CN101760234A - Hydrogenation method for improving cetane number of secondary processing diesel oil - Google Patents
Hydrogenation method for improving cetane number of secondary processing diesel oil Download PDFInfo
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Abstract
The invention relates to a hydrogenation method for improving the cetane number of secondary processing diesel oil, which comprises the following steps: mixing secondary processing diesel oil and vegetable oil and/or animal fat; carrying out hydrogenation reaction by mixed ingredients and hydrogenation refining catalysts through contact in the existence of hydrogen; and cooling, separating and fractionating reaction outflow materials to obtain diesel oil products with mixed ingredients as the reference. The method provided by the invention can process low-quality diesel oil distillate with high sulfur content, high nitrogen content and small cetane number. The clean diesel oil products with low sulfur content, high polycyclic aromatic hydrocarbon and large cetane number can be obtained. Because the addition proportion of the vegetable oil is controlled, the influence on the hydrogenation catalysts by water generated in the reaction is reduced, the device operation period is prolonged, and in addition, the yield of obtained diesel oil products is high.
Description
Technical field
The invention belongs to a kind of method at the following refining hydrocarbon ils of the situation that has hydrogen, more particularly, is a kind of method of hydrotreating that improves cetane number of secondary processing diesel oil.
Background technology
Along with improving constantly of environmental protection requirement, people are also more and more higher to the vehicle fuel specification requirement.In the worldwide up-to-date fuel specification, the diesel oil index has been made strict control.Mainly be that sulphur content to diesel product has had stricter restriction.For example, the sulphur content of Europe regulation derv fuel oil from the Europe III emission standard of enforcement in 2000 is less than 350 μ g/g, and sulphur content requires to be reduced to below the 50 μ g/g in the Europe IV emission standard that came into effect in 2005, expectation is in the Europe V standard of implementing in 2009, and sulphur content further is reduced to below the 10 μ g/g.Simultaneously, various new diesel oil standards have also been made strict regulation to product density, polycyclic aromatic hydrocarbon content and cetane value.To this, China has begun to implement gradually the fuel standard in Europe.Come into effect Europe III, Europe IV emission standard respectively in cities such as Beijing, Shanghai, planned to carry out the diesel oil index of Euro V emissions in 2010 years in 2005 and 2008.This shows how producing clean diesel is the significant problem that each enterprise of great oil refining is faced.
At present, China does not carry out strict division to city derv fuel oil and fuel diesel, and the secondary processing diesel oil in the finished diesel fuel such as the ratio of poor ignition quality fuels such as catalytic cracking diesel oil, coker gas oil are quite big.In general, catalytic cracking diesel oil is second-rate.Compare with new diesel oil specification, catalytic cracking diesel oil is foreign matter content such as sulphur, nitrogen height not only, and the content height of alkene and aromatic hydrocarbons, and cetane value is very low.Its cetane value is generally 20～30, compares with the diesel product specification that there is a big difference.Therefore, how to improve the quality of this part diesel oil, become and produce a clean diesel difficult problem.
As everyone knows, can effectively improve the diesel product quality by hydrotreatment.The sulphur content of diesel product can be reduced to below the 350 μ g/g by hydrorefined method, even can satisfy requirement less than the Europe IV emission standard of 50 μ g/g.But hydrorefined method is very little to producing effects of the character such as cetane value of improving catalytic cracking diesel oil.Generally be merely able to make diesel-fuel cetane number to improve 3～5 units.Therefore, each oil company and research institution have all developed hydro-upgrading or hydrocracking process and the suitable catalyzer thereof of handling poor quality catalytic cracking diesel both at home and abroad.Can obtain the higher diesel product of cetane value by the open loop cracking reaction.But, owing to all contain the molecular sieve of some amount in hydro-upgrading or the hydrocracking catalyst, can reduce the yield of diesel product in the hydrogenation process, reduced the diesel product amount.Simultaneously, the operational volume air speed of general hydro-upgrading and hydrocracking is all less than hydrofining, and running cost and plant investment are bigger.
A kind of method of improving the catalytic cracking diesel oil cetane value is disclosed among the CN1289832A.This method is used two kinds of catalyzer: a kind of non-noble metal hydrogenation catalyst for refining and a kind of catalyst for hydro-upgrading that contains molecular sieve.In the hydrogen dividing potential drop is 4.5～8.0MPa, 320～440 ℃ of temperature of reaction, volume space velocity 0.4～2h
-1, hydrogen to oil volume ratio 500～800Nm
3/ m
3Condition under, can make the diesel product cetane value improve 10 units, the heavy % in diesel yield＞90.
On the other hand, vegetables oil more and more is subjected to common people's attention as a kind of renewable resources.The plant oil composition mainly is the lipid acid or the fatty acid ester of long-chain, through obtaining the very high diesel oil distillate of cetane value after deoxygenation and the chain rupture.Therefore, up-to-date research can be raw material production high hexadecane value component with vegetables oil.But, need regularly to replenish sulfide to reactive system because sulfur-bearing hardly in the vegetables oil can keep sulphided state in order to make hydrogenation catalyst.Make process cost increase.Simultaneously, owing to generate a large amount of water behind the vegetables oil hydrogenation, for the hydrogenation catalyst of routine, water-content is too high can to influence the intensity and the activity stability of catalyzer, thereby influences the device operational cycle.
US 5705722 has introduced the method that a kind of moving (planting) thing oil hydrogenation is produced the high hexadecane value blend component.Animal oil (or vegetables oil) under hydroconversion condition and hydrogen in the presence of with Co-Mo or Ni-Mo catalyzer contact reacts, obtain a kind of liquid of diesel oil distillate scope, through separating, fractionation obtains the additive of high hexadecane value.Hydrogenation conditions wherein is: hydrogen dividing potential drop 4～15MPa, 370～450 ℃ of temperature of reaction, volume space velocity 0.5～5h
-1
Introduced a kind of among the US 2006/0186020A1 to mix catalytic cracking diesel oil, coker gas oil and the mixing raw material thereof of 1～75 heavy % vegetables oil.Use a kind of non-noble metal hydrogenation catalyst for refining, the catalyst activity metal component is NiMo or CoMo.In the hydrogen dividing potential drop is 4.0～10.0MPa, 320～400 ℃ of average reaction temperature, volume space velocity 0.5～2h
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3Condition under, can obtain cetane value height, density is low, oxidation stability is good diesel product, it is big that cetane value improves the amplitude that improves than the diesel oil distillate individual curing.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of is the method for hydrotreating of raw material production high hexadecane value diesel component with secondary processing diesel oil inferior.
Method provided by the invention comprises: secondary processing diesel oil mixes with vegetables oil and/or animal grease, its mixing raw material is in the presence of hydrogen, contact with Hydrobon catalyst, at 300～450 ℃ of average reaction temperature, hydrogen dividing potential drop 3.2～8.0MPa, volume space velocity 2.1～6.0h
-1, hydrogen to oil volume ratio 300～800Nm
3/ m
3Condition under carry out hydrogenation reaction, its reaction effluent obtains diesel product after cooling, separation and fractionation, be benchmark with the mixing raw material, by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～35%.
Adopt method provided by the invention, can handle high-sulfur, high nitrogen, low-cetane poor-quality diesel-oil by cut fraction.Can be under demulcent operational condition comparatively, obtain that sulphur content is low, polycyclic aromatic hydrocarbon content and the high clean diesel product of cetane value.Quality product is improved largely than raw material, is good diesel oil blending component.The present invention adopts conventional hydrofining flow process, and flow process is simple, working pressure is low, facility investment and process cost are all lower.Simultaneously, controlled the mixed ratio of vegetables oil, reduced the influence of water generation reaction, prolonged the device operational cycle activity of hydrocatalyst, and the diesel product yield height that obtains.
Embodiment
In the diesel product index, cetane value principal reaction diesel product combustionproperty.The diesel combustion that cetane value is high is even, the thermo-efficiency height; And the heat that the combustion processes of the low diesel oil of cetane value is sent is inhomogeneous, has increased fuel consumption.Therefore, the new diesel product specification of quality has all proposed higher requirement to diesel-fuel cetane number.Europe III and Europe VI emission standard require the cetane value of diesel product to reach more than 46 and 51 respectively.
The height of diesel cetane-number is determined by its chemical constitution and fractions consisting.The cetane value Changing Pattern of each family's hydro carbons is: for the highest, alkene, isomeric alkane and naphthenic hydrocarbon are placed in the middle with the cetane value of alkane for the different hydrocarbons of same carbon number, and the aromatic hydrocarbon especially cetane value of condensed-nuclei aromatics is minimum.The hydro carbons of same structure is along with the increase cetane value of carbon number increases.
The secondary processing means are that the level of crude oil processing improves in the refinery as catalytic cracking, realize the heavy oil lighting, one of important means of voluminous gasoline, diesel oil.Because the feedstock property of processing is poor, and the reaction that is taken place is cracking reaction, and the unsaturated hydrocarbons of catalytic cracking diesel oil and aromaticity content are all higher, thereby the cetane value of catalytic cracking diesel oil is very low, usually less than 25, differ greatly with present diesel product index request.
On the other hand, contain C in the vegetables oil
12～C
20Triglyceride level or tri-fatty class material.Can obtain C after its process hydrogenation deoxidation and the chain rupture
12～C
20Paraffinic hydrocarbons, this cut has very high cetane value.
By above analysis and understanding to diesel oil distillate hydrocarbon composition and cetane value and composition, the specific embodiment of the present invention is:
Mix a certain amount of vegetables oil and/or animal grease is a raw material with the secondary processing diesel oil of poor quality, in the presence of hydrogen, contact, obtain the diesel product that cetane value improves with Hydrobon catalyst.
Described hydrofining reaction condition is: 300～450 ℃ of average reaction temperature, preferred 330～380 ℃; Hydrogen dividing potential drop 3.2～8.0MPa, preferred 4.0～6.4MPa; Volume space velocity 2.1～6h
-1, preferred 2.1～4.0h
-1Hydrogen to oil volume ratio 300～800Nm
3/ m
3, preferred 400～600Nm
3/ m
3
Hydrogenation products enters high-pressure separator successively and light pressure separator carries out gas-liquid separation, and separating obtained hydrogen-rich gas mixes in Returning reactor inlet and the stock oil after circulating hydrogen compressor boosts; The liquid phase stream of gained enters fractionating system, obtains naphtha fraction, fine-quality diesel oil product after fractionation.
Because the reaction of vegetables oil hydrogenation deoxidation can produce water, reduces hydrogenation catalyst intensity for fear of these moisture, causes the hydrogenation catalyst mechanical damage, increases beds pressure reduction, so the ratio that needs controlling plant oil to mix.With the mixing raw material is benchmark, and by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～35%, is preferably 5～30%.The boiling spread of described mixing raw material is 180～700 ℃.
Described secondary processing diesel oil is selected from one or more in catalytic cracking diesel oil, coker gas oil, catalytic pyrolysis diesel oil, visbreaking diesel oil, thermo-cracking diesel oil, the DCL/Direct coal liquefaction diesel oil.
Described vegetables oil is to be selected from plam oil, soybean oil, rapeseed oil, Oleum Gossypii semen, Semen Maydis oil, Rice pollard oil, sunflower oil, peanut oil, Viscotrol C, sesame oil, Fructus Zanthoxyli oil, tea oil, Oleum Cocois, sweet oil, coptis wood oil, tung oil, rosin oil, the Chinese vegetable tallow one or more, and described animal grease is selected from one or more in lard, butter, sheep oil, the fish oil.
Described Hydrobon catalyst is non-noble metal supported catalyzer, carrier is unformed aluminum oxide and/or silica-alumina supports, load on metal component on this carrier and be in VIB or the VIII family at least a in the base metal, the group vib metal is preferably Mo and/or W, and VIII family metal is preferably Co and/or Ni.
Preferred described Hydrobon catalyst, with the catalyzer is benchmark, it consists of: nickel oxide 1～10 heavy %, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina, with described carrier is benchmark, and the content of the silicon oxide in the preferred silica-alumina is 2～45 heavy %, and the content of aluminum oxide is 55～98 heavy %; The content of further preferred silicon oxide is 5～40 heavy %, and the content of aluminum oxide is 60～95 heavy %.Described silica-alumina has the specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferred silica-alumina is 150～350m
2/ g, more preferably 180～300m
2/ g, the pore volume of preferred silica-alumina is 0.4～1ml/g, more preferably 0.5～0.8ml/g.
Described Hydrobon catalyst contains to be selected from and contains in oxygen or the nitrogenous organism one or more, and preferred oxygen-containing organic compound is selected from one or more in organic alcohol, the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetate, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, citric acid, tartrate, the oxysuccinic acid one or more, organic compounds containing nitrogen can be quadrol, EDTA and ammonium salt thereof.Described organism is 0.03-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide compound, is preferably 0.08-1.5.The preferred Hydrobon catalyst of the present invention, the reactive behavior height can be under demulcent reaction conditions comparatively, the sulphur in the effective elimination raw material, nitrogen impurity, and, also help the carrying out of aromatic hydrocarbons saturated reaction because its hydrogenation performance is good.
Under the preferred situation, the upstream of described Hydrobon catalyst also is filled with the hydrogenation protecting agent, is benchmark with the integer catalyzer, by volume, and the filling ratio of described hydrogenation protecting agent is 1～30%.
This hydrogenation protecting agent can load on catalyzer on unformed aluminum oxide and/or the silica-alumina supports at least a base metal in VIB and the VIII family.This hydrogenation protecting catalyst has bigger pore volume and specific surface area usually, and for example pore volume is generally 0.5-1.0ml/g, and specific surface area is generally 120-220m
2/ g.In the agent of the top of Hydrobon catalyst filling hydrogenation protecting, reduce of the influence of the water of vegetables oil hydrogenation deoxidation reaction gained to Hydrobon catalyst, thus the activity cycle and the stability that prolong Hydrobon catalyst.
Under the preferred situation, the downstream of described Hydrobon catalyst also is filled with catalyst for hydro-upgrading, is benchmark with the integer catalyzer, by volume, and the filling ratio of described hydrogenation protecting agent is 1～30%.
Described catalyst for hydro-upgrading contains a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, in oxide compound and with the catalyzer total amount is benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, content 1～15 heavy % of nickel and/or cobalt, this carrier is made up of aluminum oxide and zeolite, and the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50.Described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%.Described zeolite is selected from one or more in faujusite, mordenite, zeolite L, omega zeolite, ZSM-4 zeolite, the Beta zeolite, and preferred y-type zeolite, particularly preferred zeolite are that total acid content is 0.02 to less than 0.5 mmole/gram.
The used catalyst for hydro-upgrading of the present invention has the good shape open loop ability of selecting, and can make the open loop cracking of the above cyclic aromatic compounds of dicyclo in the raw material, thereby reach the reduction polycyclic aromatic hydrocarbon content, improves the purpose of cetane value and reduction density.Simultaneously, owing to Hydrocracking of polycyclic aromatic hydrocarbons, isomery, reduced the space steric effect of difficult desulfurization species, for the further ultra-deep hydrodesulfuration in back provides condition.Studies show that, the chemical reaction of double ring arene is followed following approach: become naphthane after most of double ring arene hydrogenation is saturated, become two Yuans naphthenic hydrocarbon after the further hydrogenation of part naphthane is saturated, another part naphthane becomes mononuclear aromatics through the open loop cracking reaction, and the further more saturated single-ring naphthene that becomes of hydrogenation of the mononuclear aromatics of part.Above-mentioned reaction process, except the open loop cracking reaction of naphthane does not have the reversed reaction, all the other hydrogenation saturated reactions all have reversed reaction to take place, and therefore a corresponding chemical equilibrium is arranged.The catalyst for hydro-upgrading that the present invention uses has good open loop cracking ability, promoted that naphthane open loop cracking is the generation of mononuclear aromatics reaction, thereby broken the chemical equilibrium of entire reaction network, make entire reaction to carry out smoothly, thereby reach the purpose that improves the product cetane value along the saturated course of repeated hydrogenation after the naphthane open loop cracking.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Used Hydrobon catalyst (trade names are RS-1000), hydrogenation protecting agent (RG-1), catalyst for hydro-upgrading (trade names are RIC-1) among the embodiment.Above-mentioned catalyzer is catalyzer Chang Ling branch office of China Petrochemical Corp. and produces.
Used stock oil A is that a kind of diesel oil from the heavy catalytic cracking is mixed 5 heavy % plam oils among the embodiment.Stock oil B is that a kind of diesel oil from the heavy catalytic cracking is mixed 10 heavy % plam oils.Stock oil C is that diesel oil from the heavy catalytic cracking is mixed 30 heavy % plam oils.Stock oil D is that diesel oil from the heavy catalytic cracking is mixed 50 heavy % plam oils.The main character of various raw materials is as shown in table 1.
Embodiment 1
Stock oil A contacts with Hydrobon catalyst under hydrorefined condition and reacts, its resultant of reaction is after refrigerated separation, the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, obtains being on a small quantity naphtha fraction and fine-quality diesel oil cut.Be filled with the hydrogenation protecting agent in the upstream of Hydrobon catalyst, the hydrogenation protecting agent is 1: 9 with the admission space ratio of Hydrobon catalyst.The reaction conditions of present embodiment is as shown in table 2, and after 1000 hours, the diesel product main character is as shown in table 3 with above-mentioned flow process continuous operation.As can be seen from Table 3, the sulphur content of diesel product is 50 μ g/g, and cetane value is 38.4, has improved 13.9 units and diesel product yield than raw material and can reach more than the 98 heavy %.
Embodiment 2
Stock oil B and hydrogen are successively through two reaction zones, contact with catalyst for hydro-upgrading with Hydrobon catalyst successively, carry out hydrofining and selective opening cracking reaction respectively, the admission space ratio of Hydrobon catalyst and catalyst for hydro-upgrading is 8: 2, after the resultant of reaction cooling, the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction and fine-quality diesel oil cut.The reaction conditions of present embodiment is as shown in table 2, and after 1000 hours, the diesel product main character is as shown in table 3 with above-mentioned flow process continuous operation.As can be seen from Table 3, the sulphur content of diesel product is 22 μ g/g, reaches Europe IV emission standard.The diesel product cetane value reaches 42.6, compares with raw material, has improved 15.7 units, is fine clean diesel blend component; And diesel product yield reaches more than the 95 heavy %.
Embodiment 3
Stock oil C reacts under the effect of Hydrobon catalyst, and its resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, obtains being on a small quantity naphtha fraction and fine-quality diesel oil cut.The reaction conditions of present embodiment is as shown in table 2, and after 1000 hours, the diesel product main character is as shown in table 3 with above-mentioned flow process continuous operation.As can be seen from Table 3, the sulphur content of diesel product is less than 50 μ g/g, reaches the requirement of Europe IV emission standard to sulphur content; The diesel product cetane value has improved 10.9 units than raw material, and diesel yield is more than 98 heavy %.
Comparative Examples 1
Stock oil D reacts under the effect of Hydrobon catalyst, and its resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, obtains being on a small quantity naphtha fraction and fine-quality diesel oil cut.Its reaction conditions is identical with embodiment 3, and after 800 hours, the present embodiment test-results sees Table 4 with above-mentioned flow process continuous operation.By the result of table 4 as can be seen: when palmitic mixed ratio increased to 50 heavy %, it is little that the character of hydrogenated products is improved influence.But diesel product yield will reduce significantly; Because water generation reaction increases considerably, can have a strong impact on the activity stability of hydrogenation catalyst simultaneously.
Table 1 stock oil character
| Raw material | Stock oil A | Stock oil B | Stock oil C | Stock oil D |
| Density (20 ℃), g/cm 3 | ??0.9192 | ??0.9189 | ??0.9180 | ??0.9170 |
| Sulphur content, weight % | ??0.40 | ??0.38 | ??0.30 | ??0.22 |
| Nitrogen content, μ g/g | ??442 | ??419 | ??330 | ??236 |
| Oxygen level, weight % | ??0.86 | ??1.35 | ??3.58 | ??5.80 |
| Boiling range (D86), ℃ |
| Raw material | Stock oil A | Stock oil B | Stock oil C | Stock oil D |
| Initial boiling point | ??206 | ??213 | ??225 | ??233 |
| ??50％ | ??289 | ??300 | ??319 | ??369 |
| Final boiling point (95%) | ??408 | ??637 | ??641 | ??655 |
| Cetane value | ??24.5 | ??26.9 | ??32.2 | ??37.5 |
Table 2 operational condition
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Stock oil | ??A | ??B | ??C |
| The hydrogen dividing potential drop, MPa | ??6.4 | ??6.4 | ??6.4 |
| Temperature of reaction, ℃ | ??355 | ??350/360 | ??360 |
| Volume space velocity during liquid, h -1 | ??3.0 | ??2.1 | ??2.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | ??500 | ??700 | ??500 |
Table 3 diesel product character
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 ℃), g/cm 3 | ??0.8731 | ??0.8365 | ??0.8560 |
| Sulphur content, μ g/g | ??50 | ??22 | ??45 |
| Nitrogen content, μ g/g | ??5 | ??＜1 | ??4 |
| The bromine valency, gBr/100g | ??0.6 | ??- | ??0.5 |
| C, heavy % | ??87.66 | ??- | ??87.74 |
| H, heavy % | ??12.14 | ??- | ??12.18 |
| Cetane value | ??38.4 | ??42.6 | ??45.6 |
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Cetane value improves | ??13.9 | ??15.7 | ??13.4 |
| Diesel yield, heavy % | ??＞98 | ??＞95 | ??＞95 |
Table 4 Comparative Examples 1 diesel product character
| Numbering | |
| Density (20 ℃), g/cm 3 | ??0.8470 |
| Sulphur content, μ g/g | ??60 |
| Nitrogen content, μ g/g | ??10 |
| The bromine valency, gBr/100g | ??0.5 |
| Cetane value | ??48.5 |
| Cetane value improves | ??11.0 |
| Diesel yield, heavy % | ??87 |
Claims (10)
1. method of hydrotreating that improves cetane number of secondary processing diesel oil, secondary processing diesel oil mixes with vegetables oil and/or animal grease, its mixing raw material is in the presence of hydrogen, contact with Hydrobon catalyst, at 300～450 ℃ of average reaction temperature, hydrogen dividing potential drop 3.2～8.0MPa, volume space velocity 2.1～6.0h
-1, hydrogen to oil volume ratio 300～800Nm
3/ m
3Condition under carry out hydrogenation reaction, its reaction effluent obtains diesel product after cooling, separation and fractionation, be benchmark with the mixing raw material, by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～35%.
2. in accordance with the method for claim 1, it is characterized in that, in the described mixing raw material, is benchmark with the mixing raw material, and by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～30%.
3. in accordance with the method for claim 1, it is characterized in that the boiling spread of described mixing raw material is 180～700 ℃.
4. in accordance with the method for claim 1, it is characterized in that described secondary processing diesel oil is selected from one or more in catalytic cracking diesel oil, coker gas oil, catalytic pyrolysis diesel oil, visbreaking diesel oil, thermo-cracking diesel oil, the DCL/Direct coal liquefaction diesel oil.
5. in accordance with the method for claim 1, it is characterized in that described vegetables oil is to be selected from plam oil, soybean oil, rapeseed oil, Oleum Gossypii semen, Semen Maydis oil, Rice pollard oil, sunflower oil, peanut oil, Viscotrol C, sesame oil, Fructus Zanthoxyli oil, tea oil, Oleum Cocois, sweet oil, coptis wood oil, tung oil, rosin oil, the Chinese vegetable tallow one or more, described animal grease is selected from one or more in lard, butter, sheep oil, the fish oil.
6. in accordance with the method for claim 1, it is characterized in that described mixing raw material is at 330～380 ℃ of average reaction temperature, hydrogen dividing potential drop 4.0～6.4MPa, volume space velocity 2.1～4.0h
-1, hydrogen to oil volume ratio 400～600Nm
3/ m
3Condition under carry out hydrogenation reaction.
7. in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst is non-noble metal supported catalyzer, carrier is unformed aluminum oxide and/or silica-alumina supports, load on metal component on this carrier and be in VIB or the VIII family at least a in the base metal, the group vib metal is Mo and/or W, and VIII family metal is Co and/or Ni.
8. in accordance with the method for claim 1, it is characterized in that the upstream of described Hydrobon catalyst also is filled with the hydrogenation protecting agent, is benchmark with the integer catalyzer, by volume, and the filling ratio of described hydrogenation protecting agent is 1～30%.
9. in accordance with the method for claim 1, it is characterized in that the downstream of described Hydrobon catalyst also is filled with catalyst for hydro-upgrading, is benchmark with the integer catalyzer, by volume, and the filling ratio of described hydrogenation protecting agent is 1～30%.
10. in accordance with the method for claim 9, it is characterized in that described catalyst for hydro-upgrading contains a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, in oxide compound and with the catalyzer total amount is benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, content 1～15 heavy % of nickel and/or cobalt, this carrier is made up of aluminum oxide and zeolite, and the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50.
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