CN102443429A - Hydro-processing method for producing ultra-low sulfur diesel - Google Patents
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Abstract
A hydro-processing method for producing ultra-low sulfur diesel comprises the following steps: completely dissolving the hydrogen I in diesel fraction raw oil to enter into a first hydro-processing reaction zone to be contacted with hydro-processing catalyst under pure liquid phase; reacting under the temperature of 340 to 400 DEG C; mixing the effluent of the first hydro-processing reactor with the hydrogen II to enter into a second hydro-processing reaction zone to be contacted with the hydro-processing catalyst under the state of pure liquid phase or low hydrogen-oil ratio; reacting under the reaction temperature of 240-320 DEG C, and cooling and separating the effluent of the second hydro-processing reaction zone to obtain diesel product. The method of the invention can be used for translating the diesel fraction with high sulfur content into ultra-low sulfur diesel product with good color, wherein the sulfur content can meet the Euro IV and Euro V discharge standard requirement and simultaneously, the chromaticity is less than 0.5.
Description
Technical field
The invention belongs to a kind of method at the following refining hydrocarbon ils of the situation that has hydrogen, more particularly, is a kind of method of hydrotreating of production super low sulfur clean diesel.
Background technology
Along with improving constantly of environmental protection requirement, the specification requirement of people's vehicle fuel is also increasingly high.In the worldwide up-to-date fuel specification, the diesel oil index has been made strict control.Wherein mainly the diesel oil sulphur content has been had than more strict in the past requirement.For example; Europe from the Europe III emission standard of enforcement in 2000 regulation derv fuel oil sulphur content less than 350 μ g/g; And sulphur content requires to be reduced to below the 50 μ g/g in the Europe IV emission standard that came into effect in 2005; In the Europe V standard that came into effect in 2009, sulphur content further is reduced to below the 10 μ g/g.The petrol and diesel oil product index of China has followed European fuel standard basically.Come into effect the sulphur content standard of Europe III emission standard in cities such as Beijing, Shanghai, come into effect the product index that is equivalent to Europe IV emission standard in 2008, will carry out the diesel oil index of Euro V emissions very soon in 2005.This shows how producing clean diesel is the significant problem that each enterprise of great oil refining is faced.
All kinds of sulfide are along with the difference of molecular size, molecular structure, substituent quantity and substituting group position in diesel oil distillate, and its hydrodesulfurization activity difference is very big.The reactive behavior of mercaptan, disulphide and thiophene far above dibenzothiophene class sulfide, under the demulcent hydrogenation conditions, just can remove; And substituent dibenzothiophene class sulfide is arranged on the ortho position of sulphur atom, and owing to have space steric effect, its hydrodesulfurization activity is minimum, the speed of its hydrogenating desulfurization is also very low under harsh reaction conditions.But, just must the dibenzothiophene class sulfide of these difficult multi-substituents that react be removed if satisfy the requirement of ultra-low-sulphur diesel.
With existing technological production super low sulfur clean diesel (sulphur content is less than 50 μ g/g), must under original complete processing, improve the severity of operation.Usually the measure of taking comprises the raising temperature of reaction, improves the reactive hydrogen dividing potential drop and reduces air speed etc.But the raising temperature of reaction not only has a strong impact on catalyzer work-ing life, the device cycle of operation is shortened, and can produce a large amount of split products, bring yield to descend, and product colour deepens and the colourity problem of unstable.And high hydrogen dividing potential drop has proposed more requirement to equipment, causes production cost to rise significantly; Reduce volume space velocity and mean the reduction unit capacity.Therefore, concerning prior art, improve severity and can bring problems such as running cost improves, the operational cycle shortens, product yield is low.On the other hand, develop the continuous increase with the high-sulfur crude oil proportion to the heaviness direction, make the intractability of diesel oil distillate further increase, be difficult to reach the quality product requirement of clean diesel with conventional unifining technology along with processing raw material.
US4776945 discloses a kind of method that adopts two kinds of synergetic forms of catalyzer to reach the raising hydrogenation degree of depth.The strong NiMo catalyzer of hydrogenation activity (account for total amount 15～85%) is adopted on the upper strata, takes off 25% sulphur; The deep desulfuration that lower floor continues with the CoMoP catalyzer of desulfurization effect.Finally can obtain the diesel product of sulphur content less than 500 μ g/g.This method adopts two conversion zones, and after raw oil carried out preparatory unifining through first section, the hydrodesulfurizationreaction reaction zone that gets into second section was carried out deep desulfuration.This method can be produced doctor negative clean diesel, but because the sweetening effectiveness of first reaction zone is not obvious, and volume space velocity is lower, product can not reach the specification of ultra-low-sulphur diesel simultaneously.
US5403470 discloses a kind of method of improving the diesel product color; This method adopts two reactor drums; One is counter-current reactor instead, and at the index request that reaches product than the sulphur that removes raw material under the exacting terms and nitrogen, wherein sulphur content is less than 500ppm; The two anti-concurrent flow reactor that adopt are relatively removing the chromoplastid compound under the demulcent condition.This method can obtain the low-sulfur diesel-oil of good colors.Because existing counter-current reactor has co-current reactor again in this method, so flow process and complicated operation, and the sulphur content of diesel product can not satisfy the requirement of Europe IV, Euro V emissions.
US5114562 discloses a kind of through using two kinds of catalyzer to be superimposed upon the hydrofinishing process of same reactive system.Two sections two kinds of catalyzer of this method (wherein two sections is noble metal catalyst).Raw oil comprises straight-run diesel oil, catalytic cracking diesel oil, hydrogen cracking diesel oil, thermally splitting diesel oil and composition thereof.Adopting this method can be 0.1～2% diesel raw material with sulphur content, and the production sulphur content is less than＜0.05.Aromaticity content reduces significantly.
US6123835A discloses a kind of method that adopts two-stage method to produce low-sulfur, low aromatics diesel.This method in reactor drum with the hydroprocessing process of hydrogen treat raw material.Biliquid phase hydroprocessing process may further comprise the steps; Raw material and mixing diluents; Before reactor drum, the mixture of thinner/raw material is carried out saturatedly with hydrogen, form the biliquid phase mixture of a kind of raw material/thinner/hydrogen, before reactor drum, other gas delivery in this biliquid phase mixture is come out then; Then the mixture of this raw material/thinner/hydrogen is contacted with catalyzer in the reactor drum and react, remove sulphur, nitrogen, oxygen, metal and other impurity.
Summary of the invention
The object of the invention provides a kind of hydroprocessing process of producing ultra-low-sulphur diesel, and technical problem to be solved is that operation control catalyst bed temperature rise effectively exists the bed local temperature too high under the high temperature when producing ultra-low-sulphur diesel.The problem that the device operational cycle is short.
Method provided by the invention is: hydrogen I all is dissolved into and gets into the first hydrotreatment reaction zone in the diesel oil distillate raw oil; Under the condition of pure liquid phase, contact with hydrotreating catalyst; Under the condition of 340～400 ℃ of temperature of reaction, react; The elute of first hydrotreating reactor is mixed into the second hydrotreatment reaction zone with hydrogen II again, under the state of pure liquid phase or low hydrogen/gasoline ratio, contacts with hydrotreating catalyst, in temperature of reaction is to react under 240～320 ℃ the condition; The elute of the second hydrotreatment reaction zone obtains diesel product after cooling, separation.
In traditional fixed bed diesel oil hydrogenation reactor drum, hydrogen-oil ratio used in the hydrogenation process is considerably beyond the required numerical value of chemical reaction, and this is because hydrogen is not only reactant, and is main heat-transfer medium.When ordinary production, use circulating hydrogen compressor to set up hydrogen gas circulating system, take away reaction heat through a large amount of round-robin hydrogen, reduce the amplitude that temperature of reaction changes, relax the temperature rise of reactor catalyst bed.In addition, higher hydrogen dividing potential drop also helps suppressing the reaction of condensation green coke.Therefore, traditional fixed bed diesel oil hydrogenation reactor drum is a trickle bed, is three-phase reaction system: gas phase (hydrogen), liquid phase (oil) and solid phase (catalyzer).
Hydrogen I of the present invention all is dissolved in the diesel oil distillate raw oil, is meant the saturated solution that has formed diesel oil distillate raw oil and hydrogen.Pure liquid phase is meant the hydrogen that does not have gas phase in the reaction system.
Other reaction conditionss of the first hydrotreatment reaction zone are: reaction pressure 2.0～10.0MPa, volume space velocity 1.5～5.0h
-1Diesel oil distillate raw oil is at the first hydrotreatment reaction zone, main under the reaction conditions of high temperature, higher space velocity reactions such as olefin saturation, hydrodenitrification reaction, hydrodesulfurization reaction, aromatic hydrocarbons are saturated takes place.Most sulfide and nitride in the raw material are removed, and are that the second hydrotreatment reaction zone provides the raw material that carries out ultra-deep desulfurization.In first hydrotreatment reaction zone is pure liquid phase state, and therefore, this reaction zone is at high temperature operated control catalyst bed temperature rise effectively, avoids the bed local temperature too high.Prolonged the device operational cycle.The temperature rise of the said first hydrotreatment reaction zone is less than 5 ℃.
Said hydrogen I is new hydrogen, i.e. fresh hydrogen, and said hydrogen II is recycle hydrogen and/or new hydrogen.
Other reaction conditionss of the second hydrotreatment reaction zone are: reaction pressure 2.0～10.0MPa, hydrogen to oil volume ratio are smaller or equal to 100Nm
3/ m
3, volume space velocity 3.0～10.0h
-1The reaction effluent of the first hydrotreatment reaction zone carries out further hydrogenating desulfurization, hydrodenitrification, alkene is saturated and the reaction of part cycloalkanes selective opening under the reaction conditions of relatively low temperature, high-speed.Because the first hydrotreatment reaction zone is the removal of sulfur compounds that removes easily; Remaining all is benzothiophene kind and the dibenzothiophene class sulfide that is difficult to remove; Particularly 4, the 6-dibenzothiophene is the most difficult sulfide that removes owing to there is space steric effect.It effectively removes the path is exactly that one of them benzene ring hydrogenation is saturated, breaks its two dimensional structure, forms the naphthenic hydrocarbon of chair form or boat form structure, and then the desulphurization reaction that carries out the C-S bond rupture.And under conventional unifining condition, can there be thermodynamics equilibrium limit in the aromatic hydrogenation reaction, and high temperature can be unfavorable to the aromatic hydrogenation saturated reaction.Therefore under relatively low temperature, carry out the reaction of fractional saturation hydrogenation of polycyclic aromatic hydrocarbons, thus these the most difficult sulphur compounds that remove of effective elimination.In addition, the chromoplastid in the diesel oil distillate is the polycyclic aromatic hydrocarbons of fractional saturation, and further at low temperatures saturated a part of aromatic hydrocarbons can the hydrogenation decolouring improve the diesel product stability in storage, thereby improve product colour.
In embodiment preferred, the second hydrotreatment reaction zone is the low hydrogen/gasoline ratio state therein, and hydrogen to oil volume ratio is smaller or equal to 100Nm
3/ m
3, be preferably 40～70Nm
3/ m
3This moment, said hydrogen II was a recycle hydrogen, and perhaps the mixing hydrogen of recycle hydrogen and new hydrogen is provided with circulating hydrogen compressor, carries out the small quantity of hydrogen circulation.
In another preferred embodiment, the second hydrotreatment reaction zone is pure liquid phase, and hydrogen to oil volume ratio is 0.This moment, said hydrogen II was new hydrogen, did not carry out hydrogen recycle, did not promptly have circulating hydrogen compressor.
The said first hydrotreatment reaction zone elute is circulated to first hydrotreatment reaction zone inlet as turning oil, mixes with diesel oil distillate raw oil, and recycle ratio (ratio of turning oil and fresh feed) is 1～4: 1.The first hydrotreating reactor elute that loops back all is dissolved into hydrogen I in this mixing oil with after diesel oil distillate raw oil mixes again.Turning oil is that the ratio of turning oil and fresh feed is according to the property adjustments of fresh feed as the medium of the new hydrogen of dissolving.
The said second hydrotreatment reaction zone elute is as turning oil; Be circulated to first hydrotreatment reaction zone inlet and/or second hydrotreatment reaction zone inlet; Elute with the diesel oil distillate raw oil and/or the first hydrotreatment reaction zone mixes respectively, and recycle ratio (ratio of turning oil and fresh feed) is 1～4: 1.The second hydrotreatment reaction zone elute that loops back is with after diesel oil distillate raw oil mixes, and perhaps with after round-robin first hydrotreatment reaction zone elute and diesel oil distillate raw oil mix, hydrogen I all is dissolved in this mixing oil again.The second hydrotreating reactor elute that loops back all is dissolved into hydrogen II in this mixing oil with after the elute of the first hydrotreatment reaction zone mixes again.
The hydrotreating catalyst of filling is the non-noble metal catalyzer of group vib base metal and/or VIII family that loads on unformed aluminum oxide and/or the silica-alumina supports in the said first hydrotreatment reaction zone and the second hydrotreatment reaction zone; Wherein the group vib base metal is Mo and/or W, and VIII family base metal is Ni and/or Co.
Two kinds of hydrotreating catalysts of the said first hydrotreatment reaction zone grading loading load hydrotreating catalyst I and hydrotreating catalyst II successively according to the flow direction of reactant flow, and its admission space ratio is 6: 4～8: 2; The second hydrotreatment reaction zone only loads hydrotreating catalyst I, and wherein the reactive metal of hydrotreating catalyst I is Co and Mo, and the reactive metal of hydrotreating catalyst II is Ni and W, or be Ni and Mo, perhaps be Ni, Mo and W.
Diesel oil distillate raw oil is straight-run diesel oil, and perhaps straight-run diesel oil is mixed experienced part secondary processing diesel oil, is benchmark with straight-run diesel oil, and it is 1%～50% that secondary processing diesel oil is mixed experienced ratio.Said secondary processing diesel oil is selected from catalytic cracking diesel oil, coker gas oil, coal and produces in the diesel oil distillate of oil one or more.
Advantage of the present invention:
1, uses method provided by the invention, can the doctor positive diesel oil distillate be converted into the diesel product of super low sulfur, good colors.Wherein sulphur content can satisfy Europe IV, Euro V emissions requirement, and its ASTMD1500 colourity is less than 0.5 simultaneously.This method flexible operation is easy, can adopt different reaction conditions according to raw oil character such as sulphur content, nitrogen content, boiling range scope, satisfies the product quality indicator of different grades.
2, be pure liquid phase state in first hydrotreatment reaction zone of the present invention, therefore, this reaction zone is at high temperature operated control catalyst bed temperature rise effectively, avoids the bed local temperature too high.Prolonged the device operational cycle.
Description of drawings
Fig. 1 is the schematic flow sheet of the hydroprocessing process preferred embodiment one of production ultra-low-sulphur diesel provided by the invention.
Fig. 2 is the schematic flow sheet of the hydroprocessing process preferred embodiment two of production ultra-low-sulphur diesel provided by the invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further explained, but therefore do not limited the present invention.Omitted many equipment among the figure, like pump, interchanger etc., but this is known to those of ordinary skills.
As shown in Figure 1; In the preferred embodiment one circulating hydrogen compressor is set, the second hydrotreatment reaction zone is operated under the state of low hydrogen/gasoline ratio, and its flow process is described in detail as follows: from the fresh diesel oil distillate raw oil of pipeline 1 and from the turning oil of pipeline 17; And mix from the new hydrogen of pipeline 2; Fully dissolve through static mixer 3, the liquid phase mixture of gained gets into reactor drum 4 (the first hydrotreatment reaction zone), under the effect of hydrotreating catalyst, reacts.The reaction effluent of reactor drum 4 can partly loop back the inlet of static mixer 3 through pipeline 17; Remainder is through pipeline 5 to reactor drum 6 (the second hydrotreatment reaction zone); Also can be all through pipeline 5 with get into reactor drum 6 after recycle hydrogen from pipeline 7 mixes, under the effect of hydrotreating catalyst, further react.The reaction effluent of reactor drum 6 advances HP separator 9 through pipeline 8 and carries out gas-liquid separation, and isolated gas phase is delivered to circulating hydrogen compressor 18 through pipeline 19, and supercharging circulates as recycle hydrogen after pipeline 7 is extracted out.The separating obtained liquid phase of HP separator can be all through pipeline 10 through light pressure separator 11 further gas-liquid separations; Also can part loop back the inlet of static mixer 3 through pipeline 20, pipeline 17, remainder through pipeline 10 through light pressure separator 11 further gas-liquid separations.Light pressure separator 11 gas separated are extracted out through pipeline 12, and separating obtained liquid gets into separation column 14 through pipeline 13.Separation column 14 separating obtained refining petroleum naphthas are extracted out through pipeline 15, and the refined diesel oil of gained is through pipeline 16 withdrawing devices at the bottom of the tower.
As shown in Figure 2; Circulating hydrogen compressor is not set in the preferred embodiment two, and the second hydrotreatment reaction zone is operated under the state of pure liquid phase, and its flow process is described in detail as follows: from the fresh diesel oil distillate raw oil of pipeline 1 and from the turning oil of pipeline 17; And mix from the new hydrogen of pipeline 2; Fully dissolve through static mixer 3, the liquid phase mixture of gained gets into reactor drum 4 (the first hydrotreatment reaction zone), under the effect of hydrotreating catalyst, reacts.The reaction effluent of reactor drum 4 can partly loop back the inlet of static mixer 3 through pipeline 17; Remainder is through pipeline 5 to reactor drum 6 (the second hydrotreatment reaction zone); Also can be all through pipeline 5 with get into reactor drum 6 after new hydrogen from pipeline 2 mixes fully in static mixer 21, under the effect of hydrotreating catalyst, further react.The reaction effluent of reactor drum 6 advances HP separator 9 through pipeline 8 and carries out gas-liquid separation, and isolated gas phase is extracted out through pipeline 19.The separating obtained liquid phase of HP separator can be all through pipeline 10 through light pressure separator 11 further gas-liquid separations; Also can partly loop back the inlet of static mixer 3 through pipeline 20, pipeline 17; Part loops back the inlet of static mixer 21 through pipeline 22, pipeline 5, remainder through pipeline 10 through light pressure separator 11 further gas-liquid separations.Light pressure separator 11 gas separated are extracted out through pipeline 12, and separating obtained liquid gets into separation column 14 through pipeline 13.Separation column 14 separating obtained refining petroleum naphthas are extracted out through pipeline 15, and the refined diesel oil of gained is through pipeline 16 withdrawing devices at the bottom of the tower.
Following embodiment will further explain method provided by the invention, but therefore do not limit the present invention.
Specifically the consisting of of used catalyst A among the embodiment is benchmark with catalyzer integral body, and in oxide compound, Co is 3.0 weight %, and Mo is 15.0 weight %, and carrier is γ-Al
2O
3The commercial trade mark of catalyst B is RS-1000, is the Chang Ling catalyst plant production of catalyzer branch office of China Petrochemical Industry.
Used raw oil A is a kind of straight-run diesel oil among the embodiment, and raw oil B is the mixing raw material of a kind of catalytic diesel oil and straight-run diesel oil, and wherein catalytic diesel oil accounts for 20% (weight).The main character of various raw materials is as shown in table 1.
Embodiment 1
Raw oil A and new hydrogen thorough mixing get into static mixer, and liquid phase gets into the first hydrotreatment reaction zone then, under the high temperature high-speed, carry out the deep hydrodesulfurizationof reaction; Its resultant of reaction is divided into two portions; A part is circulated to the static mixer inlet, and another part gets into the second hydrotreatment reaction zone after recycle hydrogen mixes, under the low temperature high-speed, carry out ultra-deep desulfurization, decolouring and aromatic hydrocarbons saturated reaction; Its resultant of reaction is after refrigerated separation; The hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained gets into fractionating system, isolates refining naphtha fraction, fine-quality diesel oil cut.Wherein the catalyzer of first reaction zone and second reaction zone is catalyst A, and the reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3.
Can find out that from table 3 sulphur content of product is 5 μ g/g, polycyclic aromatic hydrocarbon content is 1.5 weight %, and colourity is 0.5, and cetane index is 59.5, is the clean diesel that satisfies Euro V emissions, and diesel product yield can reach more than the 99 weight %.
Behind raw oil B and the new hydrogen thorough mixing, get into static mixer, pure then liquid phase gets into the first hydrotreatment reaction zone, under the high temperature high-speed, carries out the deep hydrodesulfurizationof reaction; Behind its resultant of reaction and the new hydrogen thorough mixing; Get into static mixer; Pure then liquid phase gets into the second hydrotreatment reaction zone, under the low temperature high-speed, carries out ultra-deep desulfurization, decolouring and aromatic hydrocarbons saturated reaction, and its resultant of reaction is after refrigerated separation; The liquid fraction of gained partly gets into fractionating system, isolates refining naphtha fraction, fine-quality diesel oil cut; Remainder is circulated to first hydroconversion reaction zone and second hydrotreatment reaction zone inlet.First reaction zone flows to loading catalyst A and catalyst B successively according to reactant flow, and its admission space ratio is 8: 2.The second reaction zone loading catalyst A.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3.
Can find out that from table 3 sulphur content of product is 7 μ g/g, colourity is 0.5, and cetane index is 54.3, is the clean diesel that satisfies Euro V emissions, and diesel product yield is more than 99 weight %.
Table 1 raw oil character
| The raw oil numbering | A | B |
| Type of feed | Straight-run diesel oil | MDO Medium diesel oil |
| Density (20 ℃), g/cm 3 | 0.832 | 0.848 |
| Sulphur content, μ g/g | 9700 | 8760 |
| Nitrogen content, μ g/g | 97 | 180 |
| The bromine valency, gBr/100g | 0.95 | - |
| Aromatic hydrocarbons, weight % | 21.2 | 27.5 |
| Polycyclic aromatic hydrocarbons, weight % | 10.5 | 15.5 |
| Cetane index (ASTM D4737) | 55.4 | 49.7 |
| Boiling range ASTM D-1160, ℃ | ||
| IBP | 188 | 180 |
| 10％ | 224 | 226 |
| 50％ | 277 | 281 |
| 90％ | 338 | 340 |
| FBP | 365 | 368 |
Table 2 operational condition
| Numbering | Embodiment 1 | |
| Raw oil | A | B |
| First hydroconversion reaction zone | ||
| Reaction pressure, MPa | 6.4 | 6.4 |
| Temperature of reaction, ℃ | 360 | 360 |
| Volume space velocity during liquid, h -1 | 2.7 | 2.5 |
| Recycle ratio | 3 | 4 |
| Second hydroconversion reaction zone | ||
| Reaction pressure, MPa | 6.0 | 6.2 |
| Temperature of reaction, ℃ | 280 | 280 |
| Volume space velocity during liquid, h -1 | 6.3 | 5.8 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 70 | - |
| Recycle ratio | - | 4 |
Table 3 main products character
| Numbering | Embodiment 1 | |
| Density (20 ℃), g/cm 3 | 0.811 | 0.825 |
| Sulphur content, μ g/ |
5 | 7 |
| Nitrogen content, μ g/g | ＜0.5 | ＜1 |
| The bromine valency, gBr/100g | ＜0.5 | ＜0.5 |
| Polycyclic aromatic hydrocarbons, weight % | 1.5 | 1.8 |
| Cetane index, ASTM D-4737 | 59.5 | 54.3 |
| Diesel yield, weight % | ＞99 | ＞99 |
| Colourity, ASTM D-1500 | 0.5 | 0.5 |
Claims (10)
1. hydroprocessing process of producing ultra-low-sulphur diesel; It is characterized in that; Hydrogen I all is dissolved into and gets into the first hydrotreatment reaction zone in the diesel oil distillate raw oil; Under the condition of pure liquid phase, contact with hydrotreating catalyst, under the condition of 340～400 ℃ of temperature of reaction, react, the elute of first hydrotreating reactor is mixed into the second hydrotreatment reaction zone with hydrogen II again; Under the state of pure liquid phase or low hydrogen/gasoline ratio, contacting with hydrotreating catalyst, is to react under 240～320 ℃ the condition in temperature of reaction; The elute of the second hydrotreatment reaction zone obtains diesel product after cooling, separation.
2. according to the described method of claim 1, it is characterized in that the said first hydrotreatment reaction zone elute is circulated to first hydrotreatment reaction zone inlet as turning oil, mixes with diesel oil distillate raw oil, recycle ratio is 1～4: 1.
3. according to the described method of claim 1; It is characterized in that; The said second hydrotreatment reaction zone elute is as turning oil; Be circulated to first hydrotreatment reaction zone inlet and/or second hydrotreatment reaction zone inlet, the elute with the diesel oil distillate raw oil and/or the first hydrotreatment reaction zone mixes respectively, and recycle ratio is 1～4: 1.
4. according to the described method of claim 1, it is characterized in that said hydrogen I is new hydrogen, said hydrogen II is recycle hydrogen and/or new hydrogen.
5. according to the described method of claim 1, it is characterized in that the temperature rise of the said first hydrotreatment reaction zone is less than 5 ℃.
6. according to the described method of claim 1, it is characterized in that other reaction conditionss of the said first hydrotreatment reaction zone are: reaction pressure 2.0～10.0MPa, volume space velocity 1.5～5.0h
-1
Other reaction conditionss of the second hydrotreatment reaction zone are: reaction pressure 2.0～10.0MPa, hydrogen to oil volume ratio are smaller or equal to 100Nm
3/ m
3, volume space velocity 3.0～10.0h
-1
7. according to the described method of claim 6, it is characterized in that the hydrogen to oil volume ratio of the said second hydrotreatment reaction zone is 40～70Nm
3/ m
3
8. according to the described method of claim 1; It is characterized in that; The hydrotreating catalyst of filling is the non-noble metal catalyzer of group vib base metal and/or VIII family that loads on unformed aluminum oxide and/or the silica-alumina supports in the said first hydrotreatment reaction zone and the second hydrotreatment reaction zone; Wherein the group vib base metal is Mo and/or W, and VIII family base metal is Ni and/or Co.
9. according to the described method of claim 8; It is characterized in that; Two kinds of hydrotreating catalysts of the said first hydrotreatment reaction zone grading loading load hydrotreating catalyst I and hydrotreating catalyst II successively according to the flow direction of reactant flow, and its admission space ratio is 6: 4～8: 2; The second hydrotreatment reaction zone only loads hydrotreating catalyst I, and wherein the reactive metal of hydrotreating catalyst I is Co and Mo, and the reactive metal of hydrotreating catalyst II is Ni and W, or be Ni and Mo, perhaps be Ni, Mo and W.
10. according to the described method of claim 1, it is characterized in that diesel oil distillate raw oil is straight-run diesel oil; Perhaps straight-run diesel oil is mixed experienced part secondary processing diesel oil, is benchmark with straight-run diesel oil, and it is 1%～50% that secondary processing diesel oil is mixed experienced ratio.
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| CN104232154A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Distillate oil hydro-upgrading method |
| CN104560175A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ultra-deep hydrodesulfurization method for improving mixing proportion of inferior diesel |
| CN111171861A (en) * | 2018-11-09 | 2020-05-19 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation process and liquid-phase hydrogenation reactor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232154A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Distillate oil hydro-upgrading method |
| CN104232154B (en) * | 2013-06-21 | 2016-04-06 | 中国石油天然气股份有限公司 | A kind of distillate hydrogenation method for modifying |
| CN104560175A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Ultra-deep hydrodesulfurization method for improving mixing proportion of inferior diesel |
| CN104560175B (en) * | 2013-10-29 | 2016-06-22 | 中国石油化工股份有限公司 | Improve the ultra-deep hydrodesulfuration method of poor ignition quality fuel mixed ratio |
| CN111171861A (en) * | 2018-11-09 | 2020-05-19 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation process and liquid-phase hydrogenation reactor |
| CN111171861B (en) * | 2018-11-09 | 2021-12-07 | 中国石油化工股份有限公司 | Liquid-phase hydrogenation process and liquid-phase hydrogenation reactor |
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| CN102443429B (en) | 2014-07-02 |
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