CN109777510A - A kind of method for hydrogen cracking improving jet fuel yield - Google Patents
A kind of method for hydrogen cracking improving jet fuel yield Download PDFInfo
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- CN109777510A CN109777510A CN201711118963.1A CN201711118963A CN109777510A CN 109777510 A CN109777510 A CN 109777510A CN 201711118963 A CN201711118963 A CN 201711118963A CN 109777510 A CN109777510 A CN 109777510A
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- distillate
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 61
- 239000000446 fuel Substances 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000005336 cracking Methods 0.000 title claims abstract description 31
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- 239000002283 diesel fuel Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
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- 239000002808 molecular sieve Substances 0.000 claims description 18
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- 230000003247 decreasing effect Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
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- 230000008569 process Effects 0.000 description 25
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- 238000004519 manufacturing process Methods 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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Abstract
The present invention discloses a kind of method for hydrogen cracking for improving jet fuel yield, including the following contents: (1) entering hydrofining reactor after feedstock oil is mixed with hydrogen, contacted with Hydrobon catalyst and the refining reactions such as hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbons saturation occur；(2) the generation oil and hydrogenation tail oil that step (1) obtains are mixed into hydrocracking reactor, carry out hydrocracking reaction, mix between different beds with recycle oil, continue to react；(3) the generation oil that step (2) obtains enters separation system, hydrogen is obtained to be recycled, it obtains generation distillate and enters fractionating system, obtain gas, naphtha, jet fuel, diesel oil distillate, hydrogenation tail oil, it is recycled to hydrocracking reactor entrance after the generation oil mixing that the same step of hydrogenation tail oil (1) obtains, the diesel oil distillate returns to hydrocracking reactor bed.This method inceasing output of jet fuel and can improve jet fuel product quality.
Description
Technical field
The present invention relates to a kind of method for hydrogen cracking for improving jet fuel yield, specifically a kind of system optimization is more
Produce the method for hydrogen cracking of high-quality jet fuel.
Background technique
As distillate demand is continuously increased between city's field alignment, refinery is needed to produce more intermediate oils, newly
Fuel standard tightened up requirement is proposed to the index of vapour, diesel oil.Obviously, time processing means and FCC technique is not
Market is able to satisfy to the index request of clean fuel.Hydrocracking process is not only the secondary operation hand of heavy charge lighting
Section even more obtains high-quality jet fuel from inferior raw material and cleans a kind of important means of diesel oil.
Hydrocracking unit one-time investment is bigger, and operating cost is also relatively high.Therefore, the major research in countries in the world is public
Department is all largely studied positive to reduce the cost being hydrocracked, and makes great progress.In terms of catalyst:
The major patent quotient in the world had all in recent years constantly been catalyzed the emphasis that the update of catalyst develops as oneself technology
The material of agent, activity, service life, stability and reduction catalyst cost of catalyst etc. have done a large amount of work.In work
In terms of skill: distillate hydrocracking technology is quite mature, and each major oil companies are advanced optimizing the same of hydrocracking operation
When, innovative point is placed on group technology relevant to being hydrocracked, cost is reduced by optimum organization technique；In addition, logical
The further investigation to being hydrocracked is crossed, the inherent connection between catalyst performance and feedstock property and purpose product quality is sought
System establishes suitable catalyst grade and matches the emphasis that system is also the current area research.
United States Patent (USP) (US 4172815) discloses single hop circulation plus hydrogen a kind of while that produce jet fuel and diesel oil and splits
Change method, process flow are as follows: heavy raw oil after being hydrocracked, product by fractionation, obtain jet fuel fraction,
Diesel oil distillate and tail oil；Jet fuel fraction is completely or partially mixed with tail oil, sends hydrocracking reactor back to.This process flow
Apparent, the disadvantage is that although jet fuel is hydrocracked again improves quality, its yield reduces more, hydrogen consumption and increases, and
Investment also increases more.
United States Patent (USP) (US 5026472) discloses one kind and is hydrocracked and product cut oil repeated hydrogenation purification Joint Production
The method of high-quality jet fuel.Its process flow can be briefly described are as follows: cracker comes out product and passes through thermal high twice point
After device separation, obtained kerosene distillate repeated hydrogenation in finishing reactor is refined, and wherein used catalyst is precious metal catalyst
Agent；Finishing reactor comes out product and the heavy distillate of cracker is mixed into fractionating column.This method technical characterstic is
Only kerosene distillate is refined, achievees the purpose that produce jet fuel.But this method needs to increase more equipment, and adds hydrogen
Purification catalyst used is noble metal catalyst, and cost is larger, and cannot obtain the hydrogenation tail oil of high quality.
Chinese patent (CN 1272524) discloses the work of a kind of middle pressure hydrocracking and the combination of kerosene Deep Hydrotreating
Skill process.The process is at one by the kerosene distillate oil of higher arene content obtained in middle pressure hydrocracking process compared with low pressure
Power, hydrogen purity be higher, compared with aromatic hydrocarbons saturation is carried out under conditions of low reaction temperatures, and used catalyst is containing Pt or Ni reduction-state gold
The catalyst of category.The patent can the kerosene distillate well to higher arene content handle, obtain qualified jet combustion
Material.But this method needs to increase more equipment, and the internal circulating load of kerosene distillate is larger, increases plant investment, and operate
It is increasingly complex.
A kind of method for producing jet fuel and/or diesel oil, tail oil is disclosed in Chinese patent (CN1343758A), and
It discloses and recycle oil is back to hydrocracking reactor, optional part jet fuel returns to hydrotreating reactor.Wherein
Recycle oil is simultaneously not belonging to any product in practice.This method propose the design that part fraction is recycled back to cracker,
But fail to achieve the purpose that maximum produces jet fuel.
Summary of the invention
It is mentioned for the current hydrocracking technology for producing jet fuel existing deficiency, present invention when increasing production jet fuel
It is capable of the method for hydrogen cracking of inceasing output of jet fuel for one kind, and improves jet fuel product quality.
A kind of method for hydrogen cracking of raising jet fuel yield of the invention, including the following contents:
(1) after feedstock oil is mixed with hydrogen enter hydrofining reactor, contact with Hydrobon catalyst generation hydrodesulfurization,
The refining reactions such as hydrodenitrogeneration, aromatic hydrocarbons saturation；
(2) the generation oil and hydrogenation tail oil that step (1) obtains are mixed into hydrocracking reactor, carry out hydrocracking reaction,
It is mixed between different beds with recycle oil, continues to react；
(3) the generation oil that step (2) obtains enters separation system, and acquisition hydrogen is recycled, and acquisition generation distillate, which enters, to be divided
System is evaporated, gas, naphtha, jet fuel, diesel oil distillate, hydrogenation tail oil are obtained, what the same step of hydrogenation tail oil (1) obtained
It is recycled to hydrocracking reactor entrance after generating oil mixing, it is excellent between the diesel oil distillate returns to hydrocracking reactor bed
Diesel oil distillate is selected to fractionate out at least two fractions by boiling range weight difference, any fraction returns to hydrocracking reactor catalyst bed
Interlayer, wherein the heavy end diesel oil return hydrocracking reactor after by hydrocracking catalyst bed height it is big
In light fraction diesel oil return hydrocracking reactor after by hydrocracking catalyst height, the light fraction
Oil, heavy distillate be according to the light of the different diesel oil distillates that fractionate out, weight in contrast.
The method for hydrogen cracking according to the present invention for improving jet fuel yield, feedstock oil described in step (1) generally wrap
Including boiling range is 350~620 DEG C of heavy end, as can be various vacuum gas oil (VGO)s (VGO) obtained in petroleum refining process,
One or more of deasphalted oil (DAO), coker gas oil (CGO), heavy-cycle oil (HCO), be also possible to from coal tar,
Liquefied coal coil etc..Refining secondary processing diesel oil fraction, such as fuels from FCC LCO (LCO), coker gas oil can also be mixed.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the method for the present invention, step (2) hydrocracking reactor should include at least two catalyst bed, generally include 3~
5 catalyst beds.Wherein described 2 or multiple catalyst beds can be set in a reactor, or can divide
It is not set in two or more reactors.The hydrocracking catalyst of 2~6 kinds of different activities of hydrocracking reactor grading loading
Agent considers that catalyst regeneration changes agent conveniently, preferably the hydrocracking catalyst of 2~4 kinds of different activities of grading loading.It is equipped with grade
It fills out for the hydrocracking catalyst of 2 kinds of different activities, hydrocracking catalyst (along logistics direction) admission space ratio is generally
1:5~5:1, preferably 1:3~3:1.By taking the hydrocracking catalyst of 4 kinds of different activities of grading loading as an example, hydrocracking catalyst
Agent (along logistics direction) admission space is than being generally 1~3:1~3:1~3:1~3, preferably 1:1:1:1.
The hydrocracking catalyst of the different activities refers mainly to molecular sieve content difference and tenor difference, generally
Along logistics direction, molecular sieve content is successively decreased 3~6wt%, and tenor is incremented by 2~4wt%.The hydrocracking catalyst is to be modified Y
Molecular sieve and aluminium oxide are carrier, perhaps using modified Y molecular sieve, amorphous silica-alumina and aluminium oxide as carrier or with amorphous
Sial and aluminium oxide are carrier, using VI B race (such as tungsten, molybdenum) and/or VIII race (such as nickel, cobalt) metal as active metal component, catalysis
Simultaneously containing one or more of elements such as some auxiliary agents such as phosphorus, titanium, zirconium in agent.It generally uses to contain on general industry and divide
Son sieve and/or unformed hydrocracking catalyst.On the basis of the weight of catalyst, in hydrocracking catalyst VI B race and/or
The content of VIII race's active metal component is generally 15 ~ 35wt%, and the content of modified Y molecular sieve is 3~40wt% in catalyst, preferably
For 12~30wt%.
The lattice constant of modified Y molecular sieve is generally 2.425~2.435nm in the hydrocracking catalyst, preferably
2.425 to less than 2.435nm(2.425~< 2.435nm).The SiO of modified Y molecular sieve2/Al2O3Molar ratio is generally 5~50,
Relative crystallinity is 90~120%.
In method for hydrogen cracking of the invention, the operating condition in the hydrocracking reaction area is generally, and reacts hydrogen partial pressure 5
~20MPa, 280~427 DEG C of average reaction temperature, 0.1~10h of volume space velocity-1, hydrogen to oil volume ratio 300~3000.It is usually next
The average reaction temperature of the relatively upper bed hydrocracking catalyst of the average reaction temperature of bed hydrocracking catalyst wants high (edge
The temperature difference between the adjacent bed in logistics direction) 2~20 DEG C, preferably 3~5 DEG C.
Diesel oil distillate is fractionated out three fractions by boiling range weight, remembered respectively by a kind of preferred embodiment in the present invention
For diesel oil distillate 3, diesel oil distillate 2, diesel oil distillate 1, hydrocracking reactor is set as 4 beds, wherein diesel oil distillate 3 follows
Ring is between first and second bed of hydrocracking reactor；Diesel oil distillate 2 is recycled to hydrocracking reactor second and third bed
Interlayer；Diesel oil distillate 1 is recycled between hydrocracking reactor third and the 4th bed；Hydrogenation tail oil is recycled to cracker and enters
Mouthful.The boiling range of the diesel oil distillate 1 is generally 240 ~ 300 DEG C；It is highly preferred that the boiling range of diesel oil distillate 1 is 260 ~ 290 DEG C.Institute
The boiling range for stating diesel oil distillate 2 is generally 290 ~ 340 DEG C；It is highly preferred that the boiling range of diesel oil distillate 2 is 291 ~ 330 DEG C.The diesel oil
The boiling range of fraction 3 is generally 330 ~ 380 DEG C；It is highly preferred that the boiling range of diesel oil distillate 3 is 331 ~ 370 DEG C.The hydrogenation tail oil evaporates
The boiling range divided is typically greater than 350 DEG C；It is highly preferred that the boiling range of hydrogenation tail oil fraction is greater than 371 DEG C.
In terms of the hydrocracking technology of existing volume increase jet fuel mainly has following two:
(1) jet fuel is produced by process using primary.This method increases production jet fuel yield, on the one hand selects jet fuel
The high hydrocracking catalyst of selectivity, but the general activity of such catalyst is lower, and initial reaction temperature is higher, calefactive interzone phase
To small, the cycle of operation of device is influenced, jet fuel volume increase is limited, is not able to satisfy enterprise demand.On the other hand conversion ratio is improved,
But lighter hydrocarbons and naphtha yield also can be increased considerably accordingly, the lighter hydrocarbons and stone for hydrocracking unit, in fractionating system
Often there is bottleneck in cerebrol separation.And chemical hydrogen consumption can also increase considerably, the corresponding decline of jet fuel selectivity.
(2) component for overweighting jet fuel fraction is recycled back to hydrofining reactor entrance or hydrocracking reactor enters
Mouthful, increase production jet fuel.This method also results in naphtha, lighter hydrocarbons yield increases considerably, and jet fuel selectively declines,
The usual freezing point of jet fuel obtained simultaneously is higher, and limitation freezing point qualification becomes the bottleneck of jet fuel volume increase, influences jet combustion
Expect yield.
The present invention is based on hydrocracking reaction mechanism: preferentially cracking heavy constituent (macromolecular), is split according to grading loading plus hydrogen
Change the response characteristic of catalyst and the weight of recycle oil, sets the recycle oil feed entrance point of science.Each recycle oil of the present invention
Refer to each fraction for overweighting jet fuel part, including diesel oil distillate and tail oil fraction.Chemically react angle, diesel oil distillate warp
Crossing either shallow cracking can be obtained jet fuel fraction, therefore, the diesel oil distillate of different boiling ranges is recycled to respectively and is hydrocracked instead
Between each bed for answering device, is conducive to control secondary cracking reaction generation, improves the selectivity of production jet fuel.
Compared with prior art, the method for the present invention has the following characteristics that
(1) present invention effectively avoids the generation of second pyrolysis, can increase considerably the jet fuel yield of hydrocracking unit.
Compared with other methods, the selectivity of jet fuel is higher, better quality；In addition, hydrogen consumption is low.
(2) with once by process compared with, circulation process of the invention can be realized substantially under lower conversion level
Degree increases the purpose of jet fuel, avoids lighter hydrocarbons, naphtha yield increase causes fractionating system bottleneck.
(3) since circulation diesel oil distillate, tail oil fraction temperature are lower, be recycled to respectively hydrocracking reactor entrance and
Between bed, cold hydrogen can be played the role of, to reduce or without reinjecting cold hydrogen, reduce cold hydrogen reserve level, reduce recycle hydrogen
Compressor load, realizing reduces energy consumption.It solves usual hydrocracking unit hydrofining reactor outlet and is hydrocracked instead
The problem for answering the device entrance temperature difference larger.
(4) layering filling of the present invention by different type hydrocracking catalyst in the reactor, depth coupling are different
The functionality advantage of hydrocracking catalyst improves jet fuel product quality.Solve diesel oil distillate, tail oil circulation production spray
The low deficiency of gas fuel freezing point.
Detailed description of the invention
Fig. 1 is a kind of flow diagram for the method for hydrogen cracking for improving jet fuel yield of the present invention.
Specific embodiment
In method for hydrogen cracking of the present invention, wherein Hydrobon catalyst described in step (1) can add hydrogen for conventional
Catalyst for refining, catalyst include carrier and the hydrogenation active metals that are loaded.On the basis of the weight of catalyst, generally include
Metal component of group VIB in the periodic table of elements, if tungsten and/or molybdenum are calculated as 10wt%~35wt% with oxide, preferably 15wt%~
30wt%；Group VIII metal such as nickel and/or cobalt are calculated as 1wt %~7wt%, preferably 1.5wt%~6wt% with oxide.Carrier is
Inorganic refractory oxide is selected generally from aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc..It can choose existing various
Commercial catalysts, such as FF-14, FF-24,3936,3996, FF- of Fushun Petrochemical Research Institute (FRIPP) development
16, the Hydrobon catalysts such as FF-26, FF-36, FF-46, FF-56, FF-66；HC-K, HC-P of Uop Inc.'s production；
TK-555, TK-565 catalyst of Topsoe company production, also can according to need and are prepared by the common sense of this field.
Followed by method for hydrogen cracking of the specific embodiment to a kind of raising jet fuel yield of the invention make into
The explanation of one step.
Examples 1 to 3
Using Iranian VGO as feedstock oil, selects FF-46 pretreating catalyst by hydrocracking to be equipped with hydrocracking catalyst I/ and hydrogen is added to split
Change the catalyst system of catalyst II/ hydrocracking catalyst III/ hydrocracking catalyst IV.Four kinds of hydrocracking catalysts
Using amorphous silica-alumina and modified Y molecular sieve as carrier.Hydrocracking catalyst I/ hydrocracking catalyst in embodiment 1-3
The volume ratio of II/ hydrocracking catalyst III/ hydrocracking catalyst IV is 1:1:1:1.
In reaction stagnation pressure 15.0MPa, refining stage and cracking zone hydrogen to oil volume ratio are respectively 900:1 and 1100:1, refining stage
It is respectively 1.1h with the fresh material volume space velocity of cracking zone-1And 1.2h-1, control refined oil nitrogen content is 5~8 ug.g-1, carry out
The engineer testing that 370 DEG C of conversion ratios of > are about 60wt%~80wt%, has investigated the product quality of each fraction.
Feedstock oil specific nature is shown in Table 1, and catalyst fundamental property is shown in Table 2, process condition and the results are shown in Table 3~table 4.
It is described in detail in conjunction with method for hydrogen cracking of the attached drawing to a kind of raising jet fuel yield of the invention.Such as figure
Shown in 1, a kind of method for hydrogen cracking process of raising jet fuel yield of the invention is as follows: feedstock oil (1) heated furnace adds
(can also stokehold mix hydrogen) be mixed after heat with new hydrogen (23), recycle hydrogen (22) enter hydrofining reactor (4) and is urged with hydrofinishing
Agent contact, the refining reactions such as hydrodesulfurization, hydrodenitrogeneration, which occur, reduces temperature after generation oily (5) is mixed with circulation tail oil (21)
Degree after the hydrocracking catalyst of the first bed, generates oil and the diesel oil of circulation evaporates into hydrocracking reactor (7)
Divide 3(20) it is mixed into the second bed, after reaction, generate the diesel oil distillate 2(19 of oil with circulation) it is mixed into third bed, instead
Ying Hou generates the diesel oil distillate 1(18 of oil with circulation) it is mixed into the 4th bed, it generates oily (8) and enters high-pressure separator (9),
Isolated hydrogen (10) is recycled through compressor (12)；Isolated liquid distillate oily (11) enters low pressure separator
(13), fractionating system (14) are entered back into, are fractionated out gas (15), naphtha cut (16), jet fuel fraction (17), diesel oil evaporates
Divide 1(18), diesel oil distillate 2(19), diesel oil distillate 3(20) and hydrogenation tail oil fraction (21).
Embodiment 4
Using Iranian VGO as feedstock oil, selects FF-46 pretreating catalyst by hydrocracking to be equipped with hydrocracking catalyst I/ and hydrogen is added to split
Change the catalyst system of catalyst II.Two kinds of hydrocracking catalysts are using amorphous silica-alumina and modified Y molecular sieve as carrier.It is real
The volume ratio for applying hydrocracking catalyst I/ hydrocracking catalyst II in example 4 is 1:1.
In reaction stagnation pressure 15.0MPa, refining stage and cracking zone hydrogen to oil volume ratio are respectively 900:1 and 1100:1, refining stage
It is respectively 1.1h with the fresh material volume space velocity of cracking zone-1And 1.2h-1, control refined oil nitrogen content is 5~8 ug.g-1, carry out
The engineer testing that 370 DEG C of conversion ratios of > are about 70wt%, has investigated the product quality of each fraction.
Feedstock oil specific nature is shown in Table 1, and catalyst fundamental property is shown in Table 2, process condition and the results are shown in Table 3~table 4.
It is described in detail in conjunction with method for hydrogen cracking of the attached drawing to a kind of raising jet fuel yield of the invention.Such as figure
Shown in 1, a kind of method for hydrogen cracking process of raising jet fuel yield of the invention is as follows: feedstock oil (1) heated furnace adds
(can also stokehold mix hydrogen) be mixed after heat with new hydrogen (23), recycle hydrogen (22) enter hydrofining reactor (4) and is urged with hydrofinishing
Agent contact, the refining reactions such as hydrodesulfurization, hydrodenitrogeneration, which occur, reduces temperature after generation oily (5) is mixed with circulation tail oil (21)
Degree after the hydrocracking catalyst of the first and second bed, generates the diesel oil of oil with circulation into hydrocracking reactor (7)
Fraction (18,19,20) is mixed into third bed, after reaction, generates oily (8) and enters high-pressure separator (9), isolated hydrogen
Gas (10) is recycled through compressor (12)；Isolated liquid distillate oily (11) enters low pressure separator (13), enters back into
Fractionating system (14) fractionates out gas (15), naphtha cut (16), jet fuel fraction (17), diesel oil distillate (18,19,
And hydrogenation tail oil fraction (21) 20).
Embodiment 5
Using Iranian VGO as feedstock oil, selects FF-46 pretreating catalyst by hydrocracking to be equipped with hydrocracking catalyst I/ and hydrogen is added to split
Change the catalyst system of catalyst II/ hydrocracking catalyst III.Three kinds of hydrocracking catalysts with amorphous silica-alumina and change
Property Y molecular sieve be carrier.Hydrocracking catalyst I/ hydrocracking catalyst II/ hydrocracking catalyst III in embodiment 5
Volume ratio is 1:1:1.
In reaction stagnation pressure 15.0MPa, refining stage and cracking zone hydrogen to oil volume ratio are respectively 900:1 and 1100:1, refining stage
It is respectively 1.1h with the fresh material volume space velocity of cracking zone-1And 1.2h-1, control refined oil nitrogen content is 5~8 ug.g-1, carry out
The engineer testing of 370 DEG C of conversion ratio about 70wt% of >, has investigated the product quality of each fraction.
Feedstock oil specific nature is shown in Table 1, and catalyst fundamental property is shown in Table 2, process condition and the results are shown in Table 3~table 4.
It is described in detail in conjunction with method for hydrogen cracking of the attached drawing to a kind of raising jet fuel yield of the invention.Such as figure
Shown in 1, a kind of method for hydrogen cracking process of raising jet fuel yield of the invention is as follows: feedstock oil (1) heated furnace adds
(can also stokehold mix hydrogen) be mixed after heat with new hydrogen (23), recycle hydrogen (22) enter hydrofining reactor (4) and is urged with hydrofinishing
Agent contact, the refining reactions such as hydrodesulfurization, hydrodenitrogeneration, which occur, reduces temperature after generation oily (5) is mixed with circulation tail oil (21)
Degree after the hydrocracking catalyst of the first bed, generates oil and the diesel oil of circulation evaporates into hydrocracking reactor (7)
Divide 2(20) it is mixed into the second bed, after reaction, generates the diesel oil distillate 1(18 of oil and circulation, 19) be mixed into third bed
Layer after reaction, generates oily (8) and enters high-pressure separator (9), isolated hydrogen (10) is recycled through compressor (12)；
Isolated liquid distillate oily (11) enters low pressure separator (13), enters back into fractionating system (14), fractionates out gas (15),
Naphtha cut (16), jet fuel fraction (17), diesel oil distillate 1(18,19), diesel oil distillate 2(20) and hydrogenation tail oil fraction
(21).
Comparative example 1 ~ 2
Using Iranian VGO as feedstock oil, business FF-46 pretreating catalyst by hydrocracking and FC-32 hydrocracking catalyst are selected,
Routine is respectively adopted once by process, tail oil complete alternation process, in reaction stagnation pressure 15.0MPa, refining stage and cracking zone hydrogen are oily
Volume ratio is respectively 900:1 and 1100:1, and refining stage and the fresh material volume space velocity of cracking zone are respectively 1.1h-1And 1.2h-1, control
Refined oil nitrogen content processed is 5~8 ug.g-1, engineer testing is compared, the product quality of each fraction has been investigated.Concrete outcome
It is shown in Table 2~4.
1 feedstock oil property list of table
| Feedstock oil | Iranian VGO | Feedstock oil | Iranian VGO |
| Density (20 DEG C)/g.cm-3 | 0.9072 | Viscosity (50 DEG C)/mm2.s-1 | 23.52 |
| Boiling range/DEG C | Viscosity (100 DEG C)/mm2.s-1 | 5.618 | |
| IBP/10% | 305/361 | Carbon residue, wt% | 0.21 |
| 30%/50% | 394/417 | Sulphur, wt% | 1.98 |
| 70%/90% | 443/481 | Nitrogen/ug.g-1 | 1228 |
| 95%/EBP | 509/533 | Carbon, wt% | 85.42 |
| BMCI value | 45.0 | Hydrogen, wt% | 12.48 |
| Condensation point/DEG C | 34 |
2 catalyst fundamental property of table
| Catalyst | FF-46 | It is hydrocracked and urges Agent I | Hydrocracking catalyst Agent II | Hydrocracking catalyst Agent III | Hydrocracking catalyst Agent IV |
| Face shaping | Clover item | Cylindrical bars | Cylindrical bars | Cylindrical bars | Cylindrical bars |
| Particle diameter, mm | 1.1~1.3 | 1.5~1.7 | 1.5~1.7 | 1.5~1.7 | 1.5~1.7 |
| Item is long, mm | 3~8 | 3~8 | 3~8 | 3~8 | 3~8 |
| Modified Y molecular sieve contains Amount, wt% | — | 28 | 24 | 20 | 16 |
| Lattice constant, nm | — | 2.437 | 2.434 | 2.431 | 2.428 |
| SiO2/Al2O3Molar ratio | — | 15 | 20 | 26 | 31 |
| Relative crystallinity * | — | 105 | 105 | 105 | 105 |
| Chemical composition, m%: | |||||
| NiO | 4.0 | 6.5 | 6.8 | 7.1 | 7.4 |
| MoO3 | 24.0 | — | — | — | — |
| WO3 | — | 19.0 | 21.0 | 23.0 | 25.0 |
* relative crystallinity: Xc=Wc (Wc+Wa), Wc and Wa is respectively weight hundred shared by crystalline portion and non-crystallized part in formula
Score.
Table 3 is hydrocracked technological condition
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | |
| The present invention Process | The present invention Process | The present invention Process | The present invention Process | The present invention Process | It is primary logical Cross process | Diesel oil distillate, tail Oil distillate complete alternation | |
| React stagnation pressure, MPa | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Each bed of cracker Layer reaction temperature/DEG C | 376/ 378/ 380/382 | 378/ 380/ 382/384 | 380/ 382/ 384/386 | 380/ 380/ 383/383 | 380/ 382/ 385/385 | 388 | 385 |
| Volume space velocity, h-1 | 1.1/1.2 | 1.1/1.2 | 1.1/1.2 | 1.1/1.2 | 1.1/1.2 | 1.1/ 1.2 | 1.1/1.2 |
| Hydrogen to oil volume ratio, v/v | 900:1/ 1100:1 | 900:1/ 1100:1 | 900:1/ 1100:1 | 900:1/ 1100:1 | 900:1/ 1100:1 | 900:1/ 1100:1 | 900:1/1100:1 |
| 360 DEG C of conversion ratios of >, wt% | ~65 | ~70 | ~75 | ~70 | ~70 | ~85 | ~99.8 |
The distribution of 4 hydrocracked product of table and major product quality
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | |
| Naphtha yield, % | 31.87 | 31.89 | 32.54 | 32.05 | 32.39 | 26.23 | 40.23 |
| Jet fuel yield, % | 62.29 | 61.87 | 61.07 | 61.33 | 61.09 | 36.84 | 54.21 |
| Jet fuel selectivity, % | |||||||
| Density (20 DEG C)/gcm-3 | 0.8065 | 0.8047 | 0.8054 | 0.8049 | 0.8052 | 0.8087 | 0.8082 |
| Boiling range/DEG C | 145~270 | 144~269 | 144~271 | 144~270 | 145~271 | 145~272 | 145~269 |
| Freezing point/DEG C | <-65 | <-65 | <-65 | <-65 | <-65 | <-60 | <-60 |
| Smoke point/mm | 25 | 26 | 27 | 25 | 26 | 24 | 24 |
| Aromatic hydrocarbons, v% | 8.9 | 7.1 | 6.9 | 7.8 | 7.3 | 10.7 | 9.7 |
| Naphthalene system hydrocarbon, v% | 0.13 | 0.10 | 0.12 | 0.11 | 0.12 | 0.15 | 0.14 |
The preferred embodiment of the present invention has been described above in detail, still, the tool during present invention is not limited to the embodiments described above
Body details within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, these letters
Monotropic type all belongs to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (15)
1. a kind of method for hydrogen cracking for improving jet fuel yield, it is characterised in that: including the following contents:
(1) after feedstock oil is mixed with hydrogen enter hydrofining reactor, contact with Hydrobon catalyst generation hydrodesulfurization,
Hydrodenitrogeneration, aromatic hydrocarbons saturated reaction；
(2) the generation oil and hydrogenation tail oil that step (1) obtains are mixed into hydrocracking reactor, carry out hydrocracking reaction,
It is mixed between different beds with recycle oil, continues to react；
(3) the generation oil that step (2) obtains enters separation system, and acquisition hydrogen is recycled, and acquisition generation distillate, which enters, to be divided
System is evaporated, gas, naphtha, jet fuel, diesel oil distillate, hydrogenation tail oil are obtained, what the same step of hydrogenation tail oil (1) obtained
It is recycled to hydrocracking reactor entrance after generating oil mixing, the diesel oil distillate returns to hydrocracking reactor catalyst bed
Between.
2. according to the method described in claim 1, it is characterized by: diesel oil distillate is fractionated by boiling range weight difference in step (3)
At least two fraction out, any fraction returns to hydrocracking reactor catalyst bed interlayer, wherein the heavy end diesel oil returns
Return hydrocracking reactor after by hydrocracking catalyst bed height be greater than light fraction diesel oil return be hydrocracked
After reactor by hydrocracking catalyst height, the described light fraction oil, heavy distillate are according to fractionating out
Different diesel oil distillates are in contrast.
3. according to the method described in claim 1, it is characterized by: feedstock oil boiling range described in step (1) is 350~620 DEG C
Heavy end.
4. according to the method described in claim 4, it is characterized by: feedstock oil is selected from vacuum gas oil (VGO), deasphalted oil, coking watt
One or more of this oil, heavy-cycle oil, coal tar, liquefied coal coil.
5. according to the method described in claim 1, it is characterized by: step (2) hydrocracking reactor should be urged including at least two
Agent bed, wherein described 2 or multiple catalyst beds are set in a reactor, or be respectively arranged at two or
In multiple reactors.
6. according to the method described in claim 1, it is characterized by: 2~6 kinds of different activities of hydrocracking reactor grading loading
Hydrocracking catalyst.
7. according to the method described in claim 6, it is characterized by: the hydrocracking catalyst of 2 kinds of different activities of grading loading
When hydrocracking catalyst along logistics direction admission space ratio be 1:5~5:1.
8. according to the method described in claim 6, it is characterized by: the hydrocracking catalyst of 4 kinds of different activities of grading loading
When hydrocracking catalyst along logistics direction admission space ratio be 1~3:1~3:1~3:1~3.
9. according to the method described in claim 6, it is characterized by: the hydrocracking catalyst of the different activities is molecular sieve
Content difference and tenor are different, and along logistics direction, molecular sieve content is successively decreased 3~6wt%, and tenor is incremented by 2~4wt%.
10. according to the method described in claim 6, it is characterized by: the hydrocracking catalyst is with modified Y molecular sieve and oxygen
Change aluminium is carrier, perhaps using modified Y molecular sieve, amorphous silica-alumina and aluminium oxide as carrier or with amorphous silica-alumina and oxidation
Aluminium is carrier, using VI B race and/or VIII race's metal as active metal component, on the basis of the weight of catalyst, and hydrocracking catalyst
The content of VI B race and/or VIII race's active metal component is 15 ~ 35wt% in agent, in catalyst the content of modified Y molecular sieve be 3~
40wt%。
11. according to the method described in claim 10, it is characterized by: modified Y molecular sieve in the hydrocracking catalyst
Lattice constant is 2.425~2.435nm, the SiO of modified Y molecular sieve2/Al2O3Molar ratio is 5~50, relative crystallinity 90
~120%.
12. according to the method described in claim 1, it is characterized by: the operating condition in the hydrocracking reaction area is reaction
5~20MPa of hydrogen partial pressure, 280~427 DEG C of average reaction temperature, 0.1~10h of volume space velocity-1, hydrogen to oil volume ratio 300~3000.
13. according to the method described in claim 1, it is characterized by: the temperature difference is 2~20 DEG C between the adjacent bed in logistics direction.
14. according to the method described in claim 1, it is characterized by: diesel oil distillate is fractionated out three fractions by boiling range weight,
It is denoted as diesel oil distillate 3, diesel oil distillate 2, diesel oil distillate 1 respectively, hydrocracking reactor is set as 4 beds, wherein diesel oil evaporates
3 are divided to be recycled between first and second bed of hydrocracking reactor；Diesel oil distillate 2 is recycled to hydrocracking reactor second and
Between three beds；Diesel oil distillate 1 is recycled between hydrocracking reactor third and the 4th bed；Hydrogenation tail oil is recycled to cracking reaction
Device entrance.
15. according to the method described in claim 1, it is characterized by: the boiling range of the diesel oil distillate 1 is 240 ~ 300 DEG C；It is described
The boiling range of diesel oil distillate 2 is 290 ~ 340 DEG C；The boiling range of the diesel oil distillate 3 is 330 ~ 380 DEG C.
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