CN102465012B - A kind of inferior diesel oil deep hydrodesulfurizationmethod method - Google Patents
A kind of inferior diesel oil deep hydrodesulfurizationmethod method Download PDFInfo
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- 238000000034 method Methods 0.000 title abstract description 58
- 239000002283 diesel fuel Substances 0.000 title abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 60
- 239000001257 hydrogen Substances 0.000 abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 30
- 239000005864 Sulphur Substances 0.000 abstract description 29
- 239000003054 catalyst Substances 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007789 gas Substances 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 6
- 230000036961 partial effect Effects 0.000 abstract description 6
- 229910017313 Mo—Co Inorganic materials 0.000 abstract description 5
- 229910017318 Mo—Ni Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 150000004767 nitrides Chemical class 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 32
- 230000000694 effects Effects 0.000 description 20
- 238000005516 engineering process Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
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- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 239000000295 fuel oil Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 238000007670 refining Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of inferior diesel oil deep hydrodesulfurizationmethod method.First stock oil and hydrogen enter the first reactor through process furnace, contact under Hydrofinishing conditions with Mo-Ni hydrogenation catalyst, carry out conventional hydrofining reaction, remove most nitride and partial vulcanization thing; Generate oil to enter air lift and mix in hydrogen device, remove the hydrogen sulfide and ammonia that dissolve in oil, and make hydrogen in oil, reach dissolving state of saturation, be then mixed into the second reactor with hydrogen make-up and contact with Mo-Co system Hydrobon catalyst, carry out deep desulfuration reaction.The inventive method, for the catalytic diesel oil cut of petroleum chemical enterprise's poor quality, fraction of coker gas oil or Medium diesel oil cut, adopts this processing method can produce sulphur content and is less than the even lower ultra-low sulfur clean diesel of 50 μ g/g.
Description
Technical field
The present invention relates to a kind of method of inferior diesel oil deep hydrodesulfurizationmethod, particularly a kind of hydrogenation method needing production ultra-low-sulphur diesel.
Background technology
Along with the increasingly stringent that countries in the world require environmental regulation, the index of derv fuel oil is more and more stricter, and producing ultra-low-sulphur diesel becomes the common topic paid close attention in the whole world.The developed countries such as ultra-low-sulphur diesel (ULSD) refers to that sulphur content is less than the even lower automotive diesel fuels of 50 μ g/g, American-European have taken the lead in requiring that this country must perform the quality standard of ultra-low-sulphur diesel.In recent years; along with the Chinese government is to the continuous attention of environment protection; in some big cities; as Beijing, Shanghai, Guangzhou etc. or be about to carry out sulphur content and be less than the derv fuel oil standard of 50 μ g/g; can predict in the near future, mandatory provision is also used ultra-low-sulphur diesel by other cities, the whole nation.
Along with heaviness and the in poor quality of crude oil, the sulphur content of diesel oil distillate is also more and more higher, the ratio being difficult to the heterocycle sulfocompound of desulfurization is also more and more higher, and produce low sulfur diesel product, particularly production sulphur content is less than the even lower diesel product of 50 μ g/g more and more because of difficulty.Produce ultra-low-sulphur diesel product with current method of hydrotreating the most widely, general measure is the Intake Quantity increasing catalyzer, improves temperature of reaction, reduces the methods such as air speed.But these methods have certain shortcoming, it is larger that the Intake Quantity increasing catalyzer requires reactor volume to do, and the one-time investment of catalyzer is also larger; Improve temperature of reaction and can increase energy consumption, increase the operating severity of device, affect the long period steady running of device; Reduce the output that treatment capacity can reduce product, these method Dou Shi oil refining enterprise are not acceptant.
Producing the most economical way of ultra-low-sulphur diesel in prior art is use high-activity hydrogenation catalyst, but activity of hydrocatalyst increase rate newly developed is limited, is difficult to the speed meeting diesel quality upgrading.Therefore, while adopting high activated catalyst newly developed, new Technology be adopted to combine with it, just can obtain more significantly effect.
In diesel oil ultra-deep hydrodesulfuration technology, the basic Hydrobon catalyst adopting conventional technical process higher with activity.The FH-UDS series of diesel fuel deep hydrodesulfurizationof catalyzer that such as Fushun Petrochemical Research Institute (FRIPP) develops, at home many cover Large Scale Industrial Process are applied, nominal data shows to produce the ultra-low-sulphur diesel that sulphur content is less than 50 μ g/g; The Commercial application of the RS-1000 Hydrobon catalyst that Research Institute of Petro-Chemical Engineering (RIPP) develops shows, under suitable processing condition, also can produce the ultra-low-sulphur diesel of 50 μ g/g.Although adopt these working methods also can produce ultra-low sulfur clean diesel at present, processing condition are all comparatively harsh, and energy consumption is also higher, and the long period steady running of device also exists hidden danger.
CN101591566A discloses a kind of grading method of catalyst of deep hydrodesulfurizationof of diesel oil.Reactor is divided into four reaction areas by the method, load the hydrogenation catalyst of different activities metal types and different metal content respectively, by the grating of the catalyzer of different system, give full play to the desulfurization advantage of respective catalyzer in different desulfurization stage, by the synergistic effect between respective catalyzer, improve the activity of integer catalyzer, under the processing condition comparatively relaxed, the ultra-low-sulphur diesel that sulphur content meets state IV standards can be obtained.Although the method can obtain good sweetening effectiveness, desulphurizing activated increase rate is limited, the filling of catalyzer and draw off comparatively complicated, and the catalyzer drawn off is difficult to separation reuses, and causes cost to increase.
CN1211459A discloses a kind of diesel oil adverse current deep hydrodesulfurizationof, Porous deproteinized bone method, the key of invention be to use low temperature diesel oil distillate particularly this reaction gained liquid-phase product through cooled diesel oil distillate, as the cooling raw material of reactive system, effectively have adjusted the gas in diesel oil countercurrent hydrogenation treatment reactor, flow quantity distribution, effectively reduce the logistics flux that liquid flooding region easily occurs, device is operated more steady, the inventive method can also be improved the quality of products simultaneously.Although the method can obtain good hydrogenating desulfurization, de-fragrant effect, the quiet run of device and the stable performance of reactor lower part catalyst activity all have problems.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of inferior diesel oil deep hydrodesulfurizationmethod, the inventive method can realize the deep hydrodesulfurizationof of poor ignition quality fuel, and product sulphur content meets and is less than the even lower quality index requirement of 50 μ g/g.
Poor ignition quality fuel deep hydrogenation desorption method of the present invention comprises following content:
Under hydroprocessing conditions, first stock oil and hydrogen enter the first reactor through process furnace, contact under Hydrofinishing conditions with Mo-Ni hydrogenation catalyst, carry out conventional hydrofining reaction, remove most nitride and partial vulcanization thing; Gained reaction effluent enters air lift and mixes in hydrogen storage equipment, remove the hydrogen sulfide and ammonia that dissolve in oil, and make hydrogen in oil, reach dissolving state of saturation, then be mixed into the second reactor to contact with Mo-Co system Hydrobon catalyst with hydrogen make-up, carry out deep desulfuration reaction, finally obtain the clean diesel product of ultra-low sulfur.
According to hydrogenation modification method of the present invention, in a kind of embodiment, described air lift mixes hydrogen gas stripping column and the gas liquid mixer that hydrogen storage equipment comprises series connection.Described hydrogen gas stripping column preferred thermal high hydrogen gas stripping column.
Described gas liquid mixer can select static mixer or dynamic mixer, the different shapes hybrid element of static mixer by arranging in mixing tank, mass-transfer efficiency between fluid is improved greatly, static mixing implement body as the static mixer such as SV type, SL type, SH type, SX type, SK type of domestic-developed, the static mixer such as ISG type, SMV type of external exploitation.The moving member that dynamic mixer is arranged by hybrid instrument, improves the mass-transfer efficiency between fluid, concrete as star gear shape mixing tank, sound gear ring shape mixing tank, crescent moon trough mixer or ball-and-socket type mixing tank etc.
In another embodiment of the invention, described air lift is mixed hydrogen storage equipment and is comprised an air lift and mix hydrogen device.Described air lift is mixed hydrogen device and is comprised stripper section, divider and mixed hydrogen partial.In the stripper section on top, can also filler be set; The liquid dispenser that divider can adopt this area conventional, and mixed hydrogen partial can comprise difform hybrid element or moving member, as mixed hydrogen partial can comprise the moving member such as gear, blade.Hydrogen enters air lift from middle part and bottom respectively and mixes hydrogen device, the Main Function of hydrogen that middle part enters is that air lift goes out conventional hydro and generates hydrogen sulfide in oil and ammonia, then comparatively clean oil product is after divider, the reverse contact of hydrogen entered with bottom that flow downward fully mixes, under the effect of dynamic mixers, make hydrogen in oil product, reach dissolving state of saturation.Surplus hydrogen mixes hydrogen device top row's hydrogen mouth from air lift and discharges, and reaches hydrogen and dissolves and enter reactor after fat oil product mix with hydrogen make-up and carry out hydrogenation reaction.
In inferior diesel oil deep hydrodesulfurizationmethod method of the present invention, technical process adopts single hop hydrogenation technique flow process.Hydroprocessing operations condition comparatively relaxes, and the first reactor hydrogen pressures 4.0MPa ~ 12.0MPa, is preferably 4.8MPa ~ 9.0MPa; Temperature of reaction is 260 DEG C ~ 420 DEG C, is preferably 280 DEG C ~ 380 DEG C; Volume space velocity is 0.5h
-1~ 4.0h
-1, be preferably 1.0h
-1~ 3.0h
-1; Hydrogen to oil volume ratio is 100 ~ 800, preferably 200 ~ 600; Second reactor hydrogen pressures 4.0MPa ~ 12.0MPa, is preferably 4.8MPa ~ 8.0MPa; Temperature of reaction is 270 DEG C ~ 430 DEG C, is preferably 300 DEG C ~ 400 DEG C; Volume space velocity is 0.5h
-1~ 4.0h
-1, be preferably 1.0h
-1~ 3.0h
-1; Hydrogen to oil volume ratio is 100 ~ 800, preferably 200 ~ 600.
In inferior diesel oil deep hydrodesulfurizationmethod method of the present invention, the hydrotreating catalyst that the first reactor uses is Mo-Ni series hydrocatalyst.The composition of catalyzer comprises: molybdenum oxide 23wt% ~ 26wt%, nickel oxide 3.7wt% ~ 4.1wt%, and with oxide basis active metal total content for 26wt% ~ 30wt%, carrier is silicon-containing alumina.The Hydrobon catalyst that second reactor uses is Mo-Co series hydrocatalyst.The composition of catalyzer comprises: molybdenum oxide 18wt% ~ 21wt%, cobalt oxide 3wt% ~ 5wt%, with oxide basis active metal total content for 21wt% ~ 26wt%.
The inventive method is compared with common diesel hydrofining technology flow process, technical process is more close, only newly-increased a set of air lift mixes hydrogen storage equipment, but the unapproachable effect of ordinary method can be reached, realize the effect of deep hydrodesulfurizationof of diesel oil, product sulphur content meets the GB clean diesel requirement being not more than 50 μ g/g, and reaction conditions comparatively relaxes.
The inventive method need increase an air lift and mix hydrogen storage equipment.The Main Function that gas mixes hydrogen storage equipment is: one, remove the hydrogen sulfide instead generated and an ammonia, make the catalyzer of the second reactor give play to better sweetening effectiveness; Two, make to enter hydrogen in the oil product of the second reactor and reach dissolving state of saturation, can speed of reaction be accelerated, obtain better hydrogenation effect.Diesel oil hydrogenation process is carried out usually under solution-air mixed phase reaction conditions, the factor affecting hydrogenation effect mainly the speed that spread to catalyst surface by liquid film of hydrogen and a large amount of hydrogen sulfide and ammonia to the restraining effect of hydrogenation reaction.Therefore, in hydrogenation process, increase air lift hydrogen-dissolving device can well reduce the impact of these two aspects factor on hydrogenation effect.The present invention mixes hydrogen storage equipment by efficient air lift and is fully mixed with diesel raw material by hydrogen, makes hydrogen reach dissolving state of saturation, and removes the hydrogen sulfide and ammonia that affect hydrogenation reaction simultaneously, reaches the object of killing two birds with one stone.Experiment shows, the inventive method mixes hydrogen storage equipment by increasing air lift, adopts single stage process flow process can reach effect more better than conventional single stage process technology.Cost of investment and process cost can be reduced simultaneously.The inventive method adopts simple technical process, under the processing condition comparatively relaxed, obtains technique effect more better than existing single hop hydrogenation technique.
Accompanying drawing explanation
Fig. 1 is a kind of concrete technology schematic flow sheet of inferior diesel oil deep hydrodesulfurizationmethod method of the present invention.
Wherein: 1-diesel raw material, 2-process furnace, 3-hydrogen make-up, 4-first reactor, 5-interchanger, 6-air lift mixes hydrogen device, 7-second reactor, 8-circulating hydrogen compressor, 9-venting port, 10-separator, 11-treated oil.
Embodiment
Detailed process and the effect of inferior diesel oil deep hydrodesulfurizationmethod method of the present invention is further illustrated below in conjunction with accompanying drawing.
As described in Figure 1, a concrete mode of poor-quality diesel-oil by cut fraction hydrodesulfurizationprocess process of the present invention comprises following content: adopt single stage process flow process, first process furnace 2 is entered after poor-quality diesel-oil by cut fraction raw material 1 mixes with hydrogen, then the first reactor 4 is being entered, carry out conventional hydrofining reaction, use catalyzer for Mo-Ni system high-activity hydrogenation catalyst in reactor 4, the composition of catalyzer generally comprises: molybdenum oxide 23wt% ~ 26wt%, nickel oxide 3.7wt% ~ 4.1wt%, with oxide basis active metal total content for 26wt% ~ 30wt%, remove nitride most in stock oil and partial vulcanization thing, the air lift that reactant enters two anti-tops through interchanger 5 is mixed in hydrogen device 6, carry out air lift with new hydrogen 3 and can make hydrogen in oil product, reach dissolving state of saturation, then enter the second reactor 7 and carry out deep desulfuration reaction, excessive gas is discharged from venting port 9, the catalyzer that reactor 7 uses is Mo-Co system Hydrobon catalyst, generate oil and enter separator 10, hydrogen-rich gas and air lift are mixed after hydrogen device 6 top mixed gas mixes and are recycled through circulating hydrogen compressor 8, new hydrogen 3 can fill into after circulating hydrogen compressor 8, treated oil 11 is obtained bottom separator 10.
First reactor catalyst adopts the non-noble metal hydrogenation catalyst of Mo-Ni system, has the advantages that hydrogenation activity is higher.The composition of catalyzer generally comprises: molybdenum oxide 26wt% ~ 30wt% (wt% is weight percentage), nickel oxide 3.7wt% ~ 4.1wt%, with oxide basis active metal total content for 26wt% ~ 30wt%.Support of the catalyst is generally refractory porous oxide, as aluminum oxide, silicon oxide, titanium oxide, zirconium white etc., can contain other adjuvant component.The hydrogenation catalyst that second reactor uses is Mo-Co system Hydrobon catalyst, the composition of catalyzer comprises: molybdenum oxide 18wt% ~ 21wt% (wt% is weight percentage), cobalt oxide 3wt% ~ 5wt%, with oxide basis active metal total content for 21wt% ~ 26wt%.According to feedstock property, can need load hydrogenation protecting agent on the first reactor top, Intake Quantity is 5% ~ 20% of reactor hydrogenation catalyst volume.
Through the diesel raw material of the inventive method process, product can reach following character: S < 50 μ g/g, even lower, other character meet the index request of state IV derv fuel oil blend component, solve the requirement that each oil refining enterprise produces ultra-low-sulphur diesel product.
Described diesel raw material is catalytic diesel oil, coker gas oil, Pyrolysis gas oil PGO or with other diesel oil mix wet goods, require that 95% recovered temperature is less than 365 DEG C, sulphur content is generally greater than 1.5wt%, be preferably 1.5wt% ~ 2.0wt%.The contents such as concrete technology condition can be determined by those skilled in the art according to material elementses such as the character of raw material, quality product requirements.
The invention has the advantages that: process poor-quality diesel-oil by cut fraction, sulphur content can be produced and be less than the even lower ultra-low-sulphur diesel of 50 μ g/g, the requirement of GB clean diesel to sulphur content can be met.After solving poor ignition quality fuel hydrogenation, product sulphur content is difficult to the difficult problem meeting Standard, and this technical process is simple, operates easier.If adopt existing conventional single hop hydrogenation method, be difficult to reach identical effect.
The following examples illustrate the present invention further.
Experiment uses the FF-36 hydrogenation catalyst and FHUDS-3 hydrogenation catalyst that the Hydrobon catalyst that catalyzer is industrial application is Fushun Petrochemical Research Institute's recent development development and production, and its physico-chemical property index is in table 1.
Embodiment 1
Diesel raw material 1 enters the first hydrogenator, and reaction conditions is: hydrogen pressure component 5.8MPa, temperature of reaction 352 DEG C, and hydrogen to oil volume ratio is 300: 1; Effluent enters the second hydrogenator after air lift hydrogen-dissolving device, and reaction conditions is: hydrogen pressure component 5.5MPa, temperature of reaction 348 DEG C, and hydrogen to oil volume ratio is 200: 1, cumulative volume air speed 1.9h
-1.Stock oil character and product property list in table 2.
From table 2, adopt this Technology the sulphur content of diesel product can be reduced to 50 below μ g/g, meet GB IV clean diesel standard.
Embodiment 2
Diesel raw material 2 enters the first hydrogenator, and reaction conditions is: hydrogen pressure component 6.0MPa, temperature of reaction 361 DEG C, and hydrogen to oil volume ratio is 350: 1; Effluent enters the second hydrogenator after air lift hydrogen-dissolving device, and reaction conditions is: hydrogen pressure component 5.8MPa, temperature of reaction 349 DEG C, and hydrogen to oil volume ratio is 150: 1, cumulative volume air speed 2.0h
-1.Stock oil character and product property list in table 3.
From table 3, adopt this Technology the sulphur content of diesel product can be reduced to 50 below μ g/g, meet GB IV clean diesel standard.
Embodiment 3
Diesel raw material 3 enters the first hydrogenator, and reaction conditions is: hydrogen pressure component 7.0MPa, temperature of reaction 370 DEG C, and hydrogen to oil volume ratio is 300: 1; Effluent enters the second hydrogenator after air lift hydrogen-dissolving device, and reaction conditions is: hydrogen pressure component 6.7MPa, temperature of reaction 358 DEG C, and hydrogen to oil volume ratio is 300: 1, cumulative volume air speed 1.9h
-1.Stock oil character and product property list in table 4.
From table 4, adopt this Technology the sulphur content of diesel product can be reduced to 10 below μ g/g, meet GB V clean diesel standard.
Comparative example 1
Adopt conventional single hop hydrogenation technique flow processing diesel raw material 1, comparative test result lists in table 5.
From table 5, adopt this Technology to compare with conventional single hop hydrogenation technique, when the sulphur content generating oil is suitable, the inventive method processing condition comparatively relax.
The physico-chemical property index of table 1 catalyzer
| Catalyzer is numbered | FF-36 | FHUDS-3 |
| Chemical constitution, wt% | ||
| MoO 3 | 23.7 | 20.0 |
| NiO | 3.8 | |
| CoO | 4.1 | |
| Physical properties | ||
| Pore volume, mL/g | ≮0.32 | ≮0.29 |
| Specific surface area, m 2/g | ≮160 | ≮200 |
| Shape | Trifolium | Trifolium |
Table 2 embodiment 1 stock oil character and test-results
Table 3 embodiment 2 stock oil character and test-results
Table 4 embodiment 3 stock oil character and test-results
Table 5 comparative example 1 test-results
Claims (12)
1. an inferior diesel oil deep hydrodesulfurizationmethod method, under diesel oil hydrogenation treatment condition, first stock oil and hydrogen enter the first reactor through process furnace, contact under Hydrofinishing conditions with Mo-Ni hydrogenation catalyst, carry out conventional hydro refining reaction; Gained reaction effluent enters air lift and mixes in hydrogen storage equipment, remove the hydrogen sulfide and ammonia that generate and dissolve in oil, and make hydrogen in oil, reach dissolving state of saturation, then be mixed into the second reactor to contact with Mo-Co system Hydrobon catalyst with hydrogen make-up, carry out deep desulfuration reaction, finally obtain the clean diesel product of ultra-low sulfur; Wherein, the hydrogen to oil volume ratio of the first reactor is the hydrogen to oil volume ratio of the 100 ~ 800, second reactor is 100 ~ 800.
2. in accordance with the method for claim 1, it is characterized in that, described air lift mixes hydrogen gas stripping column and the gas liquid mixer that hydrogen storage equipment comprises series connection.
3. in accordance with the method for claim 2, it is characterized in that, described hydrogen gas stripping column is thermal high hydrogen gas stripping column.
4. in accordance with the method for claim 2, it is characterized in that, described gas liquid mixer selects static mixer or dynamic mixer.
5. in accordance with the method for claim 4, it is characterized in that, described static mixer is selected from SV type, SL type, SH type, SX type, SK type, ISG type or SMV type static mixer; Described dynamic mixer is selected from star gear shape mixing tank, sound gear ring shape mixing tank, crescent moon trough mixer or ball-and-socket type mixing tank.
6. in accordance with the method for claim 1, it is characterized in that, described air lift is mixed hydrogen storage equipment and is comprised air lift and mix hydrogen device.
7. in accordance with the method for claim 6, it is characterized in that, described air lift is mixed hydrogen device and is comprised stripper section, divider and mixed hydrogen partial.
8. in accordance with the method for claim 1, it is characterized in that, described stock oil is the mixing oil of catalytic diesel oil, coker gas oil or they and straight-run diesel oil.
9. in accordance with the method for claim 1, it is characterized in that, the hydroprocessing operations condition of the first reactor is: hydrogen dividing potential drop 4.0MPa ~ 12.0MPa, and temperature of reaction is 260 DEG C ~ 420 DEG C, and volume space velocity is 0.5h
-1~ 4.0h
-1.
10. in accordance with the method for claim 1, it is characterized in that, the second reactor hydroprocessing operations condition is: hydrogen dividing potential drop is 4.0MPa ~ 12.0MPa, and temperature of reaction is 270 DEG C ~ 430 DEG C, and volume space velocity is 0.5h
-1~ 4.0h
-1.
11. in accordance with the method for claim 1, it is characterized in that, the composition of described Mo-Ni series hydrocatalyst comprises: molybdenum oxide 23wt% ~ 26wt%, nickel oxide 3.7wt% ~ 4.1wt%, and with oxide basis active metal total content for 26wt% ~ 30wt%, carrier is silicon-containing alumina.
12. in accordance with the method for claim 1, it is characterized in that: the composition of described Mo-Co series hydrocatalyst comprises: molybdenum oxide 18wt% ~ 21wt%, cobalt oxide 3wt% ~ 5wt%, with oxide basis active metal total content for 21wt% ~ 26wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010539088.6A CN102465012B (en) | 2010-11-05 | 2010-11-05 | A kind of inferior diesel oil deep hydrodesulfurizationmethod method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010539088.6A CN102465012B (en) | 2010-11-05 | 2010-11-05 | A kind of inferior diesel oil deep hydrodesulfurizationmethod method |
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| Publication Number | Publication Date |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2000018854A1 (en) * | 1998-09-29 | 2000-04-06 | Canadian Environmental Equipment & Engineering Technologies, Inc. | Process for treating crude oil using hydrogen in a special unit |
| CN1485413A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Process method for deep desulfurization and dearomatization of diesel oil |
| CN101724443A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for producing clean fuels through low-cost hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018854A1 (en) * | 1998-09-29 | 2000-04-06 | Canadian Environmental Equipment & Engineering Technologies, Inc. | Process for treating crude oil using hydrogen in a special unit |
| CN1485413A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Process method for deep desulfurization and dearomatization of diesel oil |
| CN101724443A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for producing clean fuels through low-cost hydrogenation |
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