CN105018137A - Hydrocracking method of low-energy-consumption, productive and high-quality jet fuel - Google Patents
Hydrocracking method of low-energy-consumption, productive and high-quality jet fuel Download PDFInfo
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- CN105018137A CN105018137A CN201410164890.XA CN201410164890A CN105018137A CN 105018137 A CN105018137 A CN 105018137A CN 201410164890 A CN201410164890 A CN 201410164890A CN 105018137 A CN105018137 A CN 105018137A
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Abstract
The invention discloses a hydrocracking method of low-energy-consumption, productive and high-quality jet fuel. The hydrocracking method comprises the steps that after being mixed with hydrogen, raw oil undergoes heat exchange twice, passes through hydrofining and first cracking reaction zones in sequence after passing through a heating furnace and is separated to obtain middle distillate, and the middle distillate enters a second cracking reaction zone to be cracked, wherein the first cracking reaction zone at least comprises two cracking catalysts, namely an upstream filling catalyst I and a downstream filling catalyst II; the catalyst I contains 15-50wt% of modified Y molecular sieve; the catalyst II contains 3-30wt% of modified Y molecular sieve; the content of the modified Y molecular sieve in the catalyst I is higher than the content of the modified Y molecular sieve in the catalyst II by 10-25%. The hydrocracking method has the advantages that the high temperature and high pressure countercurrent heat transfer technology and the hydrocracking catalyst grading technology are organically combined and the hydrocracking reaction heat is comprehensively utilized, thus improving the quality of the target product and reducing the project investment and the operation energy consumption while maintaining the selectivity of the catalysts.
Description
Technical field
The present invention relates to a kind of method for hydrogen cracking, a kind of less energy-consumption specifically uses the method for hydrogen cracking of dissimilar hydrocracking catalyst greatly preparing hihg-quality rocket engine fuel simultaneously.
Background technology
Along with the continuous increase of distillate demand between city's field alignment, need refinery to produce more intermediate oil, the index of new fuel standard to vapour, diesel oil proposes stricter requirement.Obviously, time processing means and FCC technique can not meet the index request of market to clean fuel.Hydrocracking process is not only the secondary processing means of heavy feed stock lighting, obtains a kind of important means of high-quality rocket engine fuel and clean diesel especially from inferior raw material.
Hydroeracking unit one-time investment is larger, and process cost is also higher.Therefore, countries in the world Ge great research company all carries out large quantifier elimination at the positive cost for reduction hydrocracking, makes great progress.In catalyzer: each large patent business in the world is all using the emphasis of the update of catalyzer as oneself technical development, in recent years, constantly at the material of catalyzer, activity, life-span, the stability of catalyzer and reduce the aspects such as catalyzer cost and done a large amount of work.At process aspect: distillate hydrocracking technology is quite ripe, and each major oil companies, while optimizing hydrocracking operation further, are placed on innovative point on the combination process relevant to hydrocracking, are reduced costs by optimum combination technique; In addition, by the further investigation to hydrocracking, seek the inner link between catalyst performance and feedstock property and object quality product, set up the emphasis that suitable catalyst grade part system is also this area research current.
United States Patent (USP) (US 4172815) discloses a kind of single hop circulation method for hydrogen cracking simultaneously producing rocket engine fuel and diesel oil, its technical process is: heavy raw oil is after hydrocracking, its product, through fractionation, obtains jet fuel fraction, diesel oil distillate and tail oil; Jet fuel fraction is all or part of to be mixed with tail oil, sends hydrocracking reactor back to.Although the obvious shortcoming of this technical process is rocket engine fuel carries out hydrocracking again and improve quality, its yield reduces more, hydrogen consumption and increases, and investment also increases more.
United States Patent (USP) (US 5026472), discloses a kind of hydrocracking and product cut oil repeated hydrogenation refines the method for combination producing high-quality rocket engine fuel.Its technical process can simply be described as: out product is by after twice high pressure hot separator separation for cracking case, and the kerosene(oil)fraction obtained repeated hydrogenation in refining reaction device is refined, and wherein used catalyst is noble metal catalyst; The heavy distillate of refining reaction device out product and cracking case is mixed into separation column.The method technical characterstic is only to refine kerosene(oil)fraction, reaches the object of producing rocket engine fuel.But the method needs to increase more equipment, and hydrofining catalyzer used is noble metal catalyst, and cost is comparatively large, and can not obtain high-quality hydrogenation tail oil.
Chinese patent (CN 1272524) discloses the technical process of a kind of middle pressure hydrocracking and the combination of kerosene Deep Hydrotreating.This flow process be by higher in a lower pressure, hydrogen purity for the kerosene(oil)fraction of the higher aromaticity content obtained in middle pressure hydrocracking process oil, compared with the condition of low reaction temperatures under carry out aromatic saturation, used catalyst is the catalyzer containing Pt or Ni as-reduced metal.This patent can process the kerosene(oil)fraction of higher aromaticity content well, obtains qualified rocket engine fuel.But the method needs to increase more equipment, and the internal circulating load of kerosene(oil)fraction is comparatively large, adds plant investment, and operation is more complicated.
Summary of the invention
For the deficiency of existing complete processing, the invention provides a kind of method for hydrogen cracking of high-output qulified rocket engine fuel.High Temperature High Pressure countercurrent heat-transfer technology and hydrocracking catalyst grating organically combine by the method, comprehensive utilization hydrocracking reaction heat, thus reduce construction investment and operation energy consumption.The present invention is by the layering filling in the reactor of two kinds of dissimilar hydrocracking catalysts, give full play to the feature of two kinds of dissimilar hydrocracking catalysts, can the rocket engine fuel of greatly preparing hihg-quality, also according to the market requirement, can hold concurrently and produce part high-quality hydrogenation tail oil.
The method for hydrogen cracking of the high-output qulified rocket engine fuel of a kind of less energy-consumption provided by the invention, comprises following content:
(1) after heavy raw oil and hydrogen mix, through overheated high score gas/cold mixing feed exchanger, reaction effluent/hot parallel feeding interchanger, twice heat exchange heats up, pass through again or rise to temperature of reaction without reaction heating furnace, enter hydrotreatment reaction zone to contact with Hydrobon catalyst, carry out hydrofining reaction;
(2) hydrofining reaction resultant enters the first hydrocracking reaction district, carries out hydrocracking reaction;
(3) step (2) gained reaction effluent enters separator and carries out gas-liquid separation, after being separated, obtain hydrogen-rich gas and liquid product; Hydrogen-rich gas recycles through circulating hydrogen compressor, and liquid product enters separation column to carry out fractionation and obtain gas, petroleum naphtha, rocket engine fuel and tail oil;
(4) tail oil that step (3) obtains can be whole, and also part can be mixed into the second hydrocracking reaction district with hydrogen, carry out hydrocracking further, remainder hydrogenation tail oil is as the raw material of next machining cell;
(5) resultant of reaction that step (4) obtains returns step (3), after the reaction effluent obtained mixes, carries out gas-liquid separation and fractionation with the first hydrocracking reaction district, obtains gas, petroleum naphtha and rocket engine fuel that quantity increases.
According to method for hydrogen cracking of the present invention, in wherein said step (2), comprise at least two kinds of hydrocracking catalysts in first hydrocracking reaction district, according to the engagement sequence with raw material, be respectively hydrocracking catalyst I and hydrocracking catalyst II.Described hydrocracking catalyst I with VI B race and/or VIII race's metal for active metal component, by weight, content containing modified Y molecular sieve in catalyzer I is 15 ~ 50wt%, be preferably 30 ~ 40wt%, described hydrocracking catalyst II equally with VI B race and/or VIII race's metal for active metal component, by weight, in catalyzer, the content of modified Y molecular sieve is 3 ~ 30wt%, be preferably 15 ~ 25wt%, the wherein content of modified Y molecular sieve 10 ~ 25 percentage ratios high compared with the modified Y molecular sieve content in hydrocracking catalyst II in hydrocracking catalyst I.
Wherein in the first hydrocracking reaction district, hydrocracking catalyst I is generally 1:5 ~ 5:1, preferred 1:3 ~ 3:1 with the admission space ratio of hydrocracking catalyst II.
Conventional hydrocracking catalyst can be loaded in the second described hydrocracking reaction district.As loaded separately hydrocracking catalyst I or hydrocracking catalyst II, or grating uses hydrocracking catalyst I and hydrocracking catalyst II, for circulation cracking and hydrogenation tail oil.When grating uses hydrocracking catalyst I and hydrocracking catalyst II, described hydrocracking catalyst I is generally 1:5 ~ 5:1, preferred 1:3 ~ 3:1 with the volume ratio of hydrocracking catalyst II.
Hydrocracking catalyst I recited above and hydrocracking catalyst II with modified Y molecular sieve and aluminum oxide for carrier, or with modified Y molecular sieve, amorphous aluminum silicide and aluminum oxide for carrier, with the periodic table of elements VI B race (as tungsten, molybdenum) and/or VIII race (as nickel, cobalt) metal for active ingredient, some auxiliary agents can be added as phosphorus, titanium, zirconium etc. simultaneously.General industry generally uses containing molecular sieve and/or unformed hydrocracking catalyst.With the weight of catalyzer for benchmark, in hydrocracking catalyst, the content of VI B race and/or VIII race's metal active constituent is generally 15% ~ 35% in I or II.
According to the method that the present invention discloses, in some embodiment, in hydrocracking catalyst I, the lattice constant of modified Y molecular sieve is generally 2.435 ~ 2.445nm; In hydrocracking catalyst II, the lattice constant of modified Y molecular sieve is generally 2.425 ~ 2.435nm, is preferably 2.425 to being less than 2.435nm(2.425 ~ <2.435nm).
In more preferred embodiments, the SiO of modified Y molecular sieve in hydrocracking catalyst I
2/ Al
2o
3mol ratio is generally 5.0 ~ 70.0, and its relative crystallinity is 90 ~ 130%; The SiO of modified Y molecular sieve in hydrocracking catalyst II
2/ Al
2o
3mol ratio is generally 5.0 ~ 50.0, and relative crystallinity is 90 ~ 120%.
Satisfactory hydrocracking catalyst I and hydrocracking catalyst II can select the commercial catalysts in this area.Also as required, satisfactory hydrocracking catalyst can be prepared voluntarily according to method well known in the art.
According to the method that the present invention discloses, described hydrotreatment reaction zone comprises at least one Hydrobon catalyst bed, generally includes 2 ~ 3 hydrogenation catalyst beds.The first described hydrocracking reaction district and the second hydrocracking reaction district comprise at least 2 beds respectively, usually comprise 3 ~ 5 beds respectively.Wherein said 2 or multiple beds can be arranged in a reactor, or can be arranged at respectively in plural reactor.
In method for hydrogen cracking of the present invention, two large reaction zones can be comprised, first reaction zone is made up of hydrotreatment reaction zone and the first hydrocracking reaction district, usual employing reactor or two reactors in series operations, according to the engagement sequence with reaction mass, load Hydrobon catalyst, hydrocracking catalyst I and hydrocracking catalyst II (or combination loading Hydrobon catalyst, hydrocracking catalyst I and hydrocracking catalyst II) respectively.Second reaction zone (i.e. the second hydrocracking reaction district) is arranged in an independent little reactor, hydrocracking catalyst I or hydrocracking catalyst II can be loaded separately, also can grading loading hydrocracking catalyst I and hydrocracking catalyst II, with the first reaction zone parallel operation, for the cracking and hydrogenation tail oil that circulates; Two sections of shared high-low pressure separators and separation column and hydrogen gas system.
In method for hydrogen cracking of the present invention, described Hydrobon catalyst generally comprises carrier and hydrogenation active metals.With the weight of catalyzer for benchmark, generally include metal component of group VIB in the periodic table of elements, as tungsten and/or molybdenum with oxide basis for 10% ~ 35%, be preferably 15% ~ 30%; Group VIII metal as nickel and/or cobalt with oxide basis for 1% ~ 7%, be preferably 1.5% ~ 6%.Carrier is inorganic refractory oxide, is generally selected from aluminum oxide, amorphous silicon aluminium, silicon-dioxide or titanium oxide etc.Existing various commercial catalysts can be selected, FF-14, FF-24 that such as Fushun Petrochemical Research Institute (FRIPP) develops, 3936,3996, the Hydrobon catalyst such as FF-16, FF-26, FF-36, FF-46; HC-K, HC-P catalyzer that Uop Inc. produces; TK-555, TK-565 catalyzer that Topsoe company produces, also can be prepared by the general knowledge of this area as required.
According to method for hydrogen cracking of the present invention, wherein described in step (3), the initial boiling point of tail oil is generally 270 ~ 385 DEG C.
Heavy raw oil of the present invention can comprise the suitable hydrocarbon feed of various boiling range.Typical hydrocracking raw material comprises any heavy oil or synthetic oil cut, this kind of raw material comprises straight-run gas oil, decompressed wax oil, wax tailings, delayed coking wax oil, gas oil viscosity reduction, long residuum, Fisher-Tropsch synthesis fuels or diasphaltene wet goods, also can be coal synthetic oil or coal tar wet goods.
As the technical term that this area is conventional, in the application, indication hydrofining reaction and hydrocracking condition generally comprise: reaction pressure 5.0MPa ~ 25.0MPa, preferred 6.0MPa ~ 19.0MPa; Temperature of reaction 200 DEG C ~ 480 DEG C, preferably 270 DEG C ~ 450 DEG C; Volume space velocity 0.1h
-1~ 15.0h
-1, preferred 0.2h
-1~ 3.0h
-1; Hydrogen to oil volume ratio 100:1 ~ 2500:1, preferred 400:1 ~ 2000:1.In the first hydrocracking reaction district, the average reaction temperature of usual hydrocracking catalyst II wants high 3 ~ 20 DEG C, preferably high 5 ~ 15 DEG C compared with the average reaction temperature of hydrocracking catalyst I.
Interchanger described in the inventive method can be the usual heat exchanger in this area, is preferably High Temperature High Pressure countercurrent heat-transfer winding tube interchanger.Described High Temperature High Pressure countercurrent heat-transfer winding tube interchanger can choose the existing various Patents technology in market, as, the winding tube interchanger CN 202902937U of Zhenhai Petrochemical Jianan Engineering Co., Ltd.'s exploitation, the full countercurrent heat-transfer of High Temperature High Pressure can be realized, have heat transfer efficiency high (cold and hot end heat transfer temperature difference is little, is generally 3 DEG C ~ 8 DEG C), heat interchanging area large, use that number of units is few, manufacturing expense is low and the feature such as floor space is little.
Reaction heating furnace described in the inventive method only to go into operation the intensification requirement of temperature-rise period cold zone for meeting device, and during normal running, reaction heating furnace only puts pilot burner.The design loading of reaction heating furnace is far below the popular response process furnace of same device same treatment amount, and be generally 20% ~ 60% of the similar treatment capacity of same device, construction investment and operation energy consumption reduce greatly.
Compared with prior art, method of the present invention has the following advantages:
1, the present invention is on the basis of existing hydrocracking process technology, High Temperature High Pressure countercurrent heat-transfer technology and hydrocracking catalyst grating are organically combined, technique and the set of engineering height, innovate supporting start-up method, develop the complete technology of hydrocracking of normal running flames of anger reaction heating furnace, scientific and reasonable make use of hydrogenation reaction heat, decreases construction investment, reduces fuel consumption.
2, in the inventive method, modified Y molecular sieve that two kinds of hydrocracking catalysts that hydrocracking reaction district selects contain different content, that particularly have different lattice constant is as cracking active component.Two kinds of catalyzer can example load according to a certain volume.The hydrocracking catalyst I of upstream is containing higher molecular sieve content, and it has stronger aromatic conversion ability, can be less molecule by the aromatic conversion of heavy constituent in raw material, and is distributed in heavy naphtha fraction and boat coal cut; The hydrocracking catalyst II in downstream has stronger alkane cracking capability simultaneously, the hydrocracking catalyst synergy of two kinds of differing molecular sieve content, significantly improve the quality of hydrocracked product, in particular improve the smoke point of boat coal cut, and effectively reduce the BMCI value of tail oil.
3, the present invention is by arranging independent tail oil circulation cracking case, by some or all of for the tail oil light oil be converted into based on rocket engine fuel, by adjustment operational condition, can produce the rocket engine fuel and hydrogenation tail oil that obtain high-quality flexibly.Can product slates be improved in addition, reduce dry gas yied, improve economy.
4, because two kinds of hydrocracking catalysts exist activity difference, by the arrangement filling of science order, the reaction heat of upper bed layer can be fully utilized, can not liquid hydrogen injection between bed, or few liquid hydrogen injection.Quenching hydrogen consumption and the cold hydrogen reserve level of hydroeracking unit accident (generally can reduce 30 ~ 70%) of cracking case can being greatly reduced, playing the well energy-conservation effect with reducing operating cost.
5, due to whole reactor reaction temperature show an ascending trend distribution, reactor outlet temperature is improved relatively, improve the temperature of interchanger thermal source, and the High Temperature High Pressure adverse current winding tube interchanger that the inventive method selects heat transfer efficiency high, energy can obtain more reasonably fully utilizing, can the realization response process furnace normal running flames of anger, greatly reduce fuel consumption.
6, in the present invention, two-stage reaction shares a set of separation system and hydrogen gas system, thus simplification of flowsheet greatly, reduce cost of equipment and energy consumption.
Accompanying drawing explanation
Fig. 1 is a principle process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing, method of the present invention is described in detail.
As shown in Figure 1, the technical process of the method for hydrogen cracking of the high-output qulified rocket engine fuel of a kind of less energy-consumption of the present invention is as follows: stock oil mixes with hydrogen, through overheated high score gas/cold mixing feed exchanger 1, reaction effluent/hot parallel feeding interchanger 2, twice heat exchange heats up, through going into operation, process furnace 3 rises to temperature of reaction, enters hydrotreatment reaction zone 4 and carries out hydrofining reaction, refining reaction device resultant, the first hydrocracking reaction district 5 is mixed into hydrogen, respectively with hydrocracking catalyst I 6 and hydrocracking catalyst II 7 contact reacts, reaction generation oil and stock oil are after reaction effluent/hot parallel feeding interchanger 2 heat exchange, enter high pressure hot separator 8 and carry out gas-liquid separation, high pressure hot separator 8 top hot high score gas is out after hot high score gas/cold mixing feed exchanger 1 heat exchange, cold high pressure separator 9 is entered again through air cooler cooling, hot high score gas carries out oil in cold high pressure separator 9, water, gas three phase separation, gas recycles through circulating hydrogen compressor 10 after treatment, bottom high pressure hot separator 8, hot high score oil out enters thermal low-pressure separators 11 flash distillation, heat low point of gas is mixed into cold low separator 12 flash distillation with cold high score oil after cooling, cold low point of oil and heat low point of oil are mixed into fractionating system 13, fractionation obtains gas, light naphthar 14, heavy naphtha 15, intermediate oil 16 and tail oil 17, wherein tail oil 17 can according to the market requirement, part or all of circulation and hydrogen enter the second hydrocracking reaction district 18, respectively with hydrocracking catalyst I 19 or/and hydrocracking catalyst II 20 contact reacts.Generate and oily mixing with the first hydrocracking reaction district reaction effluent go to be separated fractionating system.
Next be further described by the method for hydrogen cracking of specific embodiment to the high-output qulified rocket engine fuel of a kind of less energy-consumption of the present invention.
Embodiment 1-3
Embodiment 1-3 adopts the exemplary flow shown in Fig. 1, tail oil is all circulated to the second hydrocracking reaction district, raw materials used oil properties is in table 1, select hydrocracking catalyst I/hydrocracking catalyst II catalyst system of FF-46 hydrogenation pretreatment catalyst, different volumes ratio, the composition of catalyzer and character are in table 2.The processing condition of embodiment 1 ~ 3 and product property list in table 3,4, and in embodiment, the boiling range scope of each cut is respectively: heavy naphtha 65 ~ 160 DEG C, intermediate oil 160 ~ 300 DEG C, tail oil >300 DEG C.
Described in embodiment, one section refers to, the single hop cascade reaction district that hydrotreatment reaction zone and the first hydrocracking reaction district are formed; Described two sections refer to the second hydrocracking reaction district.
The result of embodiment 1-3 shows, adopts method for hydrogen cracking of the present invention, heavy raw oil maximum can be converted into based on the product of high-quality rocket engine fuel.
Table 1 stock oil main character
Table 2 catalyzer main character.
Table 3 hydrocracking technological condition.
* ratio of loading refers to hydrocracking catalyst I/hydrocracking catalyst II.
The distribution of table 4 hydrocracked product and character.
Comparative example 1
Stock oil, with embodiment 1-3, selects the catalyst system of FF-46 pretreating catalyst by hydrocracking and hydrocracking catalyst I.Processing condition and product property list in table 5, and in comparative example, the boiling range scope of each cut is respectively: heavy naphtha 65 ~ 160 DEG C, intermediate oil 160 ~ 300 DEG C, tail oil >300 DEG C.
The processing condition of table 5 comparative example 1 and product property.
Embodiment 4-5
Embodiment 4-5 adopts the exemplary flow shown in Fig. 1, tail oil component loops, and internal circulating load is 50% of tail oil growing amount, and its stock oil and catalyst system are with embodiment 1 ~ 3, and processing condition and product property list in table 6.In embodiment, the boiling range scope of each cut is respectively: heavy naphtha 65 ~ 160 DEG C, intermediate oil 160 ~ 330 DEG C, tail oil >330 DEG C.
Comparative example 2
Stock oil, with embodiment 1-3, selects the catalyst system of FF-46 pretreating catalyst by hydrocracking and hydrocracking catalyst I.Processing condition and product property list in table 6, and in comparative example, the boiling range scope of each cut is respectively: heavy naphtha 65 ~ 160 DEG C, intermediate oil 160 ~ 330 DEG C, tail oil >330 DEG C.
Table 6 processing condition and product property
Claims (13)
1. a method for hydrogen cracking for the high-output qulified rocket engine fuel of less energy-consumption, comprises following content:
(1) after heavy raw oil and hydrogen mix, through overheated high score gas/cold mixing feed exchanger, reaction effluent/hot parallel feeding interchanger, twice heat exchange heats up, pass through again or rise to temperature of reaction without reaction heating furnace, enter hydrotreatment reaction zone to contact with Hydrobon catalyst, carry out hydrofining reaction;
(2) hydrofining reaction resultant enters the first hydrocracking reaction district, successively with hydrocracking catalyst I and hydrocracking catalyst II contact reacts; Hydrocracking catalyst I and hydrocracking catalyst II are all containing modified Y molecular sieve, in described hydrocracking catalyst I, the content of modified Y molecular sieve is 15 ~ 50wt%, in described hydrocracking catalyst II, the content of modified Y molecular sieve is 3 ~ 30wt%, wherein in hydrocracking catalyst I content of modified Y molecular sieve compared with high 10 ~ 25 percentage ratios of the content of modified Y molecular sieve in hydrocracking catalyst II;
(3) step (2) gained reaction effluent enters separator and carries out gas-liquid separation, and gained liquid product enters separation column to carry out fractionation and obtain gas, petroleum naphtha, rocket engine fuel and tail oil;
(4) step (3) obtain tail oil partly or entirely and hydrogen be mixed into the second hydrocracking reaction district, carry out hydrocracking further;
(5) resultant of reaction that step (4) obtains returns step (3), after the reaction effluent obtained mixes, carries out gas-liquid separation and fractionation with the first hydrocracking reaction district, obtains gas, petroleum naphtha and rocket engine fuel that quantity increases.
2. in accordance with the method for claim 1, it is characterized in that, described hydrocracking catalyst I and hydrocracking catalyst II all with VI B race and/or VIII race's metal for active metal component, the content of active ingredient is 15% ~ 35% by weight.
3. in accordance with the method for claim 1, it is characterized in that, in the first described hydrocracking reaction district, hydrocracking catalyst I is 1:5 ~ 5:1 with the admission space ratio of hydrocracking catalyst II.
4. in accordance with the method for claim 1, it is characterized in that, hydrocracking catalyst I or hydrocracking catalyst II load separately in the second described hydrocracking reaction district, or grating uses hydrocracking catalyst I and hydrocracking catalyst II.
5. in accordance with the method for claim 4, it is characterized in that, in described second hydrocracking reaction district, grating uses hydrocracking catalyst I and hydrocracking catalyst II, and hydrocracking catalyst I is 1:5 ~ 5:1 with the volume ratio of hydrocracking catalyst II.
6. in accordance with the method for claim 1, it is characterized in that, in described hydrocracking catalyst I, the lattice constant of modified Y molecular sieve is 2.435 ~ 2.445nm, and in hydrocracking catalyst II, the lattice constant of modified Y molecular sieve is 2.425 ~ 2.435nm.
7. in accordance with the method for claim 6, it is characterized in that, in described hydrocracking catalyst II, the lattice constant of modified Y molecular sieve is 2.425 to being less than 2.435nm.
8., according to the method described in claim 1 or 6, it is characterized in that, in described hydrocracking catalyst I, the SiO of modified Y molecular sieve
2/ Al
2o
3mol ratio is 5.0 ~ 70.0, and its relative crystallinity is 90 ~ 130%; In described hydrocracking catalyst II, the SiO of modified Y molecular sieve
2/ Al
2o
3mol ratio is 5.0 ~ 50.0, and relative crystallinity is 90 ~ 120%.
9. according to the method that claim 1 is stated, it is characterized in that, the first hydrocracking reaction district comprises at least 2 beds, and described at least 2 beds are arranged in a reactor, or are arranged at respectively in plural reactor.
10. in accordance with the method for claim 1, it is characterized in that, described in step (3), the initial boiling point of tail oil is 270 ~ 385 DEG C.
11. in accordance with the method for claim 1, it is characterized in that, described hydrofining and the reaction conditions of hydrocracking comprise: reaction pressure 5.0MPa ~ 25.0MPa, temperature of reaction 200 DEG C ~ 480 DEG C, volume space velocity 0.1h
-1~ 15.0h
-1, hydrogen to oil volume ratio 100:1 ~ 2500:1.
12. in accordance with the method for claim 11, it is characterized in that, in the first hydrocracking reaction district, the average reaction temperature of hydrocracking catalyst II wants high 3 ~ 20 DEG C compared with the average reaction temperature of hydrocracking catalyst I.
13. in accordance with the method for claim 1, it is characterized in that, described hot high score gas/cold mixing feed exchanger, reaction effluent/hot parallel feeding interchanger are High Temperature High Pressure countercurrent heat-transfer winding tube interchanger.
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| CN105733673A (en) * | 2016-02-26 | 2016-07-06 | 武汉凯迪工程技术研究总院有限公司 | Device and method for producing environment-friendly type solvent oil from Fischer-Tropsch synthesis oil |
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| CN107304375A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil conversion process catalyst grade matches somebody with somebody process |
| CN107304375B (en) * | 2016-04-22 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of catalytic diesel oil conversion process catalyst grade matches process |
| CN109777510A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking improving jet fuel yield |
| CN109777510B (en) * | 2017-11-14 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrocracking method for improving jet fuel yield |
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