CN103773458A - Gas phase-liquid phase mixed hydrogenation method - Google Patents
Gas phase-liquid phase mixed hydrogenation method Download PDFInfo
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- CN103773458A CN103773458A CN201210408350.2A CN201210408350A CN103773458A CN 103773458 A CN103773458 A CN 103773458A CN 201210408350 A CN201210408350 A CN 201210408350A CN 103773458 A CN103773458 A CN 103773458A
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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 and hydrogen are 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; a liquid hydrogenation effluent is divided into two parts, one part is discharged so as to obtain a low-sulfur diesel oil product, and the other part is circulated to a hydrogen mixing tank. 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; and 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, 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
Technical field
The present invention relates to a kind of hydrocarbon hydroprocessing technique, specifically a kind of gas phase circulation hydrogenation and liquid phase circulation hydrogenation process integration technology.
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
Be subject to the deficiency of the molten hydrogen amount restriction of reaction feed for existing liquid phase circulation hydrogenation technique, the invention provides a kind of gas phase circulation and liquid phase circulation 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 of the present invention and liquid-phase mixing hydrogenation method comprise following content:
(1) first poor ignition quality fuel raw material enters an anti-gas phase circulation hydrogenator and carries out hydrofining reaction; Described gas phase hydrogenation reaction device is gas-liquid counter current hydrogenator, and poor ignition quality fuel raw material enters reactor from reactor top, and hydrogen enters reactor from reactor lower part;
(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) step (2) gained liquid generation oil enters mixed hydrogen tank and mixes hydrogen after mixing with straight-run diesel oil, and the mixing oil after saturated molten hydrogen enters liquid phase hydrogenation reactor and carries out hydrofining reaction; Step (2) gained gaseous effluent can enter circulating hydrogen compressor entrance and recycle after further purifying treatment;
(4) the hydrogenation reaction effluent part that step (3) obtains is bleeder after reducing valve decompression, obtains ultra-low-sulphur diesel; Another part circulation back-mixing hydrogen tank mixes hydrogen.
In Unionfining technological process of the present invention, the described poor ignition quality fuel raw material of step (1) generally includes one or more in catalytic cracking diesel oil, coker gas oil, coal tar diesel oil and shale diesel oil.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 ℃.In step (3), described step (2) gained liquid generates oil and is generally 1:5～5:1 with the ratio of straight-run diesel oil, preferably 1:3～3:1.
One 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.
According to gas phase hydrogenation of the present invention and liquid-phase hydrogenatin Unionfining technological process, the catalyzer loading in gas phase hydrogenation reaction device and liquid phase hydrogenation reactor can be identical catalyzer, also can load different catalyzer.In the inventive method, the preferred stronger catalyzer of filling hydrogenation ability in an anti-gas phase circulation hydrogenator, can select take W-Ni or Mo-Ni as active metal as an anti-Hydrobon catalyst, and this catalyzer has stronger hydrogenation saturability.The preferred Mo-Co type of two anticatalyzers Hydrobon catalyst, two anti-interior chemical reactions are take hydrodesulfurization reaction as main, and chemical hydrogen consumption amount is lower.
Gas phase hydrogenation of the present invention and liquid-phase hydrogenatin Unionfining 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 0.2h when liquid
-1～3h
-1, preferably 0.5h
-1～1.5h
-1, hydrogen to oil volume ratio 80～800, 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.
In processing method of the present invention, the Hydrobon catalyst using in step (1) and step (3) can use commercially available prod as required, also can be by the conventional knowledge preparation in this area.Wherein step (1) gas phase hydrogenation reaction device inner catalyst is preferably W-Ni type or Mo-Ni type catalyzer, and catalyst hydrogenation saturability is stronger.The catalyzer wherein using in step (3) liquid phase hydrogenation reactor is preferably Mo-Co type catalyzer, and this catalyzer has higher direct desulfurization activity under high-speed.Wherein said Mo-Co type catalyzer is take Mo, Co metal as active ingredient, take aluminum oxide or silicon-containing alumina as carrier; Described Mo-Ni or W-Ni type catalyzer be take Mo, Ni or W, Ni metal as active ingredient, take aluminum oxide or silicon-containing alumina as carrier.Consisting of of described Mo-Co type catalyzer, Mo-Ni or W-Ni type catalyzer: take the weight of catalyzer as benchmark, tungsten or molybdenum are take oxide compound content as 8wt%～28wt%, and cobalt or nickel are take oxide compound content as 2wt%～15wt%; The specific surface area of catalyzer is generally 100～650m
2/ g, pore volume is generally 0.15～0.8mL/g.
Compared with prior art, gas phase hydrogenation of the present invention and liquid-phase hydrogenatin Unionfining technological process have following characteristics:
The present invention fully takes into account the features of gas phase circulation hydrogenation technique and liquid phase circulation hydrogenation technique, reasonably by two kinds of technique combinations effectively: first the inferior feedstock oils such as coker gas oil, catalytic diesel oil, shale diesel oil, coal tar diesel oil distillate enter gas phase circulation hydrogenator and carry out hydrofining reaction, dose W-Ni or the Mo-Ni type catalyzer that hydrogen saturability is stronger this reactor is in-built, and coordinate suitable operational condition to reach the objects such as deep hydrogenation denitrogenation, Tuo Fang and deoxidation.Meanwhile, part contains sterically hindered sulfide has eliminated space steric effect after aromatic saturation, is conducive to it and in two anti-liquid phase hydrogenation reactors, further carries out deep desulfuration.Gas-liquid counter current hydrogenation gained generates oil and straight-run diesel oil and is mixed into enter after hydrogen tank mixes and in liquid phase hydrogenation reactor, carries out deep desulfuration reaction.Due to after an anti-gas phase circulation hydrogenator reaction, the aromatic hydrocarbons in poor-quality diesel-oil by cut fraction is by fully saturated, and its hydrogen-consuming volume further reacting is very low, and saturated molten hydrogen amount also increases.Simultaneously, in one anti-reaction effluent, dissolve a large amount of unreacting hydrogens, can be deep desulfuration reaction hydrogen supply in liquid phase hydrogenation reactor on the one hand, after refining, the foreign matter content in poor ignition quality fuel significantly reduces on the other hand, also optimize two anti-reaction feed character, be beneficial to the carrying out of two anti-deep desulfuration reactions.Two anti-chargings are the mixing oil of treated oil, straight-run diesel oil and turning oil after an anti-hydrogenation, reaction feed hydrogen-consuming volume is low, utilize material dissolution hydrogen to react with liquid phase circulation hydrogenation reaction, and hydrogen meltage limited response hydrogen consumption should not be excessive feature adapt, be conducive to the effective use of liquid phase hydrogenation reactor.In addition, the hydrogen sulfide that one anti-gas-liquid counter current hydrogenation process generates is taken away by the hydrogen at upper reaches, 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.In liquid phase circulation hydrogenator, the high hydrodesulfurization activity catalyzer of filling Mo-Co type carries out deep desulfuration reaction, thereby finally obtains ultra-low-sulphur diesel under the reaction conditions of high-speed and high temperature.
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 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 turning oil of the straight-run diesel oil of introducing through pipeline 6 and pipeline 11, 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, part reaction effluent can be used as diesel product through pipeline 12 bleeders after reducing valve decompression, another part reaction effluent returns to mixed hydrogen tank 7 through pipeline 11.
Below by specific embodiment, technical scheme of the present invention and effect are described.
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 2 | Embodiment 3 | Embodiment 4 |
| One is anti- | ? | ? | ? | ? |
| Temperature of reaction, ℃ | 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 | 200 | 200 | 300 | 300 |
| Two is anti- | ? | ? | ? | ? |
| Temperature of reaction, ℃ | 360 | 360 | 370 | 370 |
| Reaction pressure, MPa | 6.0 | 6.0 | 4.0 | 4.0 |
| Volume space velocity, 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 2 | Embodiment 3 | Embodiment 4 |
| Sulphur content, μ g/g | 9 | 11 | 5 | 7 |
| Nitrogen content, μ g/g | <1 | <1 | <1 | <1 |
Claims (10)
1. gas phase and a liquid-phase mixing hydrogenation method, comprises following content:
(1) first poor ignition quality fuel raw material enters an anti-gas phase circulation hydrogenator and carries out hydrofining reaction; Described gas phase hydrogenation reaction device is gas-liquid counter current hydrogenator;
(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) step (2) gained liquid generation oil enters mixed hydrogen tank and mixes hydrogen after mixing with straight-run diesel oil, and the mixing oil after saturated molten hydrogen enters liquid phase hydrogenation reactor and carries out hydrofining reaction;
(4) the hydrogenation reaction effluent part that step (3) obtains is bleeder after reducing valve decompression, obtains ultra-low-sulphur diesel; Another part circulation back-mixing hydrogen tank mixes hydrogen.
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) comprises one or more in catalytic cracking diesel oil, coker gas oil, coal tar diesel oil distillate 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 (1), the operational condition of gas-liquid counter current hydrogenator is as follows: 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 80～800.
6. 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 as follows: 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, liquid phase circulation is than being 1:5～5:1.
7. in accordance with the method for claim 1, it is characterized in that, in step (3), it is 1:5～5:1 with the ratio of straight-run diesel oil that step (2) gained liquid generates oil.
8. in accordance with the method for claim 1, it is characterized in that, the catalyzer in step (1) gas phase circulation hydrogenator is W-Ni type or Mo-Ni type catalyzer, and the catalyzer using in step (3) liquid phase hydrogenation reactor is Mo-Co type catalyzer.
9. in accordance with the method for claim 8, it is characterized in that the consisting of of described Mo-Ni 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%.
10. in accordance with the method for claim 8, it is characterized in that the 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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252198A (en) * | 1989-05-10 | 1993-10-12 | Davy Mckee (London) Ltd. | Multi-step hydrodesulphurisation process |
| 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 |
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2012
- 2012-10-24 CN CN201210408350.2A patent/CN103773458B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252198A (en) * | 1989-05-10 | 1993-10-12 | Davy Mckee (London) Ltd. | Multi-step hydrodesulphurisation process |
| 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 |
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