CN105754646A - A combined method for catalytic diesel oil hydro-conversion and catalytic gasoline hydrogenation - Google Patents
A combined method for catalytic diesel oil hydro-conversion and catalytic gasoline hydrogenation Download PDFInfo
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Abstract
A combined method for catalytically cracked diesel oil hydro-conversion and catalytic gasoline hydrogenation is disclosed. Catalytically cracked diesel oil and hydrogen are mixed, fed into a hydrogenation pretreatment reactor and subjected to hydrorefining. A hydrorefining effluent is directly fed into a cracking reactor, and is brought into contact with and reacts with catalyst bed layers loaded in the cracking reactor in a graded manner. The cracking reactor is provided with at least two hydrocracking catalyst bed layers. Hydrogenation activity of the hydrocracking catalyst bed layers gradually reduces along the flowing direction of a reaction material. A hydrocracking effluent is fed into a hot high-pressure separator and separated. A liquid phase part is depressurized and then is mixed with catalytically cracked gasoline and new hydrogen, and the mixture is directly fed into a gasoline hydrogenation reactor without being heated, and is subjected to hydrogenation desulfurization. The method avoids further cracking of cracked naphtha, increases selectivity of the naphtha, increases the octane number of gasoline and increases the liquid product yield of hydrocracking.
Description
Technical field
The present invention relates to a kind of hydrocarbon hdyrotreating method, specifically a kind of catalytic diesel oil hydro-conversion and catalytic gasoline selective hydrogenation combined technique.
Background technology
Since entering new century, along with the fast development of the enhancing day by day of people's environmental consciousness, the increasingly strict and national economy of national environmental protection regulation, the demand of cleaning automotive fuel is all being continuously increased by countries in the world.Catalytic cracking (FCC) technology is one of main technique means of heavy oil lighting, the status that all occupation ratio is more important in the oil refining enterprise of countries in the world.China's catalytic cracking unit annual working ability alreadys more than 100,000,000 tons at present, is only second to the U.S..In petrol and diesel oil product are constituted, catalytically cracked gasoline accounts for about 80%, and catalytic diesel oil accounts for about 30%.In recent years, heaviness day by day along with domestic machined crude quality, the machined raw material of catalytic cracking also heaviness and in poor quality increasingly, in addition many enterprises are in order to reach to improve the purpose of quality of gasoline or propylene enhancing, catalytic cracking unit is carried out transformation or has improve the operating severity of catalytic cracking unit, the quality causing the product of catalytic cracking, particularly catalytic diesel oil worsens more.
For improving the utilization rate of petroleum resources, improve the total quality level of petrol and diesel oil fuel, realize product blending optimization and the maximized target of value of the product, meeting domestic to cleaning fuel increasing need, high aromatics diesel hydro-conversion produces the hydrogenation cracking novel technique of high added value Petroleum component and low-sulfur cleaning diesel fuel and has good application prospect.Domestic and international researcher has been also carried out substantial amounts of research work.The external existing relevant report adopting hydrocracking process technology that catalytic cracking light cycle oil is converted into ultra-low-sulphur diesel and high octane value gasoline blending component.As: the meeting of nineteen ninety-five NPRA, DavidA.Pappal et al. describes by a kind of single-stage hydrocracking Technology of Mobil, AkzoNobel/NipponKetjen and M.W.Kellogg company exploitation；NPRA meeting in 2005, VasantP.Thakkar et al. describes the LCOUnicrackingTM technology of Uop Inc.'s exploitation.It is reported, the catalytic cycle oil ingredient of low value all can be converted into high octane gasoline component and fine-quality diesel oil blending component by both the above technology.But at present, prior art there is also some problems, high aromatics diesel transformation technology main purpose is that high aromatics diesel is converted into high octane gasoline component, simultaneously, reduce the sulfur content of diesel oil and improve diesel cetane-number, the hydrogenation of gasoline component and diesel component also exists contradiction, when cracking zone catalyst hydrogenation hyperenergia, the gasoline component excessive hydrogenation that cracking generates, product octane number is relatively low, and during cracking zone catalyst hydrogenation scarce capacity, diesel product is second-rate, meanwhile, catalyst carbon deposition speed can be made to accelerate, affect long-term operation.In the process, the problem having related to selective hydrogenation, the hydrogenation selectivity improving gasoline component and diesel component becomes the problem faced by this kind of hydrocracking process needs.In addition, catalytic gasoline selective hydrogenation process is another main technique technology of high-knock rating gasoline production process, and this process also exists, and reaction pressure drop rise rapid device service cycle is short and reaction temperature raises and causes the problem that 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 FCC apparatus fractionating column, FCC gasoline carries out cutting pre-separation in fractionating column, obtains light fraction and heavy distillat；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 gasoline and middle gasoline；Middle gasoline passes sequentially through pre-hydrogenator and hydrodesulphurisatioreactors reactors, carries out the selective hydrogenation relaxed, and heavy distillat carries out depth-selectiveness hydrogenation, and the refining oily and refining light gasoline of tails of gained two parts mixes, and obtains clean gasoline product or blend component.This invention process utilizes catalytic diesel oil to take away the easy coking material that alkali-free sweetening process is formed, and is conducive to alleviating FCC gasoline hydrogenation unit problem of pressure drop.But the program have impact on the even running of catalysed fractionation device, increasing catalytic unit energy consumption, meanwhile, the independent hydrogenation process of catalytic gasoline, pipeline liquid phase ratio is less, is unfavorable for taking away the gum-former that course of reaction is formed.
Chinese patent 02110319.4 discloses a kind of method reducing sulfur content of catalytic cracking gasoline, this inventive method is by mixing in catalytic diesel oil by partially catalyzed heavy petrol component, enter catalytic diesel oil hydro-refining unit and carry out hydrofinishing process, the hydrogenation raw gasoline obtained carries out catalytic reforming process as catalytic reforming raw material, it is thus achieved that high-octane rating Reformed Gasoline.But, owing to gasoline feeding impurity content is required comparatively strict by reformer, catalytic gasoline heavy petrol and diesel component mixed hydrogenation under severe operating conditions, the antiknock component deep hydrogenations such as alkene original in catalytic cracking heavy petrol, aromatic hydrocarbons is saturated, recover aromatic hydrocarbons again through reforming process, cause the waste of this part antiknock component of catalytic cracking heavy petrol.
Summary of the invention
For Problems existing in existing high-knock rating gasoline production process, the invention provides a kind of catalytic diesel oil hydro-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 following content:
(1) described method includes catalytic diesel oil hydro-conversion part and catalytic gasoline selective hydrodesulfurization part；
(2) first catalytic cracking diesel oil carries out heat exchange with catalytic gasoline selective hydrodesulfurization reaction effluent, then heat exchange is carried out with catalytic diesel oil hydroconversion reactions effluent after mixing with hydrogen, enter weighted BMO spaces reactor after heating then through heating furnace, under Hydrofinishing conditions, carry out hydrofining reaction；
(3) hydrofining reaction effluent is not separated is directly entered hydrocracking reactor, with the hydrocracking catalyst bed haptoreaction of grading loading in cracker；The grating mode of described catalyst is: the hydrocracking catalyst of the two or more differential responses activity of grading loading in reactor, the hydrogenation activity of hydrocracking catalyst is gradually reduced according to reaction bed order from top to bottom, and the cracking activity of hydrocracking catalyst is from top to bottom gradually lowered；
(4) the reaction effluent hot high score of entrance of step (3) is easily separated, and obtains gas phase and liquid phase, and gas phase separates further and obtains naphtha cut and hydrogen-rich gas；Liquid phase part, after decompression, mixes with catalytically cracked gasoline and new hydrogen, not heated is directly entered catalytic gasoline selective hydrogenation reactor, and catalytic gasoline is carried out selective hydrodesulfurization reaction；
(5) step (4) obtains reaction effluent entrance separator and carries out gas-liquid separation, obtains gas phase and introduces the make-up hydrogen compressor entrance of hydro-conversion after depriving hydrogen sulphide processes, and gained liquid phase is fractionated into obtaining gasoline and diesel product.
The method according to the invention, wherein the catalytic gasoline selective hydrodesulfurization device in step (4) cancels the setting of circulating hydrogen compressor.After the hydrogen (i.e. new hydrogen) that hydrogen pipe network introduces enters the reaction of catalytic gasoline selective hydrogenation reactor, after elimination hydrogen sulfide, it is directly entered the make-up hydrogen compressor entrance of catalytic diesel oil hydro-conversion part, after boosted, reacts hydrogen make-up for catalytic diesel oil hydroconversion unit.
The method according to the invention, the adjustment of described hydrocracking catalyst hydrogenation activity realizes by from top to bottom reducing the mode of hydrocracking catalyst hydrogenation active metals constituent content.And the cracking activity of hydrocracking catalyst can be adjusted by the content of acidic molecular sieve and the cracking activity of molecular sieve in adjustment catalyst.According to bed from top to bottom, in the Cracking catalyst used in cracker, the content of contained Y molecular sieve is gradually reduced；Or contained Y molecular sieve content is identical, and the cracking activity of Y molecular sieve is gradually lowered.Described Y molecular sieve cracking activity refers mainly to Y molecular sieve generation aromatic hydrocarbons ring-opening reaction activity, and as cracking component alive, its cracking activity is main relevant with Y molecular sieve meleic acid amount.Can pass through to adjust SiO in Y molecular sieve2/Al2O3Molecule mol ratio realizes the adjustment of meleic acid amount on Y molecular sieve, along with Y molecular sieve SiO2/Al2O3The increase of molecule mol ratio, meleic acid amount reduces, and the active cracking activity of Y molecular sieve reduces.
In the methods of the invention, the Hydrobon catalyst of selection and hydrogenation cracking cracking agent can use commercially available prod, it is also possible to prepare according to this area Conventional wisdom.Hydrobon catalyst used by the present invention can adopt conventional hydrocracking pretreatment catalyst, generally with VI B race and/or group VIII metal for active component, with aluminium oxide or silicon-containing alumina for carrier.Group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.With the weight of catalyst for benchmark, 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, and catalyst contains WO by weight315～30%, NiO2～15%, Modified Zeolite Y 30～90%, it is preferable that 40～80%.Selected Y molecular sieve character is as follows: specific surface area 700m2/ g～900m2/ g, total pore volume 0.35ml/g～0.48ml/g, relative crystallinity 90%～130%, cell parameter 2.437～2.460, meleic acid amount 0.5～1.5mmol/g, carrier is generally aluminium oxide or amorphous silica-alumina.
In the methods of the invention, the catalyst that catalytic gasoline selective hydrogenation part is selected can use commercially available prod, it is also possible to prepares according to this area Conventional wisdom.General with aluminium oxide or silicon-containing alumina for carrier, Mo, Co are hydrogenation active component.With the weight of catalyst for benchmark, metal Mo content is calculated as 6wt% ~ 20wt% with oxide, and metal Co content is calculated as 1wt% ~ 12wt% with oxide.
In the inventive method, in hydrocracking reactor from top to bottom, it is preferable that the aperture of hydrocracking catalyst is gradually increased.In cracker, different Cracking catalyst can be loaded according to equal proportion, it is also possible to according to different ratio fillings.Generally, at 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, can further include herein below: gas phase is set between the Cracking catalyst bed that at least two is adjacent in step (3) and draws pipeline, partial gas phase logistics can be drawn pipeline via gas phase and be led to catalytic diesel oil hydro-conversion partial high pressure separator, and liquid phase and residue gas phase mixture proceed hydrocracking reaction.
Generally, at reaction conditions after raw material reaction rate of gasification (rate of gasification refers at reaction conditions, the raw material being converted into gas phase accounts for the ratio of raw material gross mass, not hydrogen) more than 30 mass %, it is preferable that gas phase is set between the Cracking catalyst bed more than 50 mass % and draws pipeline.
Described gas phase is drawn pipeline and is preferably provided at the lower section of catalyst bed interlayer gas-liquid partition tray or cold hydrogen box, and gas phase is drawn pipeline and is provided with flow control valve.During normal operating, a gas-phase space can be formed at the bottom of gas-liquid partition tray or cold hydrogen box, and gas phase is drawn pipeline opening in reactor and is arranged in this gas-phase space, and liquid phase material does not substantially enter gas phase and draws pipeline.The present invention draws pipeline opening part preferably in gas phase baffle plate is set, draw pipeline to prevent liquid phase from entering gas phase further.
The hydrogen to oil volume ratio drawing pipeline uppermost catalyst bed in gas phase is generally 700:1～3000:1, it is preferable that 800:1～1500:1；Gas phase is drawn the hydrogen to oil volume ratio of beds below pipeline and is generally 220:1～2000:1, it is preferable that 300:1～1000:1.The hydrogen-oil ratio of preferred hydrocracking reactor is higher than the hydrogen-oil ratio 200～800 of hydrofining reactor, it is most preferred that exceed 300～600.
Described gas phase is drawn the gas gas-phase objects doses of pipeline extraction and is generally the 20%～70% of recycle hydrogen tolerance (by volume), it is preferable 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 preferable that 340 DEG C～420 DEG C；Reaction pressure is 4.0MPa～15.0MPa, it is preferable that 6.0MPa～12.0MPa；During liquid, volume space velocity is 0.2h-1～6.0h-1, it is preferable that 0.5h-1～3.0h-1；Hydrogen to oil volume ratio is 100～2000, it is preferable that 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, it is preferable that 220 DEG C～320 DEG C；Reaction pressure is 0.5MPa～4.0MPa, it is preferable that 1.0MPa～3.0MPa；During liquid, volume space velocity is 0.2h-1～10.0h-1, it is preferable that 0.5h-1～6.0h-1；Hydrogen to oil volume ratio is 10～500, it is preferable that 30～300.
In the method for the present invention, the character of described catalytic cracking diesel oil is generally: density is 0.88～0.99g/cm3, it is done and is generally 360～400 DEG C, and arene content is generally 50wt%～95wt%.The sulfur content of catalytic cracking diesel oil is generally 0.2wt%～2wt%, and nitrogen content is 500 μ g/g～2000 μ g/g.The character of catalytically cracked gasoline is generally: density is 0.70～0.80g/cm3, it is done and is 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 10 μ g/g～200 μ g/g.
Compared with prior art, the advantage of the catalytic cracking diesel oil method for transformation of the present invention is:
1, in hydrocracking reactor, from top to bottom along with the intensification of cracking level, the Petroleum content cracking generation in cracker in reactant composition is from top to bottom gradually increased, and non-cracked diesel oil part is from top to bottom gradually reduced.Therefore, adopting the inventive method, cracking zone beds hydrogenation activity is from top to bottom gradually reduced, and while ensure that catalytic cracking diesel oil hydrogenation effect, decreases the hydrogenation of Petroleum, reduces hydrogen consumption, improve naphtha product octane number.Additionally, different hydrogenation activity distributions is gradually lowered from top to bottom in conjunction with cracking activity, and the Petroleum reducing reaction generation that is gradually increased in catalyst aperture is cracked into the probability of lighter hydrocarbons further, improves the yield of Petroleum.Owing to the cracking activity of the unconverted catalytic diesel oil component in bottom is higher than the cracking activity of the Petroleum component that reaction generates, and cracker bottom reaction temperature is higher, therefore, Cracking catalyst relatively low cracking activity in bottom is while meeting the further cracking of unconverted catalytic diesel oil, reduce the probability of the further cracking of the Petroleum that reaction generates, and Cracking catalyst bigger aperture in bottom also reduces Petroleum diffusional resistance on a catalyst, shorten the time of contact of Petroleum and Cracking catalyst, avoid the further cracking of the Petroleum that reaction generates, add the selectivity of Petroleum.
2, the inventive method is on the basis of hydrocracking catalyst mixed bed layer grading loading, gas phase is set between adjacent mixed catalyst bed and draws pipeline, equally possible the cracked gas phase of part (mainly include gas light and gasoline component) is directly led out hydrocracking catalyst bed, hydrogenation or the cracking reaction further of gasoline can also be further reduced to a certain extent, the octane number of gasoline can be improved on the one hand, the liquid product yield of hydrogenation cracking can also be improved simultaneously.
3, by improving the hydrogen-oil ratio of cracker, carry light component more and discharge reactor, secondary or the repeatedly cracking reaction of light component can be reduced further, and then increase hydrocracking reaction liquid receipts, improve the octane number of gasoline fraction.
4, the secondary of light component or repeatedly cracking reaction minimizing in hydrocracking reactor lower catalyst bed layer, is also beneficial to reduce the carbon deposit of beds, the service cycle of extension fixture.
5, catalytic gasoline raw material is directly entered catalytic gasoline selective hydrodesulfurization reactor reaction with the portion of non-converted diesel oil of catalytic diesel oil hydro-conversion after mixing, compared with Conventional catalytic gasoline selective hydrogenation technique, catalytic gasoline raw material heats without heat exchanger and heating furnace, therefore heat exchanger and the problem of heating slagging are decreased, unconverted catalytic diesel oil fraction enters catalytic gasoline selective hydrodesulfurization device reaction together with catalytic gasoline on the other hand, serve the effect of absorption reaction heat, reduce bed temperature rise, avoid the problem that in conventional equipment, catalytic gasoline excessive hydrogenation is increased catalytic gasoline loss of octane number by bottom excessive temperature.
6, the setting of catalytic gasoline selective hydrodesulfurization partial cancellation circulating hydrogen compressor, directly utilize pipe network hydrogen as reaction hydrogen, hydro-conversion part and catalytic gasoline selective hydrogenation device share a set of fractionating system, save investment compared with operating respectively with two covering devices.
Accompanying drawing explanation
Fig. 1 is a kind of principle process chart of the inventive method.
Fig. 2 is the another kind of principle process chart of the inventive method.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the method for the present invention is more entered the description of.
As it is shown in figure 1, catalytic cracking diesel oil initially enters catalytic gasoline selective hydrodesulfurization part low pressure heat exchanger 2, carry out heat exchange with catalytic gasoline selective hydrodesulfurization device effluent；nullThen，The heat exchanger 3 of catalytic diesel oil hydro-conversion part is entered after the boosting of boosted pump 24，It is mixed into preatreating reactors 5 through pipeline 1 with the hydrogen introduced through pipeline 4 after reaction effluent heat exchange with catalytic diesel oil hydro-conversion part and carries out hydrofining reaction，Refining reaction device reaction effluent is directly entered in cracker 7 and the beds haptoreaction of grating in cracker through pipeline 6，Reaction effluent enters hot high score 9 through pipeline 8 in high pressure heat exchanger 3 with the catalytic diesel oil raw material after low pressure heat exchanger 2 heat exchange and isolates gas phase and liquid phase after heat exchange，Gas phase portion enters separator 12 through pipeline 11 and separates naphtha cut and hydrogen，Separating obtained Petroleum enters downstream fractionation tower 20 through pipeline 13，Separate the hydrogen obtained and loop back catalytic diesel oil preatreating reactors through circulating hydrogen compressor 25 and pipeline 4；Liquid phase part and unconverted catalytic diesel oil are after decompression, being directly entered catalytic gasoline selective hydrogenation device 17 after pipeline 10 and the new hydrogen of low pressure introduced through pipeline 15 and the catalytically cracked gasoline that introduces through pipeline 14 mixs and catalytic gasoline is carried out selective hydrodesulfurization reaction, reaction effluent entrance separator 18 carries out air-liquid separation.Separate the hydrogen that obtains after depriving hydrogen sulphide processes after make-up hydrogen compressor 26 pressurizes, loop back catalytic diesel oil hydro-conversion part refining reaction device entrance through pipeline 16 and use as the new hydrogen of catalytic diesel oil hydro-conversion part, separating obtained liquid phase is through heat exchanger 2 and pipeline 19, it is partially separated with hydro-conversion after the naphtha cut of acquisition mixes and enters fractionating column 20, be fractionated into obtaining gas products 21, high-knock rating gasoline 22 and low-sulfur diesel-oil component 2.
As in figure 2 it is shown, the another kind of technological process of the inventive method is:
Catalytic cracking diesel oil initially enters catalytic gasoline selective hydrodesulfurization part low pressure heat exchanger 2, carries out heat exchange with catalytic gasoline selective hydrodesulfurization device effluent；Then, the heat exchanger 3 of catalytic diesel oil hydro-conversion part is entered after the boosting of boosted pump 24, being mixed into preatreating reactors 5 through pipeline 1 with the hydrogen introduced through pipeline 4 after reaction effluent heat exchange with catalytic diesel oil hydro-conversion part and carry out hydrofining reaction, refining reaction device reaction effluent is directly entered in cracker 7 and the beds haptoreaction of grating in cracker through pipeline 6；Between two adjacent Cracking catalyst beds, by pipeline 10 extension gas to hot high score 9；Reaction effluent through pipeline 8 enters hot high score 9 after heat exchange with the catalytic diesel oil raw material after low pressure heat exchanger 2 heat exchange in high pressure heat exchanger 3 and isolates gas phase and liquid phase, gas phase portion enters separator 12 through pipeline 11 and separates naphtha cut and hydrogen, separating obtained Petroleum enters downstream fractionation tower 20 through pipeline 13, separates the hydrogen obtained and loops back catalytic diesel oil preatreating reactors through circulating hydrogen compressor 25, pipeline 4；Liquid phase part and unconverted catalytic diesel oil are after decompression, through pipeline 14 and the new hydrogen of low pressure introduced through pipeline 15 and be directly entered catalytic gasoline selective hydrogenation device 17 after the catalytically cracked gasoline of pipeline 16 introducing mixes catalytic gasoline is carried out selective hydrodesulfurization reaction, and reaction effluent entrance separator 18 carries out air-liquid separation.Separate the hydrogen that obtains after depriving hydrogen sulphide processes after make-up hydrogen compressor 26 pressurizes, loop back catalytic diesel oil hydro-conversion part refining reaction device entrance through pipeline 27 and use as the new hydrogen of catalytic diesel oil hydro-conversion part, separating obtained liquid phase is partially separated with hydro-conversion after the naphtha cut of acquisition mixes through heat exchanger 2 and pipeline 19 and enters fractionating column 20, isolates high-knock rating gasoline 22, low-sulfur diesel-oil component 23 and gas products 21.
In the inventive method, in embodiment, refining stage adopts conventional hydrogenation pretreatment catalyst, is 30 μ g/g by adjusting refining stage reaction condition control refining stage effluent oil nitrogen content.Cracking zone has selected the different gradation mode of three kinds of Cracking catalyst of different metal content and different molecular sieve content respectively, and the physico-chemical property of the catalyst of the different cracking agent of cracking zone three kinds and catalytic gasoline selective hydrogenation part is as shown in table 1 below.
The solution of the present invention and effect are described with comparative example by the examples below.
Embodiment 1 ~ 3
Embodiment 1 ~ 3 adopts flow process such as Fig. 1 of the present invention.
According to catalyst A, catalyst B, tri-kinds of Cracking catalyst of catalyst C in beds order grading loading table 1 respectively from top to bottom in embodiment 1-3 catalytic diesel oil hydro-conversion partial cracking reactor, in three embodiments, the ratio respectively 1:1:1 of catalyst A, catalyst B and catalyst C；1:2:1 and 1:1:2.Mo-Co type catalyst D is selected in catalytic gasoline selective hydrogenation partially catalyzed agent.The composition of catalyst and character are in Table 1, and raw materials used character is in Table 2, and embodiment 1 ~ 3 reaction condition and reaction result are shown in table 3 below and table 4.
Embodiment 4
Adopt flow process shown in Fig. 2.Raw oil, operating condition and used catalyst are with embodiment 3.Wherein arranging gas between the first and second Cracking catalyst beds and draw pipeline, other are with embodiment 3.Gas phase draws gas gas-phase objects doses is recycle hydrogen tolerance 30% that pipeline is drawn.
The process conditions of embodiment and result are listed in table 3 and table 4 respectively.
The composition of table 1 embodiment Cracking catalyst and main character.
| 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 | Aluminium oxide | Aluminium oxide | Aluminium oxide | Aluminium oxide |
| Cracking Component | Y molecular sieve | Y molecular sieve | Y molecular sieve | - |
| Cracking Component is content in the carrier, wt% | 80 | 70 | 60 | - |
| Cracking catalyst average pore size, nm | 5.0 | 7.0 | 9.0 | - |
Table 2 raw oil character.
| Raw 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 adopted operating condition of table 3 embodiment 1-4.
| 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 feed 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 |
Table 4 embodiment 1-4 evaluation result.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Catalytic diesel oil hydro-conversion part | ||||
| Product slates, wt% | ||||
| Naphtha cut fraction (< 210 DEG C) | 59 | 58 | 72 | 74 |
| Diesel oil distillate (> 210 DEG C) | 35 | 35 | 20 | 20 |
| Product property | ||||
| Petroleum (< 210 DEG C) | ||||
| 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) | ||||
| 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 oil transform portion adopts the process conditions identical with embodiment 1-3, the pretreatment catalyst that in comparative example 1-4 weighted BMO spaces reactor, filling is identical with embodiment 1-3, and the nitrogen content adjusting refining stage effluent oil by controlling operating condition is 30 μ g/g, loading catalyst A in cracking zone catalyst comparative example 1, comparative example 2, loading catalyst C in comparative example 3, comparative example 4.The raw oil used in comparative example 1-4 is identical with implementing 1-3.Comparative example 1-2 catalytic gasoline selective hydrogenation part controls the product sulfur content identical with embodiment 1 and embodiment 2 respectively, adjusts reaction condition.It is listed in table 5, table 6 with comparative example 1-4 operating condition and product property.
The adopted operating condition of table 5 comparative example 1-4.
| 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 feed 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 |
Table 6 comparative example 1 ~ 4 result of the test.
| Comparative example 1 | Table is example 2 relatively | Comparative example 3 | Comparative example 4 | |
| Product slates, wt% | ||||
| Naphtha cut fraction (< 210 DEG C) | 57 | 69 | 54 | 65 |
| Diesel oil distillate (> 210 DEG C) | 35 | 20 | 35 | 20 |
| Product property | ||||
| Petroleum (< 210 DEG C) | ||||
| 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) | ||||
| 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 passes through embodiment 1, embodiment 3 finds with comparative example 1 and comparative example 2 contrast, when adopting same process condition processing table 2 Raw, comparative example 1 and comparative example 2 use the cracking agent A of high hydrogenation activity and cracking activity, when controlling with embodiment same conversion, owing to comparative example 1 and the higher hydrogenation activity of comparative example 2 catalyst make comparative example 1 and comparative example 2 when diesel oil character and naphtha yield and embodiment 1 and embodiment 3 are close, reactive hydrogen consumption will apparently higher than embodiment 1 and embodiment 3, its chemical hydrogen consumption increases by 0.4 and 0.5 unit respectively, and the gasoline component octane number generated reduces by 4 and 5.8 units respectively.Comparative example 3 and comparative example 4 use the cracking agent C of low hydrogenation activity and low cracking activity, result is when reaching with embodiment 1 and embodiment 3 same conversion, reaction temperature improves 10 DEG C, too low cracking activity and too high reaction temperature have promoted that second pyrolysis reaction carries out, make heavy naphtha yield reduce by 5 and 7 units than enforcement 1 and embodiment 3 respectively, and Petroleum octane number and product hydrogen consumption aspect are also without obvious improvement.All in all catalytic diesel oil transform portion embodiment is compared comparative example and is shown fine cracking and hydrogenation selectivity, and result of use is significantly better than comparative example.
Catalytic gasoline selective hydrogenation part comparative result shows, comparative example 1 with compare 2 compared with embodiment 1 and embodiment 2, when reaching identical desulfurization depth, when causing more greatly its average reaction temperature identical due to temperature rise, outlet temperature is higher, therefore, increase loss of octane number, product loss of octane number is apparently higher than embodiment, and when product sulfur content controls suitable with embodiment, loss of octane number exceeds 0.9 unit and 1.9 units respectively than embodiment 1 and embodiment 2.
In addition, compared to embodiment 3, embodiment 4 by extracting the Petroleum that cracking generates out between cracking bed, avoid the Petroleum further cracking in cracker bottom and hydrogenation is saturated, therefore, compared to embodiment 3, embodiment 4 catalytic diesel oil hydro-conversion part heavy naphtha yield and octane number substantially increase.
Claims (18)
1. catalytic diesel oil hydro-conversion and a catalytic gasoline selective hydrogenation integrated processes, including following content:
(1) described method includes catalytic diesel oil hydro-conversion part and catalytic gasoline selective hydrodesulfurization part；
(2) first catalytic cracking diesel oil carries out heat exchange with catalytic gasoline selective hydrodesulfurization reaction effluent, then heat exchange is carried out with catalytic diesel oil hydroconversion reactions effluent after mixing with hydrogen, enter weighted BMO spaces reactor after heating then through heating furnace, under Hydrofinishing conditions, carry out hydrofining reaction；
(3) hydrofining reaction effluent is not separated is directly entered hydrocracking reactor, with the hydrocracking catalyst bed haptoreaction of grading loading in cracker；The grating mode of described catalyst is: the hydrocracking catalyst of the two or more differential responses activity of grading loading in reactor, the hydrogenation activity of hydrocracking catalyst is gradually reduced according to reaction bed order from top to bottom, and the cracking activity of hydrocracking catalyst is from top to bottom gradually lowered；
(4) the reaction effluent hot high score of entrance of step (3) is easily separated, and obtains gas phase and liquid phase, and gas phase separates further and obtains naphtha cut and hydrogen-rich gas；Liquid phase part, after decompression, mixes with catalytically cracked gasoline and new hydrogen, not heated is directly entered catalytic gasoline selective hydrogenation reactor, and catalytic gasoline is carried out selective hydrodesulfurization reaction；
(5) step (4) obtains reaction effluent entrance separator and carries out gas-liquid separation, obtains gas phase and introduces the make-up hydrogen compressor entrance of hydro-conversion after depriving hydrogen sulphide processes, and 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 the catalytic gasoline selective hydrodesulfurization device in step (4) cancels the setting of circulating hydrogen compressor.
3. in accordance with the method for claim 2, it is characterized in that, after the hydrogen that hydrogen pipe network introduces enters the reaction of catalytic gasoline selective hydrogenation reactor, after elimination hydrogen sulfide, it is directly entered the make-up hydrogen compressor entrance of catalytic diesel oil hydro-conversion part, after boosted, reacts hydrogen make-up for catalytic diesel oil hydroconversion unit.
4. in accordance with the method for claim 1, it is characterised in that the adjustment of described hydrocracking catalyst hydrogenation activity realizes by from top to bottom reducing the mode of hydrocracking catalyst hydrogenation active metals constituent content.
5. in accordance with the method for claim 1, it is characterised in that the cracking activity of described hydrocracking catalyst adjusts by adjusting the content of acidic molecular sieve and the cracking activity of molecular sieve in catalyst.
6. the method described in claim 1 or 5, it is characterised in that it is characterized in that, according to bed from top to bottom, in the Cracking catalyst used in cracker, the content of contained Y molecular sieve is gradually reduced；Or contained Y molecular sieve content is identical, and the cracking activity of Y molecular sieve is gradually lowered.
7. in accordance with the method for claim 1, it is characterised in that described hydrocracking catalyst contains WO by weight315～30%, NiO2～15%, Modified Zeolite Y 30～90%,；Selected modified Y molecular sieve character is as follows: specific surface area 700m2/ g～900m2/ g, total pore volume 0.35ml/g～0.48ml/g, relative crystallinity 90%～130%, cell parameter 2.437～2.460, meleic acid amount 0.5～1.5mmol/g；Carrier is aluminium oxide or amorphous silica-alumina.
8. in accordance with the method for claim 1, it is characterised in that in hydrocracking reactor from top to bottom, the aperture of hydrocracking catalyst is gradually increased.
9. in accordance with the method for claim 1, it is characterised in that at the different Cracking 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 characterized in that, gas phase is set between the Cracking catalyst bed that at least two is adjacent in step (3) and draws pipeline, partial gas phase logistics is drawn pipeline via gas phase and is led to catalytic diesel oil hydro-conversion partial high pressure separator, and liquid phase and residue gas phase mixture proceed hydrocracking reaction.
11. in accordance with the method for claim 10, it is characterised in that at reaction conditions after raw material reaction rate of gasification more than 30 mass %, it is preferable that arrange between the Cracking catalyst bed more than 50 mass % gas phase draw pipeline.
12. in accordance with the method for claim 10, it is characterised in that described gas phase is drawn pipeline and is arranged on the lower section of catalyst bed interlayer gas-liquid partition tray or cold hydrogen box, gas phase is drawn pipeline and is provided with flow control valve.
13. in accordance with the method for claim 12, it is characterised in that draw pipeline opening part in gas phase and arrange baffle plate, to prevent liquid phase from entering gas phase extraction pipeline further.
14. in accordance with the method for claim 10, it is characterised in that the hydrogen to oil volume ratio drawing pipeline uppermost catalyst bed in gas phase is 700:1～3000:1, it is preferable that 800:1～1500:1；Gas phase is drawn the hydrogen to oil volume ratio of beds below pipeline and is generally 220:1～2000:1, it is preferable that 300:1～1000:1.
15. in accordance with the method for claim 10, it is characterised in that the hydrogen-oil ratio of hydrocracking reactor is higher than the hydrogen-oil ratio 200～800 of weighted BMO spaces reactor, it is preferable that exceed 300～600.
16. in accordance with the method for claim 10, it is characterised in that described gas phase draws gas gas-phase objects doses is recycle hydrogen tolerance volume flow 20%～70% that pipeline is drawn, it is preferable that 30%～60%.
17. in accordance with the method for claim 1, it is characterised in that the process conditions of described hydrofining reaction include: reaction temperature is 320 DEG C～440 DEG C, it is preferable that 340 DEG C～420 DEG C；Reaction pressure is 4.0MPa～15.0MPa, it is preferable that 6.0MPa～12.0MPa；During liquid, volume space velocity is 0.2h-1～6.0h-1, it is preferable that 0.5h-1～3.0h-1；Hydrogen to oil volume ratio is 100～2000, it is preferable that 500～1500；The process conditions of described catalytic gasoline selective hydrogenation include: reaction temperature is 200 DEG C～400 DEG C, it is preferable that 220 DEG C～320 DEG C；Reaction pressure is 0.5MPa～4.0MPa, it is preferable that 1.0MPa～3.0MPa；During liquid, volume space velocity is 0.2h-1～10.0h-1, it is preferable that 0.5h-1～6.0h-1；Hydrogen to oil volume ratio is 10～500, it is preferable that 30～300.
18. in accordance with the method for claim 1, it is characterised in that the character of described catalytic cracking diesel oil is: density is 0.88～0.99g/cm3It is done is 360～400 DEG C, and arene content is 50wt%～95wt%；The character of catalytically cracked gasoline is: density is 0.70～0.80g/cm3, doing is 180～220 DEG C, and arene content is 5wt%～20wt%, and olefin(e) centent is generally 20wt%～50wt%, and sulfur content is 0.01wt%～0.2wt%.
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| CN109954513A (en) * | 2017-12-22 | 2019-07-02 | 中国石油化工股份有限公司 | A kind of reduction-state bimetallic catalyst for hydrocracking diesel oil |
| 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 |
| CN114437803A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrotreating method for catalytic diesel oil |
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| CN114437803A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrotreating method for catalytic diesel oil |
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