CN105694957B - A kind of mononuclear aromatics is hydrogenated with lightening method - Google Patents
A kind of mononuclear aromatics is hydrogenated with lightening method Download PDFInfo
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Abstract
The invention discloses a kind of mononuclear aromatics to be hydrogenated with lightening method, and this method comprises the following steps：Under conditions of mononuclear aromatics is hydrogenated with lighting, catalytic diesel oil raw material, hydrogen-containing gas are contacted with mononuclear aromatics hydrogenation lightening catalyst, the catalyst includes：Carrier and the metallic element being supported on carrier, the carrier are prepared as follows：NaY molecular sieve is contacted in aqueous solvent with organic acid, obtains Modified NaY molecular sieve, wherein, being shaped as the opening of the channel of the Modified NaY molecular sieve is horn-like.The mononuclear aromatics hydrogenation lightening method of the present invention reduces the content of sulphur and nitrogen in diesel oil, and reduces the yield of diesel oil distillate while improve the yield of gasoline fraction.
Description
Technical field
The present invention relates to a kind of mononuclear aromatics to be hydrogenated with lightening method, more particularly to a kind of using catalytic diesel oil as raw material
Mononuclear aromatics is hydrogenated with lightening method.
Background technology
In processing of heavy oil means, RFCC extensive use at home because of its synthesis superiority of effectiveness.Catalysis is split
Micronizing technology is mainly characterized by cracking the alkane in charging and cycloalkane, does not possess broken ring substantially to aromatic hydrocarbons
Ability, therefore a large amount of condensed-nuclei aromatics are generally enriched in catalytic cracking diesel oil.The sulphur and arene content of catalytic cracking diesel oil are high,
Engine ignition poor performance, belong to diesel oil blending component inferior, be mainly used in reconciling abroad the non-derv fuel of fuel oil and
Heat oil etc..
In short supply due to petroleum resources in China, catalytic cracking diesel oil is also mainly to be used for after hydrofinishing or hydro-upgrading
Blended diesel product, statistics show in the catalytic cracking diesel oil of Sinopec affiliated oil refining enterprise production 85% be used for it is common
The production of diesel oil.Aromatic hydrogenation saturation and hydrocracking are that the main method of diesel quality is improved for Arene removal at present, but
Limitation all be present in both approaches.Aromatic hydrogenation saturation is limited to the Cetane number for improving intermediate oil.Hydrogenation splits
Solution can produce the mixture of high cetane number, but also produce small-molecule substance simultaneously, so as to reduce the yield of diesel oil.
The difficult point of catalytic cracking diesel oil processing essentially consists in that its density is big, and Cetane number is relatively low.Typically can be with by being hydrogenated with
The significantly modification of catalytic cracking diesel oil is realized, key is that resulting processing cost enterprise is difficult to receive.If it will urge
Change cracked diesel oil modification completely to derv fuel quality standard, most of aromatic hydrogenation saturation, open loop certainly will be converted
For the alkane of high cetane number, this has clearly a need for very exacting terms, and processing cost is that enterprise is difficult to receive.
Catalytic cracking diesel oil modification be enterprise product quality upgrading have in face of the problem of, how to take into account processing cost and
Economic benefit, the two is reached balance, be that enterprise considers principle and selection skill that catalytic cracking diesel oil processing scheme must comply with
The direction of art route.In China, aromatic hydrocarbons industrial chain is wide and long, is using the aromatic hydrocarbon resource selection multiple series of products chains of infiltration and development
The fundamental policies of China's aromatic hydrocarbons industry.Although development is very fast in recent years, domestic Aromatic Hydrocarbon United Plant still can not meet state
Interior demand, breach are larger.Though for the unsuitable hydro-upgrading production diesel oil of the higher poor quality catalytic cracking diesel of arene content, plus
High-knock rating gasoline is produced after hydrogen or the route of light aromatics is more competitive.
CNOOC Tianjin Chemical Research ＆ Design Institute combines with Huizhou refinery branch company of China National Offshore Oil Corporation
The set technique inferior to catalyst for urging bavin production low-carbon aromatic hydrocarbons is developed, poor quality urges bavin to pass through polycyclic aromatic hydrocarbon deep hydrodesulfurizationof
Denitrification catalyst removes sulphur nitrogen, and makes polycyclic aromatic hydrocarbon selective hydrogenation saturation and mononuclear aromatics is not hydrogenated saturation, 218 in product
~280 DEG C of cut sulphur nitrogen content is low, and based on mononuclear aromatics, mononuclear aromatics mainly includes alkylbenzene, alkylindan class, alkane
Base tetrahydronaphthalene, the molecular sieve catalyst that these mononuclear aromatics need to use chain rupture ability stronger further realize its open loop and side chain
Fracture is to realize the purpose of lighting, but alkylindan class, alkyl tetrahydro naphthalenes easily cause catalyst carbon deposit to inactivate, existing
Molecular sieve catalyst duct be easy to block, short life.
The content of the invention
The invention aims to overcome the mononuclear aromatics used in existing mononuclear aromatics hydrogenation lightening method
It is hydrogenated with lightening catalyst, molecular sieve carrier is easy to block, and causes the catalytic activity of catalyst is low, service life is short to go forward side by side one
Step have impact on the problem of mononuclear aromatics hydrogenation lighting, and provide a kind of mononuclear aromatics hydrogenation lightening method.
The present inventor has found that the duct of NaY molecular sieve greatly have impact on catalyst by multiple experiment
Activity and service life, in order to solve this problem, NaY molecular sieve with organic acid contact instead by the present inventor
Should so that the opening of the channel of Modified NaY molecular sieve is processed into bell mouth shape, so as to greatly reduce the probability that duct is blocked, prolongs
Long life.And it has furthermore been found that in the building-up process of NaY molecular sieve, add a small amount of nonionic surfactant
The modified molecular screen for enabling to the method according to the present invention to obtain is higher for the catalyst activity obtained as carrier, the life-span
It is longer, further increase mononuclear aromatics hydrogenation lighting.
To achieve these goals, the present invention provides a kind of mononuclear aromatics hydrogenation lightening method, and this method includes following
Step：Under conditions of mononuclear aromatics is hydrogenated with lighting, catalytic diesel oil raw material, hydrogen-containing gas and mononuclear aromatics are hydrogenated with lighting
Catalyst contacts, and the catalyst includes：Carrier and the metallic element being supported on carrier, the carrier are made as follows
It is standby：
NaY molecular sieve is contacted in aqueous solvent with organic acid, obtains Modified NaY molecular sieve, wherein, the modification
Being shaped as the opening of the channel of NaY molecular sieve is horn-like.
The mononuclear aromatics hydrogenation lightening method of the present invention reduces the content of sulphur and nitrogen in diesel oil, and reduces diesel oil
The yield of cut improves the yield of gasoline fraction simultaneously.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of mononuclear aromatics hydrogenation lightening method, and this method comprises the following steps：In mononuclear aromatics plus
Under conditions of hydrogen lighting, catalytic diesel oil raw material, hydrogen-containing gas are contacted with mononuclear aromatics hydrogenation lightening catalyst, it is described to urge
Agent includes：Carrier and the metallic element being supported on carrier, the carrier are prepared as follows：
NaY molecular sieve is contacted in aqueous solvent with organic acid, obtains Modified NaY molecular sieve, wherein, the modification
Being shaped as the opening of the channel of NaY molecular sieve is horn-like.
The method according to the invention, the grain size of the Modified NaY molecular sieve can be 100-500nm, preferably 200-
400nm.Modified NaY molecular sieve in the range of the grain size makes framework of molecular sieve stable.The ratio surface of the Modified NaY molecular sieve
Product is 700-750m2/ g, preferably 710-740m2/g；The pore volume of the Modified NaY molecular sieve is 0.4-0.5ml/g；It is preferred that
For 0.43-0.49ml/g.And it can be good at regeneration using the catalyst of the Zeolite synthesis to use.
The method according to the invention, in order to obtain modified NaY molecular sieve, the preferred embodiment of the present invention is by NaY
Molecular sieve contacts with organic acid.The organic acid can be one kind or more in citric acid, acetic acid, oxalic acid and ethylenediamine tetra-acetic acid
Kind, preferably acetic acid.
The method according to the invention, in order to obtain more preferable Modified NaY molecular sieve, in the preferred embodiment of the present invention,
The dosage weight of the organic acid and NaY molecular sieve is than preferably 5-20:100, more preferably 13-17:100.
The method according to the invention, in order to obtain more preferable Modified NaY molecular sieve, in the preferred embodiment of the present invention,
Contact conditions of the NaY molecular sieve with organic acid in aqueous solvent are preferably included：Temperature is 50-100 DEG C, more preferably
70-80℃.PH value is 2-5, more preferably 3-4.Time is 1-5h, more preferably 2-4h.
The method according to the invention, wherein, the step of preparing the carrier, also includes：The Modified NaY molecular sieve is entered
Row shaping, drying and roasting obtain shaping carrier.Wherein, the method be molded, dried and be calcined is well known to those skilled in the art,
Such as it can then be dried, be calcined by the Modified NaY molecular sieve with extruded moulding is carried out after aqueous solution of nitric acid kneading
Arrive.Wherein, the concentration of aqueous solution of nitric acid for example can be 1-10 weight %, and dry condition can include：Temperature is 100-130
DEG C, time 1-5h, the condition of roasting includes：Temperature is 500-600 DEG C, time 2-6h.
According to the present invention, in forming process is carried out, aluminum oxide can also be added, the amount of the aluminum oxide of addition changes with described
The weight of property NaY molecular sieve is than preferably 1-10：1, preferably 2-6：1.
The method according to the invention, the aqueous solvent is to be any containing water and solvent compatible with water.It is wherein aqueous
Solvent can also be the solvent of only water.
The method according to the invention, the NaY molecular sieve are prepared as follows：
(1) sodium aluminate, sodium hydroxide and waterglass are contacted in aqueous solvent, obtains directed agents；
(2) sodium aluminate and sodium hydroxide are mixed in aqueous solvent, then adds nonionic surfactant, mixed
Close solution；
(3) mixed solution in above-mentioned steps (2) and waterglass are mixed, adds in step (1) leading of being prepared
To agent, hydrothermal crystallizing is then carried out, obtains NaY molecular sieve.
The method according to the invention, the aqueous solvent in the step (1) are identical with the aqueous solvent in step (2).Institute
Aqueous solvent is stated to be any containing water and solvent compatible with water.Wherein aqueous solvent can also be the solvent of only water.
The method according to the invention, in the preferred embodiment of the present invention, prepare NaY molecular sieve the step of in (1), institute
Stating the condition of contact includes：Temperature is 15-30 DEG C, preferably 20-25 DEG C.Time is 10-60min, preferably 30-40min.
The method according to the invention, in the preferred embodiment of the present invention, prepare NaY molecular sieve the step of in (2), institute
Stating nonionic surfactant can be polysorbas20, tween 21, polysorbate40, polysorbate60, Tween61, Tween 80, sorbimacrogol oleate100 and tell
One or more in temperature 85, preferably polysorbas20.
The method according to the invention, in the preferred embodiment of the present invention, prepare NaY molecular sieve the step of in (3), water
The temperature of thermal crystallisation can be 60-120 DEG C, preferably 80-100 DEG C.
The method according to the invention, the metallic element can be the one or more in Ni, Mo, W, Re and Co, preferably
For the one or more in Ni, Mo and W.
With the method for the invention it is preferred on the basis of the gross weight of catalyst, the content of metallic element is 10-50 weights
Measure %, preferably 20-30 weight %；The content of carrier is 50-90 weight %, preferably 70-80 weight %.One can so be entered
Step improves the catalytic activity of catalyst.
As long as the purpose of the present invention can be achieved in the catalyst containing aforementioned component of the present invention, its preparation method can be this
The conventional selection in field, the present invention can be prepared as follows to this without particular/special requirement, catalyst of the invention：
(1) water miscible metal salt (such as nickel nitrate, ammonium paramolybdate and sodium tungstate) and deionized water are mixed and made into water
Solution, using saturation impregnation carrier of the present invention；
(2) carrier after impregnating is dried by 90-150 DEG C and 350-550 DEG C of roasting 2-6h post-processes to obtain catalyst.
Wherein, optional wider range of the species of nickel salts solution, such as nickel nitrate.The species of molybdenum salts solution
Optional wider range, such as ammonium paramolybdate.Optional wider range of the species of metal tungsten salt solution, such as sodium tungstate.Rhenium metal
Optional wider range of the species of solution, such as perrhenic acid.Optional wider range of the species of Cobalt salts solution, such as chlorination
Cobalt.For the one or more in preferably water miscible metal salt nickel nitrate, ammonium paramolybdate and sodium tungstate of the invention.
According to the present invention, the monocyclic hydrogenation lighting condition can be the conventional selection in this area, and the present invention is to this nothing
Particular/special requirement.Such as temperature can be 100-500 DEG C, preferably 200-400 DEG C.
According to the present invention, the monocyclic hydrogenation lighting condition can be the conventional selection in this area, and the present invention is to this nothing
Particular/special requirement.Such as pressure can be 1-8MPa, preferably 5-7MPa.
According to the present invention, the monocyclic hydrogenation lighting condition can be the conventional selection in this area, and the present invention is to this nothing
Particular/special requirement.Such as weight (hourly) space velocity (WHSV) can be 0.5-5h-1, preferably 1-2h-1。
According to the present invention, the monocyclic hydrogenation lighting condition can be the conventional selection in this area, and the present invention is to this nothing
Particular/special requirement.Such as hydrogen/oil volume ratio can be 100-800:1, preferably 500-700:1, wherein, hydrogen/oil volume ratio is hydrogen
The volume ratio of gas and catalytic diesel oil feedstock oil.
The method according to the invention, in the preferred embodiment of the present invention, the catalytic diesel oil raw material include mononuclear aromatics,
Condensed-nuclei aromatics and saturated hydrocarbons.
The method according to the invention, on the basis of the gross weight of catalytic diesel oil raw material, the content of mononuclear aromatics can be 30-
60 weight %, the content of condensed-nuclei aromatics can be 10-30 weight %, and the content of saturated hydrocarbons can be 20-50 weight %.
The method according to the invention, on the basis of the gross weight of catalytic diesel oil raw material, the content of element sulphur is 100-500 μ
G/g, the content of nitrogen is 10-50 μ g/g.
In the present invention, the pattern of molecular sieve is observed using Hitachi S-4800 types SEM (SEM).
In the present invention, using the grain size of the Mastersizer2000 laser particle analyzers analyzing molecules sieve of Britain.
In the present invention, specific surface area is BET specific surface area, pore volume according to (《(RIPP is tested petrochemical industryization analysis method
Method》) in RIPP28-90 method measure.
The present invention will be described in detail by way of examples below.But and unspecific limited to this.
Embodiment 1
(1) it is 18Na according to mol ratio under conditions of temperature is 20 DEG C2O:Al2O3:20SiO2:300H2O, by aluminic acid
Sodium, sodium hydroxide, deionized water mixing, stirring, it is completely dissolved it.Under conditions of stirring, waterglass is slowly added
In sodium aluminate solution after being completely dissolved, continue stirring 30 minutes, sealing, stand aging, obtain directed agents.
(2) it is 5Na according to mol ratio2O:Al2O3:10SiO2:200H2O, by sodium aluminate, sodium hydroxide, deionized water is mixed
Close, stirring, be completely dissolved it, then add polysorbas20 (polysorbas20 and Al2O3Mol ratio is 0.2:1), stirring makes it completely molten
Solution, obtains mixed solution.
(3) at room temperature, waterglass is added in above-mentioned mixed solution, high-speed stirred 30 minutes, then adds above-mentioned guiding
Agent, continue stirring 60 minutes, resulting silica-alumina gel is fitted into stainless steel kettle, is warming up to 90 DEG C of crystallization, it is filtered, wash
Wash, in 110 DEG C of drying, obtain NaY molecular sieve.
(4) under conditions of temperature is 70 DEG C, 13 grams of acetic acid are taken to be added to 100 grams of above-mentioned NaY molecular sieves being prepared
The aqueous solution in, the pH value of solution is 3, reacts 3 hours, obtains Modified NaY molecular sieve carrier A.Pass through SEM
Observe it and be shaped as horn-like, it is 200nm to analyze its grain size by laser particle analyzer, and carrier A property is shown in Table 1.
Embodiment 2
Method according to embodiment 1 prepares carrier, unlike：20 DEG C of temperature in step (1) replaces with 25 DEG C, stirring
30 minutes time replaced with 40 minutes；90 DEG C of warming temperature replaces with 100 DEG C in step (3)；Temperature 70 C is replaced in step (4)
For 80 DEG C, 13 grams of acetic acid replace with 17 grams of acetic acid, and pH value is that 3 to replace with pH value be 4, and reaction replaces with 4 hours for 3 hours, obtains
Modified NaY molecular sieve carrier B.By scanning electronic microscope observation, it is shaped as horn-like, and it is analyzed by laser particle analyzer
Grain size is 300nm, and the property of carrier B is shown in Table 1.
Embodiment 3
Method according to embodiment 1 prepares carrier, unlike：90 DEG C of warming temperature replaces with 110 DEG C in step (3)；
Temperature 70 C replaces with 90 DEG C in step (4), and 13 grams of acetic acid replace with 20 grams of citric acids, and pH value is that 3 to replace with pH value be 2, instead
Answer and replace with 3 hours 5 hours, obtain Modified NaY molecular sieve carrier C.By scanning electronic microscope observation, it is shaped as loudspeaker
Shape, it is 400nm to analyze its grain size by laser particle analyzer, and the property of support C is shown in Table 1.
Embodiment 4
Method according to embodiment 1 prepares carrier, unlike：Nonionic surfactant is added without in step (2) to tell
Temperature 20, obtains Modified NaY molecular sieve carrier D.By scanning electronic microscope observation, it is shaped as horn-like, passes through laser particle size
It is 500nm that instrument, which analyzes its grain size, and carrier D property is shown in Table 1.
Comparative example 1
Method according to embodiment 4 prepares carrier, unlike：Without step (4), obtained NaY molecular sieve is used
Directly as carrier E, grain size 600nm.
Table 1
As can be seen from Table 1, Modified NaY molecular sieve carrier of the invention has the advantages that specific surface area is big, and pore volume is big.
Catalyst preparation example 1
The molecular sieve carrier A being prepared in embodiment 1 and aluminum oxide, the aqueous solution of nitric acid are subjected to kneading, added nitre
The concentration of aqueous solution of acid be 4 weight %, and the mass ratio of molecular sieve carrier A and aluminum oxide is 4：1, then extruded moulding, 120 DEG C
Dry 2 hours, 550 DEG C are calcined 4 hours, obtain carrier A1。
Nickel and molybdenum are loaded to by carrier A by saturation dipping method with the aqueous solution of nickel nitrate and ammonium paramolybdate1On, then pass through
120 DEG C of dry 4h are crossed, the content that catalyst A'(Mo is obtained after 450 DEG C of roasting 4h is that the content of 12 weight %, Ni is 7 weights
Measure %).
Catalyst preparation example 2-4
Method according to catalyst preparation example 1 prepares the catalyst of same metal active component and vector contg, different
It is：Molecular sieve carrier uses B, C, D successively, obtains catalyst B', C', D'.
CATALYST PREPARATION Comparative's example 1
Method according to catalyst preparation example 1 prepares the catalyst of same metal active component and vector contg, different
It is that the carrier used is the carrier E that comparative example 1 is prepared, obtains catalyst E'.
Evaluation test example 1
Fixed bed catalyst evaluating apparatus evaluation catalyst A', B', C', D', E' are pressed in.Load in the reactor
The catalyst granules of 12g 20-40 mesh, the catalyst of loading is first at 200 DEG C, containing 0.1 weight % (relative to catalysis in hydrogen stream
Agent) H2Vulcanizing treatment is carried out under conditions of S.Reaction temperature is heated to, reactor pressure is raised to reaction pressure, H2Flow velocity is adjusted
Save as 20L/h, and be continuously pumped into reaction raw materials, mononuclear aromatics hydrogenation lighting reaction occurs in reactor.Reaction used is former
Material composition is shown in Table 2.After stable reaction 24h, with gas chromatograph (model Agilent 7890A) and GC-MS method instrument point
Analyse product liquid composition.
Wherein, the appreciation condition of mononuclear aromatics hydrogenation lighting：6.0MPa, weight (hourly) space velocity (WHSV)：1.0h-1, hydrogen/oil volume ratio
600:1, inlet temperature：380℃.Evaluation result is shown in Table 3.
The feedstock oil composition of the evaluation test example 1 of table 2
The evaluation result of the evaluation test example 1 of table 3
The catalyst activity of the present invention is high it can be seen from the data of table 3, and the effect of desulfurization removing nitric is good.Specifically,
Catalyst prepared by the catalyst and CATALYST PREPARATION Comparative's example 1 prepared by catalyst preparation example 1 can be seen that using this hair
Bright catalyst be hydrogenated with gasoline fraction yield during lighting reaction, is urged compared to prepared by the carrier using prior art
Agent be hydrogenated with gasoline fraction high income during lighting reaction, and carries out hydrogenation lighting using the catalyst of the present invention
The yield of diesel oil distillate during reaction, carry out being hydrogenated with lighting reaction compared to catalyst prepared by the carrier using prior art
When diesel oil distillate yield it is low, it is high so as to demonstrate the catalyst activity of the present invention.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of mononuclear aromatics is hydrogenated with lightening method, this method comprises the following steps：
Under conditions of mononuclear aromatics is hydrogenated with lighting, catalytic diesel oil raw material, hydrogen-containing gas and mononuclear aromatics are hydrogenated with lighting
Catalyst contacts, and the catalyst includes：Carrier and the metallic element being supported on carrier, the carrier are made as follows
It is standby：
NaY molecular sieve is contacted in aqueous solvent with organic acid, obtains Modified NaY molecular sieve, wherein, the Modified NaY point
Being shaped as the opening of the channel of son sieve is horn-like；
Wherein, the NaY molecular sieve is prepared as follows：
(1) sodium aluminate, sodium hydroxide and waterglass are contacted in aqueous solvent, obtains directed agents；
(2) sodium aluminate and sodium hydroxide are mixed in aqueous solvent, then adds nonionic surfactant, obtain mixing molten
Liquid；
(3) mixed solution in above-mentioned steps (2) and waterglass are mixed, add in step (1) directed agents being prepared,
Then hydrothermal crystallizing is carried out, obtains NaY molecular sieve.
2. according to the method for claim 1, wherein, the grain size of the Modified NaY molecular sieve is 100-500nm；It is described
The specific surface area of Modified NaY molecular sieve is 700-750m2/g；The pore volume of the Modified NaY molecular sieve is 0.4-0.5ml/g.
3. according to the method for claim 2, wherein, the grain size of the Modified NaY molecular sieve is 200-400nm；It is described
The specific surface area of Modified NaY molecular sieve is 710-740m2/g；The pore volume of the Modified NaY molecular sieve is 0.43-0.49ml/
g。
4. according to the method for claim 1, wherein, the organic acid is citric acid, acetic acid, oxalic acid and ethylenediamine tetra-acetic acid
In one or more.
5. according to the method for claim 4, wherein, the organic acid is acetic acid.
6. according to the method for claim 1, wherein, the dosage weight ratio of organic acid and NaY molecular sieve is 5-20:100.
7. according to the method for claim 1, wherein, it is described to contact NaY molecular sieve in aqueous solvent with organic acid
Condition includes：Temperature is 50-100 DEG C, pH value 2-5, time 1-5h.
8. according to the method described in claim 1, wherein, in step (1), the condition of the contact includes：Temperature is 15-30
℃；Time is 10-60min.
9. according to the method described in claim 8, wherein, in step (1), the condition of the contact includes：Temperature is 20-25
℃；Time is 30-40min.
10. according to the method described in claim 1, wherein, in step (2), the nonionic surfactant be polysorbas20,
One or more in tween 21, polysorbate40, polysorbate60, Tween61, Tween 80, sorbimacrogol oleate100 and polysorbate85.
11. according to the method described in claim 10, wherein, in step (2), the nonionic surfactant is tween
20。
12. according to the method for claim 1, wherein, in step (3), the temperature of hydrothermal crystallizing is 60-120 DEG C.
13. according to the method for claim 12, wherein, in step (3), the temperature of hydrothermal crystallizing is 80-100 DEG C.
14. according to the method for claim 1, wherein, the metallic element is one kind or more in Ni, Mo, W, Re and Co
Kind.
15. according to the method for claim 14, wherein, the metallic element is the one or more in Ni, Mo and W.
16. the method according to claim 1 or 14, wherein, on the basis of the gross weight of catalyst, the content of metallic element
For 10-50 weight %；The content of carrier is 50-90 weight %.
17. according to the method for claim 16, wherein, on the basis of the gross weight of catalyst, the content of metallic element is
20-30 weight %；The content of carrier is 70-80 weight %.
18. according to the method for claim 1, wherein, the condition of the mononuclear aromatics hydrogenation lighting includes：Inlet temperature
For 100-500 DEG C, pressure 1-8MPa, weight (hourly) space velocity (WHSV) 0.5-5h-1, hydrogen/oil volume ratio is 100-800:1.
19. according to the method for claim 1, wherein, the catalytic diesel oil raw material includes mononuclear aromatics, condensed-nuclei aromatics and satisfied
And hydrocarbon, on the basis of the gross weight of catalytic diesel oil raw material, the content of mononuclear aromatics is 30-60 weight %, the content of condensed-nuclei aromatics
For 10-30 weight %, the content of saturated hydrocarbons is 20-50 weight %.
20. the method according to claim 11, wherein, on the basis of the gross weight of catalytic diesel oil raw material, the content of element sulphur
For 100-500 μ g/g, the content of nitrogen is 10-50 μ g/g.
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