CN101434864A - Coking light distillate hydrogenation modification method - Google Patents

Coking light distillate hydrogenation modification method Download PDF

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CN101434864A
CN101434864A CNA2007101583695A CN200710158369A CN101434864A CN 101434864 A CN101434864 A CN 101434864A CN A2007101583695 A CNA2007101583695 A CN A2007101583695A CN 200710158369 A CN200710158369 A CN 200710158369A CN 101434864 A CN101434864 A CN 101434864A
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oil
hydrogen
raw material
light distillate
coking light
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CN101434864B (en
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徐大海
李扬
王震
牛世坤
刘继华
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention relates to a method used for hydrogenation modification of coking light distillate oil; under hydrogenation refining condition, the raw material of the coking light distillate oil and hydrogen are contacted with W-Mo-Ni series of hydrogenation catalysts firstly; subsequently, naphtha distillate, coal oil distillate and diesel distillate are gained by stripping and distillation; wherein, the coal oil distillate and new hydrogen enter a low-pressure hydrogenation reactor and are contacted with Ni-series of hydrogenation catalysts; the product is separated by a gas-liquid separator; and the liquid product is used as high-quality jet fuel components and the hydrogen-rich gas is returned to the coking light distillate oil raw material and used for hydrogenation refining. The method can process the coking light distillate oil with bad quality into high-quality jet fuel, high-quality naphtha and clean diesel components by simple process, has the advantages of wide application of the raw material, flexible operation, stable running, and the like, and effectively improves the economical benefits of the enterprises.

Description

A kind of coking light distillate hydrogenation modification method
Technical field
The present invention relates to a kind of method of coking light distillate raw material hydro-upgrading, specifically coking light distillate raw material hydrogenation direct production high-quality 3 #Rocket engine fuel, the method for hydrotreated naphtha of production high-quality simultaneously and low-sulfur high hexadecane value diesel component is applicable to that the refinery of delayed coking unit adopts.
Background technology
The method that at present can direct production goes out qualified rocket engine fuel mainly contains two kinds: a kind of is that crude oil obtains kerosene(oil)fraction through air distillation, handles and obtains qualified rocket engine fuel product through facing hydrogen or non-hydrogen then; Another kind is to be raw material with the vacuum distillate, adopts the high-pressure hydrocracking technology also can direct production go out qualified rocket engine fuel product.First method plant investment and process cost are lower, but are subjected to the restriction of raw material quantity, can not satisfy the demand of air system fast development; Though is raw material and adopt the high-pressure hydrocracking technology with the lower vacuum distillate of price, because device need be operated under High Temperature High Pressure, investment and tooling cost are all higher.
The delayed coking technology of residual oil is the important process process of heavy oil lighting in the refinery, all there is delayed coking unit present most refinery, coking distillate can fractionate out coker gasoline, coker gas oil and wax tailings, but all has shortcoming of poor quality, that foreign matter content is high, must after refining, could use, generally can't produce high quality boat coal component.Coking gasoline and diesel adopts the course of processing of first fractionation back end hydrogenation or first hydrogenation aftercut substantially in the prior art, and hydrogenated gasoline is as the raw material of cracking of ethylene raw material, catalytic reforming raw material or hydrogen manufacturing, and hydrogenated diesel oil is as the derv fuel oil blend component.Though above-mentioned two kinds of methods also can make coking gasoline and diesel be fully used, economic benefit needs further to improve, and the coker gasoline hydrogenation unit also through regular meeting because the too fast ordinary production that influences device of rising falls in pressure; The coker gas oil hydrogenated oil is as vehicle fuel, because country does not have profit substantially to the regulation and control in market.
Along with the continuous development of civil aviaton's cause, the demand of rocket engine fuel constantly increases.For oil refining enterprise, rocket engine fuel is a high value added product, and is good in economic efficiency, and can also also can be used as the raw material of molecular sieve dewaxing unit winter as the high-grade low-freezing diesel oil blending component.Therefore, adopt coking light distillate to produce rocket engine fuel and can improve refinery's economic benefit.
US6294079 discloses a kind of from produce the hydrofining/hydrocracking combined process method of rocket engine fuel than heavier feedstocks.This method is passed through hydrofining reactor with raw material earlier, enter then high-pressure separator tell gently, in, weigh three parts, gently, in and the part of last running enter second high-pressure separator, residue last running enters low severity hydrocracking section, product also enters second high-pressure separator.This method adopts two high-pressure separator, can maximum produce rocket engine fuel, but the technical process complexity, invest higherly, and operating also has certain difficulty.
CN1478867A discloses a kind of method of producing rocket engine fuel from coking distillate.This method adopts an acidic catalyst that contains zeolite at coker gas oil or coking gasoline and diesel raw material, under appropriate processing condition, coking stock oil is carried out hydrotreatment, and product can obtain the rocket engine fuel product after fractionation.This method is owing to adopt an acidic catalyst, and the nitrogen content of stock oil is had certain requirement, thus be not that all coking gasoline and diesel raw materials all are suitable for, and handle cycloalkyl coking distillate inferior and also acquire a certain degree of difficulty.
CN1458233A discloses a kind of method of coking full fraction oil hydrogenation refining.This method adopts the coking full fraction oil hydrogenation refining flow process, is used for production high-quality derv fuel oil fuel.This method can not obtain high-quality 3 #Rocket engine fuel.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of coking light distillate hydrogenation modification method, to reach the raising added value of product, increase the purpose of refinery's economic benefit.
The method of coking light distillate hydrogenation modification provided by the invention comprises following content: the coking light distillate raw material at first contacts with the W-Mo-Ni series hydrocatalyst under the hydrofining condition with hydrogen, pass through stripping and fractionation then, fractionation obtains naphtha fraction, kerosene(oil)fraction and diesel oil distillate, wherein kerosene(oil)fraction enters a low-voltage hydrogenation reactor with new hydrogen, contact with the Ni series hydrocatalyst, product is through gas-liquid separator, liquid product is as high-quality rocket engine fuel component, and hydrogen-rich gas returns the hydrofining of coking light distillate raw material and uses.
Coking light distillate raw material hydrofining reaction condition is: hydrogen dividing potential drop 3.4MPa~10.0MPa is preferably 4.8MPa~8.0MPa; Temperature of reaction is 260 ℃~360 ℃, is preferably 300 ℃~350 ℃; Volume space velocity is 0.5h -1~3.0h -1, be preferably 1.0h -1~2.0h -1Hydrogen to oil volume ratio is 300~800, is preferably 300~600.Kerosene(oil)fraction low-voltage hydrogenation reaction conditions is: hydrogen dividing potential drop 0.5MPa~3.0MPa is preferably 0.5MPa~2.2MPa; Temperature of reaction is 100 ℃~300 ℃, is preferably 160 ℃~240 ℃; Volume space velocity is 0.5h -1~3.0h -1, be preferably 0.8h -1~2.0h -1Hydrogen to oil volume ratio is 100~500, is preferably 200~350.
Hydrogenation process adopts two reactors, the coking light distillate raw material at first enters first reactor, reaction mass contacts with the catalyzer of high hydrogenation activity under comparatively high temps and pressure condition, remove impurity and saturated a part of aromatic hydrocarbons such as most sulphur nitrogen, product enters high-pressure separator, carries out gas-liquid separation in high-pressure separator.The isolated hydrogen-rich gas of coking light distillate raw material hydrofining reaction effluent recycles, isolated liquid product enters gas and puies forward fractionating system, the kerosene(oil)fraction that fractionates out is entering second reactor, carry out the aromatic hydrogenation saturated reaction under than the demulcent processing condition, the aromaticity content of product and smoke point just can satisfy 3 fully like this #The specification of quality of rocket engine fuel.
It is high-activity hydrofining catalyst that described Hydrobon catalyst is selected W-Mo-Ni.Its composition comprises: Tungsten oxide 99.999 35wt%~42wt%, nickel oxide 13wt%~20wt%, molybdenum oxide 12wt%~18wt%, total metal contents in soil is at 60wt%~80wt%, catalyzer contains refractory oxide solid support materials such as aluminum oxide, siliceous aluminum oxide, silicon oxide simultaneously, can also contain auxiliary agents such as titanium, zirconium, phosphorus, boron, method for preparing catalyst can adopt the coprecipitation method preparation.Described low pressure hydrocatalyst for saturating arylhydrocarbon is the Ni series catalysts, its nickel oxide content is 40wt%~60wt%, catalyzer contains refractory oxide solid support materials such as aluminum oxide, siliceous aluminum oxide, silicon oxide simultaneously, can contain a little auxiliary, auxiliary agent such as titanium, zirconium, boron, molybdenum etc., method for preparing catalyst can adopt kneading method, pickling process or coprecipitation method etc.
Through the coking light distillate raw material that the inventive method is handled, the kerosene product that obtains can directly satisfy mercaptan sulfur less than 20 μ g/g, smoke point greater than 3 of 25mm #The requirement of rocket engine fuel specification.The hydrotreated naphtha of by-product can reach S<0.5 μ g/g, N<0.5 μ g/g, and alkene can be used as the raw material of catalytic reforming raw material or preparing ethylene by steam cracking less than 1v%; Hydrogenated diesel oil can be used as low-sulfur high hexadecane value diesel oil blending component.
The initial boiling point of described coking light distillate raw material is generally 30~70 ℃, and final boiling point is generally 320~380 ℃.Contents such as concrete processing condition can be determined by those skilled in the art according to material elementses such as raw material properties, quality product requirements.
The invention has the advantages that: (raw material is at first through than the hydrofining under the severe condition by optimizing technical process and operational condition, kerosene(oil)fraction after the hydrofining carries out the low-voltage hydrogenation reaction, the new hydrogen of reactive system is adopted in the reaction of kerosene low-voltage hydrogenation, isolating hydrogen-rich gas is as the hydrogen make-up of raw material hydrofining reaction behind the kerosene low-voltage hydrogenation), and the catalyzer matching scheme of optimizing (raw material hydrofining and kerosene(oil)fraction low-voltage hydrogenation adopt the catalyzer matching scheme of optimizing), can be converted into the higher rocket engine fuel component of value, by-product high-quality hydrotreated naphtha and low-sulfur high hexadecane value diesel oil blending component simultaneously with being worth lower coking light distillate.Technical process is simple relatively, reduced the operating severity of system, easy coking when having overcome the independent hydrogenation of coker gasoline, short problem of operational cycle.Stock oil adaptability of the present invention is strong, can process various coking light distillates of different nature, and quality product can meet the demands fully.The device flexibility of operation is big, according to the variant production purpose, only needs the adjusting process condition can satisfy production high-quality 3 #The requirement of rocket engine fuel, dewaxing by molecular sieve raw material or high-grade low-freezing diesel oil blending component.
Description of drawings
Fig. 1 is the inventive method process flow diagram.
Wherein 1 is the coking light distillate raw material, 2 is recycle hydrogen, 3 is coking light distillate raw material hydrofining reactor, and 4 is coking light distillate raw material hydrofining reactor reaction product gas-liquid separator, and 5 is coking light distillate raw material hydrofining reactor liquid product separation column, 6 is kerosene(oil)fraction hydrogenation saturating reactor, 7 is kerosene(oil)fraction hydrogenation saturated reaction product gas-liquid separator, and 8 are boat product of coal component, and 9 is new hydrogen, 10 is hydrotreated naphtha, and 11 is hydrogenated diesel oil.
Embodiment
The following examples will the invention will be further described.
Coking light distillate raw material Hydrobon catalyst is the Hydrobon catalyst FH-FS catalyzer of Fushun Petrochemical Research Institute's development and production, and kerosene(oil)fraction low-voltage hydrogenation catalyzer is the hydrocatalyst for saturating arylhydrocarbon FHJ of Fushun Petrochemical Research Institute's development and production.Its physico-chemical property sees Table 1,3 #The rocket engine fuel specification sees Table 2.
Embodiment 1
Coking light distillate raw material 1 with enter first reactor after hydrogen contacts, at reaction conditions be: hydrogen pressure component 4.8MPa, volume space velocity 2.5h -1, 320 ℃ of temperature of reaction, hydrogen to oil volume ratio 500:1.Second reactor at reaction conditions is: hydrogen pressure component 1.8MPa, volume space velocity 2.0h -1, 170 ℃ of temperature of reaction, hydrogen to oil volume ratio 300:1 stock oil character and test-results list in table 3.
By table 3 as seen, hydrogenation kerosene can satisfy 3 fully #The rocket engine fuel specification standards; Hydrotreated naphtha can be used as the requirement of reformer feed, also can be used as the cracking of ethylene raw material; Hydrogenated diesel oil is a fine derv fuel oil blend component.
Embodiment 2
Coking light distillate raw material 2 with enter first reactor after hydrogen contacts, at reaction conditions be: hydrogen pressure component 5.6MPa, volume space velocity 1.8h -1, 320 ℃ of temperature of reaction, hydrogen to oil volume ratio 500:1.Second reactor at reaction conditions is: hydrogen pressure component 1.7MPa, volume space velocity 1.5h -1, 190 ℃ of temperature of reaction, hydrogen to oil volume ratio 350:1.Stock oil character and test-results are listed in table 4.
By table 4 as seen, hydrogenation kerosene can satisfy 3 fully #The rocket engine fuel specification standards; Hydrotreated naphtha can be used as the requirement of reformer feed, also can be used as the cracking of ethylene raw material; Hydrogenated diesel oil is a fine derv fuel oil blend component.
Embodiment 3
Coking light distillate raw material 3 with enter first reactor after hydrogen contacts, at reaction conditions be: hydrogen pressure component 5.6MPa, volume space velocity 1.5h -1, 330 ℃ of temperature of reaction, hydrogen to oil volume ratio 550:1.Second reactor at reaction conditions is: hydrogen pressure component 1.8MPa, volume space velocity 1.2h -1, 185 ℃ of temperature of reaction, hydrogen to oil volume ratio 300:1 stock oil character and test-results list in table 5.
By table 5 as seen, hydrogenation kerosene can satisfy 3 fully #The rocket engine fuel specification standards; Hydrotreated naphtha can be used as the requirement of reformer feed, also can be used as the cracking of ethylene raw material; Hydrogenated diesel oil is a fine derv fuel oil blend component.
Comparative Examples 1
Adopt conventional non-noble metal hydrogenation catalyst for refining (two reactors all use the Hydrobon catalyst FH-98 of Fushun Petrochemical Research Institute's development and production) to use same technical process and processing condition (by embodiment 3 processing condition) that result and present method comparing result that the coking light distillate raw material carries out hydrotreatment seen Table 6.By table 6 result as seen, adopt conventional non-noble metal hydrogenation catalyst for refining gained rocket engine fuel product smoke point can not satisfy 3 #Rocket engine fuel is not less than the requirement of 25mm, the quality product that other index also obtains far below the inventive method.
The character index request of table 1 catalyzer
The catalyzer numbering FH-FS FHJ
Reactive metal MoO 3-WO 3-NiO NiO
Carrier γ-Al 2O 3 γ-Al 2O 3
Active metallic content, wt% 60.0~80.0 40.0~60.0
Physical properties
Pore volume, ml/g 0.18~0.25 ≮0.30
Specific surface area, m 2/g ≮130 80~170
Tap density, g/ml 1.20~1.40 0.90~1.20
Table 23 #The rocket engine fuel specification
Project Specification
Density (20 ℃), g/ml 0.775~0.830
Boiling range,
10% recovered temperature, ℃ Be not higher than 205
Final boiling point, ℃ Be not higher than 300
Sulphur, μ g/g Be not more than 2000
Mercaptan sulfur, μ g/g Be not more than 20
Aromatic hydrocarbons, m% (quality) Be not more than 20
Alkene, m% (quality) Be not more than 5.0
Smoke point, mm Be not less than 25
Table 3 embodiment 1 stock oil character and test-results
Oil property Raw material 1 Hydrotreated naphtha Hydrogenation kerosene Hydrogenated diesel oil
Density, g/cm 3 0.7710 0.7116 0.7953 0.8649
Boiling range (IBP~EBP), ℃ 60~331 58~140 137~247 243~33U
S,μg/g 759 <0.5 <1.0 5.6
N,μg/g 584 <0.5 <1.0 2.8
Mercaptan sulfur, μ g/g <1.0
Composition/v%
Alkene 38.2 <1.0 <0.1
Aromatic hydrocarbons 1.6
Smoke point, mm 37.0
Cetane value 64
Table 4 embodiment 2 stock oil character and test-results
Oil property Raw material 2 Hydrotreated naphtha Hydrogenation kerosene Hydrogenated diesel oil
Density, g/cm 3 0.7435 0.7048 0.7812 0.8604
Boiling range (IBP~EBP), ℃ 34~346 36~142 137~241 243~343
S,μg/g 9300 <0.5 <1.0 5.6
N,μg/g 188 <0.5 <1.0 2.8
Mercaptan sulfur, μ g/g <1.0
Composition/v%
Alkene 27.3 <1.0 <0.1
Aromatic hydrocarbons 2.7
Smoke point, mm 34.0
Cetane value 58
Table 5 embodiment 3 stock oil character and test-results
Oil property Raw material 3 Hydrotreated naphtha Hydrogenation kerosene Hydrogenated diesel oil
Density, g/cm 3 0.7511 0.7028 0.7809 0.8569
Boiling range (IBP~EBP), ℃ 54~336 58~160 157~239 243~338
S,μg/g 9300 <0.5 <1.0 5.6
N,μg/g 188 <0.5 <1.0 2.8
Mercaptan sulfur, μ g/g <1.0
Composition/v%
Alkene 33.8 <1.0 <0.1
Aromatic hydrocarbons 3.8
Smoke point, mm 31.5
Cetane value 55
Table 6 comparative example 1 and the inventive method comparative test result
Oil property Raw material 3 Conventional hydrogenation kerosene Present method hydrogenation kerosene
Density, g/cm 3 0.7421 0.7816 0.7809
Boiling range (IBP~EBP), ℃ 54~336 153~243 157~239
S,μg/g 9300 76 <1.0
N,μg/g 188 9.7 <1.0
Mercaptan sulfur, μ g/g <1.0 <1.0
Composition/v%
Aromatic hydrocarbons 24.8 3.8
Smoke point, mm 22.6 31.5

Claims (10)

1, a kind of coking light distillate hydrogenation modification method, comprise following content: the coking light distillate raw material at first contacts with the W-Mo-Ni series hydrocatalyst under the hydrofining condition with hydrogen, pass through stripping and fractionation then, fractionation obtains naphtha fraction, kerosene(oil)fraction and diesel oil distillate, wherein kerosene(oil)fraction enters a low-voltage hydrogenation reactor with new hydrogen, contact with the Ni series hydrocatalyst, product is through gas-liquid separator, liquid product is as high-quality rocket engine fuel component, and hydrogen-rich gas returns the hydrofining of coking light distillate raw material and uses.
2, in accordance with the method for claim 1, it is characterized in that coking light distillate raw material hydrofining reaction condition is: hydrogen dividing potential drop 3.4MPa~10.0MPa, temperature of reaction is 260 ℃~360 ℃, volume space velocity is 0.5h -1~3.0h -1, hydrogen to oil volume ratio is 300~800.
3, in accordance with the method for claim 1, it is characterized in that kerosene(oil)fraction low-voltage hydrogenation reaction conditions is: hydrogen dividing potential drop 0.5MPa~3.0MPa, temperature of reaction is 100 ℃~300 ℃, volume space velocity is 0.5h -1~3.0h -1, hydrogen to oil volume ratio is 100~500.
4, in accordance with the method for claim 1, it is characterized in that coking light distillate raw material hydrofining reaction condition is: the hydrogen dividing potential drop is 4.8MPa~8.0MPa, and temperature of reaction is 300 ℃~350 ℃, and volume space velocity is 1.0h -1~2.0h -1, hydrogen to oil volume ratio is 300~600.
5, in accordance with the method for claim 1, it is characterized in that kerosene(oil)fraction low-voltage hydrogenation reaction conditions is: the hydrogen dividing potential drop is 0.5MPa~2.2MPa, and temperature of reaction is 160 ℃~240 ℃, and volume space velocity is 0.8h -1~2.0h -1, hydrogen to oil volume ratio is 200~350.
6, in accordance with the method for claim 1, it is characterized in that W-Mo-Ni series hydrocatalyst reactive metal composition comprises: Tungsten oxide 99.999 35wt%~42wt%, nickel oxide 13wt%~20wt%, molybdenum oxide 12wt%~18wt% are 60wt%~80wt% in oxide compound reactive metal total content.
7, in accordance with the method for claim 1, it is characterized in that the Ni series catalysts is 40wt%~60wt% in nickel oxide content.
8,, it is characterized in that W-Mo-Ni series hydrocatalyst and Ni series catalysts contain the refractory oxide solid support material according to claim 6 or 7 described methods.
9, in accordance with the method for claim 1, it is characterized in that the isolated hydrogen-rich gas of coking light distillate raw material hydrofining reaction effluent recycles.
10, in accordance with the method for claim 1, the initial boiling point that it is characterized in that the coking light distillate raw material is 30~70 ℃, and final boiling point is 320~380 ℃.
CN2007101583695A 2007-11-15 2007-11-15 Coking light distillate hydrogenation modification method Active CN101434864B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101942335A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Gasoline and diesel oil combined hydrogenation process
CN101942334A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Production method of molecular sieve dewaxing raw material
CN102268292A (en) * 2010-06-07 2011-12-07 中国石油化工集团公司 Combined hydrogenation method
CN102268293A (en) * 2010-06-07 2011-12-07 中国石油化工集团公司 Hydrogenation combined process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172843A (en) * 1960-05-03 1965-03-09 Dssulfubization process
US3540999A (en) * 1969-01-15 1970-11-17 Universal Oil Prod Co Jet fuel kerosene and gasoline production from gas oils
CN1205312C (en) * 2002-05-15 2005-06-08 中国石油化工股份有限公司 Process for coking full fraction oil hydrogenation refining
CN1246425C (en) * 2002-08-29 2006-03-22 中国石油化工股份有限公司 Method of producing jet fuel from coking distillate

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101942335A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Gasoline and diesel oil combined hydrogenation process
CN101942334A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Production method of molecular sieve dewaxing raw material
CN101942335B (en) * 2009-07-09 2013-04-10 中国石油化工股份有限公司 Gasoline and diesel oil combined hydrogenation process
CN101942334B (en) * 2009-07-09 2013-10-09 中国石油化工股份有限公司 Production method of molecular sieve dewaxing raw material
CN102268292A (en) * 2010-06-07 2011-12-07 中国石油化工集团公司 Combined hydrogenation method
CN102268293A (en) * 2010-06-07 2011-12-07 中国石油化工集团公司 Hydrogenation combined process
CN102268293B (en) * 2010-06-07 2014-01-15 中国石油化工集团公司 Hydrogenation combined process
CN102268292B (en) * 2010-06-07 2014-02-26 中国石油化工集团公司 Combined hydrogenation method

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