CN101987971A - Method for producing high-octane petrol by inferior diesel - Google Patents
Method for producing high-octane petrol by inferior diesel Download PDFInfo
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- CN101987971A CN101987971A CN200910162161XA CN200910162161A CN101987971A CN 101987971 A CN101987971 A CN 101987971A CN 200910162161X A CN200910162161X A CN 200910162161XA CN 200910162161 A CN200910162161 A CN 200910162161A CN 101987971 A CN101987971 A CN 101987971A
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Abstract
The invention relates to a method for producing high-octane petrol by inferior diesel. A mixture of diesel raw oil and hydrogen gas reacts with a hydrorefining catalyst in a first reaction zone and a hydrocracking catalyst in a second reaction zone in sequence, the saturation depth of arene in the first reaction zone is controlled, i.e. compared with diesel raw oil, the saturation ratio of two-ring and more than two-ring arene in reaction effluent of the first reaction zone is more than 50%, and taking the liquid components of the reaction effluent of the first reaction zone as a reference, the content of single-ring arene is increased to more than 40% by mass. Low-sulfur high-octane petrol can be produced from inferior diesel fractions with high arene content by using the single-pass process flow and a method of properly controlling reaction depth, and meanwhile, a low-sulfur clean diesel blend component can also be produced.
Description
Technical field
The present invention relates to a kind of is the hydrocarbon ils cleavage method that obtains low boiler cut existing under the situation of hydrogen, more particularly, is a kind of method of being produced stop bracket gasoline by poor ignition quality fuel.
Background technology
Along with the quick growth of crude oil heaviness development and market to the light-end products demand, in China, as the working ability development of the catalytic cracking technology of light materialization of heavy oil major technique rapidly, China's catalyzed cracking processing ability accounts for about 1/3rd of crude oil time processing ability, and is at the forefront in the world.Yet along with the raising of catalyzed cracking processing ability, the output of China's catalytic diesel oil increases year by year, degradation, mainly shows as aromatic hydrocarbons, sulphur, nitrogen, olefin(e) centent height, cetane value is low and stability is poor.Especially because stock oil and catalytic cracking process different, total aromaticity content of catalytic cracking diesel oil does not wait to content the 80 quality % from 50 quality %, and the above aromaticity content of dicyclo and dicyclo is more than 40 quality %.And this part catalytic diesel oil accounts for 1/3rd of Chinese commodity diesel oil share.Meanwhile, along with the continuous enhancing of people's environmental consciousness, environmental regulation has proposed more strict requirement to the quality of diesel oil, thereby to cause great majority be the requirement that its diesel product of refinery of main processing technology is difficult to satisfy market quality with catalytic cracking technology.In addition, the diesel oil of some non-petroleum base cuts, for example the diesel oil distillate of coal direct liquefaction oil or coal tar also is difficult to satisfy the requirement of market quality owing to sulphur, nitrogen, aromaticity content height.Therefore, the oil product that is processed into high added value with poor ignition quality fuel seems particularly important and urgent.
On the other hand, the catalytic gasoline proportion is up to 78% in present China gasoline pool, the alkene that causes gasoline with the sulphur content height, aromaticity content is low, octane value is relative on the low side, therefore, market also needs to develop a kind of production technology of producing low-sulfur, high-octane rating clean gasoline.
The technology of poor ignition quality fuel production high added value oil product mainly contains hydrofining and hydrocracking two classes.Adopt conventional hydrofining technology to handle poor ignition quality fuel, though can remove impurity such as sulphur in the diesel oil, nitrogen effectively, diesel product cetane value increase rate is limited, and the diesel oil variable density is also little; Adopt traditional hydrocracking process processing poor ignition quality fuel, though can the good low-sulfur diesel-oil blend component of production product performance, need comparatively harsh reaction conditions, and its naphtha fraction yield is low.Though perhaps can produce petroleum naphtha to greatest extent, the naphtha fraction octane value of its production is lower, and its research octane number (RON) only has about 75.
US 7,384, and 542B1 discloses a kind of method of producing low-sulfur diesel-oil and stop bracket gasoline.This patent enters hydrogenating desulfurization, hydrodenitrification reaction zone with straight-run diesel oil and/or light wax tailings (LCGO), catalytic cracking diesel oil (LCO) enters the hydrocracking reaction district, the product of two reaction zones enters cold high score, cold low branch after mixing, and enters the fractionating system separation then and obtains high-octane number component and low-sulfur diesel-oil.The hydrocracking reaction district adopts amorphous or contains the hydrocracking catalyst of low molecular sieve level in this invention.This invention can be processed straight-run diesel oil and/or LCGO, and the LCO of 149～343 ℃ of parts, and 87,＞193 ℃ of sulphur content of diesel fraction of 88～193 ℃ of heavy naphtha fraction octane values that obtain are less than 10ppm, cetane index 46.
US 4,985, disclose a kind of technology of producing stop bracket gasoline in 134.This invention raw material boiling spread is 150～327 ℃ LCO, i.e. light constituent in the catalytic cracking light cycle oil.The hydrocracking catalyst that is adopted contains Y zeolite, USY molecular sieve or dealuminzation Y zeolite.In addition, in the fractionation product oil greater than gasoline fraction less than 232 ℃ or be back to the hydrocracking reactor inlet or be back to catalytic cracking reaction zone less than 260 ℃ middle runnings.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of producing stop bracket gasoline by poor ignition quality fuel.Specifically, be will solve prior art processing poor ignition quality fuel and produce gasoline the time, the poor ignition quality fuel raw material is done low, and problem such as gained gasoline products octane value is low.
Method provided by the invention, comprise: the diesel raw material oil-hydrogen mixture is earlier in first reaction zone and Hydrobon catalyst contact reacts, the reaction effluent of first reaction zone enters second reaction zone and hydrocracking catalyst contact reacts without separation, the reaction effluent of second reaction zone is through cooling, obtain hydrogen-rich gas and product liquid after the separation, control the aromatic hydrocarbons saturation depth of first reaction zone, promptly with diesel raw material oil phase ratio, the saturation exponent of dicyclo and the above aromatic hydrocarbons of dicyclo is more than 50% in the reaction effluent of described first reaction zone, and the liquid ingredient with the reaction effluent of first reaction zone is a benchmark, and its mononuclear aromatics content is increased to more than the 40 quality %.
At first reaction zone, i.e. hydrofining reaction district, the poor ignition quality fuel raw material mainly carries out reactions such as hydrogenating desulfurization, hydrodenitrification and aromatic hydrocarbons are saturated.Pass through the degree of depth of control hydrofining reaction process among the present invention, impel the above aromatic hydrocarbons of dicyclo and dicyclo to be saturated to mononuclear aromatics, avoiding supersaturation is naphthenic hydrocarbon, in reducing diesel oil in the foreign matter contents such as sulphur, nitrogen, reduce dicyclo and the above aromaticity content of dicyclo, and increase mononuclear aromatics content.At second reaction zone, promptly in the hydrocracking reaction district, liquid ingredient in the reaction effluent of first reaction zone (hydrofining product oil) carries out selective opening on hydrogenation-cracking function catalyzer, reactions such as cracking, make the short-side chain alkylbenzene effectively, the mononuclear aromatics side chain selectivity that cetane value such as naphthane are low is carried out open loop, reactions such as cracking, impel in the diesel oil distillate mononuclear aromatics than small molecules to be converted into benzene in the gasoline fraction, high-octane rating components such as toluene are improved gasoline fraction product hydrocarbon composition thereby reach, improve the purpose of gasoline fraction product octane value.Keep simultaneously more macromolecular long chain alkane in the diesel oil distillate as far as possible or have the naphthenic hydrocarbon of long side chain or high hexadecane value component such as aromatic hydrocarbons, thereby reach the purpose that improves the diesel product cetane value, improves the product diesel quality.
In another preferred version of the present invention, control the aromatic hydrocarbons saturation depth of first reaction zone, with diesel raw material oil phase ratio, the saturation exponent of dicyclo and the above aromatic hydrocarbons of dicyclo is more than 60% in the reaction effluent of described first reaction zone, and the liquid ingredient with the reaction effluent of first reaction zone is a benchmark, and its mononuclear aromatics content is increased to more than the 50 quality %.
The present invention adopts a conventional through type technical process of hydrofining-hydrocracking, without any intermediate section from, the device flow process is simple, easy handling can utilize conventional device transformation, the investment and the process cost of equipment are lower.In the described one-pass technical process, hydrofining reaction district and hydrocracking reaction district can be arranged in the reactor, also can be arranged in two reactors.
The boiling spread of diesel raw material oil of the present invention is 165～400 ℃, and total aromaticity content is higher than 65 quality %, and preferred total aromaticity content is 65～90 quality %, and wherein the content of dicyclo and the above aromatic hydrocarbons of dicyclo is higher than 40 quality %, preferred 40～65 quality %.In the diesel oil distillate of the straight-run diesel oil of described diesel raw material grease separation catalytic cracking light cycle oil, heavy catalytic cycle oil, naphthenic base crude, the coker gas oil of naphthenic base crude, coal direct liquefaction oil, the diesel oil distillate of coal tar one or more.
The reaction conditions of described first reaction zone and second reaction zone is: hydrogen dividing potential drop 3.0～10.0MPa, preferred 4.0～6.5MPa, 300～450 ℃ of temperature of reaction, preferred 350～430 ℃, hydrogen to oil volume ratio 400～1600Nm
3/ m
3, preferred 500～1200Nm
3/ m
3, volume space velocity 0.2～2.5h during liquid
-1, preferred 0.4～1.5h
-1
The Hydrobon catalyst in described first reaction zone and the loadings of the hydrocracking catalyst in second reaction zone are to determine according to the nitrogen content of the stock oil of being processed.When diesel raw material oil nitrogen content is that 700 μ g/g-2000 μ g/g are when above, Hydrobon catalyst is 5: 1～1: 5 with hydrocracking catalyst admission space ratio, be preferably 3: 1～1: 1, when diesel raw material oil nitrogen content during less than 700 μ g/g, Hydrobon catalyst is 1: 1～1: 5 with hydrocracking catalyst admission space ratio, is preferably 1: 1～1: 2.
If carbon residue or metal content are higher in the stock oil; for falling, the pressure that prevents beds reaches limit value too quickly; can load the hydrogenation protecting agent that accounts for hydrofining agent volume total amount 5～20% at Hydrobon catalyst bed top respectively, to protect Primary Catalysts, to avoid the quick coking of bed.Protective material is made up of the gamma-aluminium oxide carrier with diplopore distribution of 1.0～5.0 heavy % nickel oxide, 5.5～10.0 heavy % molybdenum oxides and surplus.
Described Hydrobon catalyst is VIII family base metal and/or the group vib non-precious metal catalyst that loads on composite alumina and/or the combined oxidation silicon carrier.Preferred Hydrobon catalyst consists of: in oxide compound and with the catalyzer total amount is benchmark, and the content of nickel and/or cobalt is 1～10 heavy %, and molybdenum and tungsten sum are greater than 10～50 heavy %, and fluorine 1～10 weighs %, and all the other are aluminum oxide and silicon oxide.This Hydrobon catalyst has good hydrogenating desulfurization, hydrodenitrification performance, and the saturated performance of aromatic hydrocarbons of part, can be used for the hydrotreatment of poor-quality diesel-oil by cut fraction, impurity such as the sulphur in the energy effective elimination raw material, nitrogen, and appropriateness is carried out the aromatic hydrocarbons saturated reaction, impel the above aromatic hydrocarbons of dicyclo and dicyclo to be saturated to mononuclear aromatics, avoiding supersaturation is naphthenic hydrocarbon.
Described hydrocracking catalyst is VIII family base metal and/or the group vib non-precious metal catalyst that loads on the complex carrier, in oxide compound and with the catalyzer total amount is benchmark, catalyzer mesolite content is the heavy % of 1-90, the heavy % of aluminum oxide 5-80, metal component 3～30 heavy % of group VIII metal component 1～15 heavy %, group vib.Preferred hydrocracking catalyst has following composition: fluorine 0.5～5.0 heavy %, nickel oxide 2.5～6.0 heavy %, Tungsten oxide 99.999 10～38 heavy %, all the other are carrier, zeolite in this carrier is the mixture of a kind of large pore zeolite and a kind of mesopore zeolite, in catalyzer, large pore zeolite contains 1～65 heavy %, mesopore zeolite contains the heavy % of 1-50.Described hydrocracking catalyst has good selective cracking function, this cracking catalyst has good selectivity to reactions such as the fracture of mononuclear aromatics side chain, naphthane selective opening and disconnected side chains, make the mononuclear aromatics generation selective cracking reaction in the diesel oil distillate generate high-octane rating gasoline components such as benzene, toluene, thereby improve the gasoline fraction hydrocarbon composition, increase the octane value of gasoline fraction.
The present invention adopts one-pass technical process, adopt the method for appropriateness control reaction depth, can be higher than 89 gasoline fraction less than 50 μ g/g, research octane number (RON) by the poor-quality diesel-oil by cut fraction production sulphur content of high aromaticity content, can also the production sulphur content improve 10 clean diesel blend components more than the unit than stock oil simultaneously less than 50 μ g/g, actual measurement cetane value.In addition, the present invention has adopted a kind of hydrocracking reaction flow process of routine, easy handling, and facility investment is lower.
Description of drawings
Accompanying drawing is a schematic flow sheet of being produced the method for stop bracket gasoline by poor ignition quality fuel provided by the invention.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.Accompanying drawing is a schematic flow sheet of being produced the stop bracket gasoline method by poor ignition quality fuel provided by the invention.Omitted many equipment among the figure, as pump, interchanger, compressor etc., but this is known to those of ordinary skills.
The flow process of method provided by the invention is described in detail as follows: from the stock oil process raw oil pump 2 of pipeline 1, preheating is after pipeline 11 is mixed into first reactor 3 with hydrogen or hydrogen-rich gas from pipeline 10, contact with Hydrobon catalyst, carry out desulfurization, denitrogenation and appropriate aromatic hydrocarbons saturated reaction.The reaction effluent of first reactor 3 contacts with hydrocracking catalyst from directly entering second reactor 4 without any intermediate section through pipeline 12, carries out the cracking reaction of suitable selectivity side chain fracture.The reaction effluent of second reactor 4 enters cold high pressure separator 5 through pipeline 13 and carries out gas-liquid separation, and separating obtained hydrogen-rich gas enters circulating hydrogen compressor 7 through pipeline 15, through boosting after pipeline 10 returns the inlet of first reactor 3 and second reactor 4.Cold high pressure separator 5 isolated liquid streams enter light pressure separator 6 through pipeline 14 and carry out further gas-liquid separation, and separating obtained gas is through pipeline 17 dischargers, and the product liquid of gained enters fractionating system 8 through pipeline 16 and carries out the component cutting.Isolating diesel oil distillate is extracted out through pipeline 18, and isolating gasoline fraction is extracted out through pipeline 19.
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
The trade names of Hydrobon catalyst A are RN-10 among the embodiment, the trade names of Hydrobon catalyst B are RS-1000, the trade names of hydrocracking catalyst C are RT-5, and all catalyzer are produced by China PetroChemical Corporation's Chang Ling catalyst plant.
Used stock oil D and E are respectively from different catalytic cracking unit among the embodiment, and its character is listed in table 1.As can be seen from Table 1, total aromaticity content of stock oil D and E has all surpassed more than the 75 quality %, the content of the dicyclo of stock oil D and the above aromatic hydrocarbons of dicyclo is up to 46.9 quality %, and cetane value only is 20.6, the content of the dicyclo of stock oil E and the above aromatic hydrocarbons of dicyclo is up to 58.6 quality %, and cetane value is the poor-quality diesel-oil by cut fraction of high aromaticity content less than 19.3.
Embodiment 1
Stock oil D enters hydrogenator with hydrogen, successively with the Hydrobon catalyst B of first reaction zone, the hydrocracking catalyst C contact reacts of second reaction zone, reacted effluent without any intermediate section from entering high-pressure separator, light pressure separator, through refrigerated separation, hydrogen-rich gas recycles, product liquid enters fractionating system and is separated into gasoline fraction and diesel oil distillate, Hydrobon catalyst is 3: 2 with the admission space ratio of hydrocracking catalyst, control the aromatic hydrocarbons saturation depth of first reaction zone, promptly with diesel raw material oil phase ratio, the saturation exponent of dicyclo and the above aromatic hydrocarbons of dicyclo is 69.7% in the reaction effluent of described first reaction zone, and the liquid ingredient with the reaction effluent of first reaction zone is a benchmark, and its mononuclear aromatics content is 51.6 quality %.Reaction conditions is as shown in table 2, and product yield and character are as shown in table 3.
As can be seen from Table 3, the yield of gasoline fraction product is 43.5 heavy %, sulphur content 32 μ g/g, gasoline fraction research octane number (RON) 91.4, motor-method octane number 80.9; The actual measurement cetane value of diesel oil distillate product is 30.9, compares with raw material, and cetane value improves 10.3 units, and sulphur content is less than 50 μ g/g.
Stock oil D enters hydrogenator with hydrogen, successively with the Hydrobon catalyst A of first reaction zone, the hydrocracking catalyst C contact reacts of second reaction zone, reacted effluent without any intermediate section from entering high-pressure separator, light pressure separator, through refrigerated separation, hydrogen-rich gas recycles, product liquid enters fractionating system and is separated into gasoline fraction and diesel oil distillate, Hydrobon catalyst is 1: 1 with the admission space ratio of hydrocracking catalyst, control the aromatic hydrocarbons saturation depth of first reaction zone, promptly with diesel raw material oil phase ratio, the saturation exponent of dicyclo and the above aromatic hydrocarbons of dicyclo is 54.9% in the reaction effluent of described first reaction zone, and the liquid ingredient with the reaction effluent of first reaction zone is a benchmark, and its mononuclear aromatics content is 52.5 quality %.Reaction conditions is as shown in table 2, and product yield and character are as shown in table 3.
As can be seen from Table 3, the yield of gasoline fraction product is 38.8 heavy %, sulphur content 38 μ g/g, gasoline fraction research octane number (RON) 89.4, motor-method octane number 80.5; The actual measurement cetane value of diesel oil distillate product is 30.6, compares with raw material, and cetane value improves 10 units, and sulphur content is less than 50 μ g/g.
Stock oil E enters hydrogenator with hydrogen, successively with the Hydrobon catalyst A of first reaction zone, the hydrocracking catalyst C contact reacts of second reaction zone, reacted effluent without any intermediate section from entering high-pressure separator, light pressure separator, through refrigerated separation, hydrogen-rich gas recycles, product liquid enters fractionating system and is separated into gasoline fraction and diesel oil distillate, Hydrobon catalyst is 2: 3 with the admission space ratio of hydrocracking catalyst, control the aromatic hydrocarbons saturation depth of first reaction zone, promptly with diesel raw material oil phase ratio, the saturation exponent of dicyclo and the above aromatic hydrocarbons of dicyclo is 55.0% in the reaction effluent of described first reaction zone, and the liquid ingredient with the reaction effluent of first reaction zone is a benchmark, and its mononuclear aromatics content is 51.8 quality %.Reaction conditions is as shown in table 2, and product yield and character are as shown in table 3.
As can be seen from Table 3, the yield of gasoline fraction product is 49.0 heavy %, and sulphur content is less than 50 μ g/g, gasoline fraction research octane number (RON) 92.0, motor-method octane number 81.3; The actual measurement cetane value of diesel oil distillate product is 30.1, compares with raw material, and cetane value improves 10.8 units, and sulphur content is less than 50 μ g/g.
Table 1
| Stock oil | D | E |
| Density (20 ℃), g/cm 3 | 0.9340 | 0.9472 |
| Viscosity (20 ℃), mm 2/s | 5.115 | 4.831 |
| The bromine valency, gBr/100g | 10.8 | 13.2 |
| Refractive power, n D 20 | 1.5427 | 1.5523 |
| Sulphur, μ g/g | 7600 | 14000 |
| Nitrogen, μ g/g | 1075 | 455 |
| Cetane value | 20.6 | ＜19.3 |
| Total aromaticity content, quality % | 76.5 | 78.7 |
| The above aromaticity content of dicyclo, quality % | 46.9 | 58.6 |
| Boiling range (ASTM D-86), ℃ | ||
| Initial boiling point | 206 | 184 |
| 10％ | 231 | 224 |
| 50％ | 280 | 269 |
| Final boiling point | 365 | 372 |
Table 2
| Numbering | Embodiment 1 | |
|
| Stock oil | D | D | E |
| Hydrofining/hydrocracking catalyst | B/C | A/C | A/C |
| Reaction conditions | |||
| The hydrogen dividing potential drop, MPa | 5.5 | 4.5 | 5.0 |
| Temperature of reaction, ℃ | 360/400 | 380/390 | 360/410 |
| The cumulative volume air speed, h -1 | 1.0 | 0.8 | 1.0 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 700 | 800 | 900 |
Table 3
| Embodiment 1 | |
|
|
| Gasoline fraction character: | |||
| Yield, weight % | 43.5 | 38.8 | 49.0 |
| Density (20 ℃), g/cm 3 | 0.7780 | 0.7840 | 0.7930 |
| Sulphur content, μ g/g | 32 | 38 | ＜50 |
| Research octane number (RON) | 91.4 | 89.4 | 92.0 |
| Motor-method octane number | 80.9 | 80.5 | 81.3 |
| Boiling range ASTM D-86, ℃ | |||
| IBP | 57 | 60 | 49 |
| 10％ | 70 | 72 | 69 |
| 50％ | 133 | 115 | 136 |
| FBP | 198 | 203 | 200 |
| Diesel oil distillate character: | |||
| Density (20 ℃), g/cm 3 | 0.8950 | 0.9010 | 0.9129 |
| Sulphur content, μ g/g | ＜50 | ＜50 | ＜50 |
| Cetane value | 30.9 | 30.6 | 30.1 |
| The cetane value improvement value | 10.3 | 10.0 | 10.8 |
| Boiling range ASTM D-86, ℃ | |||
| IBP | 205 | 197 | 195 |
| 10％ | 218 | 220 | 218 |
| 50％ | 248 | 255 | 260 |
| FBP | 370 | 368 | 372 |
Claims (10)
1. method of producing stop bracket gasoline by poor ignition quality fuel, the diesel raw material oil-hydrogen mixture is earlier in first reaction zone and Hydrobon catalyst contact reacts, the reaction effluent of first reaction zone enters second reaction zone and hydrocracking catalyst contact reacts without separation, the reaction effluent of second reaction zone is through cooling, obtain hydrogen-rich gas and product liquid after the separation, it is characterized in that, control the aromatic hydrocarbons saturation depth of first reaction zone, promptly with diesel raw material oil phase ratio, the saturation exponent of dicyclo and the above aromatic hydrocarbons of dicyclo is more than 50% in the reaction effluent of described first reaction zone, and the liquid ingredient with the reaction effluent of first reaction zone is a benchmark, and its mononuclear aromatics content is increased to more than the 40 quality %.
2. in accordance with the method for claim 1, it is characterized in that, control the aromatic hydrocarbons saturation depth of first reaction zone, with diesel raw material oil phase ratio, the saturation exponent of dicyclo and the above aromatic hydrocarbons of dicyclo is more than 60% in the reaction effluent of described first reaction zone, and the liquid ingredient with the reaction effluent of first reaction zone is a benchmark, and its mononuclear aromatics content is increased to more than the 50 quality %.
3. in accordance with the method for claim 1, it is characterized in that the boiling spread of described diesel raw material oil is 165～400 ℃, total aromaticity content is higher than 65 quality %, and wherein the content of dicyclo and the above aromatic hydrocarbons of dicyclo is higher than 40 quality %.
4. in accordance with the method for claim 1, it is characterized in that one or more in the diesel oil distillate of the straight-run diesel oil of described diesel raw material grease separation catalytic cracking light cycle oil, heavy catalytic cycle oil, naphthenic base crude, the coker gas oil of naphthenic base crude, coal direct liquefaction oil, the diesel oil distillate of coal tar.
5. in accordance with the method for claim 1, it is characterized in that the reaction conditions of described first reaction zone and second reaction zone is: hydrogen dividing potential drop 3.0～10.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～1600Nm
3/ m
3, volume space velocity 0.2～2.5h during liquid
-1
6. in accordance with the method for claim 1, it is characterized in that the reaction conditions of described first reaction zone and second reaction zone is: hydrogen dividing potential drop 4.0～6.5MPa, 350～430 ℃ of temperature of reaction, hydrogen to oil volume ratio 500～1200Nm
3/ m
3, volume space velocity 0.4～1.5h during liquid
-1
7. in accordance with the method for claim 1, it is characterized in that, when diesel raw material oil nitrogen content is 700 μ g/g-2000 μ g/g, Hydrobon catalyst is 5: 1～1: 1 with hydrocracking catalyst admission space ratio, when diesel raw material oil nitrogen content during less than 700 μ g/g, Hydrobon catalyst is 1: 1～1: 5 with hydrocracking catalyst admission space ratio.
8. in accordance with the method for claim 1, it is characterized in that, when diesel raw material oil nitrogen content is 700 μ g/g-2000 μ g/g, Hydrobon catalyst is 3: 1～1: 1 with hydrocracking catalyst admission space ratio, when diesel raw material oil nitrogen content during less than 700 μ g/g, Hydrobon catalyst is 1: 1～1: 2 with hydrocracking catalyst admission space ratio.
9. in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst is VIII family base metal and/or the group vib non-precious metal catalyst that loads on composite alumina and/or the combined oxidation silicon carrier.
10. in accordance with the method for claim 1, it is characterized in that, described hydrocracking catalyst is VIII family base metal and/or the group vib non-precious metal catalyst that loads on the complex carrier, in oxide compound and with the catalyzer total amount is benchmark, catalyzer mesolite content is the heavy % of 1-90, the heavy % of aluminum oxide 5-80, metal component 3～30 amount % of group VIII metal component 1～15 heavy %, group vib.
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