CN105623718B - A kind of method of hydrotreating for producing cleaning diesel oil - Google Patents
A kind of method of hydrotreating for producing cleaning diesel oil Download PDFInfo
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Abstract
A kind of method of hydrotreating for producing cleaning diesel oil.Diesel oil distillate feedstock oil mixed with hydrogen after into reactor, successively with Hydrobon catalyst I and Hydrobon catalyst II haptoreactions, reaction effluent separated and is fractionated, and obtains diesel product；The Hydrobon catalyst I is the load hydrogenation catalyst for refining that activated metal component is cobalt molybdenum, and the Hydrobon catalyst II is body phase Hydrobon catalyst.Using method provided by the invention, poor-quality diesel-oil by cut fraction is handled under the conditions of mitigation, low-sulfur or the cleaning diesel product of super-low sulfur can be obtained.The present invention compared with the existing technology, can obtain the ultra-low-sulphur diesel that sulfur content meets Europe V standards, while catalyst system is with good stability under the operating condition of mitigation.
Description
Technical field
The invention belongs to a kind of methods for refining hydrocarbon ils in the presence of hydrogen, are that a kind of production is clear more specifically
The method of hydrotreating of cleaning diesel oil.
Background technology
With the continuous improvement of environmental protection requirement, people are also higher and higher to vehicle fuel specification requirement.In world's model
It encloses in interior newest fuel specification, stringent control is made that diesel oil index.Wherein mainly to diesel oil sulfur content have than with
Toward more strict requirements.European Union member countries have come into effect V discharge standard of Europe from 2009, and the standard is by the sulphur of diesel product
Content is limited in below 10 μ g/g.China come into effect from 2010 be equivalent to EuropeⅢ emission standard (sulfur content be less than 350 μ g/
G) III standard of state, Beijing area took the lead in carrying out in 2008 the discharge standard for being equivalent to Europe IV, it is specified that diesel oil sulfur content is less than
50 μ g/g come into effect the discharge standard for being equivalent to Europe V for 2012, it is specified that diesel oil sulfur content is less than 10 μ g/g.
With existing technology production ultra-low sulfur clean diesel (sulfur content is less than 10 μ g/g), it is necessary in original processing technology
Under, improve the severity of operation.The measure being usually taken includes improving reaction temperature, improve reaction hydrogen partial pressure and reducing air speed
Deng.But reaction temperature is improved, not only seriously affects catalyst service life, shortens the device cycle of operation, and can be generated big
The pyrolysis product of amount, bring yield decline and product colour deepen with colourity it is unstable the problem of.And high hydrogen partial pressure pair is set
It is standby to propose more requirements, production cost is caused significantly to rise；Reduce volume space velocity mean reduce unit capacity or
Person increases reactor volume.Therefore, how to produce ultra-low-sulphur diesel is an important problem economically feasible.
All kinds of sulfide are with molecular size, molecular structure, the quantity of substituent group and substituent group position in diesel oil distillate
The difference put, hydrodesulfurization activity difference are very big.The dibenzo thiophene that the reactivity of mercaptan, disulphide and thiophene is far above
Fen class sulfide, it just can remove under the hydrogenation conditions of mitigation；And on the ortho position of sulphur atom substituted base two
Benzothiophene kind sulfide, since with space steric effect, hydrodesulfurization activity is minimum, in harsher reaction item
The rate of its hydrodesulfurization is also very low under part.But if to meet the requirement of ultra-low-sulphur diesel, these hardly possiblies must just be reacted
Multi-substituent dibenzothiophenes class sulfide removing fall.
CN102876374A discloses a kind of method of inferior distillate oil hydrofinishing desulfurization, raw material diesel oil and hydrogen mixing
After pass sequentially through four reaction areas, reaction product, into piece-rate system, obtains product liquid and hydrogen-rich gas through cooling；First is anti-
Area is answered to load first kind catalyst, the mixture of first kind catalyst and the second class catalyst is loaded in second reaction zone,
The second class catalyst of filling in 3rd reaction zone, loads first kind catalyst, wherein first kind catalyst in the 4th reaction zone
For Mo-Co catalyst, the second class catalyst is W-Mo-Ni catalyst or W-Ni catalyst.This method can only produce state IV standards
Diesel product.
US 200610196809A1, which are disclosed, a kind of to carry out diesel oil hydrofining using differential responses areas or is hydrocracked
Method, this method use two reactors, high-pressure separator are added between two reactors, to remove first reactor generation
The gaseous impurities such as hydrogen sulfide and ammonia, and then hydrofinishing effect is improved, but high pressure hydrogen stripping tower is set in this method, it invests into
This and operating cost are high.
The content of the invention
The purpose of the present invention is providing a kind of method of hydrotreating for producing cleaning diesel oil on the basis of existing technology, to be solved
Certainly be the prior art production cleaning diesel oil when, the problems such as operating condition is harsh, poor catalyst stability.
Method provided by the invention is：Diesel oil distillate feedstock oil enters reactor after being mixed with hydrogen, anti-in hydrofinishing
Should under the conditions of, successively with Hydrobon catalyst I and Hydrobon catalyst II haptoreactions, reaction effluent separated
And fractionation, obtain diesel product；The Hydrobon catalyst I is the load hydrogenation essence that activated metal component is cobalt-molybdenum
Catalyst processed, the Hydrobon catalyst II are body phase Hydrobon catalysts, which is characterized in that the hydrofinishing catalysis
Agent I contains carrier and load cobalt and molybdenum on the carrier, and the carrier is aluminium oxide and/or silica-alumina, institute
Hydrobon catalyst is stated to be made using method comprising the following steps：With a kind of maceration extract impregnated carrier, dipping is consolidated
Body substance is dried, and the maceration extract contains at least one cobalt compound, at least one molybdate compound, at least one and contains
Phosphorus compound and citric acid, the concentration for the cobalt compound counted using cobalt element in the maceration extract is 0.01-0.1g/mL, with molybdenum
The concentration of the molybdate compound of element meter is 0.05-0.4g/mL, and the concentration for the phosphorus-containing compound counted using P elements is 0.005-
0.1g/mL, the concentration of citric acid is 0.05-0.5g/mL, with ultraviolet-visible spectrum analysis and characterization, λ≤1 of the maceration extract, λ
For the ratio of spectral peak peak height at spectral peak peak height at 517 ± 10nm in ultraviolet-visible spectrum and 772 ± 10nm.
The admission space ratio of the Hydrobon catalyst I and Hydrobon catalyst II is 20：80-80：20.
The Hydrobon catalyst I contains the cobalt and molybdenum of carrier and load on the carrier, and the carrier is oxygen
SiClx-aluminium oxide.On the basis of the total amount of the Hydrobon catalyst I, in terms of oxide, the content of cobalt is 1-10 weights
% is measured, the content of molybdenum is 5-50 weight %.Preferably, the content of cobalt is 1-7 weight %, and the content of molybdenum is 8-45 weight %.Into
Preferably, the content of cobalt is 3-7 weight % to one step, and the content of molybdenum is 12-30 weight %.
The Hydrobon catalyst I is made using method comprising the following steps：It, will with a kind of maceration extract impregnated carrier
Dipping obtains solid matter and is dried, the maceration extract contain at least one cobalt compound, at least one molybdate compound,
At least one phosphorus-containing compound and citric acid, the concentration for the cobalt compound counted using cobalt element in the maceration extract is 0.01-
0.1g/mL, the concentration for the molybdate compound counted using molybdenum element as 0.05-0.4g/mL, phosphorus-containing compound in terms of P elements it is dense
It spends for 0.005-0.1g/mL, the concentration of citric acid is 0.05-0.5g/mL, with ultraviolet-visible spectrum analysis and characterization, the dipping
λ≤1 of liquid, λ be in ultraviolet-visible spectrum at 517 ± 10nm at spectral peak peak height and 772 ± 10nm spectral peak peak height ratio.
In the preferred embodiment, it is preferable that the concentration of the cobalt compound in the maceration extract in terms of cobalt element
For 0.02-0.09g/mL, such as 0.05-0.08g/mL；The concentration for the molybdate compound counted using molybdenum element as 0.08-0.35g/mL,
Such as 0.1-0.25g/mL；The concentration for the phosphorus-containing compound counted using P elements is 0.007-0.08g/mL, such as 0.01-0.03g/mL；
The concentration of citric acid is 0.05-0.4g/mL, such as 0.08-0.25g/mL, with ultraviolet-visible spectrum analysis and characterization, the maceration extract
λ=0-0.95, it is highly preferred that λ=0-0.80.
According to the preferred embodiment, following methods preparation may be employed in the maceration extract：(1) by cobalt compound,
Molybdate compound, phosphorus-containing compound and citric acid are mixed with water, and dissolving is reacted into solution；(2) solution that step (1) obtains is existed
At a temperature of 60-300 DEG C reaction 0.5 it is small when -200 it is small when；Wherein, the dosage of each component makes each component in the maceration extract finally obtained
Content meet subject to previously described requirement.In step (2), the temperature is preferably 75-200 DEG C, more preferably 80-150
DEG C, such as 80-120 DEG C.In step (2), when the time of the reaction is preferably 1-100 small, when more preferably 2-50 is small, such as 1-
10h.Step (2) can carry out in closed container (such as autoclave), can also be carried out in open system.
According to the preferred embodiment, the cobalt compound is selected from water-soluble cobalt compound, for example, containing cobalt gold
Belong to more than one or both of salt, the oxide of the metal component containing cobalt and hydroxide of the metal component containing cobalt of component.Institute
The specific example for stating cobalt compound can include but is not limited to the nitrate of cobalt, the chloride of cobalt, the sulfate of cobalt, the first of cobalt
Hydrochlorate, the acetate of cobalt, the phosphate of cobalt, the citrate of cobalt, the oxalates of cobalt, the carbonate of cobalt, cobalt subcarbonate,
The hydroxide of cobalt, the phosphate of cobalt, the phosphide of cobalt, the sulfide of cobalt, the aluminate of cobalt, the molybdate of cobalt, the wolframic acid of cobalt
It is more than one or both of oxide of salt and cobalt.Preferably, the cobalt compound is oxalates, the carbonic acid of cobalt of cobalt
Salt, the subcarbonate of cobalt, the hydroxide of cobalt, the phosphate of cobalt, the molybdate of cobalt, the tungstates of cobalt and cobalt oxide in
One or more.It is highly preferred that the cobalt compound is the subcarbonate of cobalt and/or the carbonate of cobalt.
According to the preferred embodiment, the molybdate compound is selected from water-soluble molybdate compound, for example, containing molybdenum gold
Belong to the salt of component and/or the oxide of the component containing molybdenum.The specific example of the molybdate compound can include but is not limited to
It is more than one or both of ammonium molybdate, the heteropolyacid salt of molybdenum and molybdenum oxide.
According to the preferred embodiment, the phosphorus-containing compound can be phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
More than one or both of sodium dihydrogen phosphate and disodium hydrogen phosphate, it is preferably phosphoric acid.
According to the preferred embodiment, the content of silica and aluminium oxide can be normal in the silica-alumina
Rule selection.Preferably, in the silica-alumina, the content of silica can be 2-45 weight %, be preferably 5-40 weights
%, further preferably 5-30 weight % are measured, such as 10-20 weight %；The content of aluminium oxide can be 55-98 weight %, preferably
It is more preferably 70-95 weight %, such as 80-90 weight % for 60-95 weight %.
According to the preferred embodiment, the dipping can be that saturation impregnates, or excessive dipping.Usually,
The ratio of maceration extract by volume and carrier by weight can be 0.5-10：1, it is preferably 0.7-8：1.When the dipping
During excessively to impregnate, in the presence of having free solution in the mixture obtained in dipping, preferably include before being dried
The step of filtering, to remove free solution.
According to the preferred embodiment, the drying can carry out under normal conditions.Usually, the drying can be with
It is carried out at a temperature of 100-300 DEG C, preferably 120-280 DEG C.When the duration of the drying can be 1-12 small, it is preferably
When 2-8 is small.In a preferred embodiment, dried product can be used directly as catalyst, can also be roasted
It is used after burning as catalyst.The roasting can carry out under normal conditions.Usually, the temperature of the roasting can be
350-550 DEG C, be preferably 400-500 DEG C.When the duration of the roasting can be 1-8 small, when being preferably 2-6 small.
In a kind of preferred embodiment of the present invention, the Hydrobon catalyst I can also contain any not shadow
It rings the performance of catalyst or the substance of catalyst performance can be improved.Boron component can such as be contained, based on the element and with catalyst
On the basis of, the content of boron is no more than 10 weight %, is preferably 0.5-6 weight %.
The Hydrobon catalyst II contains at least one group VIII metal component, at least two group vib metal groups
Point and organic additive, wherein, a kind of group VIII metal component, at least two group vib metal components and organic additive contain
Amount meets：mR:[VIIIx(VIB-1)y(VIB-2)z]O2；Wherein, in a kind of group vib metal component, VIB-2 generations, are represented with VIB-1
Table another kind group vib metal component, R represent at least one organic additive, and m represents every mole of [VIIIx (VIB-1) y (VIB-
2)z]O2In contained organic additive molal quantity, the value range of m is 0.1~2, with group VIII metal component, VIB-1 metals
On the basis of component and the total amount of VIB-2 metal components, x, y, z represent group VIII metal component respectively, VIB-1 metal components,
The molar fraction of VIB-2 metal components, x, y, the value range of z meet (y+z)：X=10：1~1：10.
The group VIII metal component is selected from iron, cobalt, one or more of nickel, vib metals component be selected from chromium,
At least two in molybdenum and tungsten, the x, y, the value range of z meet (y+z)：X=5：1~1：5, and y：Z=5：1~1：5.
The organic additive is selected from organoammonium compound, one or more of sulfonate and organic phosphate.It is organic
Ammonium compounds is selected from tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, tetrapropylammonium hydroxide, six methines
Tetramine, dodecyl trimethyl ammonium chloride；Sulfonate is selected from dodecyl sodium sulfate, neopelex.
Also contain binding agent in Hydrobon catalyst II, on the basis of catalyst, the content of the binding agent is no more than
75 weight %.The binding agent is selected from one or more of silica, aluminium oxide, silica-alumina, preferably described viscous
The content for tying agent is no more than 50 weight %.
The preparation method of the Hydrobon catalyst II is：By the chemical combination of at least one metal component containing group VIII
Object, at least two compound, organic additive and water containing different group vib metal components are mixed with mixed liquor, using acid or
The pH value of alkali adjustment mixed liquor is 7~11, and it is room temperature to 250 DEG C that the mixed liquor, which is placed in reaction kettle in, reaction temperature, instead
When being 1~24 small between seasonable, filter afterwards simultaneously dry.
The body phase Hydrobon catalyst II of the present invention is compared with traditional load hydrogenation catalyst, activated centre density
It is much higher, there is higher hydrodesulfurization, denitrogenation and arene saturating activity.
The present invention enters dress after the diesel oil distillate feedstock oil that need to carry out hydrodesulfurization is mixed with supplement hydrogen and recycle hydrogen
There are two types of in the reactor of Hydrobon catalyst, reactor top dispenses the load hydrogenation for having currently preferred high activity
Catalyst for refining I carries out desulfurization to non-thiophene-type sulfide, thiophene-based and the benzothiophene kind sulfides for being easy to desulfurization.Instead
Answer device lower part that it is de- to carry out hydrogenation to the sulfide of more difficult desulfurization equipped with a kind of higher active body phase Hydrobon catalyst II
Sulphur, and it is carried out at the same time the reactions such as hydrodenitrogeneration, alkene saturation and aromatic hydrocarbons saturation.
The hydrofining reaction condition is：250~430 DEG C of reaction temperature, preferably 280~390 DEG C, hydrogen partial pressure 1.0~
12.0MPa, preferably 2.0~8.0MPa, 0.1~9.0h of volume space velocity during liquid-1, preferably 0.3~6.0h-1, hydrogen to oil volume ratio 100
~1500Nm3/m3, preferably 150~1000Nm3/m3。
The reaction effluent of gained sequentially enters high-pressure separator and low pressure separator carries out gas-liquid point after heat exchange
From, by the separating obtained hydrogen-rich gas of high-pressure separator after circulating hydrogen compressor boosts at the top of most of Returning reactor,
Small part is as quenching hydrogen back to cold hydrogen box between bed；Enter fractionating system through the liquid phase stream obtained by low pressure separator, pass through
Naphtha cut, fine-quality diesel oil product are obtained after fractionation.
The diesel oil distillate feedstock oil is in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil
One or more, boiling range scope are 180 DEG C~400 DEG C.
Advantages of the present invention is：
1st, the Hydrobon catalyst of two kinds of high activities is carried out grading by the present invention, by the sulfide in diesel oil different
Stage substep removes, and obtains the ultra-low-sulphur diesel product for meeting V standard of the Europe IV standard or Europe.Compared with prior art, it is of the invention
Reaction condition mitigate, the air speed of hydrogenation reaction can be further improved, increase the treating capacity of device and/or the rule of reduction device
Mould.
2nd, method provided by the invention employs preferred two kinds of catalyst and carries out rational gradation composition, can not only give full play to
The two hydrogenation activity has synergistic effect well, and entire catalyst system has more good stability, can be significantly
Improve the service cycle of device.
Specific embodiment
The following examples will be further described method provided by the invention, but therefore not limit this
Invention.
In following embodiment and comparative example, ultraviolet-visible light spectrum analysis (UV-Vis) is public using U.S. Perkin-Elmer
The multi-functional spectrophotometry instrument of Lambda35 types of department, in light neon source, measurement wavelength 286nm, slit width
1.0nm, sample detection time 4.5min, detection step-length 2.0s experiment condition under measure solution in the range of 450-900nm
Ultra-violet absorption spectrum.
In following embodiment and comparative example, the content of each element is analyzed in catalyst, using commercially available from Rigaku
The 3271E types Xray fluorescence spectrometer of electric machine industry Co., Ltd. measures.
Hydrobon catalyst I used in the present embodiment is prepared using following methods.
(1) 27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids are weighed respectively to be put into
In 55mL deionized waters, be heated to 80 DEG C be stirred dissolving 1 it is small when, obtain brownish red settled solution.The solution is put into burning
It in cup, is heated to 90 DEG C and when constant temperature 8 is small under stiring, adds water to 85mL, obtain clarifying maceration extract S1.The λ value of maceration extract S1,
Cobalt (Co), molybdenum (Mo), the concentration (g/mL) of phosphorus (P) and citric acid (CTA) are listed in table 1.
Table 1
| Co(g/mL) | Mo(g/mL) | P(g/mL) | CTA(g/mL) | λ | |
| S1 | 0.05 | 0.21 | 0.017 | 0.09 | 0.78 |
(2) by 2000 grams of aluminium hydrate powders (dry glue powder of Chang Ling refinery company catalyst plant production, 71 weight % of butt)
It is uniformly mixed with 1039 grams of Ludox (Haiyang Chemical Plant, Qingdao's product, dioxide-containing silica are 30 weight %).It is mixed by what is obtained
It closes object and is extruded into the butterfly item that circumscribed circle diameter is 1.4 millimeters with banded extruder, and the wet bar of extrusion is connect when 120 DEG C of dryings 4 are small
It when 600 DEG C of roastings 3 are small, it is 18.0 weight % that silica content in carrier Z1, carrier Z1, which is made, alumina content 82.0
Weight %.The water absorption rate of Z1 is 0.85.
(3) S1 solution is settled to 85mL, it is then small in 120 DEG C of dryings 2 successively when 100 grams of carrier Z12 of saturation dipping are small
When, when 250 DEG C of dryings 3 are small, catalyst D1 is obtained, composition is shown in Table 2.
Table 2
| MoO3(weight %) | CoO (weight %) | P2O5(weight %) | C (weight %) | |
| D1 | 20.5 | 4.0 | 2.2 | 1.7 |
Hydrobon catalyst II used is body phase Hydrobon catalyst in embodiment.Consisting of with hydrofinishing
On the basis of catalyst II, 21 weight % of tungsten oxide, 14 weight % of molybdenum oxide, 35 weight % of nickel oxide, binding agent is aluminium oxide, is contained
It measures as 30 weight %.
Hydrobon catalyst III is identical with catalyst used in patent CN101591566B used in comparative example,
It forms and is：It is counted by oxide and on the basis of total catalyst weight, cobalt is 3.0 heavy %, and molybdenum is 13.5 heavy %.Hydrofinishing is catalyzed
The specific surface area of agent III is 198m2/ g, pore volume 0.35ml/g.The catalyst is from including using the method impregnated to carrying alumina
Molybdenum salt and cobalt salt are introduced in body, and prepares by dry and roasting that the molybdenum salt is ammonium molybdate, cobalt salt is cobalt nitrate.The drying
Temperature is 100~300 DEG C, when drying time is 1~6 small；Calcination temperature is 350~550 DEG C, when drying time is 1~6 small,
Labeled as D.
Feedstock oil C used is the mixture of a kind of straight run and catalytic diesel oil in embodiment, main character such as 3 institute of table
Show.
Table 3
| Raw material diesel oil is numbered | C |
| Density (20 DEG C), g/cm3 | 0.8588 |
| Refractive power, nd20 | 1.4841 |
| Sulfur content, μ g/g | 12000 |
| Nitrogen content, μ g/g | 220 |
| Bromine valency, gBr/100g | 2.0 |
| Boiling range ASTM D-1160, DEG C | |
| IBP | 210 |
| 50% | 299 |
| 90% | 355 |
| FBP | 383 |
Embodiment 1
Using diesel raw material C, wherein sulfur content is 12000 μ g/g.Feedstock oil C enters hydrogenation reactor together with hydrogen,
Successively with the Hydrobon catalyst I of the first reaction zone, the Hydrobon catalyst II haptoreactions of second reaction zone, essence is hydrogenated with
The admission space ratio of catalyst I and Hydrobon catalyst II processed are 1: 1, and reaction condition is as shown in table 4, product property such as table
Shown in 5.
As can be seen from Table 5, using method provided by the invention, acquired 7.9 μ g/g of diesel product sulfur content meet
The standard requirement of V sulfur content of Europe.
Comparative example 1
Using diesel raw material C, wherein sulfur content is 12000 μ g/g.Feedstock oil C enters hydrogenation reactor together with hydrogen,
It contacts and is reacted with Hydrobon catalyst I and Hydrobon catalyst III successively, Hydrobon catalyst I and hydrogenation essence
The admission space ratio of catalyst III processed is 1: 1, and reaction condition is as shown in table 4, and product property is as shown in table 5.
As can be seen from Table 5, acquired diesel product sulfur content is 36.4 μ g/g, higher than 1 diesel product of embodiment
Sulfur content three times are more.
Table 4
Table 5
Embodiment 2
Using raw material same as Example 1 and Catalyst packing scheme, catalyst stability experiment is carried out, is keeping table
Under 6 process conditions, the variation of diesel product sulfur content is investigated, specific data are listed in table 7.
Comparative example 2
Using the raw material identical with comparative example 1 and Catalyst packing scheme, catalyst stability experiment is carried out, is keeping table
Under 6 process conditions, the variation of diesel product sulfur content is investigated, specific data are listed in table 7.
Table 6
| Number | Embodiment 2 | Comparative example 2 |
| Hydrogen partial pressure, MPa | 6.4 | 6.4 |
| Reaction temperature, DEG C | 355/355 | 355/355 |
| Total volume air speed, h-1 | 1.5 | 1.5 |
| Hydrogen to oil volume ratio, Nm3/m3 | 300 | 300 |
Table 7
| Embodiment 2 | Comparative example 2 | |
| The duration of runs | Product sulfur content/μ g/g | Product sulfur content/μ g/g |
| 20h | 7.9 | 36.4 |
| 200h | 9.0 | 39.1 |
| 500h | 10.2 | 41.3 |
| 1000h | 12.5 | 46.7 |
| 1500h | 13.2 | 52.4 |
| 2000h | 14.8 | 64.8 |
As can be seen from Table 7, operation period is after 2000h, and the sulfur content of diesel product remains to be maintained in embodiment 2
Relatively low level, and in identical service cycle, the sulfur content of diesel product has been up to 64.8 μ g/g in comparative example 2.By
This can be seen that using method provided by the invention, and entire catalyst system has more good stability.
Claims (9)
1. a kind of method of hydrotreating for producing cleaning diesel oil, diesel oil distillate feedstock oil enters reactor after being mixed with hydrogen, is being hydrogenated with
Under the conditions of refining reaction, successively with Hydrobon catalyst I and Hydrobon catalyst II haptoreactions, reaction effluent into
Row separation and fractionation, obtain diesel product；The Hydrobon catalyst I is the support type that activated metal component is cobalt-molybdenum
Hydrobon catalyst, the Hydrobon catalyst II are body phase Hydrobon catalysts, which is characterized in that the hydrogenation essence
Catalyst I processed contains the cobalt and molybdenum of carrier and load on the carrier, and the carrier is aluminium oxide and/or silica-oxygen
Change aluminium, the Hydrobon catalyst I is made using method comprising the following steps：With a kind of maceration extract impregnated carrier, will soak
Stain obtains solid matter and is dried, and the maceration extract contains at least one cobalt compound, at least one molybdate compound, extremely
Lack a kind of phosphorus-containing compound and citric acid, the concentration for the cobalt compound counted in the maceration extract using cobalt element is 0.01-0.1g/
ML, as 0.05-0.4g/mL, the concentration of the phosphorus-containing compound in terms of P elements is the concentration for the molybdate compound counted using molybdenum element
0.005-0.1g/mL, the concentration of citric acid is 0.05-0.5g/mL, with ultraviolet-visible spectrum analysis and characterization, the maceration extract
λ≤1, λ be in ultraviolet-visible spectrum at 517 ± 10nm at spectral peak peak height and 772 ± 10nm spectral peak peak height ratio；The leaching
Stain liquid is prepared using following methods：(1) cobalt compound, molybdate compound, phosphorus-containing compound and citric acid are mixed with water, it is molten
Solution is reacted into solution；(2) by the solution that step (1) obtains at a temperature of 60-300 DEG C reaction 0.5 it is small when -200 it is small when；
The Hydrobon catalyst II contain at least one group VIII metal component, at least two group vib metal components and
Organic additive, wherein, the content of a kind of group VIII metal component, at least two group vib metal components and organic additive expires
Foot：mR:[VIIIx(VIB-1)y(VIB-2)z]O2；Wherein, a kind of group vib metal component is represented with VIB-1, VIB-2 represents another
A kind of group vib metal component, R represent at least one organic additive, and m is represented every mole [VIIIx (VIB-1) y (VIB-2) z]
O2In contained organic additive molal quantity, the value range of m is 0.1~2, with group VIII metal component, VIB-1 metal components
On the basis of the total amount of VIB-2 metal components, x, y, z represent group VIII metal component, VIB-1 metal components, VIB-2 gold respectively
Belong to the molar fraction of component, x, y, the value range of z meets (y+z)：X=10：1~1：10.
2. according to the method described in claim 1, it is characterized in that, the Hydrobon catalyst I and Hydrobon catalyst
The admission space ratio of II is 20：80-80：20.
3. according to the method described in claim 1, it is characterized in that, cobalt compound in the maceration extract in terms of cobalt element
Concentration is 0.02-0.09g/mL, and the concentration for the molybdate compound counted using molybdenum element is 0.08-0.35g/mL, in terms of P elements
The concentration of phosphorus-containing compound is 0.007-0.08g/mL, and the concentration of citric acid is 0.05-0.4g/mL, with ultraviolet-visible spectrum point
Analysis characterization, λ=0-0.95 of the maceration extract.
4. according to the method described in claim 1, it is characterized in that, the carrier be silica-alumina, the silica-
Silica content in aluminium oxide is 2-45 weight %, and the content of aluminium oxide is 55-98 weight %.
5. according to the method described in claim 1,3 or 4, which is characterized in that using the total amount of the Hydrobon catalyst I as base
Standard, in terms of oxide, the content of cobalt is 1-10 weight %, and the content of molybdenum is 5-50 weight %.
6. according to the method for claim 1, which is characterized in that in the Hydrobon catalyst II, group VIII gold
Belong to component and be selected from iron, cobalt, one or more of nickel, vib metals component in chromium, molybdenum and tungsten at least two, institute
X is stated, the value range of y, z meet (y+z)：X=5：1~1：5, and y：Z=5：1~1：5.
7. according to the method for claim 1, which is characterized in that described organic to add in the Hydrobon catalyst II
Object is added to be selected from organoammonium compound, one or more of sulfonate and organic phosphate.
8. according to the method for claim 1, which is characterized in that the hydrofining reaction condition is：Reaction temperature 250~
430 DEG C, 1.0~12.0MPa of hydrogen partial pressure, 0.1~9.0h of volume space velocity during liquid-1, 100~1500Nm of hydrogen to oil volume ratio3/m3。
9. according to the method for claim 1, which is characterized in that the hydrofining reaction condition is：Reaction temperature 280~
390 DEG C, 2.0~8.0MPa of hydrogen partial pressure, 0.3~6.0h of volume space velocity during liquid-1, 150~1000Nm of hydrogen to oil volume ratio3/m3。
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