CN105524655B - Heavy oil hydrodenitrogenation method - Google Patents
Heavy oil hydrodenitrogenation method Download PDFInfo
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- CN105524655B CN105524655B CN201410575543.6A CN201410575543A CN105524655B CN 105524655 B CN105524655 B CN 105524655B CN 201410575543 A CN201410575543 A CN 201410575543A CN 105524655 B CN105524655 B CN 105524655B
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Abstract
The invention discloses a heavy oil hydrodenitrogenation method. The heavy oil hydrodenitrogenation method comprises that under hydrotreatment conditions, in the presence of hydrogen, heavy oil-containing crude oil orderly contacts with a hydrodemetallization catalyst, a hydrodesulfurization catalyst, a hydrostturation catalyst and a hydro-denitrification catalyst so that hydrogenation product oil is obtained, wherein after contacting with the hydrodesulfurization catalyst and before contacting with the hydrostturation catalyst, the product obtained through contact with the hydrodesulfurization catalyst is subjected to gas stripping so that a liquid and gas containing hydrogen are obtained and the process of contact with the hydro-denitrification catalyst is carried out in the presence of a sulfur-containing material flow. The heavy oil hydrodenitrogenation method can substantially improve a heavy oil denitrification rate and a heavy oil hydrogenation rate, improve a liquid product yield in heavy oil hydrogenation and saves a production cost.
Description
Technical field
The present invention relates to a kind of method of heavy-oil hydrogenation denitrogenation.
Background technology
Residual hydrogenation technology is a kind of Heavy Oil Processing Technology of high liquid product yield, is quickly pushed away in China at present
Extensively.The catalytic cracking that residual hydrogenation equipment is mainly downstream provides relatively low impurity (sulfur, nitrogen, metal etc.) content and low carbon residue
Raw material, effectively increases yield of light oil and the product property of refinery.The nitrogen content generating oil in Residue Hydrotreating Technology is one
Item important indicator, the too high acid centre poisoning and deactivation easily making catalytic cracking catalyst of nitrogen content, lead to the increase of green coke amount, liquid
A series of problems, such as product yield declines.
Nitrogen-containing compound in oil is mainly nitrogenous heterocyclic compound, with the increase of petroleum distillate boiling range, nitrogenizes
The content of thing increases.And residual oil is enriched substantial amounts of nitrogen-containing compound in oil, these nitrogen-containing compounds mainly with pyrroles and
Pyridine is elementary cell, and the macromolecular compound of upper multiple phenyl ring, cycloalkane and saturated hydrocarbons side chain.It is hydrogenated with residual oil
In processing procedure, hydrodenitrogeneration is the course of reaction of a multi-step, and nitrogen-containing compound occurs outer in the presence of catalyst first
The hydrogenation saturation of portion's aromatic ring, hydrogenation ring-opening reaction, then just can carry out nitrogenous heterocyclic hydrogenation saturation, and C-N key finally occurs
Hydrogenolysis, generate corresponding hydro carbons and ammonia.
The means of the denitrification percent of fixed bed Residue Hydrotreating Technology raising at present predominantly change highly active residual hydrogenation denitrogenation
Catalyst.For example, CN1448470A, CN1339562A, CN1070418A, CN1086534A, CN101890383A,
The prior arts such as CN103627424A, US3446730A, US3444074A, US4522709A and US4406779A propose application
Catalyst in heavy oil or residual hydrogenation process and preparation method thereof etc., by using in fixed bed residual hydrogenation reactor
State catalyst described in the prior art and can reach the method improving residual hydrogenation denitrification percent.
However, because the nitrogen content in hydrotreated feed oil is high, the catalyst even with above-mentioned prior art enters
Also it is only capable of during row denitrogenation maintaining good catalysis activity within a period of time that reactor has just begun to use, prolong with use time
Long, the catalysis activity decline of above-mentioned catalyst is more serious, so that being accomplished by more catalyst changeout within the shorter cycle, seriously
Increased production cost.
Content of the invention
It is an object of the invention to provide a kind of method with high heavy-oil hydrogenation denitrification percent, the method can significantly carry
Improve heavy-oil hydrogenation rate, the yield of the product liquid during raising heavy-oil hydrogenation while high heavy oil denitrification percent, and then save
Production cost.
To achieve these goals, the present invention provides a kind of method of heavy-oil hydrogenation denitrogenation, and the method includes：At hydrogenation
Under the conditions of reason, in presence of hydrogen, by the raw oil containing heavy oil successively with Hydrodemetalation catalyst, hydrodesulfurization catalytic
Agent, hydrocatalyst for saturating contact with hydrodenitrogenation catalyst, obtain hydrogenated oil；Wherein, with Hydrobon catalyst
After contact and before contacting with hydrocatalyst for saturating, the product obtaining after being contacted with Hydrobon catalyst is carried out
Air stripping, obtains liquid phase thing and the gas gas-phase objects containing hydrogen, the process contacting with hydrodenitrogenation catalyst is in the presence of sulfur-bearing logistics
Carry out.
The present invention on the basis of existing heavy-oil hydrogenation handling process, by material is being connect with Hydrobon catalyst
After touching and carried out air stripping to remove sulfur-containing compound (such as hydrogen sulfide) before contacting with hydrocatalyst for saturating, and plus
Inject the nitrogen content that the method for sulfur-bearing logistics can effectively reduce in hydrogenated oil in hydrogen denitrification process, improve heavy-oil hydrogenation mistake
The yield of the product liquid in journey, and then save production cost.Further such that the high hydrogenated oil of this denitrification percent is beneficial to
Follow-up catalytic cracking process.Can be seen that under the premise of remaining condition identical from the result of embodiments of the invention, contrast
Embodiment 1 and the result of embodiment 4, sulfur-bearing logistics used in hydrodenitrogeneration reaction zone in embodiment 1 makes hydrogen sulfide
When content is 2 weight %, denitrification percent is than high in embodiment 4.And the method for the present invention is to the species of catalyst, filling side
All there is no particular limitation for nitrogen content in method, the species of raw oil and raw oil, using the denitrification percent of the method for the present invention
More than all more than 50 weight %, denitrification percent is substantially compared with the height in comparative example.And the method for the present invention is especially for having height
The raw oil of nitrogen content has very high nitric efficiency；And the method for prior art often cannot make there is the former of high nitrogen-containing
Nitrogen content in material significantly reduces.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the process chart that method according to embodiments of the invention 1 carries out residual hydrogenation denitrogenation.
Fig. 2 is that the method for the comparative example 1 according to the present invention carries out the process chart of residual hydrogenation denitrogenation.
Fig. 3 is that the method for the comparative example 2 according to the present invention carries out the process chart of residual hydrogenation denitrogenation.
Fig. 4 is that the method for the comparative example 3 according to the present invention carries out the process chart of residual hydrogenation denitrogenation.
Description of reference numerals
I HDM reaction zone II HDM reaction zone
III high pressure air stripping area IV is hydrogenated with saturated reaction area
V hydrodenitrogeneration reaction zone VI Oil-gas Separation area
VII desulphurization of recycle hydrogen area VII-1 does not contain sulfur cycle hydrogen compressor
VII-2 note sulfur oil pump III-1 supplements hydrogen compressor
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method of heavy-oil hydrogenation denitrogenation, the method includes：Under hydroprocessing conditions, in hydrogen
In the presence of, by the raw oil containing heavy oil successively with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating
Contact with hydrodenitrogenation catalyst, obtain hydrogenated oil；Wherein, after contacting with Hydrobon catalyst and with hydrogenation
Saturation catalyst contact before, the product obtaining after contacting with Hydrobon catalyst carries out air stripping, obtain liquid phase thing and
Gas gas-phase objects containing hydrogen, the process being contacted with hydrodenitrogenation catalyst is carried out in the presence of sulfur-bearing logistics.
In method of the present invention, it should be strongly noted that the de- gold with hydrogenation successively of the raw oil containing heavy oil
When metal catalyst, Hydrobon catalyst, hydrocatalyst for saturating contact with hydrodenitrogenation catalyst, the main reaction occurring divides
It is not HDM reaction, hydrodesulfurization reaction, hydrogenation saturated reaction and hydrodenitrogeneration reaction.But, in hydrotreating bar
Under part, during the raw oil containing heavy oil is contacted with Hydrodemetalation catalyst, also have a small amount of hydrogenation saturation anti-
Answer and hydrodesulfurization reaction occurs；During contacting with Hydrobon catalyst, also have a small amount of HDM anti-
Saturated reaction and should be hydrogenated with occur.In this regard, those skilled in the art know, the present invention is not explained in detail.
According to method of the present invention, de- with Hydrodemetalation catalyst, hydrogenation successively to the raw oil containing heavy oil
There is no particular limitation for the form that sulfur catalyst, hydrocatalyst for saturating contact with hydrodenitrogenation catalyst, under preferable case,
In the present invention, the process being contacted with hydrodenitrogenation catalyst is included：Described sulfur-bearing logistics is introduced and urges containing described hydrodenitrogeneration
The hydrodenitrogeneration reaction zone of agent, sulfur-bearing logistics produces hydrogen sulfide gas under hydroprocessing conditions so that existing in hydrogen sulfide
Under, the product obtaining after being contacted with hydrocatalyst for saturating is contacted with described hydrodenitrogenation catalyst and occurs hydrodenitrogeneration anti-
Should.
According to method of the present invention, the described process contacting with hydrodenitrogenation catalyst can be containing described hydrogenation
The hydrodenitrogeneration reaction zone of denitrification catalyst is carried out.
According to method of the present invention, the consumption of preferably described sulfur-bearing logistics makes the hydrodenitrogeneration of every 100 weight portions
Hydrogen sulfide containing 0.1-20 weight portion in the gas gas-phase objects of reaction zone, the further preferably hydrogen sulfide of 1-5 weight portion.That is,
In method of the present invention, in material with hydrodenitrogenation catalyst contact process, de- with hydrogenation with respect to 100 weight portions
Nitrogen catalyst contact region in gas gas-phase objects (in the present invention, this gas gas-phase objects includes hydrocarbons and non-hydrocarbonaceous materials, and
Non-hydrocarbonaceous materials mainly include hydrogen, hydrogen sulfide and ammonia etc.), the consumption of described sulfur-bearing logistics is to make and hydrodenitrogeneration catalysis
The content of the hydrogen sulfide in gas gas-phase objects in the region of agent contact is 0.1-20 weight portion；In order to advantageously in hydrodenitrogeneration with
And prevent hydrodenitrogenation catalyst usage cycles too short, preferably the content of sulfur-containing compound is 1-5 weight portion.People in the art
The sulfuration in gas gas-phase objects in the region that member can be contacted with hydrodenitrogenation catalyst using various conventional technique means detections
The content of hydrogen, method of the present invention is not limited to this.
According to method of the present invention, to the species of described sulfur-bearing logistics, there is no particular limitation, as long as at hydrogenation
Hydrogen sulfide gas can be produced under the conditions of reason, the materials such as Carbon bisulfide in described sulfur-bearing logistics, can be contained.Preferable case
Under, in order to obtain so that denitrification percent is higher, the described sulfur-bearing logistics of the present invention includes Carbon bisulfide, dimethyl disulfide and its spreads out
Biological, dimethyl disulfide and its derivant, organic polythiaether and its derivant, mercaptan and its derivant, thiophene and its derivative
Thing, straight-run diesel oil, decompressed wax oil, catalytic diesel oil, catalytic cycle oil, catalytic slurry steam oil, coker gas oil, wax tailings, take off
At least one in coal tar and solvent refining tapped oil.More preferably described sulfur-bearing logistics is Carbon bisulfide, Methyl disulfide
At least one in ether, straight-run diesel oil, decompressed wax oil, catalytic diesel oil and catalytic cycle oil.
In method of the present invention, to the introducing method of described sulfur-bearing logistics, there is no particular limitation, this area skill
Described sulfur-bearing logistics can be introduced hydrodenitrogeneration reaction zone using conventional use of various methods by art personnel.For example in the present invention
In described method, described sulfur-bearing logistics can be introduced by hydrodenitrogeneration reaction zone using note sulfur oil pump etc..
In method of the present invention, to the described method carrying out air stripping, there is no particular limitation, under preferable case,
In method of the present invention, in order to improve hydrogen-oil ratio and be conducive to carrying out air stripping, described air stripping is in the presence of hydrogen make-up
Under carry out, the presence of hydrogen make-up also help carry out further be hydrogenated with saturated reaction.Specifically, according to side of the present invention
Method, the described method carrying out air stripping includes：In the presence of hydrogen make-up, obtain after contacting with Hydrobon catalyst
Product introduces air stripping area and carries out air stripping.In the present invention, to the consumption of described hydrogen make-up, there is no particular limitation, as long as described
The pressure that the consumption of hydrogen make-up enables in the reactor of described hydrotreating remains basicly stable, for example, make institute
The hydrogen dividing potential drop stated in the reactor of hydrotreating maintains between 5.0-22.0MPa.And, in order to easy and simple to handle, this
Bright described air stripping is introduced air stripping area using the product obtaining after directly being contacted with Hydrobon catalyst and carries out high pressure gas
The method carrying is carried out, without to described contact with Hydrobon catalyst after the product that obtains reduced pressure or cooling at
Reason.The temperature and pressure in described air stripping area maintains in the range of hydroprocessing condition, and for example temperature is 330-450 DEG C, hydrogen
Partial pressure is 5.0-22.0MPa.
In method of the present invention, liquid phase thing and the gas phase containing hydrogen are divided into by the product obtained by air stripping
Thing, wherein, the liquid phase thing obtaining after air stripping proceeds hydrotreating, and obtained gas gas-phase objects are containing hydrogen, ammonia and sulfur
Change the mixture of hydrogen etc..In the method for the invention, can also include described gas phase mixture being carried out separate, obtain not sulfur-bearing
Hydrogen, the hydrogen of described not sulfur-bearing can be introduced into anti-for circulation hydrogenation in the hydrogenation process of heavy oil by compressor
Should.
In the method for the invention, described air stripping process is carried out in the presence of hydrogen make-up, and described hydrogen make-up is permissible
Air stripping process is introduced by compressor.
According to method of the present invention, to the condition of described hydrotreating, there is no particular limitation, people in the art
Member can carry out hydrotreating using hydroprocessing condition commonly used in the art to heavy oil, it is preferred, however, that in order to
Obtain higher hydrodenitrogeneration rate, the hydroprocessing condition in method of the present invention can include：Hydrogen dividing potential drop is 5.0-
22.0MPa, reaction temperature are 330-450 DEG C, volume space velocity is 0.1-3.0h-1, the volume ratio of hydrogen and raw oil be 350-
2000：1.
According to method of the present invention, preferably described full with Hydrodemetalation catalyst, Hydrobon catalyst, hydrogenation
With catalyst contact with hydrodenitrogenation catalyst respectively in the HDM reaction zone containing Hydrodemetalation catalyst, contain
The hydrodesulfurizationreaction reaction zone of Hydrobon catalyst, the hydrogenation saturated reaction area containing hydrocatalyst for saturating and de- containing hydrogenation
The hydrodenitrogeneration reaction zone of nitrogen catalyst is carried out.
In the present invention, described HDM reaction zone can be a bed or of a reactor
Multiple beds of individual reactor, can also be multiple beds of multiple reactors.
In the present invention, described hydrodesulfurizationreaction reaction zone can be a bed of a reactor or one
Multiple beds of reactor, can also be multiple beds of multiple reactors.
In the present invention, described hydrogenation saturated reaction area can be a bed of a reactor or one
Multiple beds of reactor, can also be multiple beds of multiple reactors.
In the present invention, described hydrodenitrogeneration reaction zone can be a bed of a reactor or one
Multiple beds of reactor, can also be multiple beds of multiple reactors.
In the case of more preferably, according to method of the present invention, described HDM reaction zone, hydrodesulfurization reaction
Area, hydrogenation saturated reaction area and hydrodenitrogeneration reaction zone include at least one hydrogenation reactor respectively；More preferably include 1-5 respectively
Individual hydrogenation reactor.
Under preferable case, according to method of the present invention, described HDM reaction zone, hydrodesulfurizationreaction reaction zone,
Hydrogenation saturated reaction area and hydrodenitrogeneration reaction zone include at least one beds respectively；More preferably include 1-5 respectively
Beds, wherein 1-5 beds can arrange in a reactor can also be respectively disposed at different anti-
Answer in device.
In method of the present invention, to the type of described hydrogenation reactor, there is no particular limitation, under preferable case
Under, described hydrogenation reactor includes at least one in fixed bed, moving bed and ebullated bed, more preferably fixed bed.
In method of the present invention, described HDM reaction zone can only using a kind of catalyst it is also possible to
Using multiple catalysts, generally use can be joined using multiple catalysts level for fixed bed hydrogenation reactor.
In method of the present invention, described hydrodesulfurizationreaction reaction zone can be only using a kind of catalyst it is also possible to make
With multiple catalysts, generally use can be joined using multiple catalysts level for fixed bed hydrogenation reactor.
In method of the present invention, described hydrogenation saturated reaction area can be only using a kind of catalyst it is also possible to make
Use multiple catalysts；Described hydrodenitrogeneration reaction zone can be only using a kind of catalyst, it is possible to use multiple catalysts.
In method of the present invention, the species of one or more catalyst of above-mentioned use is not particularly limited
Fixed.
In method of the present invention, described HDM reaction zone, hydrodesulfurizationreaction reaction zone and hydrodenitrogeneration are anti-
The Hydrodemetalation catalyst of filling, Hydrobon catalyst and hydrodenitrogenation catalyst in area is answered to be the hydrogenation catalyst of routine
Agent species, is known to professional and technical personnel in the field, here is not described in detail.
In method of the present invention, in described hydrogenation saturated reaction area, residual hydrogenation saturation catalyst can be loaded,
Its active metal component can be at least one in nickel-molybdenum, nickel-cobalt-molybdenum, nickel-tungsten and nickel-cobalt-tungsten, is wherein more preferably
At least one in nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum；Active metal load capacity can be：Molybdenum and/or tungsten 5-40 weight %, cobalt
And/or nickel 1-8 weight %.The residual hydrogenation saturation catalyst of filling in described hydrogenation saturated reaction area, its carrier can be oxygen
Change aluminum, at least one in silicon dioxide and amorphous silicon aluminium, wherein more preferably aluminium oxide.In described hydrogenation saturated reaction area
The residual hydrogenation saturation catalyst of filling, its specific surface area can be 100-300 rice2/ gram, its pore volume can be 0.2-0.8
Ml/g.
In method of the present invention, the packing method of one or more catalyst above-mentioned is not particularly limited
Fixed, those skilled in the art can adopt conventional use of various packing methods.
In method of the present invention, preferably described heavy oil includes at least one in reduced crude and decompression residuum.
In method of the present invention, distillate in described raw oil, can also be contained.
Under preferable case, in method of the present invention, described distillate includes decompressed wax oil, catalytic cracked oil pulp steams
At least one in fuel-displaced, catalytic cracking recycle oil, wax tailings, deasphalted oil, solvent refining tapped oil and liquefied coal coil.
Method of the present invention is applied to the raw oil with various nitrogen contents, wherein, under preferable case, institute of the present invention
In raw oil in the method stated, nitrogen content is not less than 3000 μ g/g；In the case of more preferably, in described raw oil, nitrogen content is
3000-8000μg/g.
In method of the present invention, the product obtaining after can also including being contacted with hydrodenitrogenation catalyst is carried out
Oil-gas Separation is to obtain hydrogenated oil of the present invention.The method of described Oil-gas Separation by those skilled in the art public affairs
Know, for example, Oil-gas Separation area can be introduced using the product obtaining after contacting with hydrodenitrogenation catalyst and carry out Oil-gas Separation,
Obtain hydrogenated oil.
Preferred embodiment, heavy-oil hydrogenation denitrogenation of the present invention can adopt with lower section one kind according to the present invention
Method is carried out：
(1) in presence of hydrogen, the raw oil containing heavy oil is introduced HDM reaction zone, urge with HDM
Agent contacts, and HDM reaction occurs, and obtains HDM reaction zone and generates oil and gas；
(2) by the HDM reaction zone obtaining in step (1) generate oil with gas introduce hydrodesulfurizationreaction reaction zone, with plus
, there is hydrodesulfurization reaction in hydrogen hydrodesulfurization catalyst, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas；
(3) in the presence of hydrogen make-up, the hydrodesulfurizationreaction reaction zone obtaining is generated oil introduce gas with gas in step (2)
Carry area, oil is generated to described hydrodesulfurizationreaction reaction zone and carries out air stripping, and carry out gas-liquid separation, obtain liquid phase thing and containing hydrogen
Gas gas-phase objects；
(4) the liquid phase thing obtaining in hydrogen and step (3) is introduced hydrogenation saturated reaction area, connect with hydrocatalyst for saturating
Touch, hydrogenation saturated reaction occurs, obtain hydrogenation saturated reaction area generation oil gentle；
(5) in the presence of sulfur-bearing logistics, the hydrogenation saturated reaction area obtaining is generated gentle introducing of oil add in step (4)
Hydrogen denitrification reaction area, is contacted with hydrodenitrogenation catalyst, occur hydrodenitrogeneration reaction, obtain hydrodenitrogeneration reaction zone generate oil with
Gas, then carries out Oil-gas Separation, obtains hydrogenated oil.
It should be strongly noted that the present invention above-mentioned preferred embodiment in, involved various parameters and bar
Part all can be as shown in foregoing teachings of the present invention, and the present invention will not be described here.
According to hydrogenated oil of the present invention, nitrogen content therein reduces by 50 weight % compared with the nitrogen content in raw oil
More than.
Hereinafter will be described the present invention by embodiment, but not thereby limiting the invention.Embodiment and
HDM reaction zone described in comparative example, hydrodesulfurizationreaction reaction zone, hydrogenation saturated reaction area, hydrodenitrogeneration reaction zone are all
It is respectively a reactor, the reactor being used is fixed bed reactors, each reactor only one of which beds.
Used in embodiment and comparative example, catalyst is that Sinopec Research Institute of Petro-Chemical Engineering develops, by Sinopec catalyst
The RHT series residual oil hydrocatalyst that Chang Ling branch company produces.Used in embodiment and comparative example, sulfur-bearing logistics is containing 2 weights
The catalytic diesel oil of amount % Carbon bisulfide.
Hydrogen-oil ratio in following examples and comparative example refers to the volume ratio of hydrogen and raw oil.
Embodiment 1
The raw oil that the present embodiment is used is reduced crude, and its property is as shown in table 1.Urge used in the present embodiment
The filling scheme of agent is as shown in table 2.The process chart that the present embodiment is adopted is shown in Fig. 1.Idiographic flow is：
(1) raw oil being derived from pipeline 1 is mixed with the not hydrogen sulfide containing circulating hydrogen from pipeline 3, enters hydrogenation de-
Metal reaction area I, is contacted with Hydrodemetalation catalyst, occur HDM reaction and a small amount of hydrogenation saturated reaction and
Hydrodesulfurization reaction, obtains HDM reaction zone and generates oil and gas；
(2) the HDM reaction zone obtaining in step (1) is generated oil anti-through pipeline 4 entrance hydrodesulfurization with gas
Answer area II, contact with Hydrobon catalyst, occur hydrodesulfurization reaction and the reaction of a small amount of HDM and hydrogenation full
And reaction, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas；
(3) hydrodesulfurizationreaction reaction zone obtaining in step (2) is generated oil and enter high pressure air stripping area with gas through pipeline 5
III, from pipeline 2 hydrogen make-up through supplement hydrogen compressor III-1 boosting after, through pipeline 6 to hydrodesulfurizationreaction reaction zone
Generate oil and carry out air stripping, in high pressure air stripping area, gas-liquid phase separation occurs simultaneously, obtain liquid phase thing and the gas phase containing hydrogen
Thing；
(4) gas phase after high pressure air stripping area III gas-liquid is separated enters desulphurization of recycle hydrogen area VII through pipeline 7, and oil phase is through pipe
Line 8 enters hydrogenation saturated reaction area IV with the not hydrogen sulfide containing circulating hydrogen from pipeline 9 after mixing, with hydrogenation saturation catalysis
Agent contacts, and hydrogenation saturated reaction occurs, and obtains hydrogenation saturated reaction area generation oil gentle；
(5) by the hydrogenation saturated reaction area obtaining in step (4) generate oil gentle through pipeline 10 with sequentially pass through pipeline
16th, the sulfur-bearing logistics of note sulfur oil pump VII-2 and pipeline 11 is mixed into hydrodenitrogeneration reaction zone V, connects with hydrodenitrogenation catalyst
Touch, hydrodenitrogeneration reaction occurs, obtain hydrodenitrogeneration reaction zone and generate oil and gas；
(6) the hydrodenitrogeneration reaction zone obtaining in step (5) is generated oil and enter Oil-gas Separation area with gas through pipeline 12
VI carries out Oil-gas Separation, obtains hydrogenated oil, and described hydrogenated oil flows out through pipeline 13, the gas obtaining after Oil-gas Separation
Phase thing enters desulphurization of recycle hydrogen area VII through pipeline 14 to carry out separating, and waste gas etc. is discharged through pipeline 17, the not sulfur-bearing obtaining
Hydrogen sequentially passes through pipeline 15, enters HDM reaction zone I without sulfur cycle hydrogen compressor VII-1 and pipeline 3, or warp
Pipeline 9 enters hydrogenation saturated reaction area IV.
Experimental condition is：HDM reaction zone entrance hydrogen dividing potential drop is 15.0MPa；HDM reaction zone entrance temperature
Spend for 350 DEG C, hydrodesulfurizationreaction reaction zone inlet temperature be 365 DEG C, hydrogenation saturated reaction area inlet temperature be 365 DEG C, hydrogenation de-
Nitrogen reaction zone inlet temperature is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h-1；HDM reaction zone entrance
Hydrogen-oil ratio is 800：1, hydrogenation saturated reaction area entrance hydrogen-oil ratio is 800：1.Control sulfur in gas gas-phase objects in hydrodenitrogeneration reaction zone
Change hydrogen content is 2 weight %.
The property of the hydrogenated oil being obtained using the said method of the present embodiment is shown in Table 3.From the present embodiment as can be seen that
Nitrogen content in the hydrogenated oil being obtained using the method for the present embodiment reduces 70.6 weights compared with the nitrogen content in raw oil
Amount %.
Table 1
| Analysis project | Reduced crude |
| Density (20 DEG C)/(kg/m3) | 976.0 |
| Viscosity (100 DEG C)/(mm2/s) | 174.3 |
| Carbon residue/% | 11.72 |
| Carbon content/% | 86.54 |
| Hydrogen content/% | 11.31 |
| Sulfur content/% | 1.19 |
| Nitrogen content/% | 0.51 |
| Saturation divides/% | 28.1 |
| Fragrance point/% | 36.7 |
| Colloid/% | 32.2 |
| Asphalitine/% | 3.0 |
| Nickel content/(μ g/g) | 36.6 |
| Content of vanadium/(μ g/g) | 19.2 |
Table 2
Table 3
Comparative example 1
The raw oil that this comparative example is used is in the same manner as in Example 1.The filling side of catalyst used in this comparative example
Case is in the same manner as in Example 1.The process chart that this comparative example is adopted is shown in Fig. 2.Idiographic flow is：
(1) it is derived from the raw oil of pipeline 1 and the not hydrogen sulfide containing circulating hydrogen from pipeline 3 and through pipeline 2 and mend
It is flushed with hydrogen the hydrogen mixing of compressor III-1, enters HDM reaction zone I, contact with Hydrodemetalation catalyst, occur to add
Hydrogen demetalization reaction and a small amount of hydrogenation saturated reaction and hydrodesulfurization reaction, obtain HDM reaction zone generate oil with
Gas；
(2) the HDM reaction zone obtaining in step (1) is generated oil anti-through pipeline 4 entrance hydrodesulfurization with gas
Answer area II, contact with Hydrobon catalyst, occur hydrodesulfurization reaction and the reaction of a small amount of HDM and hydrogenation full
And reaction, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas；
(3) hydrodesulfurizationreaction reaction zone obtaining in step (2) is generated oil and enter hydrogenation saturated reaction with gas through pipeline 8
Area IV, is contacted with hydrocatalyst for saturating, and hydrogenation saturated reaction occurs, and obtains hydrogenation saturated reaction area generation oil gentle；
(4) the hydrogenation saturated reaction area obtaining in step (3) is generated oil gentle anti-through pipeline 10 entrance hydrodenitrogeneration
Answer area V, contact with hydrodenitrogenation catalyst, hydrodenitrogeneration reaction occurs, obtain hydrodenitrogeneration reaction zone and generate oil and gas；
(5) the hydrodenitrogeneration reaction zone obtaining in step (4) is generated oil and enter Oil-gas Separation area with gas through pipeline 12
VI carries out Oil-gas Separation, obtains hydrogenated oil, and described hydrogenated oil flows out through pipeline 13, the gas obtaining after Oil-gas Separation
Phase thing enters desulphurization of recycle hydrogen area VII through pipeline 14 to carry out separating, and waste gas is discharged through pipeline 17, the hydrogen of the not sulfur-bearing obtaining
Gas sequentially passes through pipeline 15, enters HDM reaction zone I without sulfur cycle hydrogen compressor VII-1 and pipeline 3.
Experimental condition is：HDM reaction zone entrance hydrogen dividing potential drop is 15.0MPa；HDM reaction zone entrance temperature
Spend for 350 DEG C, hydrodesulfurizationreaction reaction zone inlet temperature be 365 DEG C, hydrogenation saturated reaction area inlet temperature be 365 DEG C, hydrogenation de-
Nitrogen reaction zone inlet temperature is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h-1；HDM reaction zone entrance
Hydrogen-oil ratio is 800：1st, hydrogenation saturated reaction area entrance hydrogen-oil ratio is 800：1.
The property of the hydrogenated oil being obtained using the said method of this comparative example is shown in Table 3.Can be seen that from this comparative example
Nitrogen content in the hydrogenated oil being obtained using the method for this comparative example reduces 29.4 weights compared with the nitrogen content in raw oil
Amount %.
Comparative example 2
The raw oil that this comparative example is used is in the same manner as in Example 1.The filling side of catalyst used in this comparative example
Case is in the same manner as in Example 1.The process chart that this comparative example is adopted is shown in Fig. 3.Idiographic flow is：
(1) raw oil being derived from pipeline 1 is mixed with the not hydrogen sulfide containing circulating hydrogen from pipeline 3, enters hydrogenation de-
Metal reaction area I, is contacted with Hydrodemetalation catalyst, occur HDM reaction and a small amount of hydrogenation saturated reaction and
Hydrodesulfurization reaction, obtains HDM reaction zone and generates oil and gas；
(2) the HDM reaction zone obtaining in step (1) is generated oil anti-through pipeline 4 entrance hydrodesulfurization with gas
Answer area II, contact with Hydrobon catalyst, occur hydrodesulfurization reaction and the reaction of a small amount of HDM and hydrogenation full
And reaction, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas；
(3) hydrodesulfurizationreaction reaction zone obtaining in step (2) is generated oil and enter high pressure air stripping area with gas through pipeline 5
III, from pipeline 2 hydrogen make-up through supplement hydrogen compressor III-1 boosting after, through pipeline 6 to hydrodesulfurizationreaction reaction zone
Generate oil and carry out air stripping, in high pressure air stripping area, gas-liquid phase separation occurs simultaneously, obtain liquid phase thing and the gas phase containing hydrogen
Thing；
(4) gas phase after high pressure air stripping area III gas-liquid is separated enters desulphurization of recycle hydrogen area VII through pipeline 7, and oil phase is through pipe
Line 8 enters hydrogenation saturated reaction area IV with the not hydrogen sulfide containing circulating hydrogen from pipeline 9 after mixing, with hydrogenation saturation catalysis
Agent contacts, and hydrogenation saturated reaction occurs, and obtains hydrogenation saturated reaction area generation oil gentle；
(5) the hydrogenation saturated reaction area obtaining in step (4) is generated oil gentle anti-through pipeline 10 entrance hydrodenitrogeneration
Answer area V, contact with hydrodenitrogenation catalyst, hydrodenitrogeneration reaction occurs, obtain hydrodenitrogeneration reaction zone and generate oil and gas；
(6) the hydrodenitrogeneration reaction zone obtaining in step (5) is generated oil and enter Oil-gas Separation area with gas through pipeline 12
VI carries out Oil-gas Separation, obtains hydrogenated oil, and described hydrogenated oil flows out through pipeline 13, the gas obtaining after Oil-gas Separation
Phase thing enters desulphurization of recycle hydrogen area VII through pipeline 14 to carry out separating, and waste gas is discharged through pipeline 17, the hydrogen of the not sulfur-bearing obtaining
Gas sequentially passes through pipeline 15, enters HDM reaction zone I without sulfur cycle hydrogen compressor VII-1 and pipeline 3, or through pipe
Line 9 enters hydrogenation saturated reaction area IV.
Experimental condition is：HDM reaction zone entrance hydrogen dividing potential drop is 15.0MPa；HDM reaction zone entrance temperature
Spend for 350 DEG C, hydrodesulfurizationreaction reaction zone inlet temperature be 365 DEG C, hydrogenation saturated reaction area inlet temperature be 365 DEG C, hydrogenation de-
Nitrogen reaction zone inlet temperature is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h-1；HDM reaction zone entrance
Hydrogen-oil ratio is 800：1st, hydrogenation saturated reaction area entrance hydrogen-oil ratio is 800：1.
The property of the hydrogenated oil being obtained using the said method of this comparative example is shown in Table 3.Can be seen that from this comparative example
Nitrogen content in the hydrogenated oil being obtained using the method for this comparative example reduces 31.4 weights compared with the nitrogen content in raw oil
Amount %.
Comparative example 3
The raw oil that this comparative example is used is in the same manner as in Example 1.The filling side of catalyst used in this comparative example
Case is in the same manner as in Example 1.The process chart that this comparative example is adopted is shown in Fig. 4.Idiographic flow is：
(1) it is derived from the raw oil of pipeline 1 and the not hydrogen sulfide containing circulating hydrogen from pipeline 3 and from pipeline 2 simultaneously warp
Cross the hydrogen mixing supplementing hydrogen compressor III-1, enter HDM reaction zone I, contact with Hydrodemetalation catalyst, send out
Raw HDM reaction and a small amount of hydrogenation saturated reaction and hydrodesulfurization reaction, obtain HDM reaction zone and generate
Oil and gas；
(2) the HDM reaction zone obtaining in step (1) is generated oil anti-through pipeline 4 entrance hydrodesulfurization with gas
Answer area II, contact with Hydrobon catalyst, occur hydrodesulfurization reaction and the reaction of a small amount of HDM and hydrogenation full
And reaction, obtain hydrodesulfurizationreaction reaction zone and generate oil and gas；
(3) hydrodesulfurizationreaction reaction zone obtaining in step (2) is generated oil and enter hydrogenation saturated reaction with gas through pipeline 8
Area IV, is contacted with hydrocatalyst for saturating, and hydrogenation saturated reaction occurs, and obtains hydrogenation saturated reaction area generation oil gentle；
(4) by the hydrogenation saturated reaction area obtaining in step (3) generate oil gentle through pipeline 10 with sequentially pass through pipeline
16th, the sulfur-bearing logistics of note sulfur oil pump VII-2 and pipeline 11 is mixed into hydrodenitrogeneration reaction zone V, connects with hydrodenitrogenation catalyst
Touch, hydrodenitrogeneration reaction occurs, obtain hydrodenitrogeneration reaction zone and generate oil and gas；
(5) the hydrodenitrogeneration reaction zone obtaining in step (4) is generated oil and enter Oil-gas Separation area with gas through pipeline 12
VI carries out Oil-gas Separation, obtains hydrogenated oil, and described hydrogenated oil flows out through pipeline 13, the gas obtaining after Oil-gas Separation
Phase thing enters desulphurization of recycle hydrogen area VII through pipeline 14 to carry out separating, and waste gas etc. is discharged through pipeline 17, the not sulfur-bearing obtaining
Hydrogen sequentially passes through pipeline 15, enters HDM reaction zone I without sulfur cycle hydrogen compressor VII-1 and pipeline 3.
Experimental condition is：HDM reaction zone entrance hydrogen dividing potential drop is 15.0MPa；HDM reaction zone entrance temperature
Spend for 350 DEG C, hydrodesulfurizationreaction reaction zone inlet temperature be 365 DEG C, hydrogenation saturated reaction area inlet temperature be 365 DEG C, hydrogenation de-
Nitrogen reaction zone inlet temperature is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h-1；HDM reaction zone entrance
Hydrogen-oil ratio is 800：1st, hydrogenation saturated reaction area entrance hydrogen-oil ratio is 800：1.Control sulfur in gas gas-phase objects in hydrodenitrogeneration reaction zone
Change hydrogen content is 2 weight %.
The property of the hydrogenated oil being obtained using the said method of this comparative example is shown in Table 3.Can be seen that from this comparative example
Nitrogen content in the hydrogenated oil being obtained using the method for this comparative example reduces 29.4 weights compared with the nitrogen content in raw oil
Amount %.
Embodiment 2
The present embodiment is carried out using method same as Example 1, except that：
Experimental condition is：HDM reaction zone entrance hydrogen dividing potential drop is 18.0MPa；HDM reaction zone entrance temperature
Spend for 360 DEG C, hydrodesulfurizationreaction reaction zone inlet temperature be 375 DEG C, hydrogenation saturated reaction area inlet temperature be 370 DEG C, hydrogenation de-
Nitrogen reaction zone inlet temperature is 380 DEG C, and the volume space velocity in hydroprocessing processes is 0.5h-1；HDM reaction zone entrance
Hydrogen-oil ratio is 1000：1, hydrogenation saturated reaction area entrance hydrogen-oil ratio is 1000：1.Control in gas gas-phase objects in hydrodenitrogeneration reaction zone
Hydrogen sulfide content is 1 weight %.
The property of the hydrogenated oil being obtained using the said method of the present embodiment is shown in Table 3.From the present embodiment as can be seen that
Nitrogen content in the hydrogenated oil being obtained using the method for the present embodiment reduces 68.6 weights compared with the nitrogen content in raw oil
Amount %.
Embodiment 3
The present embodiment is carried out using method same as Example 1, except that：
Experimental condition is：HDM reaction zone entrance hydrogen dividing potential drop is 12.0MPa；HDM reaction zone entrance temperature
Spend for 330 DEG C, hydrodesulfurizationreaction reaction zone inlet temperature be 355 DEG C, hydrogenation saturated reaction area inlet temperature be 370 DEG C, hydrogenation de-
Nitrogen reaction zone inlet temperature is 385 DEG C, and the volume space velocity in hydroprocessing processes is 1.5h-1；HDM reaction zone entrance
Hydrogen-oil ratio is 1500：1, hydrogenation saturated reaction area entrance hydrogen-oil ratio is 1200：1.Control in gas gas-phase objects in hydrodenitrogeneration reaction zone
Hydrogen sulfide content is 4 weight %.
The property of the hydrogenated oil being obtained using the said method of the present embodiment is shown in Table 3.From the present embodiment as can be seen that
Nitrogen content in the hydrogenated oil being obtained using the method for the present embodiment reduces 64.7 weights compared with the nitrogen content in raw oil
Amount %.
Embodiment 4
The present embodiment is carried out using method same as Example 1, except that：
Experimental condition is：HDM reaction zone entrance hydrogen dividing potential drop is 15.0MPa；HDM reaction zone entrance temperature
Spend for 350 DEG C, hydrodesulfurizationreaction reaction zone inlet temperature be 365 DEG C, hydrogenation saturated reaction area inlet temperature be 365 DEG C, hydrogenation de-
Nitrogen reaction zone inlet temperature is 375 DEG C, and the volume space velocity in hydroprocessing processes is 0.25h-1；HDM reaction zone entrance
Hydrogen-oil ratio is 800：1, hydrogenation saturated reaction area entrance hydrogen-oil ratio is 800：1.Control sulfur in gas gas-phase objects in hydrodenitrogeneration reaction zone
Change hydrogen content is 6 weight %.
The property of the hydrogenated oil being obtained using the said method of the present embodiment is shown in Table 3.From the present embodiment as can be seen that
Nitrogen content in the hydrogenated oil being obtained using the method for the present embodiment reduces 58.8 weights compared with the nitrogen content in raw oil
Amount %.
Embodiment 5
The present embodiment is carried out using method same as Example 3, except that：The raw oil that the present embodiment is used
For reduced crude, its property is as shown in table 4.
Table 4
| Analysis project | Reduced crude |
| Density (20 DEG C)/(kg/m3) | 986.2 |
| Viscosity (100 DEG C)/(mm2/s) | 179.2 |
| Carbon residue/% | 11.05 |
| Carbon content/% | 86.45 |
| Hydrogen content/% | 11.47 |
| Sulfur content/% | 1.37 |
| Nitrogen content/% | 0.35 |
| Saturation divides/% | 28.1 |
| Fragrance point/% | 36.7 |
| Colloid/% | 32.2 |
| Asphalitine/% | 3.0 |
| Nickel content/(μ g/g) | 36.6 |
| Content of vanadium/(μ g/g) | 19.2 |
The property of the hydrogenated oil being obtained using the said method of the present embodiment is shown in Table 3.From the present embodiment as can be seen that
Nitrogen content in the hydrogenated oil being obtained using the method for the present embodiment reduces 57.1 weights compared with the nitrogen content in raw oil
Amount %.
Embodiment 6
The present embodiment is carried out using method same as Example 1, except that：The dress of the catalyst in the present embodiment
Embankment case is as shown in table 5.
Table 5
The property of the hydrogenated oil being obtained using the said method of the present embodiment is shown in Table 3.From the present embodiment as can be seen that
Nitrogen content in the hydrogenated oil being obtained using the method for the present embodiment reduces 68.6 weights compared with the nitrogen content in raw oil
Amount %.
By result above as can be seen that during by hydrotreating being carried out using the method for the present invention, can effectively reduce
Nitrogen content in hydrogenated oil, and then save production cost.And, the result by comparative example 1 and embodiment 4 is permissible
Find out, under the premise of remaining condition identical, when the content of the hydrogen sulfide of hydrodenitrogeneration reaction zone in embodiment 1 is 2 weight %
When, denitrification percent is than high in embodiment 4.And the method for the present invention to the species of catalyst, packing method, raw oil species
And the nitrogen content in raw oil all there is no particular limitation, using the method for the present invention denitrification percent substantially compared with comparative example
High.
From the result of embodiments of the invention it can also be seen that the method for the present invention is especially for having high nitrogen-containing
Raw oil has very high nitric efficiency, and the method for prior art often cannot make containing in the raw material have high nitrogen-containing
Nitrogen quantity significantly reduces.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (17)
1. a kind of method of heavy-oil hydrogenation denitrogenation, the method includes：Under hydroprocessing conditions, in presence of hydrogen, will contain
The raw oil of heavy oil is urged with Hydrodemetalation catalyst, Hydrobon catalyst, hydrocatalyst for saturating and hydrodenitrogeneration successively
Agent contacts, and obtains hydrogenated oil；Wherein, connecing after contacting with Hydrobon catalyst and with hydrocatalyst for saturating
Before touching, the product obtaining after contacting with Hydrobon catalyst carries out air stripping, obtains liquid phase thing and the gas containing hydrogen
Phase thing, wherein, the process being contacted with hydrodenitrogenation catalyst is carried out in the presence of sulfur-bearing logistics, wherein, described sulfur-bearing logistics
Consumption makes the hydrogen sulfide containing 0.1-20 weight portion in the gas gas-phase objects of hydrodenitrogeneration reaction zone of every 100 weight portions.
2. method according to claim 1, wherein, the described process being contacted with hydrodenitrogenation catalyst is being added containing described
The hydrodenitrogeneration reaction zone of hydrogen denitrification catalyst is carried out.
3. method according to claim 1, wherein, the consumption of described sulfur-bearing logistics makes the hydrogenation of every 100 weight portions take off
Hydrogen sulfide containing 1-5 weight portion in the gas gas-phase objects of nitrogen reaction zone.
4. the method according to any one in claim 1-3, wherein, described sulfur-bearing logistics includes Carbon bisulfide, diformazan
Base disulfide and its derivant, organic polythiaether and its derivant, mercaptan and its derivant, thiophene and derivatives, straight run bavin
Oil, decompressed wax oil, catalytic diesel oil, catalytic cycle oil, catalytic slurry steam oil, coker gas oil, wax tailings, deasphalted oil and molten
Agent refines at least one in tapped oil.
5. method according to claim 4, wherein, described sulfur-bearing logistics is Carbon bisulfide, dimethyl disulfide, straight run bavin
At least one in oil, decompressed wax oil, catalytic diesel oil and catalytic cycle oil.
6. the method according to any one in claim 1-3, wherein, described air stripping is carried out in the presence of hydrogen make-up.
7. the method according to any one in claim 1-3, wherein, described hydroprocessing condition includes：Hydrogen dividing potential drop is
5.0-22.0MPa, reaction temperature are 330-450 DEG C, volume space velocity is 0.1-3.0h-1, the volume ratio of hydrogen and raw oil be
350-2000：1.
8. method according to claim 1, wherein, described and Hydrodemetalation catalyst, Hydrobon catalyst, hydrogenation
Saturation catalyst contact with hydrodenitrogenation catalyst respectively in the HDM reaction zone containing Hydrodemetalation catalyst, contain
There are the hydrodesulfurizationreaction reaction zone of Hydrobon catalyst, the hydrogenation saturated reaction area containing hydrocatalyst for saturating and contain hydrogenation
The hydrodenitrogeneration reaction zone of denitrification catalyst is carried out.
9. method according to claim 8, wherein, described HDM reaction zone, hydrodesulfurizationreaction reaction zone, hydrogenation are full
Include at least one hydrogenation reactor with reaction zone and hydrodenitrogeneration reaction zone respectively.
10. method according to claim 9, wherein, described HDM reaction zone, hydrodesulfurizationreaction reaction zone, hydrogenation
Saturated reaction area and hydrodenitrogeneration reaction zone include 1-5 hydrogenation reactor respectively.
11. methods according to claim 8, wherein, described HDM reaction zone, hydrodesulfurizationreaction reaction zone, hydrogenation
Saturated reaction area and hydrodenitrogeneration reaction zone include at least one beds respectively.
12. methods according to claim 11, wherein, described HDM reaction zone, hydrodesulfurizationreaction reaction zone, hydrogenation
Saturated reaction area and hydrodenitrogeneration reaction zone include 1-5 beds respectively.
13. methods according to any one in claim 1-3, wherein, described heavy oil includes reduced crude and decompression slag
At least one in oil.
14. methods according to any one in claim 1-3, wherein, also contain distillate in described raw oil, described
Distillate includes decompressed wax oil, catalytic cracked oil pulp steams oil, catalytic cracking recycle oil, wax tailings, deasphalted oil, solvent essence
At least one in tapped oil processed and liquefied coal coil.
15. methods according to claim 1, wherein, in described raw oil, nitrogen content is not less than 3000 μ g/g.
16. methods according to claim 1, wherein, in described raw oil, nitrogen content is 3000-8000 μ g/g.
17. methods according to claim 1, wherein, the method includes：
(1) in presence of hydrogen, the raw oil containing heavy oil is introduced HDM reaction zone, with Hydrodemetalation catalyst
, there is HDM reaction in contact, obtain HDM reaction zone and generate oil and gas；
(2) the HDM reaction zone obtaining in step (1) is generated oil and introduce hydrodesulfurizationreaction reaction zone with gas, de- with hydrogenation
Sulfur catalyst contacts, and hydrodesulfurization reaction occurs, and obtains hydrodesulfurizationreaction reaction zone and generates oil and gas；
(3) in the presence of hydrogen make-up, the hydrodesulfurizationreaction reaction zone obtaining is generated oil introduce air stripping with gas in step (2)
Area, generates oil to described hydrodesulfurizationreaction reaction zone and carries out air stripping, and carry out gas-liquid separation, obtain liquid phase thing and the gas containing hydrogen
Phase thing；
(4) the liquid phase thing obtaining in hydrogen and step (3) is introduced hydrogenation saturated reaction area, contacts with hydrocatalyst for saturating,
There is hydrogenation saturated reaction, obtain hydrogenation saturated reaction area generation oil gentle；
(5) in the presence of sulfur-bearing logistics, the hydrogenation saturated reaction area obtaining is generated the gentle hydrogenation that introduces of oil take off in step (4)
Nitrogen reaction zone, is contacted with hydrodenitrogenation catalyst, and hydrodenitrogeneration reaction occurs, and obtains hydrodenitrogeneration reaction zone and generates oil and gas,
Then carry out Oil-gas Separation, obtain hydrogenated oil.
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