CN103773474A - Gas phase-liquid phase mixed hydrogenation method - Google Patents

Gas phase-liquid phase mixed hydrogenation method Download PDF

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CN103773474A
CN103773474A CN201210408341.3A CN201210408341A CN103773474A CN 103773474 A CN103773474 A CN 103773474A CN 201210408341 A CN201210408341 A CN 201210408341A CN 103773474 A CN103773474 A CN 103773474A
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hydrogenation
diesel oil
reactor
oil
liquid phase
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CN103773474B (en
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柳伟
宋永一
刘继华
李扬
牛世坤
李士才
徐大海
丁贺
赵桂芳
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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 discloses a gas phase-liquid phase circulating mixed hydrogenation method. The gas phase-liquid phase circulating mixed hydrogenation method comprises following steps: inferior diesel oil is subjected to gas phase counter current hydrogenation reaction; obtained liquid oil is mixed with straight-run diesel oil, and an obtained mixture is subjected to saturated hydrogen dissolving, and then is delivered into a liquid phase circulating hydrogenation reactor for reaction; and then a low-sulfur diesel oil product is obtained. According to the gas phase-liquid phase circulating mixed hydrogenation method, after gas phase hydrogenation reaction, aromatic hydrocarbons of the inferior diesel oil are saturated, hydrogen consumption of further reactions is relatively low, and saturated dissolved hydrogen content is increased; at the same time, a large amount of hydrogen, which is not reacted, is dissolved in the obtained liquid oil, enough dissolved hydrogen is provided for deep desulphurization reaction in the liquid phase circulating hydrogenation reactor, two-reverse charging properties are optimized, and it is beneficial for performing of deep hydrodesulfurization reaction. The invention provides the novel method used for producing ultra-low sulphur diesel oil by taking inferior diesel oil and straight-run diesel oil as raw materials.

Description

A kind of gas phase, liquid-phase mixing hydrogenation method
Technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, a kind of by gas phase circulate hydrogenation, liquid phase circulation hydrogenation technique mixed hydrogenation technological process specifically, processing poor ignition quality fuel and straight-run diesel oil are to produce the hydrogenation method of ultra-low-sulphur diesel product.
Background technology
Along with the raising of people's environmental consciousness and the increasingly stringent of environmental regulation, produce and use fuel for cleaning vehicle more and more to become a kind of development trend.And for the cleaning of diesel oil, desulfurization and de-aromatic hydrocarbons are its keys cleaning.
At present, in diesel deep desulfurization technology, that hydrotreatment technology remains is main, be also the most effective technique means.Hydrotreatment technology is also varied, has successively occurred the Technologies such as single hop hydrogenation, single hop serial hydrogenation and two-stage hydrogenation.In addition, along with refinery is more and more stricter to the control of cost, lowly more and more be subject to the attention of refinery as the liquid phase circulation hydrogen addition technology of distinguishing feature to invest, so-called liquid phase circulation hydrogen addition technology is than conventional gas-phase circulation hydrogenation technique, liquid phase circulation hydrogenation technique reactive moieties does not arrange hydrogen gas circulating system, relying on a large amount of circulation times of liquid-phase product to carry into the dissolved hydrogen of reactive system provides fresh feed to carry out the needed hydrogen of hydrogenation reaction, owing to having cancelled circulating hydrogen compressor, plant investment and process cost are reduced.But in saving investment, provide reaction because liquid phase circulation hydrogen addition technology relies on the hydrogen being dissolved in reaction feed, therefore, the hydrogen amount that needs that can the hydrogen dissolving in charging meet chemical reaction affects huge on the result of use of liquid phase circulation hydrogenation technique.At present, conventionally adopting liquid phase circulation hydrogenator effluent part circulation back-mixing hydrogen tank in mixed hydrogen tank, to dissolve hydrogen with fresh feed provides and reacts required hydrogen, in the unconventional energy resource such as the diesel oil distillate of the secondary processing diesel oil such as catalytic diesel oil, coker gas oil and shale oil, coal tar owing to containing the foreign matter contents such as higher sulphur, nitrogen and aromatic hydrocarbons, reaction hydrogen-consuming volume is very high, therefore, the hydrogen dissolving in oil product is difficult to meet reaction needed, in traditional liquid phase circulation hydrogenation process, be difficult to the poor ignition quality fuel of high hydrogen consumption to process.
U.S. Pat 6123835 discloses a kind of liquid phase circulation hydrogenation method, and in the method, stock oil is dissolved with the hydrogen of high density by mixing/flash distillation hydrogen in mixed hydrogen tank, and then carries out liquid-phase hydrogenatin processing.Effluent after liquid-phase hydrogenatin is divided into two portions, before part direct circulation back-mixing hydrogen tank, another part is introduced into high-pressure separator and isolates unnecessary waste gas, and gained liquid continues to enter flashing tower and isolates waste gas, and the liquid after flash distillation obtains liquid product through air lift again.But for the poor ignition quality fuel hydrogenation of high hydrogen consumption, liquid-phase hydrogenatin Technology is because the molten hydrogen amount of reaction oil is limited, and being difficult to meet catalytic diesel oil reacts required hydrogen on the one hand, and reaction effect is poor; The sulphur content that raw material is higher has on the other hand caused liquid phase circulation to add the hydrogen sulfide of accumulation high density in hydrogen partial turning oil, has suppressed the carrying out that deep desulfuration reacts, and reaction effect is poor.
Summary of the invention
The deficiency that is subject to the molten hydrogen amount restriction of reaction feed for existing liquid phase circulation hydrogenation technique, the invention provides a kind of liquid phase circulation hydrogenation, gas phase circulation hydrogenation mixed hydrogenation technological process.This process unit investment is little, and Energy Intensity Reduction, can be for the production of ultra-low-sulphur diesel.
A kind of gas phase hydrogenation of the present invention, liquid-phase hydrogenatin mixed hydrogenation technological process comprise following content:
(1) hydrogen enters reactor from reactor bottom, and poor ignition quality fuel raw material enters reactor from reactor head, carries out hydrofining reaction under hydrofining condition; Described hydrogenator is gas, liquid countercurrent hydrogenation reactor, and reactor comprises at least two hydrogenation catalyst beds;
(2) the gas phase effluent that step (1) obtains leaves reactor from reactor head, and gained liquid phase generates oil and leaves reactor from reactor bottom;
(3) after step (2) gained liquid phase generation oil mixes with straight-run diesel oil, enter mixed hydrogen tank and mix after hydrogen, enter liquid phase hydrogenation reactor and carry out hydrofining reaction;
(4) step (3) obtains hydrogenation reaction effluent part bleeder after reducing valve decompression, obtains ultra-low-sulphur diesel, and another part loops back the bottom bed of step (1) gas phase hydrogenation reaction device.
According to method of hydrotreating of the present invention, the hydrogenator described in step (1) is gas-liquid counter current hydrogenator, and hydrogen enters reactor by reactor bottom, and poor ignition quality fuel stock oil autoreactor top enters reactor.In Unionfining technological process of the present invention, the described poor ignition quality fuel raw material of step (1) is selected from one or more in catalytic cracking diesel oil, coker gas oil and coal tar diesel oil or shale diesel oil conventionally.Straight-run diesel oil described in step (3) is conventional straight-run diesel oil raw material in the art, and it is done and is generally no more than 385 ℃, is generally 330 ℃~370 ℃.
Gas phase circulation hydrogenator described in step (1) comprises at least two beds, is generally 2 ~ 4 beds, preferably two beds.Described " lower catalyst bed layer " refers to any one in other beds except first bed or several beds along liquid stream direction.
The gas phase effluent that wherein step (2) obtains can be isolated after carburet hydrogen through cold high score, through further purifying, isolates after hydrogen, returns to step (1) and recycle after compressor compression.
According to mixed hydrogenation technological process of the present invention, in described step (3), the liquid phase that step (2) obtains generates oil mixes with conventional straight-run diesel oil and mixes after hydrogen, enters two anti-liquid phase hydrogenation reactors and carries out hydrogenation reaction.Wherein step (2) gained liquid phase generation oil is 1: 5~5: 1 with the mass ratio of straight-run diesel oil, preferably 1: 3~3: 1.
In processing method of the present invention, an anti-gas phase circulation hydrogenator generally reacts under the temperature of reaction, low-speed that relax and higher pressure, and two anti-liquid phase circulation hydrogenators operate under high temperature, high-speed and low pressure.High temperature, low temperature described herein, high-speed, low-speed and high pressure are relative with low pressure.
In gas phase hydrogenation of the present invention, liquid-phase hydrogenatin mixed hydrogenation technological process, the operational condition of the gas-liquid counter current hydrogenator in step (1) is as follows: 280 ℃~380 ℃ of average reaction temperature, preferably 300 ℃~340 ℃; Reaction pressure 4.0 MPa~15.0 MPa, preferably 6.0 MPa~10.0MPa; Volume space velocity when liquid (reactor inlet) 0.2h -1~3h -1, preferably 0.5h -1~1.5h -1, hydrogen to oil volume ratio 80~1000, preferably 100~300.
The operational condition of the liquid phase circulation hydrogenator in step (3) is as follows: 320 ℃~400 ℃ of average reaction temperature, preferably 340 ℃~380 ℃; Reaction pressure 3.0 MPa~10.0 MPa, preferably 4.0 MPa~8.0MPa; Volume space velocity 2.0h when liquid -1~8.0h -1, preferably 3.0h -1~6.0h -1; Liquid phase circulation is 1: 5~5: 1 than (being liquid-phase hydrogenatin treated oil turning oil/straight-run diesel oil mass ratio), preferential 1: 2~3: 1.
According to gas phase hydrogenation of the present invention, liquid-phase hydrogenatin mixed hydrogenation technological process, the catalyzer loading in gas phase hydrogenation reaction device and liquid phase hydrogenation reactor can be identical catalyzer, can be also different catalyzer.In the present invention, preferably load different catalyzer.In the inventive method, in one anti-gas phase circulation hydrogenator, conventionally load the stronger catalyzer of hydrogenation ability, as the preferred W-Ni type of Hydrobon catalyst or the Mo-Ni type hydrogenation catalyst of an anti-filling, be catalyzer take W-Ni or Mo-Ni as active metal component, this catalyzer has stronger hydrogenation saturability.Hydrogenation reaction in two anti-liquid phase hydrogenation reactors is take hydrodesulfurization reaction as main, and chemical hydrogen consumption amount is lower.The two anti-interior preferred Mo-Co type of Hydrobon catalyst catalyzer, such catalyzer has higher direct desulfurization activity under high-speed.
In processing method of the present invention, the Hydrobon catalyst using in step (1) and step (3) can be selected commercial goods catalyzer as required, also can be by the conventional knowledge preparation in this area.Wherein step (1) gas phase hydrogenation reaction device inner catalyst is W-Ni or Mo-Ni type catalyzer, catalyst hydrogenation saturability is stronger, step (3) liquid phase hydrogenation reactor inner catalyst is Mo-Co type catalyzer, and catalyzer has higher direct desulfurization activity under high-speed.Described Mo-Co type catalyzer is take Mo, Co as active metal component, take aluminum oxide or silicon-containing alumina as carrier; Described Mo-Ni or W-Ni type catalyzer be take Mo, Ni or W, Ni as active metal component, take aluminum oxide or silicon-containing alumina as carrier.
The composition of described Mo-Co type catalyzer is generally, and take the weight of catalyzer as benchmark, molybdenum is take oxide compound content as 8wt%~28wt%, and cobalt is take oxide compound content as 2wt%~15wt%.The composition of described Mo-Ni type or W-Ni type catalyzer is generally, and take the weight of catalyzer as benchmark, molybdenum or tungsten are take oxide compound content as 8wt%~28wt%, and nickel is take oxide compound content as 2wt%~15wt%.The specific surface area of catalyzer is 100~650m 2/ g, pore volume is generally 0.15~0.8mL/g.
Compared with prior art, gas phase hydrogenation of the present invention, liquid-phase hydrogenatin mixed hydrogenation technological process have following characteristics:
The present invention has taken into full account the features of gas phase circulation hydrogenation technique and liquid phase circulation hydrogenation technique, reasonably by two kinds of technique combinations effectively: first poor ignition quality fuel raw material enters gas phase circulation hydrogenator and carry out hydrofining reaction, and dose W-Ni or the Mo-Ni type catalyzer that hydrogen saturability is stronger this reactor is in-built, and coordinate the operational condition of high pressure, low-speed, suitable temperature of reaction to reach the object of degree of depth deoxidation, denitrogenation and Tuo Fang; Meanwhile, part contains sterically hindered sulfide and after aromatic saturation, has eliminated space steric effect, is conducive to it and further carries out deep desulfuration two in anti-.
Gas phase hydrogenation generates oil to be mixed with straight-run diesel oil, enters to mix hydrogen tank and mix to enter after hydrogen and in liquid phase hydrogenation reactor, carry out deep desulfuration reaction.After an anti-gas phase circulation hydrogenator reaction, the aromatic hydrocarbons in poor ignition quality fuel raw material is by fully saturated, and saturated molten hydrogen amount also increases; Simultaneously, one anti-liquid phase generates oil and is dissolved with a large amount of unreacting hydrogens, can be the deep desulfuration reaction hydrogen supply in liquid phase hydrogenation reactor on the one hand, and the anti-diesel oil that flows out has very low foreign matter content on the other hand, optimize two anti-reaction feed character, be also beneficial to the carrying out of two anti-deep desulfuration reactions; Can also reduce the liquid phase circulation ratio of liquid phase hydrogenation reactor simultaneously.
Two anti-chargings are treated oil and the straight-run diesel oil after an anti-hydrogenation, and reaction feed hydrogen-consuming volume is lower, and this reacts feature that should not be excessive because of the molten hydrogen amount of charging limited response hydrogen consumption and adapts with liquid-phase hydrogenatin, thereby are conducive to the effective use of liquid phase hydrogenation reactor.The one anti-countercurrent hydrogenation reactor that adopts, the hydrogen sulfide that reaction process generates is taken away by hydrogen, reduce by the anti-oil that generates and entered the hydrogen sulfide accumulation causing after Liquid-phase reactor, thereby slow down the restraining effect of hydrogen sulfide to deep desulfuration reaction in liquid phase hydrogenation reactor, be conducive to equally the carrying out of deep desulfuration reaction.And two anti-turning oils loop back an anti-bottom bed, also reduce an anti-reaction temperature rising, an anti-hydrogenation reaction is carried out under the state that approaches isothermal, thereby be conducive to the effective use of an anticatalyzer, thereby extended the running period of device.
Accompanying drawing explanation
Fig. 1 is the principle process schematic diagram of diesel hydrogenation process of the present invention.
Embodiment
Below in conjunction with Fig. 1, diesel hydrogenation method of the present invention is described in detail.
As shown in Figure 1, hydrogen and poor-quality diesel-oil by cut fraction stock oil are respectively via pipeline 1 and through pipeline 2, enter countercurrent hydrogenation reactor 3 with the gas-liquid counter current way of contact and carry out hydrofining reaction, countercurrent hydrogenation reactor 3 generally comprises at least two Hydrobon catalyst beds.Hydrogenator 3 gained gaseous effluents leave reactor through pipeline 5, after further processing, can use as recycle hydrogen, gained liquid generates oil through pipeline 4, after mixing with the straight-run diesel oil of introducing through pipeline 6, enter mixed hydrogen tank 7 and mix molten hydrogen together with the hydrogen of introducing through pipeline 8, mixing oil after saturated molten hydrogen can be discharged after excess hydrogen through pipeline 9, enter liquid phase hydrogenation reactor 10 and carry out hydrofining reaction, a part of reaction effluent can be used as diesel product through pipeline 12 bleeders after reducing valve decompression; Another part reaction effluent returns to the bottom bed of hydrogenator 3 through pipeline 11.
Below by specific embodiment, technical scheme of the present invention and effect are described.
Embodiment 1~4
Embodiment 1~4 adopts the flow process shown in Fig. 1 of the present invention.In following examples, use the composition of catalyzer and character in table 1.One anti-gas phase hydrogenation reaction is raw materials used for table 2 Raw is according to urging bavin: burnt bavin=50: the mixing raw material oil of 50 mass ratios, two anti-liquid-phase hydrogenatin reaction straight-run diesel oil character are as shown in table 3, wherein the oily mass ratio of straight-run diesel oil and an anti-generation is 1: 1, and embodiment 1~4 processing condition used are listed in table 4.The evaluation result of embodiment 1~4 is in table 5.
Composition and the main character of table 1 embodiment used catalyst.
Project One anti-finishing agent Two anti-finishing agents
Chemical constitution, wt% ? ?
MoO 3 20.3 18.2
NiO 6.2
CoO 6.5
Carrier Silicon-containing alumina Silicon-containing alumina
Table 2 stock oil character.
Project Catalytic diesel oil Coker gas oil Mixing raw material oil
Density (20 ℃), g/cm 3 0.9308 0.8502 0.8905
Boiling range, ℃ 190~360 185~370 185~370
Sulphur content, μ g/g 12000 9000 10500
Nitrogen content, μ g/g 700 1000 850
Aromaticity content, wt% 70 30 50
The anti-straight-run diesel oil charging of table 3 two.
Project Straight-run diesel oil
Density (20 ℃), g/cm 3 0.8308
Boiling range, ℃ 170~340
Sulphur content, μ g/g 3000
Nitrogen content, μ g/g 50
Table 4 embodiment operational condition.
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
One anti-gas phase hydrogenation reaction reactor ? ? ? ?
Average reaction temperature, ℃ 300 320 320 300
Reaction pressure, MPa 6.0 6.0 8.0 8.0
Volume space velocity, h -1 0.5 1.0 0.8 1.2
Hydrogen to oil volume ratio, v/v 200 200 200 200
Two anti-liquid phase hydrogenation reactors ? ? ? ?
Average reaction temperature, ℃ 350 350 360 360
Reaction pressure, MPa 6.0 6.0 4.0 4.0
Cumulative volume air speed, h -1 4.0 4.0 6.0 6.0
Liquid phase circulation ratio 1:2 1:2 1:1 1:1
Table 5 embodiment 1~4 evaluation result
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Sulphur content, μ g/g 8 10 3 5
Nitrogen content, μ g/g <1 <1 <1 <1

Claims (11)

1. gas phase hydrogenation, a liquid-phase hydrogenatin mixed hydrogenation technological process, comprises following content:
(1) hydrogen enters reactor from reactor bottom, and poor ignition quality fuel raw material enters reactor from reactor head, carries out hydrofining reaction under hydrofining condition; Described hydrogenator is gas, liquid countercurrent hydrogenation reactor, and reactor comprises at least two hydrogenation catalyst beds;
(2) the gas phase effluent that step (1) obtains leaves reactor from reactor head, and gained liquid phase generates oil and leaves reactor from reactor bottom;
(3) after step (2) gained liquid phase generation oil mixes with straight-run diesel oil, enter mixed hydrogen tank and mix after hydrogen, enter liquid phase hydrogenation reactor and carry out hydrofining reaction;
(4) step (3) obtains hydrogenation reaction effluent part bleeder after reducing valve decompression, obtains ultra-low-sulphur diesel, and another part loops back the bottom bed of step (1) gas phase hydrogenation reaction device.
2. in accordance with the method for claim 1, it is characterized in that, the described poor ignition quality fuel raw material of step (1) is selected from one or more in catalytic cracking diesel oil, coker gas oil, coal tar diesel oil or shale diesel oil.
3. in accordance with the method for claim 1, it is characterized in that, doing of the straight-run diesel oil described in step (3) is no more than 385 ℃.
4. in accordance with the method for claim 1, it is characterized in that, doing of the straight-run diesel oil described in step (3) is 330 ℃~370 ℃.
5. in accordance with the method for claim 1, it is characterized in that, in step (3), it is 1: 5~5: 1 with the mass ratio of straight-run diesel oil that step (2) gained liquid phase generates oil.
6. in accordance with the method for claim 5, it is characterized in that, it is 1: 3~3: 1 with the mass ratio of straight-run diesel oil that step (2) gained liquid phase generates oil.
7. in accordance with the method for claim 1, the described hydrofining condition of step (1) is, 280 ℃~380 ℃ of average reaction temperature, reaction pressure 4.0 MPa~15.0 MPa, volume space velocity 0.2h when liquid -1~3h -1, hydrogen to oil volume ratio 80~1000.
8. in accordance with the method for claim 1, it is characterized in that, in step (3), the operational condition of liquid phase circulation hydrogenator is, 320 ℃~400 ℃ of average reaction temperature, reaction pressure 3.0 MPa~10.0 MPa, volume space velocity 2.0h when liquid -1~8.0h -1.
9. in accordance with the method for claim 1, it is characterized in that, in step (4), the liquid-phase hydrogenatin effluent of circulation and the mass ratio of straight-run diesel oil are 1: 5~5: 1.
10. in accordance with the method for claim 1, it is characterized in that, in step (1), in reactor, load W-Ni type or Mo-Ni type hydrogenation catalyst; In the liquid phase hydrogenation reactor of step (3), load Mo-Co type hydrogenation catalyst.
11. in accordance with the method for claim 10, it is characterized in that, the consisting of of described Mo-Ni type or W-Ni type catalyzer, take the weight of catalyzer as benchmark, molybdenum or tungsten are take oxide compound content as 8wt%~28wt%, and nickel is take oxide compound content as 2wt%~15wt%; Consisting of of described Mo-Co type catalyzer, take the weight of catalyzer as benchmark, molybdenum is take oxide compound content as 8wt%~28wt%, and cobalt is take oxide compound content as 2wt%~15wt%.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437778A (en) * 2020-10-19 2022-05-06 中国石油化工股份有限公司 Hydrocracking process for Fischer-Tropsch synthetic oil
CN115785992A (en) * 2021-09-10 2023-03-14 中国石油化工股份有限公司 Startup method of inferior diesel hydrogenation process

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1488715A (en) * 2002-10-10 2004-04-14 中国石油化工股份有限公司 Diesel oil deep-hydro-desulfurizing-dearomatizing method
US20040238409A1 (en) * 2003-05-30 2004-12-02 Harjeet Virdi Hydrogenation of middle distillate using a counter-current reactor
CN101376837A (en) * 2007-08-27 2009-03-04 中国石油化工股份有限公司 Diesel deep desulfurization and dearomatization hydrotreating process
CN101942330A (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 Method for deep hydrogenation, sulfur removal and aromatics removal of diesel oil
CN101942327A (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 Hydrotreatment combination technology for producing ultra low sulfur diesel
CN102041063A (en) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 Method for carrying out deep hydrogenation and desulfurization on diesel
CN102041069A (en) * 2009-10-16 2011-05-04 中国石油化工股份有限公司 Gas-liquid countercurrent hydrogenation method for desulfurization, denitrification and aromatic hydrocarbon of diesel

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1488715A (en) * 2002-10-10 2004-04-14 中国石油化工股份有限公司 Diesel oil deep-hydro-desulfurizing-dearomatizing method
US20040238409A1 (en) * 2003-05-30 2004-12-02 Harjeet Virdi Hydrogenation of middle distillate using a counter-current reactor
CN101376837A (en) * 2007-08-27 2009-03-04 中国石油化工股份有限公司 Diesel deep desulfurization and dearomatization hydrotreating process
CN101942330A (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 Method for deep hydrogenation, sulfur removal and aromatics removal of diesel oil
CN101942327A (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 Hydrotreatment combination technology for producing ultra low sulfur diesel
CN102041069A (en) * 2009-10-16 2011-05-04 中国石油化工股份有限公司 Gas-liquid countercurrent hydrogenation method for desulfurization, denitrification and aromatic hydrocarbon of diesel
CN102041063A (en) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 Method for carrying out deep hydrogenation and desulfurization on diesel

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437778A (en) * 2020-10-19 2022-05-06 中国石油化工股份有限公司 Hydrocracking process for Fischer-Tropsch synthetic oil
CN114437778B (en) * 2020-10-19 2023-07-28 中国石油化工股份有限公司 Fischer-Tropsch synthetic oil hydrocracking process
CN115785992A (en) * 2021-09-10 2023-03-14 中国石油化工股份有限公司 Startup method of inferior diesel hydrogenation process

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