CN106609155A - Method used for producing clean diesel oil - Google Patents
Method used for producing clean diesel oil Download PDFInfo
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- CN106609155A CN106609155A CN201510705715.1A CN201510705715A CN106609155A CN 106609155 A CN106609155 A CN 106609155A CN 201510705715 A CN201510705715 A CN 201510705715A CN 106609155 A CN106609155 A CN 106609155A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a method used for producing clean diesel oil. The method comprises following steps: secondary processing diesel oil is subjected to cutting so as to obtain a light secondary processing diesel oil cut fraction and a heavy secondary processing diesel oil cut fraction, wherein the content of 4,6-dimethyldibenzothiophene in the light secondary processing diesel oil cut fraction is controlled to be 0 to 300<mu>g/g; the heavy secondary processing diesel oil cut fraction is introduced into a residual oil hydrogenation reactor for reaction, the light secondary processing diesel oil cut fraction and straight-run diesel oil are introduced into a diesel oil hydrogenation reactor for reaction, an obtained diesel oil hydrogenation reaction effluent is subjected to separation and fractionation successively so as to obtain a gasoline cut fraction II and a diesel oil cut fraction II, wherein the sulphur content of the diesel oil cut fraction II is lower than 10<mu>g/g. According to the method, diesel oil hydrogenation and residual oil hydrogenation are combined, processing of a large amount of secondary processing diesel oil is realized, diesel oil products capable of satisfying Euro V emission standards are produced at relatively mild conditions, and catalyst operating period is prolonged.
Description
Technical field
The invention belongs to the method that cleaning diesel oil is obtained under conditions of it there is hydrogen, more specifically, is
A kind of ultra-deep hydrodesulfuration method of secondary processing diesel oil.
Background technology
Problem of environmental pollution caused by vehicle exhaust has caused in the world extensively attention.Bavin
Oil is used as important vehicle fuel, oxysulfide (SO contained in post combustion emission waste gasX), nitrogen
Oxide (NOX) and particulate matter (PM) etc. be the major reason for causing atmosphere pollution.World wide
Interior diesel oil standard is increasingly strict, and the friendly low-sulfur of production environment or ultra-low-sulphur diesel have become countries in the world
Government and the problem of oil refining enterprise's most attention.European Union member countries came into effect the discharge of Europe V from 2009
Standard, the standard is limited in the sulfur content of diesel product below 10 μ g/g.It is American-European-Japanese wait country and
The refinery in area is generally in the ultra-low-sulphur diesel product to market supply less than 10 μ g/g.China from
The standard of state III equivalent to EuropeⅢ emission standard (sulfur content is less than 350 μ g/g) is come into effect within 2010,
Beijing area took the lead in carrying out the discharge standard equivalent to Europe IV in 2008, it is stipulated that diesel oil sulfur content is little
In 50 μ g/g, the discharge standard for coming into effect equivalent to Europe V for 2012.
But, it is secondary that oil refining enterprise produces in process of production substantial amounts of catalytic diesel oil, coker gas oil etc.
Processing diesel oil, is difficult to the hexichol containing substituent that hydrodesulfurization reaction occurs in these secondary processing diesel oils
The content of bithiophene class sulfur-containing compound is more much higher than straight-run diesel oil, and the nitrogen in secondary processing diesel oil
Content and arene content are also far above straight-run diesel oil, so straight-run diesel oil is mixed after secondary processing diesel oil
Ultra-deep hydrodesulfuration difficulty is increased considerably, and needs harsher processing conditions.Therefore, reduce
The content of the dibenzothiophenes class sulfur-containing compound containing substituent in secondary processing diesel oil, and nitrogen content
Can reduce producing the operating severity of ultra-low-sulphur diesel process with arene content, extend catalyst life
Or aggrandizement apparatus treating capacity.
CN102876374 A disclose a kind of method of inferior distillate oil hydrofinishing desulfurization, raw material bavin
Four reaction areas are passed sequentially through after oil and hydrogen mixing, the cooling of product Jing enters piece-rate system, obtains
To product liquid and hydrogen-rich gas；First reaction zone loads first kind catalyst, in second reaction zone
The mixture of filling first kind catalyst and Equations of The Second Kind catalyst, in the 3rd reaction zone Equations of The Second Kind is loaded
Catalyst, loads first kind catalyst in the 4th reaction zone, and wherein first kind catalyst is Mo-Co
Catalyst, Equations of The Second Kind catalyst is W-Mo-Ni catalyst or W-Ni catalyst.The method can only
The diesel product of production state IV standards.
The A1 of US 200610196809 disclose it is a kind of using differential responses area carry out diesel oil hydrofining or
The method being hydrocracked, the method adopts two reactors, adds high pressure to separate between two reactors
Device, to remove the hydrogen sulfide and the gaseous impurities such as ammonia of first reactor generation, and then improves hydrofinishing
High pressure hydrogen stripping tower is set in effect, but the method, and cost of investment and running cost are high.
The content of the invention
The purpose of the present invention propose it is a kind of produces cleaning diesel oil method, to solve prior art in it is secondary
The difficult problem of processing diesel oil ultra-deep hydrodesulfuration method.
The present invention provide method be：
(1) secondary processing diesel oil is cut, is divided into light secondary processing diesel oil cut and adds with again secondary
Work diesel oil distillate, wherein, the content of 4,6- dimethyl Dibenzothiophenes in light secondary processing diesel oil cut
For 0～300 μ g/g,
(2) the heavy secondary processing diesel oil cut obtained by step (1) is entered together with residual hydrogenation raw material
Enter residual hydrogenation reactor, reacted in the presence of residual oil hydrocatalyst, residual hydrogenation reaction
Effluent successively it is separated and fractionation after, obtain gasoline fraction I, diesel oil distillate I and tail oil fraction I,
(3) diesel oil distillate obtained by the light secondary processing diesel oil cut of step (1) gained, step (2)
I and straight-run diesel oil enter together diesel oil hydrogenation reactor, carry out in the presence of Hydrobon catalyst anti-
Should, diesel oil hydrogenation reaction effluent successively it is separated and fractionation after, obtain gasoline fraction II and diesel oil evaporate
II, the wherein sulfur content of diesel oil distillate II is divided to be less than 10 μ g/g.
The secondary processing diesel oil is referred in addition to straight-run diesel oil, obtained by the secondary processing process of crude oil
Diesel oil distillate, preferably described secondary processing diesel oil is catalytic cracking diesel oil and/or coker gas oil.
The present invention is by secondary processing diesel oils such as catalytic cracking diesel oil, coker gas oils according to 4,6- dimethyl two
The content of benzothiophene is cut, and is divided into lighter secondary processing diesel oil and heavier secondary operation bavin
Oil, wherein heavier secondary processing diesel oil mixes hydrotreating together in residual hydrogenation raw material, on the one hand
The viscosity of residual oil can be reduced, the intermiscibility of residual oil system is improved, promotes the hydrogenation and removing impurity of residual oil
Reaction, reduces residual oil hydrocatalyst coking.On the other hand using the high hydrogen dividing potential drop of residual hydrogenation equipment
Feature, significantly removes sulfur-bearing, the nitrogen-containing compound in heavier secondary processing diesel oil, and aromatic hydrocarbons.
Diesel oil distillate obtained by residual hydrogenation reaction together enters with lighter secondary processing diesel oil and straight-run diesel oil
Enter Diesel Oil Hydrofining Unit, produce ultra-low-sulphur diesel of the sulfur content less than 10 μ g/g.
The heavy secondary processing diesel oil cut of the entrance residual hydrogenation equipment and the weight of residual hydrogenation raw material
Than for 1：19～1：4.A certain amount of heavy secondary processing diesel oil cut is mixed in residual hydrogenation equipment,
Have little influence on the ability that residual hydrogenation equipment processes residual oil.
In step (1) of the present invention, secondary processing diesel oil according to 4,6- dimethyl Dibenzothiophenes content
Cut, be divided into light secondary processing diesel oil and weight secondary processing diesel oil, wherein, light secondary operation bavin
In oil the content of 4,6- dimethyl Dibenzothiophenes be 0～300 μ g/g, preferably 20～200 μ g/g, it is more excellent
Elect 30～100 μ g/g as.
The heavy secondary processing diesel oil cut of gained reacts together with residual hydrogenation raw material into residual hydrogenation
Device, is reacted in the presence of residual oil hydrocatalyst.Reaction stream is into high pressure hot separator point
From for gaseous stream and liquid phase stream, wherein gaseous stream is purified, boosting Posterior circle is used；It is described
The fractionation of liquid phase stream Jing normal pressures obtains gasoline fraction I, diesel oil distillate I and tail oil fraction I.
Residual hydrogenation reactor operating condition is：Hydrogen dividing potential drop 5.0MPa～22.0MPa, reaction temperature
330 DEG C～450 DEG C, volume space velocity 0.1h-1～3.0h-1, hydrogen and feedstock oil volume ratio (hydrogen-oil ratio)
350～2000.
Residual oil hydrocatalyst described in step (2) can be various existing residual oil hydrocatalysts.
It is preferred that the residual oil hydrocatalyst is loaded catalyst, its active metal component is vib gold
Category and/or group VIII metal, carrier is aluminum oxide, silica or amorphous silica-alumina.More preferably its
Active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, and carrier is aluminum oxide.The slag
Oily hydrogenation reactor type is fixed bed, moving bed or ebullated bed.
Diesel oil distillate I obtained by the light secondary processing diesel oil cut of step (1) gained, step (2) and
Straight-run diesel oil enters together diesel oil hydrogenation reactor, is reacted in the presence of Hydrobon catalyst.
The diesel oil hydrogenation reactor operating condition is：Hydrogen dividing potential drop 3.0MPa～12.0MPa, reaction temperature
300 DEG C～420 DEG C, volume space velocity 0.5h-1～4.0h-1, hydrogen and feedstock oil volume ratio (hydrogen-oil ratio)
150～1000.
The Hydrobon catalyst be loaded catalyst, its active metal component be nickel-tungsten, nickel-
Tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, carrier be aluminum oxide, silica, amorphous silica-alumina in one kind or
It is several.Can be various existing diesel oil hydrofining catalysts.
The diesel oil hydrogenation type of reactor can be gas-liquid-solid three-phase fixed-bed, or gas-liquid two
Phase fixed bed.
It is an advantage of the current invention that：
1st, the present invention is combined diesel oil hydrofining and residual hydrocracking, and processing is secondary in a large number to be added
Work diesel oil, the production under conditions of relatively relaxing meets the diesel product of Euro V emissions, extends catalysis
The operation cycle of agent.
2nd, weight secondary processing diesel oil cut is mixed in residual oil especially decompression residuum, can be greatly lowered
Residual hydrogenation equipment feedstock viscosity, improves the diffusivity and removing impurities qualitative response speed of reactant, can press down
The carbon deposit of residual hydrogenation reactor rear portion bed processed, extends the residual hydrogenation equipment operation cycle.
Description of the drawings
Fig. 1 is the method schematic diagram of the production cleaning diesel oil that the present invention is provided.
Fig. 2 is the process flow diagram that comparative example 1 and comparative example 2 are adopted.
Fig. 3 is the process flow diagram that comparative example 1 ' and comparative example 2 ' are adopted.
Specific embodiment
Accompanying drawing is the method schematic diagram of the production cleaning diesel oil that the present invention is provided, and many is eliminated in figure and is set
It is standby, such as pump, heat exchanger, compressor.The method of the present invention is given further below by accompanying drawing
Illustrate, but it is not thereby limiting the invention.
As shown in figure 1, residual oil raw material from pipeline 13, from the heavy secondary operation bavin of pipeline 14
Oil distillate enters residual hydrogenation reactor 16 after mixing with the hydrogen from pipeline 15, pipeline 22,
Reacted in the presence of residual oil hydrocatalyst；Product Jing pipeline 17 enters high pressure hot separator
18, isolated liquid product and gas-phase product, wherein gas-phase product Jing pipelines 20 are into cold anticyclone point
Further gas-liquid separation, isolated liquid product and gas-phase product are carried out from device 21.Cold anticyclone point
Gas-phase product from device removes H2Jing pipelines 22 enter circulating hydrogen compressor after S, after boosting and from pipe
Mix with feedstock oil after the new hydrogen mixing of line 15.The liquid product and cold anticyclone of high pressure hot separator 18
The liquid product difference Jing pipelines 19 of separator 21 and pipeline 23 enter fractionating column 24, and fractionation is obtained
Gas, gasoline fraction I, diesel oil distillate I and tail oil fraction I, wherein gas, gasoline fraction I and tail
Respectively Jing pipelines 25,26 and 27 go out device to oil distillate I；Diesel oil distillate I Jing pipelines 3 enter diesel oil
Hydrogenation reactor 5.
The light secondary processing diesel oil cut and the bavin of pipeline 3 of straight-run diesel oil, pipeline 2 from pipeline 1
Oil distillate I enters diesel oil hydrogenation reactor 5 after mixing with the hydrogen from pipeline 4, pipeline 9, is adding
Reacted in the presence of hydrogen catalyst for refining, diesel oil hydrogenation reaction effluent Jing pipelines 6 enter cold height
Pressure separator 7, isolated liquid product and gas-phase product；Gas-phase product removes H2Jing pipelines 9 after S
Into circulating hydrogen compressor, mix with feedstock oil after mixing with the new hydrogen from pipeline 4 after boosting.Liquid
Phase product Jing pipelines 8 enter fractionating column 10, gas, gasoline fraction II and diesel oil are obtained after being fractionated into and is evaporated
II, wherein gas and gasoline fraction II Jing pipelines 12 is divided to separate into downstream unit, diesel oil distillate II
Jing pipelines 11 go out device.
The following examples will be further described to the present invention, but and be not so limited the present invention.
The straight-run diesel oil raw material A adopted in embodiment, secondary processing diesel oil B and C, residual oil D, property
Matter is shown in Table 1, and secondary processing diesel oil is respectively cut into light secondary processing diesel oil fraction B 1, C1 and weight is secondary
Processing diesel oil distillate B2, C2, the content of 4,6- dimethyl Dibenzothiophenes is 95 μ g/g in wherein B1,
The content of 4,6- dimethyl Dibenzothiophenes is 175 μ g/g in C1.
Hydrogenation protecting agent, the Hydrobon catalyst that diesel hydrogenation test is adopted is by Sinopec catalyst
Branch company's Chang Ling catalyst plant production, trade names are respectively RG-1, RS-2000, admission space ratio
Example is 1:10.The hydrogenation protecting agent of residual hydrogenation test employing, Hydrodemetalation catalyst, hydrogenation are de-
Sulfur catalyst is respectively by the Chang Ling catalyst plant production of Sinopec catalyst branch company, trade names
RG-30A, RDM-32, RMS-30, admission space ratio is 5:45:50.
Table 1
Embodiment 1
The diesel oil of straight-run diesel oil A, light secondary processing diesel oil fraction B 1 and residual hydrogenation cellular manufacture evaporates
Divide I to mix with hydrogen latter with diesel oil hydrogenation unit is entered, enter in the presence of Hydrobon catalyst
Row deep hydrodesulfurizationof reacts, and reaction condition is：345 DEG C of reaction temperature, volume is empty during raw material fluid
Fast 1.5h-1, hydrogen dividing potential drop is 6.4MPa, hydrogen-oil ratio 500.Reactor effluent is through isolated bavin
Oil distillate II, its product property is shown in Table 2.
Residual oil raw material D, weight secondary processing diesel oil fraction B 2 mix latter with adding into residual oil with hydrogen
Hydrogen reactor, is reacted in the presence of residual oil hydrocatalyst, and reaction condition is reaction temperature
395 DEG C, volume space velocity 0.237h during raw material fluid-1, hydrogen dividing potential drop is 17.0MPa, hydrogen-oil ratio 600.
Reactor effluent through isolated gas, gasoline fraction I, diesel oil distillate I and tail oil fraction I,
Major product property is shown in Table 2.Diesel oil distillate I goes diesel oil hydrogenation reactor to be reacted.
Comparative example 1
Comparative example 1 adopts straight-run diesel oil A, secondary processing diesel oil B for raw material, technological process such as Fig. 2
It is shown.The secondary processing diesel oil B of straight-run diesel oil A, pipeline 2 from pipeline 1 with from pipeline 3
Diesel oil hydrogenation reactor 4 is entered with after the hydrogen mixing of pipeline 8, in the effect of Hydrobon catalyst
Under reacted；Product Jing pipeline 5 enters cold high pressure separator 6, isolated liquid product
And gas-phase product；Gas-phase product removes H2Jing pipelines 8 enter circulating hydrogen compressor after S, after boosting with
Mix with feedstock oil after the new hydrogen mixing of pipeline 3.The liquid product Jing pipes of cold high pressure separator 6
Line 7 enters fractionating column 9, wherein isolated gas, gasoline fraction II and diesel oil distillate II, gas
Separate into downstream unit with gasoline fraction II Jing pipelines 11, diesel oil distillate II goes out dress by pipeline 10
Put.
From the residual oil raw material of pipeline 12 mix with the hydrogen from pipeline 13 and pipeline 20 after enter
Residual hydrogenation reactor 14, is reacted in the presence of residual oil hydrocatalyst；Product Jing is managed
Line 15 enters high pressure hot separator 16, isolated liquid product and gas-phase product, and wherein gas phase is produced
Thing Jing pipelines 18 enter cold high pressure separator 19, isolated liquid product and gas-phase product.Cold height
The gas-phase product removing H of pressure separator 192Jing pipelines 20 enter circulating hydrogen compressor after S, after boosting
Mix with feedstock oil after mixing with the new hydrogen from pipeline 13.The liquid product of high pressure hot separator 16
Fractionating column 22 is entered with the liquid product difference Jing pipelines 17 and pipeline 21 of cold high pressure separator 19,
Isolated gas, gasoline fraction I, diesel oil distillate I and tail oil fraction I, wherein gas, gasoline evaporate
Respectively Jing pipelines 23,24,25 and 26 go out device to divide I, diesel oil distillate I and tail oil fraction I.Reaction
Condition and major product property are shown in Table 2.
Comparative example 1 '
The bavin that comparative example 1 is produced using straight-run diesel oil A, secondary processing diesel oil B and residual hydrogenation equipment
Oil is raw material, and technological process is as shown in Figure 3.Two of straight-run diesel oil A, pipeline 2 from pipeline 1
Secondary processing diesel oil B enters diesel oil hydrogenation reactor 4 after mixing with the hydrogen from pipeline 3 and pipeline 8,
Reacted in the presence of Hydrobon catalyst；Product Jing pipeline 5 is separated into cold anticyclone
Device 6, isolated liquid product and gas-phase product；Gas-phase product removes H2Jing pipelines 8 are entered after S
Circulating hydrogen compressor, mixes after mixing with the new hydrogen from pipeline 3 after boosting with feedstock oil.Cold anticyclone
The liquid product Jing pipelines 7 of separator 6 enter fractionating column 9, isolated gas, gasoline fraction II
With diesel oil distillate II, wherein gas and gasoline fraction II Jing pipelines 11 are into downstream unit separation, diesel oil
Cut II goes out device by pipeline 10.
From the residual oil raw material of pipeline 12 mix with the hydrogen from pipeline 13 and pipeline 20 after enter slag
Oily hydrogenation reactor 14, is reacted in the presence of residual oil hydrocatalyst；Product Jing pipeline
15 enter high pressure hot separator 16, isolated liquid product and gas-phase product, wherein gas-phase product Jing
Pipeline 18 enters cold high pressure separator 19, isolated liquid product and gas-phase product.Cold anticyclone point
Gas-phase product from device 19 removes H2Jing pipelines 20 enter circulating hydrogen compressor after S, after boosting with come
Mix with feedstock oil from after the new hydrogen mixing of pipeline 13.The liquid product of high pressure hot separator 16 and cold
The liquid product difference Jing pipelines 17 of high-pressure separator 19 and pipeline 21 enter fractionating column 22, separate
Obtain gas, gasoline fraction I, diesel oil distillate I and tail oil fraction I, wherein gas, gasoline fraction I
Respectively Jing pipelines 23,24,26 go out device with tail oil fraction I, and diesel oil distillate I Jing pipelines 25 are entered
Diesel oil hydrogenation reactor 4.Reaction condition and major product property are shown in Table 2.
Table 2
| Process conditions | Embodiment 1 | Comparative example 1 | Comparative example 1 ' |
| Diesel oil hydrogenation unit | |||
| Diesel oil unit processing capacity (relative to embodiment 1) | 1 | 0.899 | 0.975 |
| Raw material is constituted, weight | |||
| Straight-run diesel oil A, % | 36.0 | 40.0 | 36.9 |
| Secondary processing diesel oil B, % | - | 60.0 | 55.4 |
| Light secondary processing diesel oil fraction B 1, % | 37.8 | - | - |
| Diesel oil distillate I, % | 26.2 | - | 7.7 |
| Process conditions | |||
| Reactor such as entrance hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 6.4 |
| Reactor average reaction temperature, DEG C | 345 | 372 | 375 |
| Volume space velocity during reactor liquid, h-1 | 1.50 | 1.39 | 1.50 |
| Hydrogen to oil volume ratio under standard state | 500 | 500 | 500 |
| Diesel oil distillate II main characters | |||
| Sulfur content, μ g/g | 8 | 8 | 8 |
| Residual hydrogenation unit | |||
| Raw material is constituted, weight | |||
| Residual oil D, % | 81.6 | 100 | 100 |
| Weight secondary processing diesel oil fraction B 2, % | 18.4 | - | - |
| Process conditions | |||
| Reactor such as entrance hydrogen dividing potential drop, MPa | 17.0 | 17.0 | 17.0 |
| Reactor average reaction temperature, DEG C | 395 | 395 | 395 |
| Volume space velocity during reactor liquid, h-1 | 0.248 | 0.20 | 0.20 |
| Hydrogen to oil volume ratio under standard state | 600 | 600 | 600 |
| Generate oily main character | |||
| Sulfur nutrient, % | 0.5 | 0.8 | 0.8 |
| Carbon residue mass fraction, % | 6.5 | 8.4 | 8.4 |
| Nickel content, μ g/g | 5 | 9 | 9 |
| Content of vanadium, μ g/g | 8 | 11 | 11 |
| Product quality is distributed, % | |||
| Gas+gasoline fraction I | 9.2 | 8.6 | 8.6 |
| Diesel oil distillate I | 29.8 | 10.5 | 10.5 |
| Tail oil fraction I | 61.0 | 80.9 | 80.9 |
The straight-run diesel oil A, secondary processing diesel oil B of embodiment 1, comparative example 1 and comparative example 1 ' processing
It is identical with the total amount of residual oil D.
Secondary processing diesel oil B is by embodiment 1 according to the content of 4,6- dimethyl Dibenzothiophenes
95 μ g/g are cut, the content of 4,6- dimethyl Dibenzothiophenes in light secondary processing diesel oil fraction B 1
For 95 μ g/g, remaining part is attached most importance to secondary processing diesel oil fraction B 2.Wherein diesel oil hydrogenation unit processing
Straight-run diesel oil A, light secondary processing diesel oil fraction B 1 and the diesel oil distillate I from residual hydrogenation unit,
Total diesel oil processing capacity is designated as 100%, and diesel oil hydrogenation unit can be produced under 345 DEG C of mean temperature
Go out diesel oil distillate II of the sulfur content less than 10 μ g/g.Residual hydrogenation unit process residual oils D are secondary with weight to be added
Work diesel oil distillate B2, therefore air speed is higher, has reached 0.248h-1But, due to weight secondary operation bavin
The incorporation of oil distillate B2, is greatly lowered feedstock viscosity, not only improve reactant diffusivity and
Removing impurities qualitative response speed, the content for generating well cuts is lower, and can suppress residual hydrogenation reactor
The carbon deposit of rear portion bed, extends the residual hydrogenation equipment operation cycle.
The diesel oil hydrogenation unit of comparative example 1 processes straight-run diesel oil A and secondary processing diesel oil B, total diesel oil processing
Amount is only 89.9%, and diesel oil unit needs just produce sulfur content under 372 DEG C of mean temperature
Less than the diesel product of 10 μ g/g.Residual hydrogenation unit process residual oils D, although air speed only has 0.2h-1,
But because resid feed viscosity is high, diffusivity is weak, and the content for not only generating well cuts is higher,
And the carbon deposit of hydrogenation reactor rear portion bed is serious, affects the residual hydrogenation equipment operation cycle.
The diesel oil hydrogenation of comparative example 1 ' unit processing straight-run diesel oil A, secondary processing diesel oil B and diesel oil distillate I,
Total diesel oil processing capacity is 97.5%, but diesel oil hydrogenation unit is needed under 375 DEG C of mean temperature
Diesel product of the sulfur content less than 10 μ g/g can be produced.Residual hydrogenation unit process residual oils D, although
Air speed only has 0.2h-1, but because resid feed viscosity is high, diffusivity is weak, not only generates miscellaneous in oil
The content of matter is higher, and the carbon deposit of residual hydrogenation reactor rear portion bed is serious, affects residual hydrogenation
The device operation cycle.
In sum, using the solution of the present invention, not only diesel oil processing capacity is big, and diesel oil hydrogenation unit is put down
Reaction temperature is low, and Hydrobon catalyst usage cycles are long, additionally, in the generation oil of residual oil unit
The content of impurity is lower.
Embodiment 2
The diesel oil of straight-run diesel oil A, light secondary processing diesel oil cut C1 and residual hydrogenation cellular manufacture evaporates
Divide I to mix with hydrogen latter with diesel oil hydrogenation unit is entered, enter in the presence of Hydrobon catalyst
Row deep hydrodesulfurizationof reacts, and reaction condition is：353 DEG C of reaction temperature, volume is empty during raw material fluid
Fast 1.5h-1, hydrogen dividing potential drop is 6.4MPa, hydrogen-oil ratio 500.Reactor effluent is through isolated bavin
Oil distillate II, its product property is shown in Table 2.
Residual oil D, weight secondary processing diesel oil cut C2 mix latter anti-with residual hydrogenation is entered with hydrogen
Device is answered, is reacted in the presence of residual oil hydrocatalyst, reaction condition is 395 DEG C of reaction temperature,
Body speed 0.23h during raw material fluid-1, hydrogen dividing potential drop is 17.0MPa, hydrogen-oil ratio 600.Reactor effluent
Through isolated gas, gasoline fraction I, diesel oil distillate I and tail oil fraction I, major product property
It is shown in Table 2.Diesel oil distillate I carries out hydrofining reaction into diesel oil hydrogenation unit.
Comparative example 2
Comparative example 1 adopts straight-run diesel oil A, secondary processing diesel oil C for raw material, and technological process is as shown in Figure 2.
Reaction condition and major product property are shown in Table 3.
Comparative example 2 '
Comparative example 1 adopt straight-run diesel oil A, secondary processing diesel oil C and residual hydrogenation equipment production diesel oil for
Raw material, technological process is as shown in Figure 3.Reaction condition and major product property are shown in Table 3.
Table 3
| Process conditions | Embodiment 2 | Comparative example 2 | Comparative example 2 ' |
| Diesel oil hydrogenation unit | |||
| Diesel oil unit processing capacity is (relative to embodiment 1 | )1 | 0.902 | 0.977 |
| Raw material is constituted, weight | |||
| Straight-run diesel oil A, % | 36.1 | 40.0 | 36.9 |
| Secondary processing diesel oil C, % | 60.0 | 55.4 | |
| Light secondary processing diesel oil cut C1, % | 43.3 | ||
| Diesel oil distillate I, % | 20.6 | 7.7 | |
| Process conditions | |||
| Reactor such as entrance hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 6.4 |
| Reactor average reaction temperature, DEG C | 353 | 375 | 377 |
| Volume space velocity during reactor liquid, h-1 | 1.50 | 1.39 | 1.50 |
| Hydrogen to oil volume ratio under standard state | 500 | 500 | 500 |
| Diesel oil distillate II main characters | |||
| Sulfur content, μ g/g | 8 | 8 | 8 |
| Residual hydrogenation unit | |||
| Raw material is constituted, weight | |||
| Residual oil D, % | 87.0 | 100 | 100 |
| Weight secondary processing diesel oil cut C2, % | 13.0 | - | - |
| Process conditions | |||
| Reactor such as entrance hydrogen dividing potential drop, MPa | 17.0 | 17.0 | 17.0 |
| Reactor average reaction temperature, DEG C | 395 | 395 | 395 |
| Volume space velocity during reactor liquid, h-1 | 0.23 | 0.20 | 0.20 |
| Hydrogen to oil volume ratio under standard state | 600 | 600 | 600 |
| Generate oily main character |
| Sulfur nutrient, % | 0.6 | 0.8 | 0.8 |
| Carbon residue mass fraction, % | 6.9 | 8.4 | 8.4 |
| Nickel content, μ g/g | 6 | 9 | 9 |
| Content of vanadium, μ g/g | 9 | 11 | 11 |
| Product quality is distributed, % | |||
| Gas+gasoline fraction I | 9.0 | 8.6 | 8.6 |
| Diesel oil distillate I | 24.9 | 10.5 | 10.5 |
| Tail oil fraction I | 66.1 | 80.9 | 80.9 |
The straight-run diesel oil A, secondary processing diesel oil C of embodiment 2, comparative example 2 and comparative example 2 ' processing
It is identical with the total amount of residual oil D.
Secondary processing diesel oil C is by embodiment 2 according to the content of 4,6- dimethyl Dibenzothiophenes
175 μ g/g are cut, and 4,6- dimethyl Dibenzothiophenes contains in light secondary processing diesel oil cut C1
Measure as 175 μ g/g, attach most importance to secondary processing diesel oil cut C2 for remaining part.Wherein diesel oil hydrogenation unit
Processing straight-run diesel oil A, light secondary processing diesel oil cut C1 and the diesel oil distillate from residual hydrogenation unit
I, total diesel oil processing capacity is designated as 100%, and diesel oil hydrogenation unit can be under 353 DEG C of mean temperature
Produce diesel oil distillate II of the sulfur content less than 10 μ g/g.Residual hydrogenation unit process residual oils D and weight two
Secondary processing diesel oil distillate C2, therefore air speed is higher, has reached 0.23h-1But, due to weight secondary operation
The incorporation of diesel oil distillate C2, is greatly lowered feedstock viscosity, not only improves the diffusivity of reactant
With removing impurities qualitative response speed, the content for generating well cuts is lower, and residual hydrogenation can be suppressed to react
The carbon deposit of device rear portion bed, extends the residual hydrogenation equipment operation cycle.
The diesel oil hydrogenation unit of comparative example 1 processes straight-run diesel oil A and secondary processing diesel oil C, total diesel oil processing
Amount is only 90.2%, and diesel oil hydrogenation unit needs just produce sulphur under 375 DEG C of mean temperature
Diesel product of the content less than 10 μ g/g.Residual hydrogenation unit process residual oils D, although air speed only has
0.2h-1, but because resid feed viscosity is high, diffusivity is weak, not only generates the content of well cuts
It is higher, and the carbon deposit of residual hydrogenation reactor rear portion bed is serious, affects residual hydrogenation equipment operation
Cycle.
The diesel oil hydrogenation of comparative example 1 ' unit processing straight-run diesel oil A, secondary processing diesel oil C and residual hydrogenation equipment
Diesel oil distillate I, total diesel oil processing capacity is 97.7%, but diesel oil unit need it is flat at 377 DEG C
Diesel product of the sulfur content less than 10 μ g/g could be produced at temperature.Residual hydrogenation unit processes slag
Oily D, although air speed only has 0.2h-1, but because resid feed viscosity is high, diffusivity is weak, not only
The content for generating well cuts is higher, and the carbon deposit of residual hydrogenation reactor rear portion bed is serious, shadow
Ring the residual hydrogenation equipment operation cycle.
In sum, using the offer scheme of the present invention, not only diesel oil processing capacity is big, diesel oil hydrogenation list
First average reaction temperature is low, and Hydrobon catalyst usage cycles are long, additionally, residual hydrogenation unit
The content for generating well cuts is lower.
Claims (10)
1. it is a kind of to produce the method for cleaning diesel oil, including：
(1) secondary processing diesel oil is cut, is divided into light secondary processing diesel oil cut and adds with again secondary
Work diesel oil distillate, wherein, the content of 4,6- dimethyl Dibenzothiophenes in light secondary processing diesel oil cut
For 0～300 μ g/g,
(2) the heavy secondary processing diesel oil cut obtained by step (1) is entered together with residual hydrogenation raw material
Enter residual hydrogenation reactor, reacted in the presence of residual oil hydrocatalyst, residual hydrogenation reaction
Effluent successively it is separated and fractionation after, obtain gasoline fraction I, diesel oil distillate I and tail oil fraction I,
(3) diesel oil distillate obtained by the light secondary processing diesel oil cut of step (1) gained, step (2)
I and straight-run diesel oil enter together diesel oil hydrogenation reactor, carry out in the presence of Hydrobon catalyst anti-
Should, diesel oil hydrogenation reaction effluent successively it is separated and fractionation after, obtain gasoline fraction II and diesel oil evaporate
II, the wherein sulfur content of diesel oil distillate II is divided to be less than 10 μ g/g.
2. method according to claim 1, it is characterised in that the secondary processing diesel oil is referred to
In addition to straight-run diesel oil, the diesel oil distillate obtained by the secondary processing process of crude oil, preferably described two
Secondary processing diesel oil is catalytic cracking diesel oil and/or coker gas oil.
3. method according to claim 1, it is characterised in that the light secondary processing diesel oil evaporates
The content of 4,6- dimethyl Dibenzothiophenes is 20～200 μ g/g in point.
4. method according to claim 1, it is characterised in that the light secondary processing diesel oil evaporates
The content of 4,6- dimethyl Dibenzothiophenes is 30～100 μ g/g in point.
5. method according to claim 1, it is characterised in that residual hydrogenation reactor operates bar
Part is：Hydrogen dividing potential drop 5.0MPa～22.0MPa, 330 DEG C～450 DEG C of reaction temperature, volume space velocity 0.1h-1~
3.0h-1, hydrogen and feedstock oil volume ratio 350～2000.
6. method according to claim 1, it is characterised in that the residual oil hydrocatalyst is
Loaded catalyst, its active metal component is vib metals and/or group VIII metal, carrier
For aluminum oxide, silica or amorphous silica-alumina.
7. method according to claim 1, it is characterised in that the residual hydrogenation reactor class
Type is fixed bed, moving bed or ebullated bed.
8. method according to claim 1, it is characterised in that diesel oil hydrogenation reactor operates bar
Part is：Hydrogen dividing potential drop 3.0MPa～12.0MPa, 300 DEG C～420 DEG C of reaction temperature, volume space velocity 0.5h-1~
4.0h-1, hydrogen and feedstock oil volume ratio 150～1000.
9. method according to claim 1, it is characterised in that Hydrobon catalyst is load
Type catalyst, its active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, and carrier is oxidation
One or more in aluminium, silica, amorphous silica-alumina.
10. method according to claim 1, it is characterised in that the diesel oil hydrogenation reactor class
Type can be gas-liquid-solid three-phase fixed-bed, or gas-liquid two-phase fixed bed.
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