CN105754646B - A kind of catalytic diesel oil hydro-conversion and gasoline hydrogenation integrated processes - Google Patents
A kind of catalytic diesel oil hydro-conversion and gasoline hydrogenation integrated processes Download PDFInfo
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Abstract
The invention discloses a kind of catalytic cracking diesel oil hydro-conversion and gasoline hydrogenation integrated processes.Catalytic cracking diesel oil enters weighted BMO spaces reactor after being mixed with hydrogen and carries out hydrofining reaction；Refined effluent is directly entered cracker, the beds haptoreaction with grading loading in cracker；At least two hydrocracking catalyst beds are set in cracker, and according to the flow direction of reaction mass, the hydrogenation activity of hydrocracking catalyst bed is in reduction trend.It is hydrocracked effluent to be separated into hot high score, liquid phase part mixes after decompression with catalytically cracked gasoline and new hydrogen, not heated to be directly entered gasoline hydrogenation reactor, carries out hydrodesulfurization reaction.Inventive process avoids the further cracking of pressure naphtha, adds the selectivity of naphtha, improves the octane number of gasoline, while also improves the liquid product yield being hydrocracked.
Description
Technical field
The present invention relates to a kind of hydrocarbon hdyrotreating method, specifically a kind of catalytic diesel oil hydro-conversion and catalysis vapour
Oily selective hydrogenation combined technique.
Background technology
Since the new century, with the increasingly enhancing of people's environmental consciousness, national environmental protection regulation increasingly strict and
The fast development of national economy, countries in the world are all being continuously increased to the demand for cleaning automotive fuel.Catalytic cracking（FCC）Technology
It is one of main technique means of heavy oil lighting, important status is all occupied in the oil refining enterprise of countries in the world.I
State's catalytic cracking unit annual working ability alreadys exceed 100,000,000 tons at present, is only second to the U.S..In petrol and diesel oil product composition, catalysis is split
Change gasoline and account for 80% or so, catalytic diesel oil accounts for 30% or so.In recent years, as the country processes the increasingly heavy of crude quality
Change, the raw material that catalytic cracking is processed also heaviness and in poor quality increasingly, many enterprises are in order to reach improvement quality of gasoline in addition
Or the purpose of propylene enhancing, to catalytic cracking unit transform or improve the operating severity of catalytic cracking unit, led
The product of catalytic cracking is caused, the quality of particularly catalytic diesel oil more deteriorates.
To improve the utilization rate of petroleum resources, the total quality level of petrol and diesel oil fuel is improved, realizes that product blending is optimal
Change and the maximized target of value of the product, satisfaction are domestic to clean fuel increasing need, high aromatics diesel hydro-conversion
Production high added value naphtha component and low-sulfur cleaning diesel fuel be hydrocracked novel technique have well application before
Scape.Domestic and international researcher has also carried out substantial amounts of research work.It is external to be catalyzed using hydrocracking process technology
Cracking light cycle oil is converted into the relevant report of ultra-low-sulphur diesel and high octane value gasoline blending component.Such as：Nineteen ninety-five NPRA
Meeting, David A.Pappal et al. is described by Mobil, Akzo Nobel/Nippon Ketjen and M.W.Kellogg companies
A kind of single-stage hydrocracking technology of exploitation；NPRA meetings in 2005, Vasant P. Thakkar et al. describe UOP
The LCO UnicrackingTM technologies of company's exploitation.It is reported that both the above technology can be by the catalytic cycle oil group of low value
Divide and be converted into high octane gasoline component and fine-quality diesel oil blending component.But at present, prior art is high there is also some problems
Aromatics diesel transformation technology main purpose is that high aromatics diesel is converted into high octane gasoline component, meanwhile, reduce diesel oil
The hydrogenation of sulfur content and improvement diesel cetane-number, gasoline component and diesel component is there is contradiction, when cracking zone catalyst adds
During hydrogen hyperenergia, the gasoline component excessive hydrogenation of cracking generation, product octane number is relatively low, and cracking zone catalyst hydrogenation ability
When insufficient, diesel product is second-rate, meanwhile, catalyst carbon deposition speed can be caused to accelerate, influence long-term operation.In this process
In, the problem of having related to selective hydrogenation, improving the hydrogenation selectivity of gasoline component and diesel component turns into this kind of hydrogenation
The problem of cracking process needs to face.In addition, catalytic gasoline selective hydrogenation process is the another of high-knock rating gasoline production process
One main technique technology, and there is reaction pressure drop rise rapid device service cycle is short and reaction temperature rising is high causes for the process
The problem of gasoline hydrogenation process loss of octane number is big.
Chinese patent 201110321295.9 discloses a kind of catalytic cracking and gasoline hydrogenation combined technique, adjusts
The operating condition of whole FCC apparatus fractionating column, carries out cutting pre-separation to FCC gasoline in fractionating column, obtains light fraction and double distilled
Point；Light fraction carries out alkali-free sweetening, and the light fraction after alkali-free sweetening enters hydrogenation prefractionator together with thermocatalytic diesel oil, separates
Light petrol and middle gasoline；Middle gasoline passes sequentially through pre-hydrogenator and hydrodesulphurisatioreactors reactors, and the selectivity relaxed adds
Hydrogen, heavy distillat carry out depth-selectiveness hydrogenation, and gained two parts are refined, and tails is oily is mixed with refined light petrol, obtains cleaning vapour
Oil product or blend component.The invention process takes away the easy coking material of alkali-free sweetening process formation using catalytic diesel oil, favorably
In alleviation FCC gasoline hydrogenation unit problem of pressure drop.But the program have impact on the even running of catalysed fractionation device, increase catalysis dress
Energy consumption is put, meanwhile, the independent hydrogenation process of catalytic gasoline, pipeline liquid phase ratio is less, is unfavorable for taking away the life of course of reaction formation
Glue material.
Chinese patent 02110319.4 discloses a kind of method for reducing sulfur content of catalytic cracking gasoline, and the inventive method is led to
Cross and mix partially catalyzed heavy petrol component in catalytic diesel oil, enter catalytic diesel oil hydro-refining unit and carry out hydrofinishing processing,
The hydrogenation raw gasoline of acquisition carries out catalytic reforming processing as catalytic reforming raw material, obtains high-octane rating Reformed Gasoline.But by
More strict is required to gasoline feeding impurity content in reformer, catalytic gasoline heavy petrol is with diesel component in critical operation bar
Mixed hydrogenation under part, to the antiknock component deep hydrogenation saturation such as original alkene, aromatic hydrocarbons in catalytic cracking heavy petrol, then lead to
Cross reforming process and recover aromatic hydrocarbons, cause the waste of this part antiknock component of catalytic cracking heavy petrol.
The content of the invention
For problem present in existing high-knock rating gasoline production process, the invention provides a kind of catalytic diesel oil hydrogenation
Conversion and catalytic gasoline selective hydrogenation combined technique, to improve high-knock rating gasoline production process.
A kind of catalytic diesel oil hydro-conversion of the present invention and catalytic gasoline selective hydrogenation integrated processes, including it is following interior
Hold：
（1）Methods described includes catalytic diesel oil hydro-conversion part and catalytic gasoline selective hydrodesulfurization part；
（2）Catalytic cracking diesel oil is exchanged heat with catalytic gasoline selective hydrodesulfurization reaction effluent first, Ran Houyu
Exchanged heat after hydrogen mixing with catalytic diesel oil hydroconversion reactions effluent, then enter weighted BMO spaces after heated stove heat
Reactor, hydrofining reaction is carried out under Hydrofinishing conditions；
（3）Hydrofining reaction effluent is directly entered hydrocracking reactor without isolation, with level in cracker
Hydrocracking catalyst bed haptoreaction with filling；The grading mode of the catalyst is：Grading loading two in reactor
The hydrocracking catalyst of kind of above differential responses activity, the hydrogenation activity of hydrocracking catalyst is according to reaction bed by up to
Under order be gradually reduced, the cracking activity of hydrocracking catalyst from top to bottom gradually reduces；
（4）Step（3）Reaction effluent separated into hot high score, obtain gas phase and liquid phase, gas phase is further divided
From obtaining naphtha cut and hydrogen-rich gas；Liquid phase part mixes after decompression with catalytically cracked gasoline and new hydrogen, not heated
Catalytic gasoline selective hydrogenation reactor is directly entered, selective hydrodesulfurization reaction is carried out to catalytic gasoline；
（5）Step（4）Obtain reaction effluent and carry out gas-liquid separation into separator, obtain gas phase and handled through depriving hydrogen sulphide
The make-up hydrogen compressor entrance of hydro-conversion is introduced afterwards, and gained liquid phase is fractionated into obtaining gasoline and diesel product.
The method according to the invention, wherein step（4）In catalytic gasoline selective hydrodesulfurization device cancel recycle hydrogen
The setting of compressor.The hydrogen that hydrogen pipe network introduces（I.e. new hydrogen）After being reacted into catalytic gasoline selective hydrogenation reactor, warp
The make-up hydrogen compressor entrance of catalytic diesel oil hydro-conversion part is directly entered after removing hydrogen sulfide, is added after boosted for catalytic diesel oil
Hydrogen reforming unit reacts hydrogen make-up.
The method according to the invention, the adjustment of the hydrocracking catalyst hydrogenation activity is by from top to bottom reducing hydrogenation
The mode of Cracking catalyst hydrogenation active metal component content is realized.And the cracking activity of hydrocracking catalyst can pass through
The content of acidic molecular sieve and the cracking activity of molecular sieve adjust in adjustment catalyst.According to bed from top to bottom, in cracking
The content of contained Y molecular sieve is gradually reduced in used Cracking catalyst in reactor；Or contained Y molecular sieve content phase
Together, and the cracking activity of Y molecular sieve gradually reduces.Described Y molecular sieve cracking activity refers mainly to Y molecular sieve and aromatic hydrocarbons open loop occurs
Reactivity, it is mainly relevant with Y molecular sieve meleic acid amount as cracking work component, its cracking activity.Can be by adjusting Y molecules
SiO in sieve2/Al2O3Molecule mol ratio realizes the regulation of meleic acid amount on Y molecular sieve, with Y molecular sieve SiO2/Al2O3Molecule
The increase of mol ratio, meleic acid amount are reduced, and the active cracking activity of Y molecular sieve reduces.
In the methods of the invention, the Hydrobon catalyst of selection and it is hydrocracked cracking agent and can use commercially available prod,
It can also be prepared according to this area Conventional wisdom.Hydrobon catalyst used in the present invention can use conventional hydrocracking pre- place
Catalyst is managed, typically using VI B races and/or group VIII metal as active component, using aluminum oxide or silicon-containing alumina as carrier.VIth
B races metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.On the basis of the weight of catalyst, group VIB
Tenor is calculated as 8wt%~28wt% with oxide, and group VIII metal content is calculated as 2wt%~15wt% with oxide.
Described hydrocracking catalyst is typically chosen the hydrocracking catalyst containing Modified Zeolite Y, with weight
Meter catalyst contains WO3 15~30%, NiO 2~15%, Modified Zeolite Y 30~90%, preferably 40~80%.Selected Y points
Son sieve property is as follows：Specific surface area 700m2The m of/g~9002/ g, total pore volume 0.35ml/g~0.48ml/g, relative crystallinity 90%
~130%, cell parameter 2.437~2.460, meleic acid 0.5~1.5mmol/g of amount, carrier is usually aluminum oxide or amorphous silicon
Aluminium.
In the methods of the invention, the catalyst that catalytic gasoline selective hydrogenation part is selected can use commercially available prod,
It can be prepared according to this area Conventional wisdom.Typically using aluminum oxide or silicon-containing alumina as carrier, Mo, Co are hydrogenation activity group
Point.On the basis of the weight of catalyst, metal Mo contents are calculated as 6wt% ~ 20wt% with oxide, and metal Co contents are in terms of oxide
For 1wt% ~ 12wt%.
In the inventive method, the aperture of preferably hydrocracking catalyst is gradual in hydrocracking reactor from top to bottom
Increase.Different Cracking catalyst can load according to equal proportion in cracker, can also be loaded according to different ratios.One
As in the case of, in the different Cracking catalyst beds of grading loading, the ratio of two kinds of catalyst of arbitrary neighborhood is 1：10~10：
1。
The method according to the invention, it can further include herein below：In step（3）In at least two adjacent split
Setting gas phase draws pipeline between changing beds, and partial gas phase logistics can draw pipeline via gas phase and lead to catalysis bavin
Oily hydro-conversion partial high pressure separator, and liquid phase and remaining gas phase mixture continue hydrocracking reaction.
Generally, rate of gasification after raw material reacts at reaction conditions（Rate of gasification refers at reaction conditions, is converted into gas
The raw material of phase accounts for the ratio of raw material gross mass, not hydrogen）More than 30 mass %, preferably greater than 50 mass % Cracking catalyst bed
Interlayer sets gas phase to draw pipeline.
Described gas phase draws the lower section that pipeline is preferably provided at catalyst bed interlayer gas-liquid partition tray or cold hydrogen box, gas phase
Draw pipeline and flow control valve is installed.During normal operating, a gas phase sky can be formed at the bottom of gas-liquid partition tray or cold hydrogen box
Between, gas phase is drawn opening of the pipeline in reactor and is arranged in the gas-phase space, and liquid phase material does not enter gas phase extraction substantially
Pipeline.Preferably pipeline opening is drawn in the present invention in gas phase baffle plate is set, further to prevent liquid phase from drawing into gas phase
Go out pipeline.
The hydrogen to oil volume ratio that pipeline uppermost catalyst bed is drawn in gas phase is generally 700:1~3000:1, preferably 800:1
~1500:1；The hydrogen to oil volume ratio that gas phase draws beds below pipeline is generally 220:1~2000:1, preferably 300:1
~1000:1.It is preferred that the hydrogen-oil ratio of hydrocracking reactor is higher than the hydrogen-oil ratio 200~800 of hydrofining reactor, most preferably
It is higher by 300~600.
The gas phase draws the gas gas-phase objects doses that pipeline is drawn and is generally recycle hydrogen tolerance（By volume）20%~70%,
It is preferred that 30%~60%.
In the inventive method, the process conditions of described hydrofining reaction include：Reaction temperature is 320 DEG C~440 DEG C,
It is preferred that 340 DEG C~420 DEG C；Reaction pressure is the MPa of 4.0 MPa~15.0 MPa, preferably 6.0 MPa~12.0；Volume is empty during liquid
Speed is 0.2h-1~6.0h-1, preferably 0.5h-1~3.0h-1；Hydrogen to oil volume ratio is 100~2000, preferably 500~1500.
In the present invention in method, the process conditions of described catalytic gasoline selective hydrogenation include：Reaction temperature is 200 DEG C
~400 DEG C, preferably 220 DEG C~320 DEG C；Reaction pressure is 0.5MPa~4.0MPa, the MPa of preferably 1.0MPa~3.0；Body during liquid
Product air speed is 0.2h-1~10.0h-1, preferably 0.5h-1~6.0h-1；Hydrogen to oil volume ratio is 10~500, preferably 30~300.
In the method for the present invention, the property of the catalytic cracking diesel oil is generally：Density is 0.88~0.99g/cm3, its
Generally 360~400 DEG C are done, arene content is generally 50wt%~95wt%.The sulfur content of catalytic cracking diesel oil is generally
0.2wt%~2wt%, nitrogen content are the μ g/g of 500 μ g/g~2000.The property of catalytically cracked gasoline is generally：Density be 0.70~
0.80g/cm3, it does generally 180~220 DEG C, and arene content is generally 5wt%~20wt%, and olefin(e) centent is generally
20wt%~50wt%.The sulfur content of catalytically cracked gasoline is generally 0.01wt%~0.2wt%, and nitrogen content is the μ g/ of 10 μ g/g~200
g。
Compared with prior art, it is the advantages of catalytic cracking diesel oil method for transformation of the invention：
1st, in hydrocracking reactor, from top to bottom with the intensification of cracking level, reactant group in cracker
The naphtha content being cracked to form in point from top to bottom gradually increases, and non-cracked diesel oil part is from top to bottom gradually reduced.Therefore,
Using the inventive method, cracking zone beds hydrogenation activity is from top to bottom gradually reduced, and ensure that catalytic cracking diesel oil
While being hydrogenated with effect, reduce the hydrogenation of naphtha, reduce hydrogen consumption, improve naphtha product octane number.It is in addition, different
Hydrogenation activity distribution combine cracking activity and gradually reduce from top to bottom, and the gradual increase in catalyst aperture reduces reaction
The naphtha of generation is further cracked into the probability of lighter hydrocarbons, improves the yield of naphtha.Due to the unconverted catalytic diesel oil in bottom
The cracking activity of component be higher than reaction generation naphtha component cracking activity, and cracker bottom reaction temperature compared with
Height, therefore, Cracking catalyst relatively low cracking activity in bottom is while the further cracking of unconverted catalytic diesel oil is met, drop
The probability of the further cracking of the naphtha of low reaction generation, and Cracking catalyst bigger aperture in bottom also reduces stone brain
The diffusional resistance of oil on a catalyst, the time of contact of naphtha and Cracking catalyst is shortened, avoid the stone of reaction generation
The further cracking of cerebrol, add the selectivity of naphtha.
2nd, the inventive method is on the basis of hydrocracking catalyst mixed bed layer grading loading, in adjacent mixed catalytic
Gas phase is set to draw pipeline between agent bed, equally can be by partly cracked gas phase（Mainly include that gas is light and gasoline
Component）Hydrocracking catalyst bed is directly led out, further adding for gasoline can also be further reduced to a certain extent
Hydrogen or cracking reaction, the octane number of gasoline on the one hand can be improved, while the liquid product yield being hydrocracked can also be improved.
3rd, by improving the hydrogen-oil ratio of cracker, light component discharge reactor is more carried, can further be reduced
The secondary or multiple cracking reaction of light component, and then increase hydrocracking reaction liquid and receive, improve the octane number of gasoline fraction.
4th, the secondary or multiple cracking reaction of light component is reduced in hydrocracking reactor lower catalyst bed layer, also favorably
The carbon deposit for reducing beds, the service cycle of extension fixture.
5th, catalytic gasoline raw material is directly entered catalytic gasoline after being mixed with the portion of non-converted diesel oil of catalytic diesel oil hydro-conversion
Selective hydrodesulfurization reactor reaction, compared with Conventional catalytic gasoline selective hydrogenation technique, catalytic gasoline raw material without
Heat exchanger and heating stove heat, therefore the problem of reduce heat exchanger and heating slagging, on the other hand unconverted catalysis bavin
Oil distillate enters catalytic gasoline selective hydrodesulfurization device reaction together with catalytic gasoline, serves the work of absorbing reaction heat
With reducing bed temperature rise, avoid in conventional equipment bottom excessive temperature increases catalytic gasoline to catalytic gasoline excessive hydrogenation
The problem of loss of octane number.
6th, the setting of catalytic gasoline selective hydrodesulfurization partial cancellation circulating hydrogen compressor, directly made using pipe network hydrogen
For reaction hydrogen, hydro-conversion part shares a set of fractionating system with catalytic gasoline selective hydrogenation device, with two covering devices point
It Yun Zhuan not compare and save investment.
Brief description of the drawings
Fig. 1 is a kind of principle process chart of the inventive method.
Fig. 2 is another principle process chart of the inventive method.
Embodiment
More enter the description of one to the method for the present invention with specific embodiment below in conjunction with the accompanying drawings.
As shown in figure 1, catalytic cracking diesel oil initially enters catalytic gasoline selective hydrodesulfurization part low pressure heat exchanger 2,
Exchanged heat with catalytic gasoline selective hydrodesulfurization device effluent；Then, boosted pump 24 enters catalytic diesel oil after boosting
Through pipeline 1 and through pipeline after the heat exchanger 3 of hydro-conversion part, with the reaction effluent heat exchange of catalytic diesel oil hydro-conversion part
4 hydrogen introduced are mixed into preatreating reactors 5 and carry out hydrofining reaction, and finishing reactor reaction effluent is through pipeline 6
The beds haptoreaction with grading in cracker in cracker 7 is directly entered, reaction effluent is through pipeline 8
After being exchanged heat with the catalytic diesel oil raw material after the heat exchange of low pressure heat exchanger 2 in high pressure heat exchanger 3 gas phase is isolated into hot high score 9
And liquid phase, gas phase portion separate naphtha cut and hydrogen through pipeline 11 into separator 12, separating obtained naphtha is through pipe
Line 13 enters downstream fractionation tower 20, and isolated hydrogen is recycled back to catalytic diesel oil through circulating hydrogen compressor 25 and pipeline 4 and located in advance
Manage reactor；Liquid phase part be unconverted catalytic diesel oil after decompression, through pipeline 10 with through pipeline 15 introduce the new hydrogen of low pressure
Catalytic gasoline selective hydrogenation device 17 is directly entered to catalytic gasoline after being mixed with the catalytically cracked gasoline introduced through pipeline 14
Selective hydrodesulfurization reaction is carried out, reaction effluent enters separator 18 and carries out air-liquid separation.Isolated hydrogen is through de-
After hydrogen sulfide treatment through make-up hydrogen compressor 26 pressurization after, catalytic diesel oil hydro-conversion part finishing reactor is recycled back to through pipeline 16
Entrance uses as the new hydrogen of catalytic diesel oil hydro-conversion part, and separating obtained liquid phase turns through heat exchanger 2 and pipeline 19 with hydrogenation
Change and enter fractionating column 20 after being partially separated the naphtha cut mixing of acquisition, be fractionated into obtaining gas products 21, high-octane rating vapour
Oil 22 and low-sulfur diesel-oil component 23.
As shown in Fig. 2 another technological process of the inventive method is：
Catalytic cracking diesel oil initially enters catalytic gasoline selective hydrodesulfurization part low pressure heat exchanger 2, with catalytic gasoline
Selective hydrodesulfurization device effluent is exchanged heat；Then, boosted pump 24 enters catalytic diesel oil hydro-conversion portion after boosting
Through pipeline 1 and the hydrogen through the introducing of pipeline 4 after the heat exchanger 3 divided, with the reaction effluent heat exchange of catalytic diesel oil hydro-conversion part
Gas is mixed into preatreating reactors 5 and carries out hydrofining reaction, and finishing reactor reaction effluent is directly entered through pipeline 6 to be split
Change the beds haptoreaction with grading in cracker in reactor 7；In two adjacent Cracking catalyst beds
Between, pass through the extension gas of pipeline 10 to hot high score 9；Reaction effluent and the catalysis bavin after the heat exchange of low pressure heat exchanger 2
Oily raw material enters hot high score 9 through pipeline 8 after being exchanged heat in high pressure heat exchanger 3 and isolates gas phase and liquid phase, and gas phase portion is through pipeline
11 separate naphtha cut and hydrogen into separator 12, and separating obtained naphtha enters downstream fractionation tower 20 through pipeline 13,
Isolated hydrogen is recycled back to catalytic diesel oil preatreating reactors through circulating hydrogen compressor 25, pipeline 4；Liquid phase part does not turn
Low pressure new hydrogen of the catalytic diesel oil of change after decompression, through pipeline 14 and through the introducing of pipeline 15 and the catalytic cracking through the introducing of pipeline 16
Catalytic gasoline selective hydrogenation device 17 is directly entered after gasoline mixing selective hydrodesulfurization reaction is carried out to catalytic gasoline, instead
Answer effluent to enter separator 18 and carry out air-liquid separation.Isolated hydrogen is after depriving hydrogen sulphide is handled through make-up hydrogen compressor
Catalytic diesel oil hydro-conversion part finishing reactor entrance is recycled back to as catalytic diesel oil hydro-conversion after 26 pressurizations, through pipeline 27
Partial new hydrogen uses, and the naphtha that separating obtained liquid phase is partially separated acquisition through heat exchanger 2 and pipeline 19 with hydro-conversion evaporates
Enter fractionating column 20 after dividing mixing, isolate high-knock rating gasoline 22, low-sulfur diesel-oil component 23 and gas products 21.
In the inventive method, refining stage is using conventional hydrogenation pretreatment catalyst in embodiment, by adjusting refining stage
It is 30 μ g/g that reaction condition, which controls refining stage effluent oil nitrogen content,.Cracking zone has selected different metal content and different molecular respectively
Sieve the different gradation mode of three kinds of Cracking catalyst of content, the different cracking agent of three kinds of cracking zone and catalytic gasoline selective hydrogenation
The physico-chemical property of partial catalyst is as shown in table 1 below.
Illustrate the solution of the present invention and effect below by embodiment and comparative example.
Embodiment 1 ~ 3
Embodiment 1 ~ 3 is using flow such as Fig. 1 of the invention.
Order in embodiment 1-3 catalytic diesel oil hydro-conversion partial crackings reactor according to beds from top to bottom
Tri- kinds of catalyst A, catalyst B, catalyst C Cracking catalyst in grading loading table 1 respectively, in three embodiments, catalyst
A, catalyst B and catalyst C ratio are respectively 1:1:1；1:2:1 and 1:1:2.Catalytic gasoline selective hydrogenation partial catalyst
From Mo-Co type catalyst D.The composition and property of catalyst are shown in Table 1, and raw materials used property is shown in Table 2, and embodiment 1 ~ 3 reacts bar
Part and reaction result see the table below 3 and table 4.
Embodiment 4
Using flow shown in Fig. 2.Feedstock oil, operating condition and used catalyst are the same as embodiment 3.Wherein in first and
Gas fairlead line is set between two Cracking catalyst beds, and other are the same as embodiment 3.Gas phase draws the gaseous phase materials that pipeline is drawn
Measure as the 30% of recycle hydrogen tolerance.
The process conditions of embodiment are listed in table 3 and table 4 respectively with result.
The composition and main character of the embodiment Cracking catalyst of table 1.
| Project | Catalyst A | Catalyst B | Catalyst C | Catalyst D |
| Chemical composition, quality % | ||||
| MoO3 | - | - | - | 12 |
| WO3 | 24 | 20 | 18 | |
| CoO | 3 | |||
| NiO | 8 | 5 | 3 | |
| Carrier | Aluminum oxide | Aluminum oxide | Aluminum oxide | Aluminum oxide |
| Cracking Component | Y molecular sieve | Y molecular sieve | Y molecular sieve | - |
| Cracking Component content in the carrier, wt% | 80 | 70 | 60 | - |
| Cracking catalyst average pore size, nm | 5.0 | 7.0 | 9.0 | - |
The raw material oil nature of table 2.
| Feedstock oil | Catalytic diesel oil | Catalytic gasoline |
| Density, g/cm3 | 0.9324 | 0.7412 |
| Boiling range, DEG C | 192~350 | 32~205 |
| S, wt % | 1.54 | 320 |
| N, μ g/g | 800 | 40 |
| Aromatic hydrocarbons, wt % | 72 | 10 |
| Cetane number | 18 | - |
| Octane number | - | 92 |
The embodiment 1-4 of table 3 uses operating condition.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Catalytic diesel oil transform portion | ||||
| Reaction temperature, DEG C | 380 | 390 | 405 | 405 |
| Reaction pressure, MPa | 8.0 | 6.0 | 8.0 | 8.0 |
| Volume space velocity, h-1 | 1.0 | 2.0 | 1.5 | 1.5 |
| Hydrogen to oil volume ratio | 1200 | 1200 | 1200 | 1200 |
| Cracking zone feeds nitrogen content, μ g/g | 30 | 30 | 30 | 30 |
| Conversion per pass, wt% | 65 | 65 | 80 | 80 |
| Chemical hydrogen consumption, wt% | 3.32 | 3.37 | 3.64 | 3.30 |
| Catalytic gasoline selective hydrogenation part | ||||
| Average reaction temperature, DEG C | 265 | 290 | 275 | 275 |
| Reaction pressure, MPa | 1.5 | 1.5 | 1.2 | 1.2 |
| Volume space velocity, h-1 | 2.0 | 3.5 | 3.0 | 3.0 |
| Hydrogen to oil volume ratio | 300 | 300 | 200 | 200 |
The embodiment 1-4 evaluation results of table 4.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Catalytic diesel oil hydro-conversion part | ||||
| Product is distributed, wt% | ||||
| Naphtha cut cut（210 DEG C of ＜） | 59 | 58 | 72 | 74 |
| Diesel oil distillate（210 DEG C of ＞） | 35 | 35 | 20 | 20 |
| Product property | ||||
| Naphtha（210 DEG C of ＜） | ||||
| Density, g/cm-3 | 0.7606 | 0.7610 | 0.7602 | 0.7608 |
| S, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| N, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| Octane number | 92 | 93 | 91.8 | 92.2 |
| Diesel oil（210 DEG C of ＞） | ||||
| Density, g/cm-3 | 0.8802 | 0.8830 | 0.8750 | 0.8748 |
| Sulfur content, μ g/g | 7 | 10 | 5 | 5 |
| Cetane number | 27 | 30 | 33 | 34 |
| Catalytic gasoline selective hydrogenation part | ||||
| Density, g/cm-3 | 0.7389 | 0.7385 | 0.7400 | 0.7402 |
| Boiling range, DEG C | 30~205 | 30~205 | 30~205 | 30~205 |
| Sulfur content, μ g/g | 40 | 8 | 18 | 18 |
| Octane number | 91.4 | 90.3 | 91.9 | 92.1 |
Comparative example 1-4
Comparative example 1-4 catalytic diesel oils transform portion uses and embodiment 1-3 identical process conditions, comparative example 1-4 hydrogenation
Filling and identical pretreatment catalyst in embodiment 1-3 in preatreating reactors, and adjusted and refined by control operation condition
The nitrogen content of section effluent oil be 30 μ g/g, loading catalyst A in cracking zone catalyst comparative example 1, comparative example 2, comparative example 3, is compared
Compared with loading catalyst C in example 4.The feedstock oil used in comparative example 1-4 is identical with implementing 1-3.Comparative example 1-2 catalytic gasolines select
Property hydrogenation part respectively control with embodiment 1 and the identical product sulfur content of embodiment 2, adjust reaction condition.With comparative example 1-4
Operating condition and product property are listed in table 5, table 6.
The comparative example 1-4 of table 5 uses operating condition.
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Catalytic diesel oil hydro-conversion part | ||||
| Reaction temperature, DEG C | 372 | 398 | 390 | 415 |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| Volume space velocity, h-1 | 1.0 | 1.5 | 1.0 | 1.5 |
| Hydrogen to oil volume ratio | 1200 | 1200 | 1200 | 1200 |
| Cracking zone feeds nitrogen content, μ g/g | 30 | 30 | 30 | 30 |
| Conversion per pass, wt% | 65 | 80 | 35 | 80 |
| Chemical hydrogen consumption, wt% | 3.72 | 4.16 | 3.30 | 3.58 |
| Catalytic gasoline selective hydrogenation part | ||||
| Average reaction temperature, DEG C | 210 | 300 | ||
| Reaction pressure, MPa | 1.5 | 1.5 | ||
| Volume space velocity, h-1 | 2.0 | 3.5 | ||
| Hydrogen to oil volume ratio | 300 | 300 |
The result of the test of 6 comparative example of table 1 ~ 4.
| Comparative example 1 | Table is compared with example 2 | Comparative example 3 | Comparative example 4 | |
| Product is distributed, wt% | ||||
| Naphtha cut cut（210 DEG C of ＜） | 57 | 69 | 54 | 65 |
| Diesel oil distillate（210 DEG C of ＞） | 35 | 20 | 35 | 20 |
| Product property | ||||
| Naphtha（210 DEG C of ＜） | ||||
| Density, g/cm-3 | 0.7600 | 0.7602 | 0.7600 | 0.7602 |
| S, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| N, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| Octane number | 88 | 86 | 92 | 91.5 |
| Diesel oil（210 DEG C of ＞） | ||||
| Density, g/cm-3 | 0.8802 | 0.8750 | 0.8802 | 0.8750 |
| Sulfur content, μ g/g | 7 | 5 | 7 | 5 |
| Cetane number | 29 | 34 | 25 | 28 |
| Catalytic gasoline selective hydrogenation part | ||||
| Density, g/cm-3 | 0.7438 | 0.7435 | ||
| Boiling range, DEG C | 29~205 | 28~205 | ||
| Sulfur content, μ g/g | 39 | 7.0 | ||
| Octane number | 90.5 | 88.4 |
Catalytic diesel oil hydro-conversion part is contrasted with comparative example 1 and comparative example 2 and found by embodiment 1, embodiment 3,
When processing raw material in table 2 using same process condition, comparative example 1 and comparative example 2 are split using high hydrogenation activity and cracking activity
Agent A, in the case where controlling with embodiment same conversion, because comparative example 1 and the higher hydrogenation of the catalyst of comparative example 2 are lived
Property cause comparative example 1 and comparative example 2 in the case of diesel oil property and naphtha yield and embodiment 1 and embodiment 3 are similar, instead
Answer hydrogen consumption will be apparently higher than embodiment 1 and embodiment 3, its chemical hydrogen consumption increases by 0.4 and 0.5 unit respectively, and generate
Gasoline component octane number reduces by 4 and 5.8 units respectively.Comparative example 3 and comparative example 4 use low hydrogenation activity and low cracking activity
Cracking agent C, as a result in the case where reaching with embodiment 1 and the same conversion of embodiment 3, reaction temperature improve 10 DEG C, mistake
Low cracking activity and too high reaction temperature promote second pyrolysis reaction and carried out so that heavy naphtha yield is respectively than implementing
1 and embodiment 3 reduce by 5 and 7 units, and naphtha octane number and product hydrogen consumption aspect also do not improve significantly.It is overall
From the point of view of catalytic diesel oil transform portion embodiment show fine cracking and hydrogenation selectivity compared to comparative example, using effect is obvious
It is better than comparative example.
Catalytic gasoline selective hydrogenation part comparative result shows, comparative example 1 and compares 2 and embodiment 1 and the phase of embodiment 2
Than when reaching identical desulfurization depth, in the case of its average reaction temperature identical is caused because temperature rise is larger, outlet temperature is more
Height, therefore, loss of octane number is increased, product loss of octane number is apparently higher than embodiment, and product sulfur content controls and embodiment
When suitable, loss of octane number is higher by 0.9 unit and 1.9 units than embodiment 1 and embodiment 2 respectively.
In addition, compared to embodiment 3, embodiment 4 is avoided by the naphtha that extraction cracking generates between cracking bed
Further cracking and hydrogenation saturation of the naphtha in cracker bottom, therefore, compared to embodiment 3, embodiment 4 is catalyzed bavin
Oily hydro-conversion part heavy naphtha yield and octane number substantially increase.
Claims (23)
1. a kind of catalytic diesel oil hydro-conversion and catalytic gasoline selective hydrogenation integrated processes, including following content：
（1）Methods described includes catalytic diesel oil hydro-conversion part and catalytic gasoline selective hydrodesulfurization part；
（2）Catalytic diesel oil is exchanged heat with catalytic gasoline selective hydrodesulfurization reaction effluent first, is then mixed with hydrogen
Exchanged heat afterwards with catalytic diesel oil hydroconversion reactions effluent, then enter weighted BMO spaces reactor after heated stove heat,
Hydrofining reaction is carried out under Hydrofinishing conditions；
（3）Hydrofining reaction effluent is directly entered hydrocracking reactor without isolation, is equipped with level in cracker
The hydrocracking catalyst bed haptoreaction filled out；The grading mode of the catalyst is：In reactor two kinds of grading loading with
The hydrocracking catalyst of upper differential responses activity, the hydrogenation activity of hydrocracking catalyst according to reaction bed from top to bottom
Order is gradually reduced, and the cracking activity of hydrocracking catalyst from top to bottom gradually reduces；
（4）Step（3）Reaction effluent separated into hot high score, obtain gas phase and liquid phase, gas phase further separates
To naphtha cut and hydrogen-rich gas；Liquid phase part mixes after decompression with catalytic gasoline and new hydrogen, not heated to be directly entered
Catalytic gasoline selective hydrodesulfurization device, selective hydrodesulfurization reaction is carried out to catalytic gasoline；
（5）Step（4）Obtain reaction effluent and carry out gas-liquid separation into separator, obtain gas phase and draw after depriving hydrogen sulphide is handled
Enter the make-up hydrogen compressor entrance of hydro-conversion, gained liquid phase is fractionated into obtaining gasoline and diesel product.
2. in accordance with the method for claim 1, it is characterised in that step（4）In catalytic gasoline selective hydrodesulfurization dress
Put the setting for cancelling circulating hydrogen compressor.
3. in accordance with the method for claim 2, it is characterised in that the hydrogen that hydrogen pipe network introduces enters catalytic gasoline selectivity
After hydrodesulfurization unit reaction, the make-up hydrogen compressor that catalytic diesel oil hydro-conversion part is directly entered after removing hydrogen sulfide enters
Mouthful, it is that catalytic diesel oil hydroconversion unit reacts hydrogen make-up after boosted.
4. in accordance with the method for claim 1, it is characterised in that the adjustment of the hydrocracking catalyst hydrogenation activity passes through
The mode for from top to bottom reducing hydrocracking catalyst hydrogenation active metal component content is realized.
5. in accordance with the method for claim 1, it is characterised in that the cracking activity of the hydrocracking catalyst passes through adjustment
The content of acidic molecular sieve and the cracking activity of molecular sieve adjust in catalyst.
6. in accordance with the method for claim 1, it is characterised in that, made in cracker according to bed from top to bottom
The content of contained Y molecular sieve is gradually reduced in hydrocracking catalyst；Or contained Y molecular sieve content is identical, and Y molecules
The cracking activity of sieve gradually reduces.
7. in accordance with the method for claim 1, it is characterised in that described hydrocracking catalyst contains WO by weight3
15~30%, NiO 2~15%, Modified Zeolite Y 30~80%；The modified Y molecular sieve property is as follows：Specific surface area
700m2The m of/g~9002/ g, total pore volume 0.35ml/g~0.48ml/g, relative crystallinity 90%~130%, cell parameter 2.437~
2.460,0.5~1.5mmol/g of meleic acid amount；Carrier is aluminum oxide or amorphous silica-alumina.
8. in accordance with the method for claim 1, it is characterised in that, be hydrocracked in hydrocracking reactor from top to bottom
The aperture of catalyst gradually increases.
9. in accordance with the method for claim 1, it is characterised in that in the different hydrocracking catalyst beds of grading loading,
The ratio of two kinds of catalyst of arbitrary neighborhood is 1：10~10：1.
10. in accordance with the method for claim 1, it is characterised in that in step（3）In at least two adjacent being hydrocracked urge
Gas phase is set to draw pipeline between agent bed, partial gas phase logistics draws pipeline via gas phase and leads to catalytic diesel oil hydrogenation turn
Change the hot high score in part, and liquid phase and remaining gas phase mixture continue hydrocracking reaction.
11. in accordance with the method for claim 10, it is characterised in that rate of gasification is more than 30 after raw material reacts at reaction conditions
Gas phase is set to draw pipeline between quality % hydrocracking catalyst bed.
12. in accordance with the method for claim 10, it is characterised in that described gas phase draws pipeline and is arranged on beds
Between the lower section of gas-liquid partition tray or cold hydrogen box, gas phase draw pipeline flow control valve is installed.
13. in accordance with the method for claim 12, it is characterised in that draw pipeline opening in gas phase and baffle plate is set,
Further to prevent liquid phase from entering gas phase to draw pipeline.
14. in accordance with the method for claim 10, it is characterised in that draw the hydrogen oil of pipeline uppermost catalyst bed in gas phase
Volume ratio is 700:1~3000:1, the hydrogen to oil volume ratio that gas phase draws beds below pipeline is 220:1~2000:1.
15. in accordance with the method for claim 10, it is characterised in that the hydrogen to oil volume ratio of hydrocracking reactor is higher than hydrogenation
The hydrogen to oil volume ratio 200~800 of preatreating reactors.
16. in accordance with the method for claim 10, it is characterised in that the gas phase draws the gas gas-phase objects doses that pipeline is drawn and is
The 20%~70% of recycle hydrogen tolerance volume flow.
17. in accordance with the method for claim 1, it is characterised in that the process conditions of described hydrofining reaction include：Instead
It is 320 DEG C~440 DEG C to answer temperature, and reaction pressure is the MPa of 4.0 MPa~15.0, and volume space velocity is 0.2h during liquid-1~6.0h-1,
Hydrogen to oil volume ratio is 100~2000；The process conditions of described catalytic gasoline selective hydrodesulfurization include：Reaction temperature is
200 DEG C~400 DEG C, reaction pressure is 0.5MPa~4.0MPa, and volume space velocity is 0.2h during liquid-1~10.0h-1, hydrogen to oil volume ratio
For 10~500.
18. in accordance with the method for claim 1, it is characterised in that the property of the catalytic diesel oil is：Density be 0.88~
0.99g/cm3, it is done as 360~400 DEG C, and arene content is 50wt%~95wt%；The property of catalytic gasoline is：Density is
0.70~0.80g/cm3, do as 180~220 DEG C, arene content is 5wt%~20wt%, olefin(e) centent be 20wt%~
50wt%, sulfur content are 0.01wt%~0.2wt%.
19. in accordance with the method for claim 11, it is characterised in that rate of gasification is more than 50 after raw material reacts at reaction conditions
Gas phase is set to draw pipeline between quality % hydrocracking catalyst bed.
20. in accordance with the method for claim 14, it is characterised in that draw the hydrogen oil of pipeline uppermost catalyst bed in gas phase
Volume ratio is 800:1~1500:1；The hydrogen to oil volume ratio that gas phase draws beds below pipeline is 300:1~1000:1.
21. in accordance with the method for claim 15, it is characterised in that the hydrogen to oil volume ratio of hydrocracking reactor is higher than hydrogenation
The hydrogen to oil volume ratio 300~600 of preatreating reactors.
22. in accordance with the method for claim 16, it is characterised in that the gas phase draws the gas gas-phase objects doses that pipeline is drawn and is
Recycle hydrogen tolerance volume flow 30%~60%.
23. in accordance with the method for claim 17, it is characterised in that the process conditions of described hydrofining reaction include：
Reaction temperature is 340 DEG C~420 DEG C, and reaction pressure is the MPa of 6.0 MPa~12.0, and volume space velocity is 0.5h during liquid-1~3.0h-1, hydrogen to oil volume ratio is 500~1500；The process conditions of described catalytic gasoline selective hydrogenation include：Reaction temperature is 220
DEG C~320 DEG C, reaction pressure is the MPa of 1.0MPa~3.0, and volume space velocity is 0.5h during liquid-1~6.0h-1, hydrogen to oil volume ratio is
30~300.
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| CN109777510B (en) * | 2017-11-14 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrocracking method for improving jet fuel yield |
| CN109954513B (en) * | 2017-12-22 | 2021-11-05 | 中国石油化工股份有限公司 | Reduced bimetallic diesel oil hydrogenation conversion catalyst |
| CN111088073A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Hydrocracking method for catalytic diesel oil |
| CN114437803B (en) * | 2020-10-19 | 2023-07-04 | 中国石油化工股份有限公司 | Hydrotreatment method of catalytic diesel |
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