CN101148614A - One-stage serial hydrocracking method - Google Patents
One-stage serial hydrocracking method Download PDFInfo
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Abstract
The present invention discloses one-section cascade hydrocracking process, and features the hydrocracking unit comprising one hydrocracking pre-treating reactor filled with pre-treating catalyst and hydrocracking catalyst and one hydrocracking reactor filled with hydrocracking catalyst and post-hydrotreating catalyst connected serially. Compared with available technology, the hydrocracking unit of the present invention has the advantages of raised integral activity, increased treating capacity or increased operation period, and raised product quality.
Description
Technical field
The invention discloses a kind of method for hydrogen cracking, particularly a kind of one-stage serial hydrocracking method.
Background technology
Along with world economy develops rapidly, more and more to the demand of fuel oil, and the environmental regulation increasingly stringent, also more and more higher to the specification of quality of oil product, this will seek development the technology of inferior raw material production for the cleaning oil product.Hydrocracking technology is the most direct, the effective means that obtains the high quality light-end products from poor heavy raw material, has therefore obtained to develop widely and use.
Hydrocracking process can be divided into single-stage hydrocracking by being provided with of reactive moieties, one-stage serial hydrocracking and two-stage hydrocracking etc., and wherein widely used is the hydrocracking of one-stage serial.Can be divided into the one way once-through operation, forms such as part cyclical operation or extinction recycle operation by the tail oil cracking that whether circulates.
The reactive moieties of existing one-stage serial hydrocracking technology is made up of hydrocracking pretreatment reaction device and hydrocracking reactor, filling hydrocracking pretreatment catalyst loads hydrocracking catalyst in wherein hydrocracking pre-treatment (the being hydrofining) reactor in the hydrocracking reactor.Adjust the temperature of reaction of hydrocracking pretreatment reaction device, control hydrocracking pre-treatment generates the organic nitrogen compound content in the oil, the hydrocracking pre-treatment that obtains generates oil without gas-oil separation, do not isolate hydrogen sulfide and ammonia yet, directly enter hydrocracking reactor, adjust the temperature of reaction of hydrocracking reactor, the transformation efficiency of control hydrocracking process, the hydrocracking that obtains generates oil and carries out fractionation.
US6224747 and US6296758 relate to one section common polyphone hydrocracking process.US5232578 relates to hydrocracking catalyst combination loadings different in a kind of hydrocracking reactor, does not consider the situation of hydrocracking pretreatment reaction device.US4834365 relates to the different grading loading method of a kind of hydrocracking catalyst granularity, does not consider dissimilar catalyzer.
US4776945 provides a kind of single hop hydroprocessing process, be used for hydrotreatment easily causes catalyst deactivation owing to green coke hydrocarbon ils, the beds that uses in this method comprises two kinds of hydrotreating catalysts that contain dissimilar reactive metals and different auxiliary agent content, and this method is mainly used in the hydrogenating desulfurization of hydrocarbon ils.
US5439860 provides a kind of stable mixed catalyst system and the application in combined hydrogenation processing hydrocracking operation thereof.Described catalyst system is made up of two kinds of diverse catalyst mix, first kind of catalyzer is a kind of conventional hydrodenitrification and/or Hydrobon catalyst, basically do not have cracking activity, second kind of catalyzer is a kind of hydrocracking catalyst, and the effective diameter of two kinds of catalyzer is basic identical.
Along with the variation change of crude quality is bad, existing one-stage serial hydrocracking technology also needs further to improve, and improves the adaptability to raw material and the quality product of hydroeracking unit.
Summary of the invention
The invention provides a kind of improved one-stage serial hydrocracking technology, the operating severity that technological process of the present invention can effectively improve hydrocracking pretreatment reaction device further improves the quality of products, and improves the adaptability of raw material.
The improved one-stage serial hydrocracking method of the present invention comprises the steps:
(1), stock oil is mixed with hydrogen the back under hydroconversion condition by hydrocracking pretreatment reaction device, 3～6 beds are set in the hydrocracking pretreatment reaction device, wherein the bottom is provided with the bed that at least one contains hydrocracking catalyst in hydrocracking pretreatment reaction device, and all the other are hydrocracking pretreatment catalyst bed;
(2), step (1) reaction effluent enters hydrocracking reactor, 3～8 beds are set in the hydrocracking reactor, wherein the bottom is provided with the bed contain catalyst for refining behind the hydrogenation in hydrocracking reactor, and all the other are the hydrocracking catalyst bed;
(3), step (2) hydrocracking reaction effluent enters separation system, obtains corresponding product.
Wherein the described bed that contains hydrocracking catalyst of step (1) is 1～3, can constitute by hydrocracking catalyst, perhaps constitute composite catalyst bed, be preferably 2～3 composite catalyst beds that constitute by hydrocracking pretreatment catalyst and hydrocracking catalyst by hydrocracking pretreatment catalyst and hydrocracking catalyst.In the composite catalyst bed, hydrocracking pretreatment catalyst and hydrocracking catalyst are provided with along the stream flow direction, and reaction mass passes through hydrocracking catalyst then earlier by the hydrocracking pretreatment catalyst.The volume ratio of hydrocracking pretreatment catalyst and hydrocracking catalyst is 10: 1～1: 10 in each composite catalyst bed, preferred 1: 6～6: 1.In the hydrocracking pretreatment reaction device, the hydrocracking pretreatment catalyst was generally 40: 60～90: 10 with the cumulative volume ratio of hydrocracking catalyst, was preferably 60: 40～85: 15.The hydrocracking catalyst that uses in the hydrocracking pretreatment reaction device is the hydrocracking catalyst with certain nitrogen resistance.Those skilled in the art know, hydrocracking catalyst with nitrogen resistance is the hydrocracking catalyst of main cracking component as selecting with amorphous silicon aluminium, perhaps select to contain the hydrocracking catalyst that the nitrogen resistance molecular sieve is main cracking component, can select commercial hydrocracking catalyst, also can be by method preparation well known in the art.Commercial hydrocracking catalyst such as Fushun Petrochemical Research Institute develop 3973, hydrocracking catalysts such as ZHC-01, ZHC-02, ZHC-04, FC-14, FC-28, and the DHC-2 of Uop Inc., DHC-8, the hydrocracking catalysts such as ICR126 of CHEVRON company.Preparation well known in the art has the method for nitrogen resistance hydrocracking catalyst such as US3248318, US3923638, CN1253990A, CN1508227A, CN1508228A, CN1566283A etc.
The present invention is by the research to single hop serial hydrocracking technology, think and load hydrogenation pretreatment catalyst in the hydrocracking pretreatment reaction device, can make the hydrogenation pre-treatment give birth to the requirement that olefiant organic nitrogen compound content satisfies the hydrocracking charging, but because hydrogenation pretreatment catalyst is based on the saturated function of hydrogenation, cracking reaction does not take place basically, so hydrodenitrification need relatively carried out under the exacting terms, and place a part of hydrocracking catalyst at the rear portion of bed, can be with saturated polycyclic aromatic hydrocarbons generation cracking, be relatively easy to organic nitrogen compound is removed, thereby reduced temperature of reaction, just improve treatment capacity, perhaps prolonged the operational cycle; Only load hydrocracking catalyst in the common hydrocracking reactor, at most at the very small amount of back of filling, hydrocracking catalyst bed bottom catalyst for refining, play the effect that removes the mercaptan that forms in the reaction process, the present invention increases the back catalyst for refining consumption of last bed, on the basis of satisfying the hydrocracking transformation efficiency, not only solved the device operation problem that latter stage, the product mercaptans content exceeded standard like this, also further hydrocracking is generated oil and carry out hydrofining, reduce aromatic hydrocarbons, thereby further promoted the quality of product.
The plural beds of operated by rotary motion in the hydrocracking pretreatment reaction device of one-stage serial hydrocracking technology, owing to constantly carrying out of hydrogenation reaction, each beds all has certain temperature rise, and temperature rise increases when particularly processing high-sulfur stock oil.In hydrocracking pretreatment reaction device, along the flow direction of logistics, organic nitrogen compound in the reaction raw materials oil and organic sulfide content reduce gradually; In each beds, along the flow direction of logistics, the temperature of beds raises gradually.And the hydrocracking catalyst with anti-high nitrogen function generally is carrier with the amorphous silicon aluminium, perhaps contain a small amount of anti-nitrogen molecule sieve, therefore catalyzer need be operated under higher relatively temperature, utilize this characteristic, the beds of bottom is set to composite catalyst bed in the hydrocracking pretreatment reaction device, ingress at bed, temperature of reaction is relatively low, the concentration of organic nitrogen compound is higher relatively, in this part conventional hydrocracking pretreatment catalyst is set, carrying out along with reaction, bed temperature raises, and organic nitrogen compound concentration reduces, the hydrocracking catalyst that has certain anti-nitrogen function in this part setting, can satisfy its reaction conditions, the part hydrocracking reaction takes place, the polycyclic aromatic hydrocarbons of preferentially adsorbed nitrogen atom importantly, the step of going forward side by side is carried out hydrogenation and scission reaction, therefore promote the carrying out of hydrodenitrification reaction, and conventional hydrocracking pretreatment catalyst is to the comparatively difficulty that removes of this type of organonitrogen.The present invention is the recombination catalyst layer bed with the hydrocracking pretreatment catalyst bed designs of suitable location, use the hydrocracking pretreatment catalyst in the relatively low relative higher bed position of reaction bed temperature with organic nitrogen compound concentration, the major function of hydrocracking pretreatment catalyst is that desulfurization, denitrogenation, aromatic hydrocarbons are saturated etc., can give full play to its hydrogenation performance at the hydrotreating catalyst of this position.It also is strong exothermal reaction that hydrogenation takes off the impurity reaction, hydrocracking pretreatment catalyst bed part at composite catalyst bed, impurity such as the organonitrogen in the material further remove, material temperature further raises, enter the hydrocracking catalyst part this moment, hydrocracking catalyst then is under higher relatively temperature of reaction and the relatively low organonitrogen concentration conditions, and hydrocracking catalyst can be given full play to its cracking function.Composite catalyst bed technology of the present invention can improve the reactivity worth of the hydrocracking pretreatment reaction device in the one-stage serial hydrocracking technology greatly, improves nitrogen removal performance, improves the adaptability of raw material, reduces the reaction severity, improves the quality of products.
Description of drawings
Fig. 1 is a kind of operating method schematic flow sheet of the present invention.
Fig. 2 is an another kind of operating method schematic flow sheet of the present invention.
Wherein: HT-CAT represents hydrocracking pretreatment catalyst (or Hydrobon catalyst), and HC-CAT represents hydrocracking catalyst.
Embodiment
In the one-stage serial hydrocracking method of the present invention, separate the heavy ends that obtains and partly or entirely to circulate, also can be used as the raw material of other device as the charging of hydrocracking.
The Hydrobon catalyst of hydrocracking pretreatment catalyst that loads in the hydrocracking pretreatment reaction device in the inventive method and the bed filling of hydrocracking reactor bottom is conventional hydrocracking pretreatment catalyst, they can be with a kind of, also can be different.Being active ingredient with group vib and/or group VIII metal generally, is carrier with aluminum oxide or siliceous aluminum oxide, and the group vib metal is generally Mo and/or W, and the group VIII metal is generally Co and/or Ni.In the weight of catalyzer, the group vib metal content is counted 10wt%～35wt% with oxide compound, and the group VIII metal content is counted 3wt%～15wt% with oxide compound, and its character is as follows: specific surface is 100～350m
2/ g, pore volume are 0.15～0.6ml/g.Main catalyzer have that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops 3936,3996, hydrocracking pretreatment catalysts such as FF-16, FF-26, the function class that also can be external catalyst Co. exploitation is like catalyzer, HC-K, HC-P as Uop Inc., KF-847, the KF-848 etc. of the TK-555 of Topsoe company, TK-565 catalyzer and AKZO company.
The hydrocracking catalyst that loads in the hydrocracking pretreatment reaction device in the inventive method is conventional hydrocracking catalyst, be active ingredient generally with group vib and/or group VIII metal, the group vib metal is generally Mo and/or w, and the group VIII metal is generally Co and/or Ni.The carrier of this catalyzer be in aluminum oxide, siliceous aluminum oxide and the molecular sieve one or more.Because the organic nitrogen compound of some amount is arranged through hydrogenation pre-treatment and the liquid stream that enters the hydrocracking catalyst reaction zone, so it is the hydrocracking catalyst of carrier that the hydrocracking catalyst that is seated in hydrocracking pretreatment reaction device of the present invention is preferably with the amorphous silicon aluminium, or select hydrocracking catalyst with nitrogen resistance molecular sieve.Weight in catalyzer, the group vib metal content is counted 10wt%～35wt% with oxide compound, and the group VIII metal content is counted 3wt%～15wt% with oxide compound, and molecular sieve content is 5wt%～40wt%, amorphous aluminum silicide content is 10wt%～80wt%, and its specific surface is 100m
2/ g～650m
2/ g, pore volume are 0.15ml/g～0.50ml/g.Main catalyzer have that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops 3973, single-stage hydrocracking catalyzer such as FC-28, FC-14, ZHC-01, ZHC-02, ZHC-04, and DHC-2, the DHC-8 of Uop Inc. of offshore company's exploitation, the hydrocracking catalysts such as ICR126 of CHEVRON company.Wherein ZHC-02, ICR126 etc. are more suitable for process of the present invention for being the hydrocracking catalyst of cracking component with the amorphous aluminum silicide.The hydrocracking catalyst that loads in the hydrocracking reactor can be identical with the catalyzer in being seated in hydrocracking pretreatment reaction device, and is perhaps different.The carrier of hydrocracking catalyst is aluminum oxide and molecular sieve, and molecular sieve content is generally 20wt%～80wt%.Commercial hydrocracking catalyst mainly contains: the HC-12 of Uop Inc., HC-14, HC-24, HC-28, HC-34 etc. and FRIPP develop 3971,3976, FC-12, FC-16, FC-24, FC-26, FC-28, ZHC-02 etc., and the ICR126, the ICR139 that develop of CHEVRON company, ICR141 etc.
Hydrocracking pretreatment reaction device operational condition is generally in the inventive method, stagnation pressure 3.0MPa～19.0MPa, and average reaction temperature is 300 ℃～450 ℃, volume space velocity 0.1h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1.The hydrocracking reactor operational condition is generally: stagnation pressure 3.0MPa～18.0MPa, average reaction temperature is 300 ℃～450 ℃, volume space velocity 0.3h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1.In the hydrocracking reactor during liquid of reactant flow by hydrogenation post-processing catalyst bed volume space velocity be 3.0h
-1～12.0h
-1, be preferably 4.0h
-1～10.0h
-1The volume of each beds can be identical, also can be different.Average reaction temperature refers to the mean value of bed different positions temperature.
As depicted in figs. 1 and 2, stock oil 1 at first mixes with hydrogen 2 and enters the hydrocracking pretreatment reaction devices 3 that loaded hydrocracking pretreatment catalyst and hydrocracking catalyst, obtain hydrogenated oil 4 through serial hydrogenation reaction, hydrogenated oil 4 continues to be mixed into hydrogen 5 hydrocracking reactor 6 of filling hydrocracking catalyst and back catalyst for refining, through serial hydrocracking reaction, obtain hydrocracking and generate oil 7, hydrocracking generation oil 7 enters high-pressure separator 8 subsequently and carries out gas-liquid separation, the gas 9 that obtains mixes the back with new hydrogen 10 and recycles behind circulating hydrogen compressor 11, high-pressure separator 8 is separated the liquid oil 12 that obtains and is entered separation column 13, fractionation obtains gas products 14 in separation column 13, light naphtha product 15, heavy naphtha product 16, boat product of coal 17, diesel product 18 and tail oil, tail oil can be used as the 19 outer systems that throw away, also can be used as 20 with enter hydrocracking pretreatment reaction device 3 after stock oil 1 mixes, also can be used as 21 with enter hydrocracking reactor 6 after hydrogenated oil 4 mixes.
Below by embodiment the present invention program and effect are described
The stock oil character that embodiment uses sees Table 1.(wherein wt% is weight percentage)
Table 1 stock oil character
| |
1# | 2# |
| Density/gcm -3 | 0.936 | 0.920 |
| Boiling range/℃ | 360～560 | 340～550 |
| Carbon residue, wt% | 0.18 | 0.32 |
| Sulphur content, wt% | 2.38 | 1.16 |
| Nitrogen content, wt% | 0.107 | 0.168 |
| The BMCI value | 52.5 | 49.0 |
At first stock oil and hydrogen mix and enter hydrocracking pretreatment reaction device, continue to enter hydrocracking reactor then, obtain hydrocracking and generate oil and also carry out fractionation, the light ends of the different boiling ranges that obtain above and tail oil, processing condition and product property see Table 2 and table 3.
Table 2 embodiment 1-5 and comparative example processing condition and product property
| |
| Embodiment | 2 | |
|
|
|
| |
1# | 1# | 1# | 1# | 2# | 2# | |
| Hydrocracking pretreatment reaction device | |||||||
| Catalyzer | FF-26/ ZHC-02 | FF 26 | FF～26/ ZHC-02 | FF-16/ FC-28 | FF-26/ ZHC-02 | 3936/ FC-28 | |
| Catalyst ratio | 80: 20 | - | 67: 33 | 75: 25 | 75: 25 | 80: 20 | |
| The catalyst bed number of plies (each bed equal-volume) | 3 | 3 | 3 | 4 | 4 | 5 | |
| Pressure/MPa | 15.7 | 15.7 | 12.0 | 8.0 | 15.7 | 10.0 | |
| Cumulative volume air speed/h -1 | 1.4 | 1.4 | 1.5 | 1.1 | 1.8 | 1.5 | |
| Temperature of reaction/℃ | 392/412 | - | 400/418 | 398/415 | 390/410 | 392/415 | |
| Average reaction temperature/℃ | 396 | 401 | 405 | 400 | 394 | 397 | |
| Hydrogen to oil volume ratio | 1000: 1 | 1000: 1 | 900: 1 | 800: 1 | 700: 1 | 1300: 1 | |
| Generate oily nitrogen content/μ gg -1 | 12.5 | 12.9 | 14.3 | 5.4 | 3.2 | 6.7 |
| Hydrocracking reactor | |||||||
| Catalyzer | 3976/ FF-26 | 3976/ FF-26 | FC-28/ FF-26 | FC 12/ FF-26 | FC-24/ FF-16 | FC-12/ 3936 | |
| The catalyst bed number of plies (each bed equal-volume) | 4 | 4 | 4 | 5 | 5 | 5 | |
| Pressure/Mpa | 15.7 | 15.7 | 12.0 | 8.0 | 15.7 | 10.0 | |
| Volume space velocity/h -1 | 2.0/4.8 | 1.5/15.0 | 2.0/6.0 | 2.3/8.0 | 3.6/8.0 | 1.5/7.0 | |
| Cumulative volume air speed/h -1 | 1.4 | 1.4 | 1.5 | 1.8 | 2.5 | 2.0 | |
| Average reaction temperature/℃ | 382 | 380 | 395 | 385 | 378 | 385 | |
| Hydrogen to oil volume ratio | 1500∶1 | 1500∶1 | 1000∶1 | 800∶1 | 1200∶1 | 1500∶1 | |
| Product yield and product property | |||||||
| Heavy naphtha | Yield, wt% | 4.7 | 5.9 | 4.1 | 8.7 | 38.5 | 14.9 |
| Sulphur content/μ gg -1 | ＜0.5 | ＜0.5 | ＜0.5 | ＜0.5 | ＜0.5 | ＜0.5 | |
| Virtue is dived, wt% | 61.6 | 61.4 | 60.2 | 52.6 | 58.4 | 55.6 | |
| Boat coal cut | Yield, wt% | 29.9 | 28.6 | 30.5 | 23.1 | 13.6 | 24.9 |
| Sulphur content/μ gg -1 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | |
| Aromatic hydrocarbons, v% | 4.1 | 5.5 | 6.7 | 9.4 | 6.9 | 8.8 | |
| Smoke point/mm | 27 | 25 | 26 | 22 | 25 | 23 | |
| Diesel oil distillate | Yield, wt% | 33.2 | 31.9 | 35.6 | 26.3 | 16.7 | 30.5 |
| Sulphur content/μ gg -1 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | |
| Aromatic hydrocarbons, v% | 3.6 | 4.7 | 3.1 | 8.4 | 5.7 | 9.1 | |
| Cetane value | 60.4 | 58.3 | 57.9 | 51.2 | 55.6 | 54.4 | |
| The tail oil cut | Yield, wt% | 30.5 | 31.2 | 25.6 | 38.5 | 20.7 | 24.4 |
| Sulphur content/μ gg -1 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | |
| Condensation point/℃ | 32 | 33 | 30 | 35 | 29 | 33 | |
| The BMCI value | 8.0 | 10.2 | 11.5 | 16.8 | 7.3 | 12.0 | |
Table 3 embodiment 6-7 processing condition and product property
| |
|
|
| |
1# | 2# |
| Hydrocracking pretreatment reaction device | ||
| Catalyzer | FF-26、ZHC-02 | FF-26、ZHC-02 |
| Catalyzer divides three beds (equal-volume) | ||
| First bed | FF-26 | FF-26 |
| Second bed (volume ratio) | FF-26/ZHC-02(4∶1) | FF-26/ZHC-02(2∶1) |
| The 3rd bed (volume ratio) | FF-26/ZHC-02(1∶4) | FF-26/ZHC-02(1∶2) |
| Pressure/MPa | 13.7 | 15.7 |
| Cumulative volume air speed/h -1 | 1.4 | 1.8 |
| Average reaction temperature/℃ | 394 | 398 | |
| Hydrogen to oil volume ratio | 1000∶1 | 700∶1 | |
| Hydrocracking reactor | |||
| Catalyzer | FC-26/FF-26 | FC-24/FF-26 | |
| The catalyst bed number of plies (equal-volume) | 4 | 4 | |
| Pressure/Mpa | 13.7 | 15.7 | |
| Volume space velocity/h -1 | 1.41/8.0 | 2.0/8.0 | |
| Cumulative volume air speed/h -1 | 1.2 | 1.6 | |
| Average reaction temperature/℃ | 383 | 379 | |
| Hydrogen to oil volume ratio | 1500∶1 | 1200∶1 | |
| Product yield and product property | |||
| Heavy naphtha | Yield, wt% | 8.2 | 43.1 |
| Sulphur content/μ gg -1 | ＜0.5 | ＜0.5 | |
| Virtue is dived, wt% | 55.6 | 54.3 | |
| Boat coal cut | Yield, wt% | 36.1 | 13.5 |
| Sulphur content/μ gg -1 | ＜5.0 | ＜5.0 | |
| Aromatic hydrocarbons, v% | 3.9 | 4.0 | |
| Smoke point/mm | 26 | 26 | |
| Diesel oil distillate | Yield, wt% | 23.9 | 10.9 |
| Sulphur content/μ gg -1 | ＜5.0 | ＜5.0 | |
| Aromatic hydrocarbons, v% | 3.6 | 4.2 | |
| Cetane value | 61.3 | 55.1 | |
| The tail oil cut | Yield, wt% | 25.1 | 18.5 |
| Sulphur content/μ gg -1 | ＜5.0 | ＜5.0 | |
| Condensation point/℃ | 31 | 28 | |
| The BMCI value | 7.5 | 8.9 | |
By embodiment as can be seen, by technology of the present invention, can be under common hydrocracking condition, adopt existing catalytic hydroprocessing technology and equipment, can effectively reduce hydrorefined operating severity, promptly improve hydrofining section activity of such catalysts, reduce temperature of reaction, perhaps under identical temperature of reaction, improved the processing power of device, but also can improve the quality of product raw material.
Claims (10)
1. an one-stage serial hydrocracking method comprises the steps:
(1), stock oil is mixed with hydrogen the back under hydroconversion condition by hydrocracking pretreatment reaction device, 3～6 beds are set in the hydrocracking pretreatment reaction device, wherein the bottom is provided with the bed that at least one contains hydrocracking catalyst in hydrocracking pretreatment reaction device, and all the other are hydrocracking pretreatment catalyst bed;
(2), step (1) reaction effluent enters hydrocracking reactor, 3～8 beds are set in the hydrocracking reactor, wherein the bottom is provided with the bed contain catalyst for refining behind the hydrogenation in hydrocracking reactor, and all the other are the hydrocracking catalyst bed;
(3), step (2) hydrocracking reaction effluent enters separation system, obtains corresponding product.
2. in accordance with the method for claim 1, it is characterized in that the described bed that contains hydrocracking catalyst of step (1) is 1～3.
3. according to claim 1 or 2 described methods, it is characterized in that the described bed that contains hydrocracking catalyst is made of hydrocracking catalyst, perhaps constitutes composite catalyst bed by hydrocracking pretreatment catalyst and hydrocracking catalyst.
4. in accordance with the method for claim 1, it is characterized in that the described bed that contains hydrocracking catalyst is 2～3 composite catalyst beds that are made of hydrocracking pretreatment catalyst and hydrocracking catalyst.
5. in accordance with the method for claim 3, it is characterized in that in the described composite catalyst bed, hydrocracking pretreatment catalyst and hydrocracking catalyst are provided with along the stream flow direction, and reaction mass passes through hydrocracking catalyst then earlier by the hydrocracking pretreatment catalyst.
6. in accordance with the method for claim 3, it is characterized in that the volume ratio of hydrocracking pretreatment catalyst and hydrocracking catalyst is 10: 1～1: 10 in the described composite catalyst bed.
7. in accordance with the method for claim 3, it is characterized in that the volume ratio of hydrocracking pretreatment catalyst and hydrocracking catalyst is 1: 6～6: 1 in the described composite catalyst bed.
8. in accordance with the method for claim 1, it is characterized in that the hydrocracking catalyst that uses in the hydrocracking pretreatment reaction device is the hydrocracking catalyst with nitrogen resistance.
9. in accordance with the method for claim 1, it is characterized in that hydrocracking pretreatment reaction device operational condition is, stagnation pressure 3.0MPa～19.0MPa, average reaction temperature is 300 ℃～450 ℃, volume space velocity 0.1h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1; The hydrocracking reactor operational condition is: stagnation pressure 3.0MPa～18.0MPa, average reaction temperature is 300 ℃～450 ℃, volume space velocity 0.3h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 300: 1～5000: 1.
10. volume space velocity is 3.0～12.0h when in accordance with the method for claim 1, it is characterized in that the liquid of catalyst for refining bed after reactant flow is by hydrogenation in the described hydrocracking reactor
-1
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520191A (en) * | 2015-09-11 | 2017-03-22 | 中国石油化工股份有限公司 | Hydrocracking method with reinforced hydrogenation |
| CN109777483A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method of stable hydrogenation cracked product quality |
| CN109777482A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A method of extending hydrocracked product quality stability |
| CN109777484A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A method of enhancing hydrocracked product quality stability |
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| US6224747B1 (en) * | 1998-03-14 | 2001-05-01 | Chevron U.S.A. Inc. | Hydrocracking and hydrotreating |
| CN1114679C (en) * | 2000-05-19 | 2003-07-16 | 中国石油化工集团公司 | Middle-pressure hydrocracking method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106520191A (en) * | 2015-09-11 | 2017-03-22 | 中国石油化工股份有限公司 | Hydrocracking method with reinforced hydrogenation |
| CN106520191B (en) * | 2015-09-11 | 2019-03-22 | 中国石油化工股份有限公司 | It is a kind of to strengthen the method for hydrogen cracking for adding hydrogen |
| CN109777483A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method of stable hydrogenation cracked product quality |
| CN109777482A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A method of extending hydrocracked product quality stability |
| CN109777484A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A method of enhancing hydrocracked product quality stability |
| CN109777484B (en) * | 2017-11-14 | 2020-12-08 | 中国石油化工股份有限公司 | Method for enhancing quality stability of hydrocracking product |
| CN109777483B (en) * | 2017-11-14 | 2020-12-08 | 中国石油化工股份有限公司 | Method for stabilizing quality of hydrocracking product |
| CN109777482B (en) * | 2017-11-14 | 2021-07-09 | 中国石油化工股份有限公司 | Method for prolonging quality stability of hydrocracking product |
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