CN108102699B - A kind of coal tar method of comprehensive utilization - Google Patents
A kind of coal tar method of comprehensive utilization Download PDFInfo
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- CN108102699B CN108102699B CN201611052155.5A CN201611052155A CN108102699B CN 108102699 B CN108102699 B CN 108102699B CN 201611052155 A CN201611052155 A CN 201611052155A CN 108102699 B CN108102699 B CN 108102699B
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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of coal tar method of comprehensive utilization, and the method includes the following contents: coal tar enters preatreating reactors with pretreating agent and mixes, and is uniformly mixed and isolates coal tar after insoluble matter is purified through precipitating filtration treatment；Enter boiling bed hydrogenation processing reaction zone after coal tar is mixed with hydrogen after obtained purification and carries out hydrotreating；The reaction that boiling bed hydrogenation processing reaction zone obtains obtains gas, naphtha, diesel oil, wax oil and tail oil after generating the reaction effluent separation that oil is successively obtained by the fixed bed hydrogenation pretreatment reaction area being arranged in series and fixed bed hydrogenation processing reaction zone, fixed bed hydrogenation processing reaction zone.This method process is simple, it is only necessary to carry out simple modifications to existing apparatus, so that it may substantially extend the operation cycle of device, and the utilization efficiency of catalyst can be made to realize and maximized.
Description
Technical field
The present invention relates to a kind of heavy oil lighting processing methods, handle coal tar using hydrogenation technique more particularly to a kind of
Process.
Background technique
High temperature coal-tar is one of the major secondary chemical products of coke-oven gas recycling, is rich in distinctive aromatic compound
Object is valuable chemical resource.During existing rectifying separation processing technique, the yield of coal tar pitch is up to 55% or more, and
The outlet of coal tar pitch is always to restrict the bottleneck problem of coal tar processing industry.Its is cheap, seriously affects tar production enterprise
The economic benefit of industry, it is difficult to which processing forces a large amount of high temperature coal-tar to yield processing and make fuel and directly burn up, serious wave
Valuable chemical products resource is taken.Solve the problems, such as that this fundamental solution is to excavate high temperature coal-tar property deeply
Analysis, tailors distinctive processing route according to its property, final to realize " making the best use of everything ".In view of high temperature coal-tar boiling range across
Degree is big, complicated composition, the characteristics such as condensed-nuclei aromatics content height, from utilization of resources angle, compared to traditional pure chemical separating route or
Currently a popular pure of person plus hydrogen produce light-weight fuel oil route, for high temperature coal-tar " tailoring " " suitable hydrocarbon then hydrocarbon " " preferably oil
The route economy of then oil " is higher, and resource utilization is also higher.Related high temperature coal-tar production industrial chemicals takes into account production at present
The report of light-weight fuel oil is relatively fewer.
Patent CN103254928A describes a kind of method that raising high temperature coal-tar added value utilizes.This method is with high temperature
Coal tar or its with organic solvent than mixed high temperature coal-tar solution be raw material by certain mass, by batch autoclave or
Continuous fixed-bed reactor carries out the selective catalytic hydrogenation conversion reaction of high temperature coal-tar under hydrogenation catalyst effect,
Low aromatic compound is converted by the especially coal tar pitch directional catalyzing of the polycyclic aromatic hydrocarbon compound in high temperature coal-tar.We
Method is using the full fraction of high temperature coal-tar as raw material, and existing structure is relatively easy in high temperature coal-tar, relatively high pair of reactivity
The aromatic hydrocarbons such as ring, tricyclic also have the heavy constituents such as structure is complicated, the reaction biggish coal tar pitch of difficulty, under the same conditions to different work
Property component carry out plus hydrogen, it is likely that cause in system original low cyclophane cycle compound such as naphthalenes to be hydrogenated saturation and generate saturation
Hydrocarbon ultimately causes low cyclophane cycle compound loss, also results in original phenolic compound in system and be removed.And high temperature coal-tar
In phenols and naphthalenes be the industrial chemicals being of great value, using the method for the full fraction direct hydrogenation of high temperature coal-tar will cause high price
It is worth the loss of industrial chemicals；In addition, high temperature coal-tar belongs to the heavy charge of high carbon residue, high asphalitine, using traditional continuous
Fixed-bed reactor carries out plus hydrogen, it is easy to cause bed to block, cause shorten operation cycle, and batch still high-pressure installation and
It is unable to satisfy device quantity-produced requirement.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of coal tar method of comprehensive utilization.This method process is simple,
It only needs to carry out simple modifications to existing apparatus, so that it may substantially extend the operation cycle of device, and the benefit of catalyst can be made
It is realized and is maximized with efficiency.The method of the present invention organically combines fixed bed and boiling bed hydrogenation, and coal tar raw material adds by boiling
It can guarantee utmostly to obtain light-end products using fixed bed hydrogenation after the processing of hydrogen bed.
The present invention provides a kind of coal tar method of comprehensive utilization, and the method includes the following contents:
(1) coal tar enters preatreating reactors with pretreating agent and mixes, and is uniformly mixed and through precipitating filtration treatment separation
Insoluble matter is purified rear coal tar out；
(2) enter boiling bed hydrogenation processing reaction zone after coal tar is mixed with hydrogen after the purification that step (1) obtains to carry out
Hydrotreating；
(3) it is successively pre- by the fixed bed hydrogenation being arranged in series to generate oil for the reaction that boiling bed hydrogenation processing reaction zone obtains
It handles reaction zone and fixed bed hydrogenation handles reaction zone, after the reaction effluent separation that fixed bed hydrogenation processing reaction zone obtains
Obtain gas, naphtha, diesel oil, wax oil and tail oil；
Wherein, fixed bed hydrogenation pretreatment reaction area includes at least two weighted BMO spaces reactions being arranged in parallel
Device, when the pressure drop of any one weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area reaches predetermined value,
The weighted BMO spaces reactor that pressure drop reaches predetermined value is cut out from fixed bed hydrogenation pretreatment reaction area, and by the fixation
Bed hydroprocessing pretreatment reaction area, the pressure drop reach the weighted BMO spaces reactor of predetermined value and the fixed bed hydrogenation is handled instead
Area is answered to be connected in turn in series, wherein the predetermined value designs the 50%~80% of the upper limit for pressure drop, preferably
60%~70%.
In the method for the present invention, coal tar described in step (1) can be complete for the full fraction of middle coalite tar, high temperature coal-tar
One of fraction of liquid product and full fraction of coal tar that fraction, coal hydrogenation cracking obtain excision tail oil is several mixed
Close object.
In the method for the present invention, pretreating agent as described in step (1) is solvent naphtha, the boiling range of the solvent naphtha is 65~
450 DEG C, preferably 120~400 DEG C, more preferably 150~320 DEG C, in the composition of the solvent naphtha, alkane and cycloalkane contain
Amount be 70~90%, specifically can be hydrofining diesel oil, hydrofinishing naphtha, hydrofinishing washing oil, hydrofinishing light oil,
One of hydrofinishing carbolic oil or several mixtures.The mass ratio of the pretreating agent and coal tar is 1:20~1:3,
Preferably 1:10~1:5.
In the method for the present invention, the reaction temperature of preprocessor as described in step (1) is 150~250 DEG C.
In the method for the present invention, tail oil described in step (3) can be recycled back to boiling bed hydrogenation processing reaction zone, or defocus
Change reaction or as fuel oil etc..
In the method for the present invention, in the reaction initial stage, fixed bed hydrogenation pretreatment reaction area described in step (3) includes 3
~6, preferably include 3~4 weighted BMO spaces reactors being arranged in parallel.
It is when the pressure drop of a weighted BMO spaces reactor reaches the predetermined value, this plus hydrogen is pre- in the method for the present invention
Treatment reactor is cut out from fixed bed hydrogenation pretreatment reaction area, which is named as to cut out plus hydrogen
Preatreating reactors I, and by fixed bed hydrogenation pretreatment reaction area, the weighted BMO spaces reactor I cut out and institute
It states fixed bed hydrogenation processing reaction zone to be connected in turn in series, at this time the weighted BMO spaces reactor I cut out
Charging be remaining all weighted BMO spaces reactors in parallel reaction effluent；When the pressure of next weighted BMO spaces reactor
Drop cuts out the weighted BMO spaces reactor when reaching the predetermined value from fixed bed hydrogenation pretreatment reaction area, by this plus
Hydrogen pretreatment reactor is named as the weighted BMO spaces reactor II cut out, and by fixed bed hydrogenation pretreatment reaction area,
The weighted BMO spaces reactor II cut out, the weighted BMO spaces reactor I cut out and fixed bed hydrogenation processing
Reaction zone is connected in turn in series；In the manner described above, until all weighted BMO spaces reactor all
It is connected in series to.
In the method for the present invention, all weighted BMO spaces are anti-in fixed bed hydrogenation pretreatment reaction area described in step (3)
The pressure drop of device is answered not reach predetermined value simultaneously, it is two neighboring to reach closest to the weighted BMO spaces reactor for reaching pressure drop predetermined value
20% of the time difference of its pressure drop predetermined value not less than the whole device cycle of operation, preferably 20%~60%.
In the method for the present invention, by the setting of operating condition and/or the difference of catalyst bed property fixed bed is added
Each weighted BMO spaces reactor does not reach pressure drop predetermined value simultaneously in hydrogen pretreatment reaction zone, for example, can be each by controlling
Different catalyst packing heights, different inlet amounies, different feed properties, different behaviour in a weighted BMO spaces reactor
Make under the conditions of condition and identical filling height using one of different Catalyst packing density or various ways come real
Each weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area is now set not reach pressure drop predetermined value simultaneously.
In the method for the present invention, used under the conditions of identical filling height when by controlling in each weighted BMO spaces reactor
The mode of different Catalyst packing density is come when realizing, in fixed bed hydrogenation pretreatment reaction area, each of parallel connection adds hydrogen
In preatreating reactors, maximum loading density can be 400kg/m3~600kg/m3, preferably 450kg/m3~550kg/m3；
Minimum loading density can be 300kg/m3~550kg/m3, preferably 350kg/m3~450kg/m3.Preferably, loading density
The Catalyst packing density difference of immediate two weighted BMO spaces reactors is 50kg/m3~200kg/m3, preferably
80kg/m3~150kg/m3.The difference loading density can by different types of catalyst grade it is equipped tamp it is existing, such as can be with
Realize that the Catalyst packing density in each weighted BMO spaces reactor is different in different proportions by hydrotreating catalyst.
In the method for the present invention, when being realized by way of control inlet amount different in each weighted BMO spaces reactor
When, the ratio between feed volume air speed of the immediate two weighted BMO spaces reactors of inlet amount can be 1.1 ~ 3:1, preferably
1.1 ~ 1.5:1.
In the method for the present invention, when carrying out reality by way of controlling feed properties different in each weighted BMO spaces reactor
Now, the tenor difference of the immediate two weighted BMO spaces reactors of feed properties can be 5 μ of μ g/g ~ 50 g/g, excellent
It is selected as 10 μ of μ g/g ~ 30 g/g.
In the method for the present invention, when carrying out reality by way of controlling operating condition different in each weighted BMO spaces reactor
Now, it controls in operating pressure and the operating condition of the immediate two weighted BMO spaces reactors of volume space velocity, operation temperature
Difference can be 2 DEG C ~ 30 DEG C, preferably 5 DEG C ~ 20 DEG C；Or control operating pressure and operation temperature immediate two plus hydrogen
In the operating condition of preatreating reactors, volume space velocity difference is 0.1 h-1~10 h-1, preferably 0.2 h-1~5 h -1。
In the method for the present invention, according to Flow of Goods and Materials direction, hydrogenation protecting is successively loaded in each weighted BMO spaces reactor
Agent, Hydrodemetalation catalyst；Each weighted BMO spaces reactor can set according to itself process conditions and not load hydrodesulfurization
Catalyst loads a certain proportion of hydrodesulfurization catalytic after can also being set in Hydrodemetalation catalyst according to itself process conditions
Agent；The reactor in the hydrotreating reaction area successively loads Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.
In the method for the present invention, 1 or more boiling bed hydrogenation reactor is can be set in boiling bed hydrogenation processing reaction zone, excellent
Choosing 1 or 2 boiling bed hydrogenation reactor being arranged in series of setting.Boiling bed hydrogenation reactor can use boiling in the prior art
Rise a reactor.The reaction condition that boiling bed hydrogenation handles reaction zone can require specific according to feed properties and reaction conversion ratio
It determines, generally are as follows: reaction temperature is 330~450 DEG C, preferably 360~430 DEG C；Reaction pressure be 8~25MPa, preferably 10
~16MPa；Hydrogen to oil volume ratio 300:1 ~ 1000:1, preferably 600:1~900:1；Liquid volume air speed (LHSV) is 0.3 h-1
~5.0h-1, preferably 0.3 h-1~2.0h-1。
In the method for the present invention, the operating condition in fixed bed hydrogenation pretreatment reaction area are as follows: temperature is 370 DEG C~420
DEG C, preferably 380 DEG C~400 DEG C；Pressure is 10MPa~25MPa, preferably 15MPa~20MPa；Hydrogen to oil volume ratio be 300~
1500, preferably 500~800；Volume space velocity is 0.15h when raw material oil liquid-1~2h-1, preferably 0.3h-1~1h-1。
In the method for the present invention, the fixed bed hydrogenation processing reaction zone may include 1~5 hydrotreating being arranged in series
Reactor preferably includes 1~2 hydrotreating reactor being arranged in series.
In the method for the present invention, the operating condition of the fixed bed hydrogenation processing reaction zone are as follows: temperature is 370 DEG C~430 DEG C,
Preferably 380 DEG C~410 DEG C；Pressure is 10MPa~25MPa, preferably 15MPa~20MPa；Hydrogen to oil volume ratio be 300~
1500, preferably 400~800；Volume space velocity is 0.15h when raw material oil liquid-1~0.8h-1, preferably 0.2h-1~0.6h-1。
Compared with prior art, provided by the invention described, coal tar method of comprehensive utilization has the advantages that
It (1) include multiple weighted BMO spaces reactors in parallel in fixed bed hydrogenation pretreatment reaction area, so that whole
A catalyst system takes off/holds metal ability and is increased dramatically.
(2) in coal tar method of comprehensive utilization method of the present invention, when the pressure drop of a weighted BMO spaces reactor increases
When length to predetermined value, it is cut out from fixed bed hydrogenation pretreatment reaction area, and by the change of process flow, make its pressure drop not
Rapid growth again, but slowly increase in range can control until device is stopped work, and then reacts some weighted BMO spaces
The pressure drop of device will not restrict the cycle of operation of whole device.
(3) in coal tar method of comprehensive utilization of the present invention, by will in fixed bed hydrogenation pretreatment reaction area it is each
To solve weighted BMO spaces reactor pressure decrease fast from the adjustment for being parallel to series connection handover operation mode for a weighted BMO spaces reactor
The problem that speed increases, while increasing the operating flexibility and raw material adaptability of device.
(4) in coal tar method of comprehensive utilization of the present invention, by the way that weighted BMO spaces reactor parallel form is arranged
The appearance amount of metal of catalyst system is significantly increased, so that the stability of system enhances, the growth of device pressure drop is obtained
Control extends the device cycle of operation.
(5) coal tar method of comprehensive utilization of the present invention can utmostly realize the synchronous inactivation of all kinds of catalyst,
To improve the operational efficiency of device, increase economic efficiency.
(6) in coal tar method of comprehensive utilization of the present invention, by weighted BMO spaces reaction zone catalyst performance
Energy is optimized and revised with technological parameter, the cooperation with subsequent high activity desulfurization carbon residue reforming catalyst, so that whole improving
Desulfurization and carbon residue conversion performance are guaranteed while de-/appearance metal ability of catalyst.
(7) in coal tar method of comprehensive utilization of the present invention, pass through fixed bed and bubbling bed combined process, Ke Yishi
Now utmostly obtain light-end products.The method of the present invention combines fixed bed and the comprehensive advantage of ebullated bed improves dress on the whole
The operational efficiency set, increases economic efficiency.
Detailed description of the invention
Fig. 1 is a kind of schematic diagram of embodiment of coal tar method of comprehensive utilization of the present invention.
Fixed bed hydrogenation pretreatment reaction area and fixed bed hydrogenation in Fig. 2 coal tar method of comprehensive utilization of the present invention
Handle reaction zone schematic diagram.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
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.
In coal tar method of comprehensive utilization of the present invention, the predetermined value for pressure drop design the upper limit 50%~
80%, for example, 50%, 51%, 53%, 54%, 55%, 56%, 57%, 58%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%,
69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80% and model composed by any two value in them
Arbitrary value between enclosing.In the preferred case, the predetermined value designs the 60%~70% of the upper limit for pressure drop.In the present invention, institute
The maximum value that the pressure drop design upper limit refers to reactor pressure decrease is stated, when reactor pressure decrease reaches the value, reaction system needs to stop work,
The pressure drop design upper limit is usually the MPa of 0.7 MPa ~ 1.0.
In coal tar method of comprehensive utilization of the present invention, when the pressure drop difference of all weighted BMO spaces reactors
Reach predetermined value.In the preferred case, two neighboring to reach it closest to the weighted BMO spaces reactor for reaching pressure drop predetermined value
The time difference of pressure drop predetermined value is not less than 20%, the preferably 20-60% in whole service period in whole service period, for example,
20%,25%,30%,35%,40%,45%,50%,55%,60%.In the present invention, the whole service period refers to that coal tar is comprehensive
Using in method, bring into operation from device to the time experienced of stopping work.
In coal tar method of comprehensive utilization of the present invention, each of fixed bed hydrogenation pretreatment reaction area adds
Hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogeneration can be loaded in hydrogen pretreatment reactor
One of carbon residue reforming catalyst is a variety of, can load in the reactor of the fixed bed hydrogenation processing reaction zone plus hydrogen is de-
One of sulfur catalyst and hydrodenitrogeneration carbon residue reforming catalyst are a variety of.
In a preferred embodiment, it according to Flow of Goods and Materials direction, is successively loaded in each weighted BMO spaces reactor
Hydrogenation protecting agent, Hydrodemetalation catalyst and optional Hydrobon catalyst；The reaction in the hydrotreating reaction area
Device successively loads Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.It is filled according to the catalyst of the preferred embodiment
Embankment formula, so that de-/appearance metal ability of whole system is increased dramatically, while the adjustment matched by catalyst grade is so that each
The pressure drop of a weighted BMO spaces reactor increases in control range.In fixed bed hydrogenation pretreatment reaction area it is in parallel each plus
The catalyst system of hydrogen pretreatment reactor filling with it is de-/hold based on metal function so that while demetalization performance boost, by force
Change the ability to the hydro-conversion of such as gum asphalt of macromolecular in raw material, establishes base for successive depths desulfurization and the conversion of carbon residue
Plinth, so that hydrodesulfurizationreaction reaction zone is conducive to further deep reaction, therefore, compared with routine techniques, side of the present invention
Although the ratio of Hydrodemetalation catalyst improves in method, the hydro-conversion of whole desulphurizing activated and carbon residue
Performance is not only improved without reducing instead.
In the present invention, the hydrogenation protecting agent, the Hydrodemetalation catalyst, the Hydrobon catalyst and institute
Stating hydrodenitrogeneration carbon residue reforming catalyst all can be the conventional use of catalyst of fixed bed heavy-oil hydrogenation treatment process.These are urged
Agent usually with porous refractory inorganic oxide (such as aluminium oxide) for carrier, group VIB and/or group VIII metal (such as W, Mo,
Co, Ni etc.) oxide be active component, be selectively added the catalyst of the elements such as various other auxiliary agents such as P, Si, F, B.
For example, the FZC series heavy oil hydrogenating treatment catalyst produced by Sinopec Group's catalyst branch.
In the present invention, the boiling bed hydrogenation of catalyst this field routine used in the boiling bed hydrogenation reactor is urged
For agent generally using aluminium oxide as carrier, particle is spherical shape, and diameter is 0.1~0.8mm, preferably 0.1~0.6mm, wear≤
2.0wt%, catalyst specific surface are 100~300m2/ g, bore dia at least account for the 70% of total pore volume in the hole of 5~20nm；With weight
Meter, catalyst contain VI B family metal oxide (such as MoO3) 12.0%~30.0%, preferably 15.0%~25.0%, contain VIII race's metal
Oxide (such as NiO or CoO) 0.5%~10.0%, preferably 2.0%~8.0%.Containing at least one auxiliary agent, selected from following several
Element: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content are 1.0%~8.0%.
Fig. 1 is a kind of schematic diagram of embodiment of coal tar method of comprehensive utilization of the present invention, and Fig. 2 is present invention side
Fixed bed hydrogenation pretreatment reaction area and fixed bed hydrogenation handle reaction zone schematic diagram in method.Below with reference to Fig. 1, Fig. 2 to this hair
The bright coal tar method of comprehensive utilization is further described, but not thereby limiting the invention.
As shown in Figure 1 and Figure 2, coal tar method of comprehensive utilization of the present invention includes following content: coal tar raw material M1
Enter preatreating reactors R5 after mixing with pretreating agent M2, rear coal tar M3 and impurity M4 is purified after processing, is obtained
Enter boiling bed hydrogenation reactor R1 after coal tar M3 is mixed with hydrogen M21 after purification, boiling bed hydrogenation reactor R1 is obtained
The material M5 of liquid phase enters the fixed bed hydrogenation being arranged in series through feeding line 1, feeding line 2 and feeding line 3 and pre-processes instead
Area R2 and fixed bed hydrogenation is answered to handle reaction zone R3, after the reaction effluent separation that fixed bed hydrogenation processing reaction zone R3 is obtained
To gas M7, naphtha M8, diesel oil M9, wax oil M10 and tail oil M11.Wherein fixed bed hydrogenation pretreatment reaction area R2 packet
Include three weighted BMO spaces reactors being arranged in parallel, respectively weighted BMO spaces reactor A, weighted BMO spaces reactor B plus
Hydrogen pretreatment reactor C, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C into
Material mouth is connect with feeding line 1, feeding line 2 and feeding line 3 respectively, the outlet point three of the weighted BMO spaces reactor A
Road, the first via are connect through pipeline 6 with the feed inlet of weighted BMO spaces reactor B, and the second tunnel is reacted through pipeline 7 with weighted BMO spaces
The feed inlet of device C connects, and third road is connect through pipeline 10 with the feed inlet of hydrodesulphurisatioreactors reactors D；The weighted BMO spaces are anti-
Three tunnels of outlet point of device B are answered, the first via is connect through pipeline 4 with the feed inlet of weighted BMO spaces reactor A, and the second tunnel is through pipeline 5
It obtains feed inlet with weighted BMO spaces reactor C to connect, third road is connect through pipeline 11 with the feed inlet of hydrotreating reactor D；
Three tunnels of the outlet of the weighted BMO spaces reactor C point, the first via connect through the feed inlet of pipeline 8 and weighted BMO spaces reactor A
It connects, the second tunnel is connect through pipeline 9 with the feed inlet of weighted BMO spaces reactor B, and third road is through pipeline 12 and hydrotreating reaction
The feed inlet of device D connects；It is provided with valve 101 on the pipeline 1, is provided with valve 102 on the pipeline 2, on the pipeline 3
It is provided with valve 103, valve 104 is provided on the pipeline 4, valve 105 is provided on the pipeline 5, is set on the pipeline 6
It is equipped with valve 106, valve 107 is provided on the pipeline 7, valve 108 is provided on the pipeline 8, is arranged on the pipeline 9
There is valve 109, valve 1010 is provided on the pipeline 10, be provided with valve 1011 on the pipeline 11, on the pipeline 12
It is provided with valve 1012, the generation oil M6 that the hydrotreating reactor D is obtained obtains gas M7, naphtha after entering separation
M8, diesel oil M9, wax oil M10 and tail oil M11.The weighted BMO spaces reactor A, the weighted BMO spaces reactor B and described
It is each provided with the sensing unit (not shown) for monitoring pressure drop in weighted BMO spaces reactor C, and further includes control
Unit (not shown) processed, for receiving the pressure drop signal from the sensing unit, and according to pressure drop signal control with
The corresponding valve of each weighted BMO spaces reactor.
In above-mentioned coal tar method of comprehensive utilization, weighted BMO spaces reactor A, weighted BMO spaces reactor B and plus hydrogen
Preatreating reactors C can be inactivated in any order, it is preferred to use following six kinds of modes switch over operation:
Mode 1: according to weighted BMO spaces reactor A, weighted BMO spaces reactor B, the sequence of weighted BMO spaces reactor C
Reach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,
Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9
Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces
The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor A reaches predetermined value from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes valve 101, the valve 1011 of pipeline 11 and the valve 1012 of pipeline 12 of feeding line 1, opens pipeline 8
On valve 108 and pipeline 4 on valve 104 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor B and plus
Hydrogen pretreatment reactor C), weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection
To concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes the valve 102 of feeding line 2, the valve 108 of pipeline 8, the valve 109 on pipeline 9 is opened, so that plus hydrogen
Preatreating reactors C, weighted BMO spaces reactor B, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, this
When complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor C reaches the design upper limit, entire reaction system needs shutdown process.
Mode 2: according to weighted BMO spaces reactor A, weighted BMO spaces reactor C, weighted BMO spaces reactor B sequence
Reach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,
Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9
Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces
The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor A reaches predetermined value from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes valve 101, the valve 1011 of pipeline 11 and the valve 1012 of pipeline 12 of feeding line 1, opens pipeline 8
On valve 108 and pipeline 4 on valve 104 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor B and plus
Hydrogen pretreatment reactor C), weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection
To concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes the valve 103 of feeding line 3, the valve 104 of pipeline 4, the valve 105 on pipeline 5 is opened, so that plus hydrogen
Preatreating reactors B, weighted BMO spaces reactor C, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, this
When complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, entire reaction system needs shutdown process.
Mode 3: according to weighted BMO spaces reactor B, weighted BMO spaces reactor C, weighted BMO spaces reactor A sequence
Reach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,
Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9
Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces
The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor B reaches predetermined value from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes valve 102, the valve 1010 of pipeline 10 and the valve 1012 of pipeline 12 of feeding line 2, opens pipeline 9
On valve 109 and pipeline 6 on valve 106 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plus
Hydrogen pretreatment reactor C), weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection
To concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes the valve 103 of feeding line 3, the valve 106 of pipeline 6, the valve 107 on pipeline 7 is opened, so that plus hydrogen
Preatreating reactors A, weighted BMO spaces reactor C, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, this
When complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, entire reaction system needs shutdown process.
Mode 4: according to weighted BMO spaces reactor B, weighted BMO spaces reactor A, the sequence of weighted BMO spaces reactor C
Reach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,
Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9
Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces
The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor B reaches predetermined value from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes valve 102, the valve 1010 of pipeline 10 and the valve 1012 of pipeline 12 of feeding line 2, opens pipeline 9
On valve 109 and pipeline 6 on valve 106 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plus
Hydrogen pretreatment reactor C), weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection
To concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes the valve 101 of feeding line 1, the valve 109 of pipeline 9, the valve 108 on pipeline 8 is opened, so that plus hydrogen
Preatreating reactors C, weighted BMO spaces reactor A, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, this
When complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, entire reaction system needs shutdown process.
Mode 5: according to weighted BMO spaces reactor C, weighted BMO spaces reactor B, the sequence of weighted BMO spaces reactor A
Reach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,
Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9
Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces
The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor C reaches predetermined value from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes valve 103, the valve 1010 of pipeline 10 and the valve 1011 of pipeline 11 of feeding line 3, opens pipeline 7
On valve 107 and pipeline 5 on valve 105 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plus
Hydrogen pretreatment reactor B), weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection
To concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes the valve 102 of feeding line 2, the valve 107 of pipeline 7, the valve 106 on pipeline 6 is opened, so that plus hydrogen
Preatreating reactors A, weighted BMO spaces reactor B, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, this
When complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, entire reaction system needs shutdown process.
Mode 6: according to weighted BMO spaces reactor C, weighted BMO spaces reactor A, the sequence of weighted BMO spaces reactor B
Reach pressure drop predetermined value.
(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102,
Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9
Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；
(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces
The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor C reaches predetermined value from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes valve 103, the valve 1010 of pipeline 10 and the valve 1011 of pipeline 11 of feeding line 3, opens pipeline 7
On valve 107 and pipeline 5 on valve 105 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plus
Hydrogen pretreatment reactor B), weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection
To concatenated handover operation；
(3) it when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to
The pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valve
Control specifically closes the valve 101 of feeding line 1, the valve 105 of pipeline 5, the valve 104 on pipeline 4 is opened, so that plus hydrogen
Preatreating reactors B, weighted BMO spaces reactor A, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, this
When complete the 2nd time by being parallel to concatenated handover operation；
(4) when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, entire reaction system needs shutdown process.
Illustrate effect of the invention below with reference to specific embodiment, it is used in embodiment of the present invention and comparative example
Raw material is including three kinds, and respectively raw material A, raw material B, raw material C, specific nature are shown in Table 1, the boiling bed hydrogenation reaction zone setting 1
A boiling bed hydrogenation reactor, the interior catalyst loaded of the boiling bed hydrogenation reactor is boiling bed hydrogenation catalyst.Boiling
Bed hydrogenation catalyst prepares the spherical carrier of catalyst that average pore size is 13nm, and spherical catalyst particles 0.1-0.3mm is other
Catalyst preparation process is carried out referring to US7074740 and CN200710010377.5 method.It is molten that Mo-Co-P is prepared according to a conventional method
Liquid, MoO3 mass meter content is 18.00% in solution, and it is 1.05% that content, which is 3.50%, P mass content, in terms of CoO mass.With this
Solution impregnates above-mentioned carrier by incipient impregnation method and obtains final catalyst.
Boiling bed hydrogenation reactor of the present invention is a kind of three-phase fluidized bed reactor, can be used
The fluidized bed reactor that CN02109404.7, CN200610134154.5 and CN200710012680.9 etc. are announced, Neng Gouman
Sufficient gas, liquid, solid three-phase separates in fluidized bed reactor.
The type of feed of catalyst is shown in Table 2 in the Examples 1 to 3, the filling side of catalyst in the comparative example 1~3
Formula is shown in Table 3, and the reaction condition of the Examples 1 to 3 is shown in Table 4, and the reaction condition of the comparative example 1~3 is shown in Table 5, the implementation
The reaction result of example 1~3 and comparative example 1~3 is shown in Table 6.Using conventional tandem process, other difference in the comparative example 1-3
It is corresponding identical as Examples 1 to 3.Weighted BMO spaces reactor A described in the embodiment of the present invention, weighted BMO spaces reactor B,
Weighted BMO spaces reactor C is pattern, the identical reactor of size, reactor A, reactor B, reactor in the comparative example
C is pattern, the identical reactor of size.
Pretreating agent solvent oil nature used in the embodiment of the present invention and comparative example is as follows: density 0.86kg/m3(20 DEG C),
Viscosity is 5.31mm2/ s(40 DEG C), sulfur content is 55 μ g/g, and nitrogen content is 15 μ g/g, and saturation is divided into 75.70%, and aromatic hydrocarbons is
24.3%。
Embodiment 1
Weighted BMO spaces reactor A, weighted BMO spaces reactor B described in embodiment 1, in weighted BMO spaces reactor C all
Using raw material A, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, the catalyst of weighted BMO spaces reactor C are total
Loading amount, feed properties and inlet amount are identical, and the weighted BMO spaces reactor A, weighted BMO spaces reactor B plus hydrogen are pre-
Treatment reactor C, hydrodesulphurisatioreactors reactors D catalyst loaded in the way of in table 2, the operating condition is shown in Table 4, specifically
Reaction result is shown in Table 6, and the product property obtained after boiling bed hydrogenation cracking is shown in Table 7.Pretreatment used in the embodiment 1
Device reaction temperature is 200 DEG C.
Embodiment 2
In embodiment 2, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, in weighted BMO spaces reactor C
Raw material B is all used, specific nature is shown in Table 1, and each anti-Feed space velocities are different, volume space velocity when the weighted BMO spaces reactor A liquid
For 0.20h-1, volume space velocity is 0.32h when weighted BMO spaces reactor B liquid-1, volume space velocity when weighted BMO spaces reactor C liquid
For 0.44h-1.Weighted BMO spaces reactor A, weighted BMO spaces reactor B are urged using identical in weighted BMO spaces reactor C
Agent type of feed, catalyst loading pattern are shown in Table 2, and the operating condition of each reactor is shown in Table 4, and specific reaction result is shown in
Table 6.Preprocessor reaction temperature used is 220 DEG C.
Embodiment 3
It is former using being used in raw material A, weighted BMO spaces reactor B in the weighted BMO spaces reactor A in embodiment 3
Expect to use raw material C in B, weighted BMO spaces reactor C, raw material property is shown in Table 1.The weighted BMO spaces reactor A plus hydrogen
Preatreating reactors B, the inlet amount of weighted BMO spaces reactor C are identical, the weighted BMO spaces reactor A, weighted BMO spaces
Identical catalyst loading pattern is used in reactor B, weighted BMO spaces reactor C, catalyst loading pattern is shown in Table 2, described
The operating condition of each reactor is shown in Table 4, and specific reaction result is shown in Table 6.Preprocessor reaction temperature used is 180 DEG C.
Comparative example 1
Also 4 reactors, respectively reactor A, reactor B, reactor C, reactor D, reactor are used in comparative example 1
A, reactor B, reactor C are connected in the form of being sequentially connected in series with reactor D.Raw materials used A property is shown in Table 1 in comparative example 1,
The inlet amount and feed properties of reactor A are identical with the total feed of embodiment 1 and feed properties.Preprocessor used is anti-
Answering temperature is 200 DEG C.The reactor A, reactor B, the catalyst inventory of reactor C and reactor D are corresponding with embodiment
Weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D are identical, but
Be various species catalyst loadings it is different, loaded in the way of in table 3, the operating condition is shown in Table 5, specific anti-
6 should be the results are shown in Table.
Comparative example 2
Also 4 reactors, respectively reactor A, reactor B, reactor C, reactor D, reactor are used in comparative example 2
A, reactor B, reactor C are connected in the form of being sequentially connected in series with reactor D.Raw material B is used in comparative example 2, property is shown in Table
1, reactor A entrance is identical with the total inlet amount of embodiment 2 and feed properties.Preprocessor reaction temperature used is 220
℃.The reactor A, reactor B, the catalyst inventory of reactor C and reactor D are corresponding with embodiment 2 plus hydrogen is located in advance
It is identical to manage reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D, but each kind
The loadings of class catalyst are different, load in the way of in table 3, and the operating condition is shown in Table 5.
Comparative example 3
Also 4 reactors, respectively reactor A, reactor B, reactor C, reactor D, reactor are used in comparative example 3
A, reactor B, reactor C are connected in the form of being sequentially connected in series with reactor D.Comparative example 3 uses raw material A, raw material B, raw material C
Equal proportion mixed raw material, reactor A, reactor B, reactor C and reactor D use concatenated form, reactor A in comparative example
Entrance is identical as the total inlet amount of embodiment 3 and mixed feeding property.Preprocessor reaction temperature used is 180 DEG C.It is described anti-
It answers the catalyst inventory of device A, reactor B, reactor C and reactor D weighted BMO spaces reactor A corresponding with embodiment, add
Hydrogen pretreatment reactor B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D are identical, but the dress of various species catalyst
The amount of filling out is different, loads in the way of in table 3, and the operating condition is shown in Table 5.
1 feedstock property of table
Catalyst loading pattern in 2 Examples 1 to 3 of table
Catalyst loading pattern in 3 comparative example 1~3 of table
The reaction condition of 4 Examples 1 to 3 of table
The reaction condition of 5 comparative example 1~3 of table
6 steady running period of table and residual hydrogenation generate oil nature
Claims (35)
1. a kind of coal tar method of comprehensive utilization, the method includes the following contents:
(1) coal tar enters preatreating reactors with pretreating agent and mixes, and is uniformly mixed and isolates not through precipitating filtration treatment
Molten object is purified rear coal tar；
(2) enter boiling bed hydrogenation processing reaction zone after coal tar is mixed with hydrogen after the purification that step (1) obtains to carry out adding hydrogen
Processing；
(3) reaction that boiling bed hydrogenation processing reaction zone obtains generates fixed bed hydrogenation pretreatment of the oil successively by being arranged in series
Reaction zone and fixed bed hydrogenation handle reaction zone, obtain after the reaction effluent separation that fixed bed hydrogenation processing reaction zone obtains
Gas, naphtha, diesel oil, wax oil and tail oil；
Wherein, fixed bed hydrogenation pretreatment reaction area includes at least two weighted BMO spaces reactors being arranged in parallel, when
When the pressure drop of any one weighted BMO spaces reactor reaches predetermined value in fixed bed hydrogenation pretreatment reaction area, by pressure drop
The weighted BMO spaces reactor for reaching predetermined value is cut out from fixed bed hydrogenation pretreatment reaction area, and by the fixed bed hydrogenation
Pretreatment reaction area, the pressure drop reach predetermined value weighted BMO spaces reactor and the fixed bed hydrogenation processing reaction zone with
Concatenated mode is connected in turn, wherein the predetermined value designs the 50%~80% of the upper limit for pressure drop.
2. according to the method for claim 1, wherein the predetermined value designs the 60%~70% of the upper limit for pressure drop.
3. according to the method for claim 1, wherein coal tar described in step (1) is the full fraction of middle coalite tar, height
One of fraction of liquid product and full fraction of coal tar that warm full fraction of coal tar, coal hydrogenation cracking obtain excision tail oil or
Several mixture of person.
4. according to the method for claim 1, wherein the reaction temperature of preprocessor as described in step (1) be 150~
250℃。
5. according to the method for claim 1, wherein pretreating agent as described in step (1) is solvent naphtha, the solvent naphtha
Boiling range be 65~450 DEG C, in the composition of the solvent naphtha, alkane and naphthene content are 70~90%.
6. according to method described in claim 1 or 5, wherein pretreating agent as described in step (1) is solvent naphtha, described molten
The boiling range of agent oil is 120~400 DEG C, and in the composition of the solvent naphtha, alkane and naphthene content are 70~90%.
7. according to method described in claim 1 or 5, wherein pretreating agent as described in step (1) is solvent naphtha, described molten
The boiling range of agent oil is 150~320 DEG C, and in the composition of the solvent naphtha, alkane and naphthene content are 70~90%.
8. according to the method for claim 5, wherein solvent naphtha described in step (1) is hydrofining diesel oil, hydrofinishing
One of washing oil, hydrofinishing naphtha, hydrofinishing carbolic oil or several mixtures.
9. according to the method for claim 1, wherein the mass ratio of pretreating agent described in step (1) and coal tar is 1:
20~1:3.
10. according to method described in claim 1 or 9, wherein the mass ratio of pretreating agent and coal tar described in step (1)
For 1:10~1:5.
11. according to the method for claim 1, wherein when the pressure drop of a weighted BMO spaces reactor reaches described predetermined
When value, which is cut out from fixed bed hydrogenation pretreatment reaction area, by the weighted BMO spaces reactor
It is named as the weighted BMO spaces reactor I cut out, and fixed bed hydrogenation pretreatment reaction area, the cut out plus hydrogen is pre-
Treatment reactor I and fixed bed hydrogenation processing reaction zone are connected in turn in series, and what this cut out at this time adds
The charging of hydrogen pretreatment reactor I is the reaction effluent of remaining all weighted BMO spaces reactors in parallel；When next plus hydrogen
When the pressure drop of preatreating reactors reaches the predetermined value, by the weighted BMO spaces reactor from fixed bed hydrogenation pretreatment reaction
It is cut out in area, which is named as to the weighted BMO spaces reactor II cut out, and the fixed bed is added
Hydrogen pretreatment reaction zone, the weighted BMO spaces reactor II cut out, the weighted BMO spaces reactor I cut out and described
Fixed bed hydrogenation processing reaction zone is connected in turn in series；In the manner described above, until all plus hydrogen is located in advance
Reason reactor is all connected in series to.
12. according to the method for claim 1, wherein own in fixed bed hydrogenation pretreatment reaction area described in step (3)
The pressure drop of weighted BMO spaces reactor do not reach predetermined value simultaneously, it is two neighboring pre- closest to reach pressure drop predetermined value plus hydrogen
The time difference that treatment reactor reaches its pressure drop predetermined value is not less than the 20% of the whole device cycle of operation.
13. according to method described in claim 1 or 12, wherein in fixed bed hydrogenation pretreatment reaction area described in step (3)
The pressure drop of all weighted BMO spaces reactors does not reach predetermined value simultaneously, it is two neighboring closest to reach pressure drop predetermined value plus
The time difference that hydrogen pretreatment reactor reaches its pressure drop predetermined value is the 20%~60% of the whole device cycle of operation.
14. according to the method for claim 12, wherein pass through the setting of operating condition and/or catalyst bed property
Difference makes each weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area not reach pressure drop predetermined value simultaneously, passes through
Control catalyst packing height different in each weighted BMO spaces reactor, different inlet amounies, different feed properties, no
Using one of different Catalyst packing density or a variety of sides under the conditions of same operating condition and identical filling height
Formula makes each weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area not reach pressure drop predetermined value simultaneously to realize.
15. according to the method for claim 14, wherein when by controlling identical dress in each weighted BMO spaces reactor
Under the conditions of raising degree by the way of different Catalyst packing density to realize when, in the fixed bed hydrogenation pretreatment reaction
In each weighted BMO spaces reactor of area's parallel connection, maximum loading density is 400kg/m3~600kg/m3, minimum loading density is
300kg/m3~550kg/m3。
16. according to the method for claim 15, wherein when identical in each weighted BMO spaces reactor by controlling
Load height under the conditions of using different Catalyst packing density by the way of to realize when, the fixed bed hydrogenation pretreatment instead
In each weighted BMO spaces reactor for answering area's parallel connection, maximum loading density is 450kg/m3~550kg/m3；Minimum loading density
For 350kg/m3~450kg/m3。
17. according to method described in claim 15 or 16, wherein the immediate two weighted BMO spaces reactors of loading density
Catalyst packing density difference be 50kg/m3~200kg/m3。
18. according to method described in claim 15 or 16, wherein the immediate two weighted BMO spaces reactors of loading density
Catalyst packing density difference be 80kg/m3~150kg/m3。
19. according to the method for claim 14, wherein when by control in each weighted BMO spaces reactor it is different into
The mode of doses come when realizing, the ratio between feed volume air speed of the immediate two weighted BMO spaces reactors of inlet amount is 1.1 ~
3:1.
20. according to method described in claim 14 or 19, wherein when different in each weighted BMO spaces reactor by controlling
Inlet amount mode come when realizing, the ratio between the feed volume air speed of the immediate two weighted BMO spaces reactors of inlet amount is
1.1 ~ 1.5:1.
21. according to the method for claim 14, wherein when by control in each weighted BMO spaces reactor it is different into
Expect the mode of property come when realizing, the tenor difference of the immediate two weighted BMO spaces reactors of feed properties is 5 μ g/
g ~50µg/g。
22. according to method described in claim 14 or 21, wherein when different in each weighted BMO spaces reactor by controlling
Feed properties mode come when realizing, the tenor difference of the immediate two weighted BMO spaces reactors of feed properties is
10µg/g ~30µg/g。
23. according to the method for claim 14, wherein when by controlling behaviour different in each weighted BMO spaces reactor
Make the mode of condition to control the operation of operating pressure and the immediate two weighted BMO spaces reactors of volume space velocity when realizing
In condition, operation temperature difference is 2 DEG C ~ 30 DEG C, or control operating pressure and operation temperature immediate two plus hydrogen are located in advance
In the operating condition for managing reactor, volume space velocity difference is 0.1 h-1~10 h-1。
24. according to method described in claim 14 or 23, wherein when different in each weighted BMO spaces reactor by controlling
Operating condition mode come when realizing, control operating pressure and the immediate two weighted BMO spaces reactors of volume space velocity
In operating condition, operation temperature difference is 5 DEG C ~ 20 DEG C；Or control operating pressure and operation temperature immediate two plus hydrogen
In the operating condition of preatreating reactors, volume space velocity difference is 0.2 h-1~5 h -1。
25. according to the method for claim 1, wherein according to Flow of Goods and Materials direction, in each weighted BMO spaces reactor according to
Secondary filling hydrogenation protecting agent, Hydrodemetalation catalyst and optional Hydrobon catalyst；The hydrotreating reaction area
Reactor successively load Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.
26. according to the method for claim 1, wherein the ebullated bed that boiling bed hydrogenation processing reaction zone is arranged 1 or more adds
Hydrogen reactor.
27. according to method described in claims 1 or 26, wherein what boiling bed hydrogenation processing reaction zone setting 2 was arranged in series
Boiling bed hydrogenation reactor.
28. according to the method for claim 1, wherein the reaction condition of boiling bed hydrogenation processing reaction zone are as follows: reaction temperature
It is 330~450 DEG C, reaction pressure is 8~25MPa, hydrogen to oil volume ratio 300:1 ~ 1000:1, and liquid volume air speed (LHSV) is
0.3 h-1~5.0h-1。
29. according to method described in claims 1 or 28, wherein the reaction condition of boiling bed hydrogenation processing reaction zone are as follows: reaction
Temperature is 360~430 DEG C；Reaction pressure is 10~16MPa；Hydrogen to oil volume ratio 600:1~900:1；Liquid volume air speed
It (LHSV) is 0.3 h-1~2.0h-1。
30. according to the method for claim 1, wherein the operating condition in fixed bed hydrogenation pretreatment reaction area are as follows: temperature
Degree is 370 DEG C~420 DEG C, and pressure is 10MPa~25MPa, and hydrogen to oil volume ratio is 300~1500, volume space velocity when raw material oil liquid
For 0.15h-1~2h-1。
31. according to method described in claim 1 or 30, wherein the operating condition in fixed bed hydrogenation pretreatment reaction area
Are as follows: temperature is 380 DEG C~400 DEG C, and pressure is 15MPa~20MPa, and hydrogen to oil volume ratio is 500~800, volume when raw material oil liquid
Air speed is 0.3h-1~1h-1。
32. according to the method for claim 1, wherein the fixed bed hydrogenation processing reaction zone includes that 1~5 series connection is set
The hydrotreating reactor set.
33. according to method described in claim 1 or 32, wherein the fixed bed hydrogenation processing reaction zone includes that 2 series connection are set
The hydrotreating reactor set.
34. according to the method for claim 1, wherein the operating condition of the fixed bed hydrogenation processing reaction zone are as follows: temperature
It is 370 DEG C~430 DEG C, pressure is 10MPa~25MPa, and hydrogen to oil volume ratio is 300~1500, and volume space velocity is when raw material oil liquid
0.15h-1~0.8h-1。
35. according to method described in claim 1 or 34, wherein the operating condition of the fixed bed hydrogenation processing reaction zone are as follows:
Temperature is 380 DEG C~410 DEG C, and pressure is 15MPa~20MPa, and hydrogen to oil volume ratio is 400~800, volume space velocity when raw material oil liquid
For 0.2h-1~0.6h-1。
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