product hydrogen content is more, not
Conversion residual oil can be used as RFCC charging, and the industrial application of the technique is most in four kinds of techniques.
In the prior art, general by the way that hydrotreating of multiple hydrogenators realizations to heavy oil product is arranged.
And the deactivation cause of catalyst for hydrotreatment of residual oil mainly has two o'clock: catalyst metals deposition inactivation and catalyst product
Charcoal inactivation.In process residual oils raw material, the deposition of the sulfide of W metal and V will cause residual oil hydrocatalyst inactivation.Simultaneously
Identical with catalyst used for hydrogenation of distilled oil fraction inactivation is that the carbon deposit on catalyst is also the more important factor of catalyst inactivation.Slag
Multiring aromatic hydrocarbon substance includes colloid, asphalitine in catalyst surface absorption after-condensation coking formation carbon deposit in oily raw material, is caused
Catalyst inactivation.Therefore when the higher residual oil raw material of process asphaltenes, gum level, the carbon deposit on catalyst is catalyst inactivation
Major reason.
During residual hydrogenation, in order to inhibit the precipitation of asphalitine on a catalyst and carbon deposit, adopt mostly in the prior art
With high armaticity raw material, inhibit the precipitation of residual oil raw material asphalitine using the similar physical principle to mix.
CN1484684A, which is disclosed, a kind of uses replaceable reactor and can short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction
Method, this method regenerate catalyst or are replaced after protection reactor plugs or in which catalyst inactivation.Using the party
Method catalyst needs to change or regenerates the reactor and needs to stop work, and a series of relevant devices is needed to make the catalyst for regenerating or replacing
Again vulcanize.
CN102876373A discloses a kind of method for extending hydrotreater operation cycle, and this method is urged in hydrotreating
In the Steady-state inactivation stage of agent, reactor is cooled down, and feedstock oil is switched into cleaning oil, lower hydrogen-oil ratio is maintained, with most
Big oil inlet quantity rinses catalyst bed；Reaction bed temperature is increased, and injects a certain proportion of antisludging agent into cleaning oil, directly
Change circulate operation when generating in oil to fractionation column bottom without solid coke particle；Temperature is adjusted, and injects vulcanization into cleaning oil
Agent carries out supplement vulcanization to catalyst, to improve the activity of catalyst.Based on this method is devoked with physics, dissolution soft coke and
Absorption polymer on a catalyst, and device needs to cool down, cleans and mends that the sulphur time is longer, which not can be carried out normal life
It produces.
A kind of method that CN102816598A discloses de- carbon residue catalyst carbon deposit of reduction residual hydrocracking device, this method
It is one feed inlet of increase before the de- carbon residue agent bed of residual hydrocracking device, feed residue is introduced by the feed inlet
The catalytic cracking recycle oil of the high aromaticity of the 1~30% of weight increases the dissolution energy for the asphalitine being gradually precipitated in feedstock oil
Power, to reduce the coke content on catalyst.
A kind of catalytic cracking recycle oil of CN102816595A is in Combination Process of Residue Hydrotreating And Catalytic Cracking, the technique
A feed inlet is increased separately before device demetalization bed, desulfurizing agent bed and de- carbon residue agent bed, recycle oil is introduced
One or more feed inlets delay the carbon deposit speed of catalyst.But recycle oil is mixed residual oil raw material and its reactant by this method
In, residual hydrogenation unavoidably has carbon deposit generation, unobvious to the carbon deposit effect for eliminating protection reactor catalyst.
CN101037618A discloses a kind of coking inhibitor and its preparation method and application, which is selected from coal
Tar, ethylene bottom oil, catalytic cracking recycle oil, catalytic cracked oil pulp, catalytic cracking heavy oil, catalytic cracking extraction oil and coking wax
The hydro-upgrading product of one or more kinds of hydrocarbon mixtures in oil, for preventing, delaying and eliminating petroleum refining and stone
In relation to the coking in equipment and pipeline during oiling work.The inhibitor need to be added in working fluid, to the effect of removing carbon
It is limited.
Summary of the invention
The purpose of the invention is to overcome the defect of the method for existing elimination or inhibition carbon deposit, providing one kind can be
Line eliminates the carbon deposit on the catalyst of the de- carbon residue reactor of desulfurization, to extend operation cycle and realize that unloading agent readily processes
The method of poor residuum raw material.
Hard charcoal and soft charcoal can be deposited during residual hydrogenation on catalyst, the inventors of the present invention discovered through researches that, in residual oil
Under hydrogenation reaction pressure, when the oil product of high armaticity and residual oil raw material are concomitantly introduced into hydrogenation plant, although can be to drip
The dissolution of green matter has the effect of certain to remove, but this method is on the catalyst in the serious hydrogenation plant of carbon deposit situation
The cleaning effect of carbon deposit and bad；However, inventor has found under study for action, high armaticity oil product is individually (former not with residual oil
Material is together) and hydrogen be passed through in the reactor equipped with the old catalyst of residual hydrogenation when carrying out adding hydrogen, the hard charcoal meeting on old catalyst
Hydrogenation reaction occurs, since hard charcoal own molecular structure is big, being influenced by steric effect cannot be directly from catalyst active center
Activation hydrogen is obtained, but activation hydrogen can be provided in the presence of no residual oil raw material for hydrogen compound in high armaticity oil product
Or be transmitted in hard charcoal, promote hard charcoal to be converted into soft charcoal, and soft charcoal can be dissolved in high armaticity oil product and by adding hydrogen anti-
Oil product should be converted into.Based on this discovery, inventor completes technical solution of the present invention.
To achieve the goals above, of the invention that a kind of method of process residual oils raw material is provided, this method comprises: adding hydrogen
Under treatment conditions, the first material containing feed residue is introduced to and is successively taken off containing the protection reaction zone being connected in series plus hydrogen
Hydrogenation reaction is carried out in the fixed bed hydrogenation device of metal reaction area and the de- carbon residue reaction zone of desulfurization, wherein the desulfurization takes off residual
Two reactors being sequentially connected in series, respectively reactor A and reactor B are included at least in charcoal reaction zone, and come from the reaction
The material of the upstream device A, which sequentially enters in the reactor A and the reactor B, goes out device after progress hydrogenation reaction；
(a) when the fixed bed hydrogenation device reaches any one in the following conditions, the reactor A and institute are cut out
Any one in reactor B is stated, and introduces the second material containing hydrogen and cleaning oil at it into the reactor cut out
In carry out plus hydrogen cleaning treatment；And switch the material from the reactor A upstream with in the reactor cut out
Reaction effluent is concomitantly introduced into the reactor not cut out into the reactor A and the reactor B and carries out hydrogenation reaction
Go out device afterwards；
It includes any one in the following conditions that the fixed bed hydrogenation device, which needs condition to be achieved:
(1) described fixed bed hydrogenation device continuous service 15 days or more；
(2) pressure drop in the reactor A or the reactor B reaches the pressure drop upper limit；
(3) catalyst in the reactor A or the reactor B occur hot spot make the radial temperature difference of reactor >=
5℃；
Optionally, by the way that the reactor A and the alternately described hydrogenation reaction of the reactor B and described plus hydrogen is clear
It washes and handles and repeating said steps (a), until the fixed bed hydrogenation device reaches shutdown conditions；
Wherein, total arene content in the cleaning oil is 50~95 weight %.
The method of process residual oils raw material provided by the invention is capable of urging for the de- carbon residue reactor of significant ground online elimination desulfurization
Carbon deposit in agent, to extend operation cycle and realize that unloading agent is easy.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the process residual oils raw material of preferred embodiment of the invention.
Description of symbols
1, reaction zone is protected
2, demetalization reaction zone
3, reactor A
4, reactor B
5, first material
6, second material
7, third material
8, desulfurization takes off carbon residue reaction zone first reactor
01,02,03,04,05,06 is valve.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the first aspect of the present invention provides a kind of method of process residual oils raw material, this method comprises: adding
Under hydrogen treatment conditions, the first material containing feed residue is introduced to successively containing the protection reaction zone being connected in series plus hydrogen
Hydrogenation reaction is carried out in the fixed bed hydrogenation device of demetalization reaction zone and the de- carbon residue reaction zone of desulfurization, wherein the desulfurization is de-
Two reactors being sequentially connected in series, respectively reactor A and reactor B are included at least in carbon residue reaction zone, and from described anti-
It answers the material of the upstream device A to sequentially enter in the reactor A and the reactor B and goes out device after progress hydrogenation reaction；
(a) when the fixed bed hydrogenation device reaches any one in the following conditions, the reactor A and institute are cut out
Any one in reactor B is stated, and introduces the second material containing hydrogen and cleaning oil at it into the reactor cut out
In carry out plus hydrogen cleaning treatment；And switch the material from the reactor A upstream with in the reactor cut out
Reaction effluent is concomitantly introduced into the reactor not cut out into the reactor A and the reactor B and carries out hydrogenation reaction
Go out device afterwards；
It includes any one in the following conditions that the fixed bed hydrogenation device, which needs condition to be achieved:
(1) described fixed bed hydrogenation device continuous service 15 days or more；
(2) pressure drop in the reactor A or the reactor B reaches the pressure drop upper limit；
(3) catalyst in the reactor A or the reactor B occur hot spot make the radial temperature difference of reactor >=
5℃；
Optionally, by the way that the reactor A and the alternately described hydrogenation reaction of the reactor B and described plus hydrogen is clear
It washes and handles and repeating said steps (a), until the fixed bed hydrogenation device reaches shutdown conditions；
Wherein, total arene content in the cleaning oil is 50~95 weight %.
In the present invention, former using aforementioned process residual oils provided by the invention according to a kind of preferred embodiment
The method of material, when repeating said steps (a) until when the fixed bed hydrogenation device reaches shutdown conditions, method tool of the invention
There is the advantages of cycle of oparation that can be obviously prolonged fixed bed hydrogenation device.
It is anti-when what is cut out when being carried out to the reactor cut out plus hydrogen cleaning treatment in step (a) under preferable case
When the radial temperature difference in pressure drop and reactor in device being answered to be restored in values, stop drawing into the reactor cut out
Enter the second material, and the reaction effluent in the reactor not cut out is introduced in the reactor cut out and is added
Go out device after hydrogen reaction.
For step (a) of the invention, this hair provides following several preferred embodiments:
According to the first preferred embodiment, in step (a), the reactor A is cut out, and to described anti-
Answer device A to carry out plus when hydrogen cleaning treatment, when the pressure drop in the reactor A and the radial temperature difference in reactor be restored to it is default
When being worth in range, stop introducing the second material into the reactor A, and the cleaning oil in the second material is cut
It gains in the first material, and the reaction effluent in the reactor B is introduced in the reactor A and carries out adding hydrogen
Go out device after reaction.
According to second of preferred embodiment, in step (a), the reactor B is cut out, and to described anti-
Answer device B to carry out plus when hydrogen cleaning treatment, when the pressure drop in the reactor B and the radial temperature difference in reactor be restored to it is default
When being worth in range, stop introducing the third material into the reactor B, and the cleaning oil in the third material is cut
It gains in the first material, and the reaction effluent in the reactor A is introduced in the reactor B and carries out adding hydrogen
Go out device after reaction.
According to the third preferred embodiment, in step (a), the reactor A is cut out, and to described anti-
Answer device A to carry out plus when hydrogen cleaning treatment, when the pressure drop in the reactor A and the radial temperature difference in reactor be restored to it is default
When being worth in range, stop introducing the second material into the reactor A, and the cleaning oil in the second material is cut
It gains in the first material, and the reaction effluent in the reactor B is introduced in the reactor A and carries out adding hydrogen
Go out device after reaction；And
In step (a), when cutting out the reactor B, and carrying out adding hydrogen cleaning treatment to the reactor B, work as institute
When stating the radial temperature difference in pressure drop and reactor in reactor B and being restored in values, stop to the reactor B
It is middle to introduce the third material, and the cleaning oil in the third material is switched back into the first material, and by institute
It states the reaction effluent in reactor A and is introduced in the reactor B and go out device after progress hydrogenation reaction.
Under preferable case, the condition of the reactor A or the reactor B is controlled, so that filling in the fixed bed hydrogenation
When setting online shut-down, the reactor A or the reactor B are to have carried out the described plus state of hydrogen cleaning treatment at least for 24 hours.
In the present invention, according to another preferred embodiment, further, using provided by the invention aforementioned
The method of process residual oils raw material, when the condition for controlling the reactor A or the reactor B, so that in the fixed bed hydrogenation
When the reactor A or the reactor B are carry out described plus hydrogen cleaning treatment state at least for 24 hours when device is stopped work online,
Enable to introduce cleaning oil therein and the carbon deposit on the catalyst therein charcoal that disappears to react so that unload desulfurization take off it is residual
It is relatively easy to when the catalyst of charcoal reaction zone.
It is highly preferred that in the present invention, the condition of the reactor A or the reactor B is optionally controlled, so that in institute
Stating the reactor A or the reactor B when fixed bed hydrogenation device is stopped work online is cleaning to pressure drop therein and reaction
Radial temperature difference in device is restored to the state in values.In this way, the desulfurization being more conducive in method of the invention is de-
The catalyst of carbon residue reaction zone is easy to be unloaded.
Radial temperature difference of the present invention is restored to the preset value in values can be by those skilled in the art's root
Confirm according to working condition, this is not particularly limited.
It should be noted that in previous process method provided by the invention, when the fixed bed hydrogenation device formally stops
Working hour, the reactor A and the reactor B may undergo the transformation of three kinds of states, the first state be changed into reactor A and
Reactor B is to be changed into suspended state by hydrogenation reaction state；It is by hydrogenation reaction shape that second of state, which is changed into reactor A,
State is changed into suspended state, and reactor B is by adding hydrogen cleaning treatment state to be changed into suspended state；The third state is changed into instead
Answering device B is to be changed into suspended state by hydrogenation reaction state, and reactor A is by adding hydrogen cleaning treatment state to be changed into shut-down shape
State.Also, aforementioned the first state transformation is conducive to extend the operation cycle of fixed bed hydrogenation device；And aforementioned second of state
Transformation and the third state change so that unloading the catalyst of the de- carbon residue reaction zone of desulfurization becomes to be more easier.
To which the method for process residual oils raw material provided by the invention has the advantages that flexibility is high.
Under preferable case, in the method for the invention, the reactor A or reactor B and other normal process cut out is produced
Fixed bed hydrogenation device in reactor stop work online together.
Preferably, total arene content in the cleaning oil is 80~90 weight %.
Under preferable case, the two ring aromatic content in the cleaning oil is 30~80 weight %；More preferably 50~70 weights
Measure %.
Preferably, the cleaning oil is selected from straight-run diesel oil, catalytic cracking diesel oil, catalytic cracking recycle oil and cycle oil
At least one of slurry, catalytic cracked oil pulp more preferably of the invention is the catalytic cracked oil pulp for being stripped of solid particulate matter.
The catalytic cracking diesel oil of the invention can with the diesel oil of various catalytic cracking process, catalytic cracking process such as DCC,
MIP, HSCC etc..
Aforementioned second material of the invention can be identical with third material, or can be provided by the invention optional
Cleaning in oily range selects different cleaning oil to form the second material and the third material.
Preferably, the pressure drop upper limit is the design maximum pressure drop for the respective reaction device that the desulfurization takes off in carbon residue reaction zone
40~80%；It is highly preferred that the maximum that the pressure drop upper limit is the respective reaction device in the de- carbon residue reaction zone of the desulfurization is set
Count the 45~75% of pressure drop.
Under preferable case, the radial temperature difference reaches 15 DEG C~40 DEG C；It is highly preferred that the radial temperature difference reach 20 DEG C~
35℃。
Preferably, in order to more extend operation cycle of device, in step (a), the reactor A and the reactor
B be cut out every time with carry out plus hydrogen cleaning treatment before hydrogenation reaction continuous operating time be the fixed bed hydrogenation fill
The 1/8~1/2 of the continuous operation period set, more preferably 1/4~1/3.
Under preferable case, in order to more extend the operation cycle of device, in step (a), the reactor A and described anti-
Device B is answered to be cut out every time add the continuous operation period that the time of hydrogen cleaning treatment is the fixed bed hydrogenation device
1/16~1/4, more preferably 1/8~1/6.
Preferably, the dosage weight ratio of the feed residue in the first material and the cleaning oil in step (a) is
10:(1~4.5).
Under preferable case, also containing cleaning oil in the first material, and when carrying out step (a), by first object
Cleaning oil in material is cut out to be introduced in the reactor cut out and carry out adding hydrogen cleaning treatment.It is highly preferred that in step (a),
When being carried out to the reactor cut out plus hydrogen cleaning treatment, when the pressure drop in the reactor cut out and the radial temperature in reactor
When difference is restored in values, stop introducing the second material into the reactor cut out, and by second object
Cleaning oil in material switches back into the first material, and the reaction effluent in the reactor not cut out is introduced to this and is cut
Go out device after carrying out hydrogenation reaction in reactor out.
Under preferable case, consolidating before and after cutting out reactor A or reactor B in the de- carbon residue reaction zone of the desulfurization
Be Residue Hydrotreating Technology condition in fixed bed hydrogenation plant, the Residue Hydrotreating Technology condition include: hydrogen partial pressure be 5.0~
22.0MPa, reaction temperature are 330~450 DEG C, volume space velocity is 0.1~3.0h-1, hydrogen to oil volume ratio be 350~2000.
Under preferable case, the desulfurization cut out takes off in reactor A or reactor B in carbon residue reaction zone plus hydrogen cleaning
The condition of processing include: hydrogen partial pressure be 5.0~22.0MPa, reaction temperature is 300~400 DEG C, hydrogen to oil volume ratio is 50~300,
Volume space velocity is 1.0~3.0 times of the volume space velocity of the hydrogenation reaction.
Under preferable case, in fixed bed hydrogenation device of the invention, the desulfurization takes off in carbon residue reaction zone containing at least
Two concatenated fixed bed reactors and the protection reaction zone and demetalization reaction zone at least contain a fixed bed respectively
Reactor.It is highly preferred that in fixed bed hydrogenation device of the invention, the desulfurization takes off in carbon residue reaction zone containing there are three at least
Concatenated fixed bed reactors and the protection reaction zone and demetalization reaction zone at least contain a fixed bed reaction respectively
Device.
According to a kind of preferred embodiment, the reactor A in the de- carbon residue reaction zone of the desulfurization cut out is controlled
Or the condition for adding hydrogen cleaning treatment in reactor B, so that the density of the cleaning oil drops after described plus hydrogen cleaning treatment
Low value is 10~30kg/m3, more preferably 15~25kg/m3。
Preferably, hydrogenation protecting catalyst, Hydrodemetalation catalyst plus hydrogen are filled in the fixed bed hydrogenation device
Desulphurization catalyst and carbon residue hydrogenation conversion catalyst, the hydrogenation protecting catalyst, Hydrodemetalation catalyst, hydrodesulfurization are urged
Carrier in agent and carbon residue hydrogenation conversion catalyst is each independently selected from least one in aluminium oxide, silica and titanium oxide
Kind.It is highly preferred that the carrier is via the element modified rear modified support obtained selected from boron, germanium, zirconium, phosphorus, chlorine and fluorine.
Under preferable case, the hydrogenation protecting catalyst, Hydrodemetalation catalyst, Hydrobon catalyst and carbon residue add
Active metal component in hydrogen reforming catalyst is each independently in the non-noble metal j element selected from group VIB and group VIII
At least one；It is highly preferred that the hydrogenation protecting catalyst, Hydrodemetalation catalyst, Hydrobon catalyst and carbon residue
Active metal component in hydrogenation conversion catalyst is each independently in nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum and cobalt-molybdenum at least
A kind of combination.
Under preferable case, the filling of the size and catalyst of the reactor A of the invention and the reactor B
Situation is identical.
Aforementioned catalytic agent of the invention can the commercial catalysts selected from this field routine or the routine using the prior art
Method is prepared.
There is no particular limitation for the admission space ratio of method of the invention to the catalyst of various species, can be this field
The interior Catalyst packing volume ratio that residual oil is carried out routinely to use when hydrotreating.Each catalysis is listed in the embodiment of the present invention
A kind of admission space ratio of agent, those skilled in the art should not be construed as limiting the invention.
Preferably, the feed residue is decompression residuum and/or reduced crude.
Under preferable case, the colloid-stabilised coefficient of the first material is not more than 2.0.Normal heptane is being added with feed residue
Mass fraction normalized conductivity in the process changes to characterize the coagulation of feed residue studies on asphaltene, when by generation asphalitine coagulation
(normal heptane/residual oil) ratio is defined as colloid-stabilised coefficient.
It preferably, include fixed bed hydrogenation reactor in the fixed bed hydrogenation device of the invention, the fixed bed is anti-
Answering device includes at least one in upflow fixed bed reactor, down-type fixed-bed reactor and reverse-flow fixed bed reactors
Kind.The fixed bed reactors that the logistics that the down-type fixed-bed reactor refers to flows from up to down；The up flow type is solid
Fixed bed reactor refers to the fixed bed reactors of the bottom-up flowing of logistics；The reverse-flow fixed bed reactors refer to liquid
The fixed bed reactors opposite with gas flow.
In the method for the invention, cleaning oil is used to carry out plus can be with the step of hydrogen cleaning treatment and the step of hydrogenation reaction
Repeatedly carry out.Also, when repeating to add hydrogen cleaning treatment and hydrogenation reaction, to each secondary cleaning treatment and each time plus hydrogen
The condition of reaction and the type of the cleaning oil used are not particularly limited, it is not required that it must be the same every time, as long as
In the range of aforementioned definition of the present invention can realization device extend operation cycle and realize unload agent be easy.
Method (the technique that preferred embodiment illustrates process residual oils raw material of the invention is provided below in conjunction with Fig. 1
Process):
As shown in Figure 1, valve 01, valve 04 and valve 05 are opened, valve 02, valve 03 and valve 06 when device goes into operation
Close, first material 5 sequentially enter protection reaction zone 1, demetalization reaction zone 2, desulfurization take off carbon residue reaction zone first reactor 8,
Reactor A 3 and reactor B 4, after running a period of time,
When the pressure drop in the reactor A 3 reaches the pressure drop upper limit or catalyst therein hot spot occurs and leads to radial temperature
When difference is excessive, or when described fixed bed hydrogenation device continuous service 15 days or more, valve 03 is opened, and valve 01 is closed, and is taken off
Sulphur takes off the logistics that carbon residue reaction zone first reactor 8 comes out and is directly entered reactor B 4；Second material 6 enters reactor A 3, so
The logistics that carbon residue reaction zone first reactor 8 comes out is taken off with desulfurization afterwards and is mixed into reactor B 4, goes forward side by side and one walks out of device.It is preferred that
In the case of, reactor 3A cleaning makes the radial temperature difference in pressure drop therein and reactor be restored to preset value for a period of time
When in range, stop introducing the second material 6 into the reactor A 3, it is highly preferred that by clear in the second material 6
Washing oil switches back into the first material 5, and valve 06 and valve 02 are opened, and valve 05 and valve 04 are closed, by the reactor
Reaction effluent in B4, which is introduced in the reactor A 3, goes out device after progress hydrogenation reaction；
When the pressure drop in the reactor B 4 reaches the pressure drop upper limit or catalyst therein hot spot occurs and leads to radial temperature
When difference is excessive, or when described fixed bed hydrogenation device continuous service 15 days or more, valve 03, valve 04 and valve 05 are closed
It closes, valve 01, valve 02 and valve 06 are opened, and the cleaning oil are cut out from the first material 5, and cut out the reaction
Device B4, and the third material 7 containing hydrogen and the cleaning oil is introduced in the reaction into the reactor B 4 cut out
It carries out adding hydrogen cleaning treatment in device B4；And the reaction effluent of carbon residue reaction zone first reactor 8 will be taken off from the desulfurization
It is concomitantly introduced into the reaction effluent in the reactor B 4 into the reactor A 3 after carrying out hydrogenation reaction and goes out device；
Preferably, when the pressure drop in the reactor B 4 and the radial temperature difference in reactor are restored in values, valve
02, valve 03 and valve 06 are closed, and valve 01, valve 04 and valve 05 are opened, and are stopped into the reactor B 4 described in introducing
Third material 7；It is highly preferred that the cleaning oil in the third material 7 is switched back into the first material 5, and will be described
Reaction effluent in reactor A 3, which is introduced in the reactor B 4, goes out device after progress hydrogenation reaction；
It repeats above operation, reactor A 3 and reactor B 4 are alternatively introduced into after cleaning oil operates a period of time and are incorporated to residual oil again
Add in the reaction process of hydrogen until device is stopped work.
Particularly, the method (process flow) and system of process residual oils raw material of the invention are not limited to shown in FIG. 1
Form, and should be all modes that preceding solution of the present invention is included, those skilled in the art should not be construed as to this
The limitation of invention.
Method provided by the invention compared with prior art, also has the advantages that following specific:
(1) method of the invention is after cutting out a concatenated desulfurization and taking off carbon residue reactor, by cleaning oil and a small amount of hydrogen
It is introduced into the reactor cut out, remaining residual oil raw material in the reactor can be displaced；
(2) when cutting out reactor, carbon deposit deposition is higher on catalyst therein, and activity is relatively low, even if at this time
Cleaning oil is introduced, reaction temperature rising will not be too high；
(3) after the reactor for taking off carbon residue reaction zone due to cutting out desulfurization, device is also being continued to run, and is cleaned oil introducing and is cut out
Reactor after, the charcoal that can disappear with the carbon deposit on catalyst reacts, eliminate catalyst on carbon deposit, to restore catalyst
Activity, extend the operation cycle of device；
(4) method of the invention can also make desulfurization take off when the catalyst reactor of carbon residue reaction zone unloads agent also more
It is easy；
(5) method flexible operation of the invention can be actually needed according to production and process conditions and process is adjusted flexibly.
It below will the present invention will be described in detail by example.In following instance, in case of no particular description,
The various raw materials used are all from commercially available.
Catalyst used below is developed by Sinopec Research Institute of Petro-Chemical Engineering and by catalyst Chang Ling point
The residual hydrocracking catalyst series of company's production.Wherein RG series is hydrogenation protecting catalyst, and RDM series is plus hydrogen is de- golden
Metal catalyst, RMS series are Hydrobon catalyst, and RCS is carbon residue hydrogenation conversion catalyst.
The property of feed residue, cleaning oil and miscella is as shown in table 1.
Embodiment and comparative example carries out (the design maximum pressure drop of reactor on medium-sized tester as shown in Figure 1
For 0.8MPa), as shown in figure 1, protecting loaded catalyst in reaction zone 1 is 40mL, and demetalization reaction zone 2, the de- carbon residue of desulfurization are anti-
Answer area's first reactor 8, loaded catalyst is 100mL in reactor A 3 and reactor B 4.
Protective agent RG-30B catalyst is all loaded in protection reaction zone 1；
RDM-32 catalyst is all loaded in demetalization reaction zone 2；
Desulfurization, which takes off, successively loads RDM-33B catalyst and RMS-30 catalyst in carbon residue reaction zone first reactor 8, and each two
The admission space ratio of person is 20:80.
RCS-30 catalyst and RCS-31 (the admission space ratio of the two are successively loaded in reactor A 3 and reactor B 4
For 40:60).
Embodiment 1
Feed residue and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
It includes: volume space velocity that reactor 8, reactor A 3 and reactor B 4, which are Residue Hydrotreating Technology condition in fixed bed hydrogenation device,
For 0.195h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa；
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.15 weight %, 0.30 weight % of nitrogen content, 6.0 weight % of carbon residue, 20 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 4 months, desulfurization is taken off into 8 outlet streams of carbon residue reaction zone first reactor and is introduced directly into reaction
Device B4, cleans oil A and a small amount of hydrogen enters reactor A 3, and reactor A 3 exports effluent and enters in reactor B 4, reactor A 3
After cleaning oil A being added operating 1 month, stop into cleaning oil A, and 4 outlet streams of reactor B are introduced into reactor A 3, device is transported again
After turning 3 months, desulfurization is taken off into 8 outlet streams of carbon residue reaction zone first reactor and is introduced directly into reactor A 3, cleaning oil A and on a small quantity
Hydrogen enters reactor B 4, and the outlet of reactor B 4 effluent is entered in reactor A 3, and cleaning oil A fortune is added in reactor B 4
After turning 1 month, stop into cleaning oil A, and 3 outlet streams of reactor A are introduced into reactor B 4, protects reaction zone 1, de- gold at this time
Belong to reaction zone 2, the average reaction temperature of desulfurization de- carbon residue reaction zone first reactor 8, reactor A 3 and reactor B 4 is 386
DEG C, show that catalyst is all also active.
The weight ratio of the cleaning oil A and feed residue that apply in the technique of the present embodiment are 18:82, when introducing cleaning oil A
Reactor A 3 or reactor B 4 in reaction condition be hydrogen partial pressure 15.0MPa, hydrogen to oil volume ratio 100, volume space velocity is
0.185h-1, to clean oily A density decreasing value to be 16kg/m by controlling reaction temperature3。
Embodiment 2
Feed residue and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
It includes: volume space velocity that reactor 8, reactor A 3 and reactor B 4, which are Residue Hydrotreating Technology condition in fixed bed hydrogenation device,
For 0.20h-1, hydrogen to oil volume ratio 750:1, hydrogen partial pressure 15.0MPa.
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.15 weight %, 0.30 weight % of nitrogen content, 6.0 weight % of carbon residue, 20 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 6 months, desulfurization is taken off into 8 outlet streams of carbon residue reaction zone first reactor and is introduced directly into reaction
Device B4, cleans oil B and a small amount of hydrogen enters reactor A 3, and reactor A 3 exports effluent and enters in reactor B 4, reactor A 3
After cleaning oil B being added operating 1 month, stops into cleaning oil B, and 4 outlet streams of reactor B are introduced into reactor A 3, protect at this time
Reaction zone 1, demetalization reaction zone 2, desulfurization take off the average anti-of carbon residue reaction zone first reactor 8, reactor A 3 and reactor B 4
Answering temperature is 382 DEG C, shows that catalyst is all also active.
The weight ratio of the cleaning oil B and feed residue that apply in the technique of the present embodiment are 25:75, when introducing cleaning oil B
Reactor A 3 in reaction condition be hydrogen partial pressure be 15.0MPa, hydrogen to oil volume ratio 240, volume space velocity 0.285h-1, lead to
Control reaction temperature is crossed to clean oily B density decreasing value to be 22kg/m3。
Embodiment 3
It is anti-that miscella and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
Device 8, reactor A 3 and reactor B 4 are answered, be Residue Hydrotreating Technology condition in fixed bed hydrogenation device includes: that volume space velocity is
0.224h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.12 weight %, 0.28 weight % of nitrogen content, 5.8 weight % of carbon residue, 18 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 4 months, the residual oil raw material in miscella is introduced into protection reaction zone 1, desulfurization is taken off into carbon residue
8 outlet streams of reaction zone first reactor are introduced directly into reactor B 4, and the cleaning oil A and a small amount of hydrogen in miscella enter reaction
Device A3, reactor A 3 export effluent and enter in reactor B 4, after cleaning oil A is added operating 1 month in reactor A 3, stop into cleaning
Oily A, and 4 outlet streams of reactor B are introduced into reactor A 3, protect reaction zone 1, demetalization reaction zone 2, desulfurization to take off carbon residue at this time
The average reaction temperature of reaction zone first reactor 8, reactor A 3 and reactor B 4 is 378 DEG C.
The reaction condition in reactor A 3 when being introduced into cleaning oil A is hydrogen partial pressure 15.0MPa, hydrogen to oil volume ratio 100, body
Product air speed is 0.126h-1, to clean oily A density decreasing value to be 16kg/m by controlling reaction temperature3。
Comparative example 1
Feed residue and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
It includes: volume space velocity that reactor 8, reactor A 3 and reactor B 4, which are Residue Hydrotreating Technology condition in fixed bed hydrogenation device,
0.195h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.15 weight %, 0.30 weight % of nitrogen content, 6.0 weight % of carbon residue, 20 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
Device protects reaction zone 1, demetalization reaction zone 2, desulfurization to take off carbon residue reaction zone first and react after continuously running 9 months
The average reaction temperature of device 8, reactor A 3 and reactor B 4 is 390 DEG C.
Comparative example 2
It is anti-that miscella and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
Device 8, reactor A 3 and reactor B 4 are answered, be Residue Hydrotreating Technology condition in fixed bed hydrogenation device includes: that volume space velocity is
0.224h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.12 weight %, 0.28 weight % of nitrogen content, 5.8 weight % of carbon residue, 18 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
Device protects reaction zone 1, demetalization reaction zone 2, desulfurization to take off carbon residue reaction zone first and react after continuously running 5 months
The average reaction temperature of device 8, reactor A 3 and reactor B 4 is 384 DEG C.
It can be seen that from the result of embodiment 1-3 and comparative example 1-2 using method provided by the invention, can significantly prolong
Operation cycle of growth device, and catalyst average reaction temperature is lower show that desulfurization takes off urging for catalyst in carbon residue reaction zone
Change activity preferably.
Embodiment 4
Feed residue and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
It includes: volume space velocity that reactor 8, reactor A 3 and reactor B 4, which are Residue Hydrotreating Technology condition in fixed bed hydrogenation device,
For 0.22h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.When device brings into operation, the pressure drop of reactor A 3 is
0.20MPa。
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.15 weight %, 0.30 weight % of nitrogen content, 6.0 weight % of carbon residue, 20 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 6000h, logistics is taken off carbon residue reaction from desulfurization by 3 pressure drop rise of reactor A to 0.70MPa
Area's first reactor 8 is directly introduced into reactor B 4, cleans oil A and a small amount of hydrogen enters reactor A 3,3 outlet stream of reactor A
Object enters in reactor B 4 out, and device protects reaction zone 1, demetalization reaction zone 2, the de- carbon residue of desulfurization anti-operate 1000 hours again after
Area's first reactor 8, reactor A 3 and the series connection of reactor B 4 is answered to stop work.
The weight ratio of the cleaning oil A and feed residue that apply in the technique of the present embodiment are 18:82, when introducing cleaning oil A
Reactor A 3 in reaction condition be hydrogen partial pressure be 15.0MPa, hydrogen to oil volume ratio 100, volume space velocity 0.208h-1, lead to
Control reaction temperature is crossed to clean oily A density decreasing value to be 16kg/m3。
Embodiment 5
Feed residue and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
It includes: volume space velocity that reactor 8, reactor A 3 and reactor B 4, which are Residue Hydrotreating Technology condition in fixed bed hydrogenation device,
For 0.22h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.When device brings into operation, 3 pressure drop of reactor A is
0.20MPa。
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.15 weight %, 0.30 weight % of nitrogen content, 6.0 weight % of carbon residue, 20 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 6000h, logistics is taken off carbon residue reaction from desulfurization by 3 pressure drop rise of reactor A to 0.70MPa
Area's first reactor 8 is directly introduced into reactor B 4, cleans oil B and a small amount of hydrogen enters reactor A 3,3 outlet stream of reactor A
Object enters in reactor B 4 out, and device protects reaction zone 1, demetalization reaction zone 2, the de- carbon residue of desulfurization anti-operate 2000 hours again after
Area's first reactor 8, reactor A 3 and the series connection of reactor B 4 is answered to stop work.
The mass ratio of the cleaning oil B and residual oil raw material that apply in the technique of the present embodiment are 10:90, when introducing cleaning oil B
Reactor A 3 in reaction condition be hydrogen partial pressure be 15.0MPa, hydrogen to oil volume ratio 240, volume space velocity 0.105h-1, lead to
Control reaction temperature is crossed to clean oily B density decreasing value to be 22kg/m3。
Embodiment 6
It is anti-that miscella and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
Device 8, reactor A 3 and reactor B 4 are answered, be Residue Hydrotreating Technology condition in fixed bed hydrogenation device includes: that volume space velocity is
0.253h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.When device brings into operation, 4 pressure drop of reactor B is
0.18MPa。
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.12 weight %, 0.28 weight % of nitrogen content, 5.8 weight % of carbon residue, 18 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 6000h, 4 pressure drop rise of reactor B to 0.70MPa, the feed residue in miscella enters
Reaction zone 1 is protected, the cleaning oil A and a small amount of hydrogen in miscella enter reactor B 4, and reactor B 4 exports effluent and enters instead
It answers in device A3, the straight connecting device of logistics that reactor A 3 exports, device protects reaction zone 1, demetalization anti-operate 800 hours again after
It answers area 2, desulfurization to take off carbon residue reaction zone first reactor 8, reactor A 3 and the series connection of reactor B 4 to stop work.
It is 15.0MPa that the reaction condition in reactor B 4 when being introduced into cleaning oil A, which is hydrogen partial pressure, hydrogen to oil volume ratio 100,
Volume space velocity is 0.142h-1, to clean oily A density decreasing value to be 16kg/m by controlling reaction temperature3。
Comparative example 3
Feed residue and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
It includes: volume space velocity that reactor 8, reactor A 3 and reactor B 4, which are Residue Hydrotreating Technology condition in fixed bed hydrogenation device,
0.22h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.When device brings into operation, the pressure drop of reactor A 3 is
0.20MPa。
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.15 weight %, 0.30 weight % of nitrogen content, 6.0 weight % of carbon residue, 20 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 6000h, logistics is taken off carbon residue reaction from desulfurization by 3 pressure drop rise of reactor A to 0.70MPa
Area's first reactor 8 is directly introduced into reactor B 4, and a small amount of hydrogen enters the purging of reactor A 3 and maintains temperature, and device operates again
Reaction zone 1, demetalization reaction zone 2, reactor A 3 and the series connection of reactor B 4 is protected to stop work after 1000 hours.
Comparative example 4
It is anti-that miscella and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
Device 8, reactor A 3 and reactor B 4 are answered, be Residue Hydrotreating Technology condition in fixed bed hydrogenation device includes: that volume space velocity is
0.253h-1, hydrogen to oil volume ratio 700:1, hydrogen partial pressure 15.0MPa.When device brings into operation, 4 pressure drop of reactor B is
0.18MPa。
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.12 weight %, 0.28 weight % of nitrogen content, 5.8 weight % of carbon residue, 18 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 6000h, 4 pressure drop rise of reactor B to 0.70MPa, the logistics that reactor A 3 is exported is straight
Connecting device, a small amount of hydrogen, which enters the purging of reactor B 4 maintains temperature, device to operate 800 hours again after, protects reaction zone 1, de- gold
Belong to reaction zone 2, desulfurization takes off carbon residue reaction zone first reactor 8, reactor A 3 and the series connection of reactor B 4 are stopped work.
Comparative example 5
Feed residue and hydrogen sequentially enter protection reaction zone 1, demetalization reaction zone 2, the de- carbon residue reaction zone first of desulfurization
Reactor 8, reactor A 3 and reactor B 4, cleaning oil A takes off 8 entrance of carbon residue reaction zone first reactor and be introduced to from desulfurization adds hydrogen
Be in device, in fixed bed hydrogenation device Residue Hydrotreating Technology condition include: volume space velocity be 0.220h-1, hydrogen to oil volume ratio
For 700:1, hydrogen partial pressure 15.0MPa.When device brings into operation, 4 pressure drop of reactor B is 0.18MPa.
Entire operation cycle keeps the product property after residual hydrocracking are as follows: sulfur content
0.12 weight %, 0.28 weight % of nitrogen content, 5.8 weight % of carbon residue, 18 μ g/g of heavy metal (Ni+V) meet RFCC charging
It is required that.
After device continuously runs 6000h, 4 pressure drop rise of reactor B to 0.70MPa, the logistics that reactor A 3 is exported is straight
Connecting device, a small amount of hydrogen, which enters the purging of reactor B 4 maintains temperature, device to operate 800 hours again after, protects reaction zone 1, de- gold
Belong to reaction zone 2, desulfurization takes off carbon residue reaction zone first reactor 8, reactor A 3 and the series connection of reactor B 4 are stopped work.
In this comparative example, the dosage weight ratio of residual oil raw material and cleaning oil A are 87:13.
Respectively on the catalyst loaded in first reactor or reactor A 3 after embodiment 4-6 and comparative example 3-5 shut-down
Carbon deposit analyzed, analysis the results are shown in Table 2 and table 3.By table 2 and table 3 it can be seen that coke content and corresponding in embodiment 4-6
Comparative example is compared, and carbon content is greatly reduced, and is conducive to drawing off for the catalyst reactor.
Table 1: the property of feed residue and cleaning oil and its miscella
Table 2: the average content (g/100g fresh catalyst) of charcoal on 8 catalyst of first reactor
Table 3: the average content (g/100g fresh catalyst) of charcoal on 3 catalyst of reactor A
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (18)
1. a kind of method of process residual oils raw material, this method comprises: under hydroprocessing conditions, by first containing feed residue
Material, which is introduced to, successively takes off consolidating for carbon residue reaction zone containing the protection reaction zone, hydrodemetallization reaction zone and desulfurization being connected in series
Hydrogenation reaction is carried out in fixed bed hydrogenation plant, wherein be sequentially connected in series in the de- carbon residue reaction zone of the desulfurization including at least two
Reactor, respectively reactor A and reactor B, and the material from the reactor A upstream sequentially enters the reactor A
With in the reactor B carry out hydrogenation reaction after go out device；
(a) when the fixed bed hydrogenation device reaches any one in the following conditions, the reactor A and described anti-is cut out
Answer any one in device B, and into the reactor cut out introduce containing hydrogen and cleaning oil second material with wherein into
Row plus hydrogen cleaning treatment；And switch the material from the reactor A upstream with reacting in the reactor cut out
Effluent is concomitantly introduced into the reactor not cut out into the reactor A and the reactor B to go out after progress hydrogenation reaction
Device；
It includes any one in the following conditions that the fixed bed hydrogenation device, which needs condition to be achieved:
(1) described fixed bed hydrogenation device continuous service 15 days or more；
(2) pressure drop in the reactor A or the reactor B reaches the pressure drop upper limit；
(3) there are radial temperature difference >=5 DEG C that hot spot makes reactor in the catalyst in the reactor A or the reactor B；
Optionally, by will be at the reactor A and the alternately described hydrogenation reaction of the reactor B and described plus hydrogen cleaning
It manages and repeating said steps (a), until the fixed bed hydrogenation device reaches shutdown conditions；
Wherein, total arene content in the cleaning oil is 50~95 weight %.
2. according to the method described in claim 1, wherein, in step (a), carrying out adding at hydrogen cleaning to the reactor cut out
When reason, when the pressure drop in the reactor cut out and the radial temperature difference in reactor are restored in values, stop to
The second material is introduced in the reactor cut out, and the reaction effluent in the reactor not cut out is introduced to this and is cut out
Reactor in carry out hydrogenation reaction after go out device.
3. method according to claim 1 or 2, wherein the condition of the reactor A or the reactor B is controlled, so that
When the fixed bed hydrogenation device is stopped work online, the reactor A or the reactor B are to have carried out the cleaning of described plus hydrogen
The state of processing at least for 24 hours.
4. according to the method described in claim 1, wherein, total arene content in the cleaning oil is 80~90 weight %.
5. method described in any one of -4 according to claim 1, wherein the two ring aromatic content in the cleaning oil is 30
~80 weight %；Preferably 50~70 weight %.
6. according to the method described in claim 1, wherein, the cleaning oil is split selected from straight-run diesel oil, catalytic cracking diesel oil, catalysis
Change at least one of recycle oil and catalytic cracked oil pulp.
7. method described in any one of -6 according to claim 1, wherein the pressure drop upper limit is that the de- carbon residue of the desulfurization is anti-
Answer the 40~80% of the design maximum pressure drop of the respective reaction device in area；Preferably,
The pressure drop upper limit is the 45~75% of the design maximum pressure drop of the respective reaction device in the de- carbon residue reaction zone of the desulfurization.
8. method described in any one of -6 according to claim 1, wherein the radial temperature difference of the reactor is 15~40
℃；Preferably 20~35 DEG C.
9. method according to claim 7 or 8, wherein in step (a), the reactor A and the reactor B exist
It is cut out every time add the continuous operating time of the hydrogenation reaction before hydrogen cleaning treatment as the fixed bed hydrogenation device
Continuous operation period 1/8~1/2, preferably 1/4~1/3.
10. the method according to any one of claim 7-9, wherein in step (a), the reactor A and described
Reactor B is being cut out every time add the continuous operation period that the time of hydrogen cleaning treatment is the fixed bed hydrogenation device
1/16~1/4, preferably 1/8~1/6.
11. method described in any one of -6 according to claim 1, wherein feed residue and step in the first material
Suddenly the dosage weight ratio of the cleaning oil in (a) is 10:(1~4.5)；Preferably,
Also containing cleaning oil in the first material, and when carrying out step (a), the cleaning oil in the first material is cut out
It carries out adding hydrogen cleaning treatment to be introduced in the reactor cut out.
12. according to the method for claim 11, wherein in step (a), carrying out adding hydrogen cleaning to the reactor cut out
When processing, when the pressure drop in the reactor cut out and the radial temperature difference in reactor are restored in values, stop
The second material is introduced into the reactor cut out, and the cleaning oil in the second material is switched back into first object
In material, and the reaction effluent in the reactor not cut out is introduced in the reactor cut out after progress hydrogenation reaction
Device.
13. method described in any one of -6 according to claim 1, wherein cut out the desulfurization and take off in carbon residue reaction zone
It is Residue Hydrotreating Technology condition, the residual hydrogenation in fixed bed hydrogenation device before and after reactor A or reactor B
Process conditions include: hydrogen partial pressure be 5.0~22.0MPa, reaction temperature is 330~450 DEG C, volume space velocity is 0.1~3.0h-1、
Hydrogen to oil volume ratio is 350~2000.
14. according to claim 1 or method described in 13, wherein the desulfurization cut out takes off the reactor A in carbon residue reaction zone
Or in reactor B plus hydrogen cleaning treatment condition include: hydrogen partial pressure be 5.0~22.0MPa, reaction temperature is 300~400
DEG C, hydrogen to oil volume ratio be 50~300, volume space velocity is 1.0~3.0 times of volume space velocity of the hydrogenation reaction.
15. according to the method for claim 14, wherein control the reactor in the de- carbon residue reaction zone of the desulfurization cut out
In A or reactor B plus hydrogen cleaning treatment condition so that after described plus hydrogen cleaning treatment the cleaning oil density drop
Low value is 10~30kg/m3, preferably 15~25kg/m3。
16. according to the method described in claim 1, wherein, be filled in the fixed bed hydrogenation device hydrogenation protecting catalyst,
Hydrodemetalation catalyst, Hydrobon catalyst and carbon residue hydrogenation conversion catalyst, the hydrogenation protecting catalyst plus hydrogen are de-
Carrier in metallic catalyst, Hydrobon catalyst and carbon residue hydrogenation conversion catalyst is each independently selected from aluminium oxide, oxygen
At least one of SiClx and titanium oxide；Preferably,
The carrier is via the element modified rear modified support obtained selected from boron, germanium, zirconium, phosphorus, chlorine and fluorine.
17. according to the method for claim 16, wherein the hydrogenation protecting catalyst, Hydrodemetalation catalyst plus hydrogen
Active metal component in desulphurization catalyst and carbon residue hydrogenation conversion catalyst is each independently selected from group VIB and Section VIII
At least one of non-noble metal j element of race；Preferably,
In the hydrogenation protecting catalyst, Hydrodemetalation catalyst, Hydrobon catalyst and carbon residue hydrogenation conversion catalyst
Active metal component be each independently at least one of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum and cobalt-molybdenum combination.
18. according to the method described in claim 1, wherein, the feed residue is decompression residuum and/or reduced crude；It is preferred that
Ground,
The colloid-stabilised coefficient of the first material is not more than 2.0.
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