CN106675648A - Hydrogenation method for enhancing cetane number of inferior diesel - Google Patents

Hydrogenation method for enhancing cetane number of inferior diesel Download PDF

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Publication number
CN106675648A
CN106675648A CN201510761517.7A CN201510761517A CN106675648A CN 106675648 A CN106675648 A CN 106675648A CN 201510761517 A CN201510761517 A CN 201510761517A CN 106675648 A CN106675648 A CN 106675648A
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catalyst
diesel
reaction
molecular sieve
hydrogenation
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CN106675648B (en
Inventor
彭冲
曾榕辉
方向晨
刘涛
黄新露
吴子明
白振民
孙士可
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a hydrogenation method for enhancing cetane number of inferior diesel. The method comprises the following steps: (1) sufficiently mixing the inferior diesel raw material and a powdery hydrofining catalyst in a mixer to obtain a catalyst-raw oil feed mixture; (2) adding the feed mixture and hydrogen into an ebullated bed reactor from the reactor bottom filled with a mixture of a hydrodefreezing catalyst and a hydrogenation modification catalyst, and carrying out hydrogenation reaction; (3) discharging the reaction stream containing the powdery hydrofining catalyst out of the top of the ebullated bed reactor into a stable reactor, and carrying out supplementary hydrofining; and (4) carrying out solid-liquid separation on the material obtained in the step (3), and sending the liquid phase into a fractionating system to obtain the high-quality low-pour-point low-sulfur high-cetane-number diesel product. The method reasonably combines the temperature drop in the hydrodefreezing process and the temperature rise in the hydrogenation modification process, thereby lowering the low-pour-point high-cetane-number diesel, lowering the hot-spot temperature of the device and prolonging the operating cycle on the premise of ensuring the high diesel yield.

Description

A kind of method of hydrotreating for improving cetane number of inferior diesel oil
Technical field
The present invention relates to a kind of hydrogenation modification method of poor ignition quality fuel, especially a kind of production method that high-quality high cetane number diesel oil is produced by fluidized bed reactor.
Background technology
Fuel of the diesel oil as compression ignition engine, irreplaceable effect is played during the productive life of modernization as non-renewable resources, the fuel of the delivery vehicles such as automobile, tank, aircraft, tractor, rolling stock or other machinery can be used as, it is also possible to generate electricity, warm oneself.The difference of industry and environment is used according to it, user also has very big difference for the quality requirement of diesel product, for in the people that extremely frigid zones or winter are lived, the demand of low freezing point diesel fuel remains high always, and traditional shape slective cracking technique can process the heavy diesel fuel cut of the content of wax, and pour point depression amplitude is up to 20～50 DEG C, while obtaining low freezing point diesel fuel, also diesel oil distillate scope can be widened, yield is improved, is to solve the highly useful and advanced technology that low freezing point diesel fuel produces problem.
The situation of China is also similar to, particularly in recent years, with the national economic development and the continuous improvement of environmental consciousness, for the requirement more and more higher of diesel quality, the popularity rate of diesel refining rises year by year, in addition in northern cold area, in addition to the requirement to diesel oil regular refiner property, condensation point become it is requisite require one of index, therefore, it is possible to improve the yield and quality of low-coagulation diesel oil, meet the market demand has become Han Qu oil refining enterprise major issue of interest.And shape slective cracking and combinations thereof technique can be used to produce low-sulfur low-coagulation diesel oil as one of Main Means for reducing condensation point of diesel oil, be conducive to improving the economic benefit of oil refining enterprise.
Diesel oil shape slective cracking technology refers in the presence of hydrogen also known as hydro dewaxing, the diesel raw material of the content of wax by the bifunctional catalyst surface containing active metal and molecular sieve, so as to reduce wax molecule content therein.Its dewaxing principle is under certain operating conditions, raw material is set to contact with Hydrodewaxing catalyst with hydrogen mixing, it is cracked into small molecule alkane, the aromatic hydrocarbons with short side alkane, the cycloalkane of belt length side chain and belt length side chain grade high condensation point compositional selecting in raw material, and other components do not change substantially, the purpose of the condensation point for reducing oil product is finally reached.Many advantages, such as there is course of reaction hydrogen to consume that relatively low, adaptability to raw material is strong, energy consumption is relatively low, technological process is simple, can constitute process integrations or independently use with other hydrogenation processes due to it, therefore be widely used.At present many oil refining enterprise of northern China Han Qu employ this technology production low-coagulation diesel oil.
CN1257107A describes a kind of method for producing high-grade low-freezing diesel oil by distillate.Using hydrofinishing and hydro dewaxing one-stage serial flow process, including two beds of Hydrobon catalyst and Hydrodewaxing catalyst, hydro dewaxing adopts Ni/ZSM-5 catalyst to the method.The method is larger in the temperature drop of Hydrodewaxing catalyst bed, and the yield of diesel oil distillate and the raising of depression effeCt are subject to a definite limitation, reduce the service life of Hydrodewaxing catalyst.
CN102051232A describes a kind of method of diesel oil hydrogenation pour point depression, the method is by the property of adjustment catalyst so as to good with diesel oil depression effeCt, the characteristics of diesel oil distillate high income, but due to the group technology for still adopting hydrofinishing and hydro dewaxing to connect, contradiction is still present between depression effeCt and diesel oil distillate yield.
CN102453531A describes a kind of method of diesel hydro-pour-reducing, although improve the average reaction temperature of Hydrodewaxing catalyst, using the temperature rise of refining agent, increases the utilization rate of pour point depression catalyst, but
The reaction temperature of each bed outlet is still of a relatively high, and the cycle receives certain restriction.
CN01134271.4 discloses a kind of combined hydrogenation method for producing high cetane number, low-coagulation diesel oil.The method is first to contact feedstock oil, hydrogen with catalyst for hydro-upgrading or hydrocracking catalyst, reaction effluent is then contacted with Hydrodewaxing catalyst without isolation, reaction effluent Jing coolings enter high-pressure separator, the product liquid isolated enters fractionating system, and the gas rich in hydrogen loops back reactor.The method can simultaneously improve the Cetane number of diesel oil in same covering device and reduce the condensation point of diesel oil, and the Cetane number of diesel product is improved more than 6 units compared with feedstock oil.
CN99113293.9 discloses a kind of method for producing high-quality low-coagulation diesel oil with high hexadecane value by distillate.The method directly connects hydro dewaxing with hydrofinishing, hydro-upgrading, realize hydrofinishing-hydro-upgrading-hydro dewaxing-section serial flow, use the strong Hydrobon catalyst of anti-coking performance and with relatively strong anti-ammonia, the hydro-upgrading of capacity antacid and Hydrodewaxing catalyst so that the technique have it is refined/depression effeCt is good, diesel yield is high, adaptability to raw material is strong, diesel cetane-number is high, technological process is simple and the characteristics of flexible products scheme.
The content of the invention
For the problem that prior art is present, the present invention provides a kind of method of hydrotreating for improving cetane number of inferior diesel oil.The characteristics of the inventive method makes full use of fluidized bed reactor back-mixing, the temperature drop of hydro dewaxing process and the temperature rise during hydro-upgrading are carried out reasonably to combine utilization, while ensureing diesel oil in high yield, produce low condensation point, high cetane number diesel oil, the hot(test)-spot temperature of device is reduced, extends service cycle.
A kind of raising cetane number of inferior diesel oil method of hydrotreating that the present invention is provided, including herein below：
（1）Poor ignition quality fuel raw material is sufficiently mixed in a mixer with powder Hydrobon catalyst, obtains the mixed feeding of catalyst and feedstock oil；
（2）Mixed feeding enters fluidized bed reactor with hydrogen from the reactor bottom equipped with Hydrodewaxing catalyst and catalyst for hydro-upgrading is mixed, and carries out hydrogenation reaction；Wherein described hydrogenation reaction includes hydro dewaxing reaction, arenes selectivity open loop（Continuous side chain）Reaction and hydrofining reaction etc.；
（3）Logistics Jing fluidized bed reactor top is discharged after reaction comprising powder Hydrobon catalyst, is entered and is stablized reactor, carries out supplementing hydrofinishing；
（4）Step（3）The material Jing separation of solid and liquid of acquisition, liquid phase enters fractionating system, obtains high-grade low-freezing, low-sulfur, high cetane number diesel product.
In the inventive method, described poor ignition quality fuel raw material is conventional pour point depression raw material inferior i.e. high freezing point diesel fuel, and typically all more than 0 DEG C, preferred condensation point is more than 5 DEG C for condensation point.Various straight-run diesel oils, the secondary processing diesel oil that can be obtained for processing naphthene base crude, intermediate base crude or paraffinic base crude oil（Coker gas oil, catalytic diesel oil etc.）In one or several, the said components that preferred processing paraffinic base crude oil is obtained.The diesel raw material does generally 350～440 DEG C, preferably 370～400 DEG C.
In the inventive method, described powder Hydrobon catalyst can be powder Hydrobon catalyst commonly used in the art, and its granularity is generally 50～2000 μm, and preferably 500～1500 μm, described powder catalyst can flow with oil product.Typically with group vib and/or group VIII metal as active component, with aluminum oxide or silicon-containing alumina as carrier, vib metals are generally Mo and/or W, and group VIII metal is generally Co and/or Ni.On the basis of the weight of catalyst, vib metals content is calculated as 8wt%～28wt% with oxide, and group VIII tenor is calculated as 2wt%～15 wt% with oxide.
The inventive method step（1）Mixed feeding in, powder Hydrobon catalyst addition is calculated as 20～200 μ g/g with metal.
In the inventive method, described blender can use multistage shear pump, it is also possible to using the mixing arrangement commonly used in the art such as static mixer, ultrasonic oscillator.
In the inventive method, described Hydrodewaxing catalyst is the conventional pour point depression catalyst in this area.Described catalyst includes the silica-alumina supports containing shape slective cracking molecular sieve and hydrogenation active metals.Described shape slective cracking molecular sieve is hydrogen type molecular sieve, and the molecular sieve can be selected from one or more in Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve, preferred ZSM-5 molecular sieve；The silica alumina ratio of the shape slective cracking molecular sieve is generally 10～150, preferably 20～120.Hydrogenation active metals described in Hydrodewaxing catalyst can be the group VIII in the periodic table of elements and/or group vi metallic element, and wherein group VIII active metal can be Ni and/or Co, and group vi active metal is W and/or Mo.On the basis of the weight of catalyst, the content that hydrogenation active metals component is counted with oxide is as 10%～30%, it is 70%～90% containing shape slective cracking molecular sieve silica-alumina supports content, wherein shape slective cracking molecular sieve content in silica-alumina supports is 10%～40%, and remaining is aluminum oxide.Described Hydrodewaxing catalyst can select existing various commercial catalysts, such as Fushun Petrochemical Research Institute（FRIPP）The Hydrodewaxing catalysts such as FDW-1, FDW-3 of development；Can also be prepared by the general knowledge of this area as needed, for example, be referred to the content disclosed in CN1952074A, CN1352231A, CN101143333A, CN102451748A and prepare satisfactory Hydrodewaxing catalyst.
Catalyst for hydro-upgrading described in the inventive method is the hydrogenation conversion catalyst containing molecular sieve, a kind of hydrogenation catalyst for being exclusively used in diesel modifying is referred to, with aromatic hydrocarbons open loop（Continuous side chain）Selective high the characteristics of.Described catalyst for hydro-upgrading includes catalyst carrier and active component, active component is selected from least one group vib metal and at least one group VIII metal, group vib metal oxide content is 10wt%～30wt%, and group VIII metal oxide content is 2wt%～15wt%.；Catalyst carrier consists of aluminum oxide 40wt%～80wt%, amorphous silica-alumina 0wt%～20wt%, the 0.40～0.52mL/g of pore volume of Y molecular sieve 5wt%～30wt%, wherein Y molecular sieve, 750～900m of specific surface2/ g, 2.420～2.500nm of lattice constant, SiO2/Al2O3Molecular proportion 7～15, described catalyst for hydro-upgrading it is salic be a kind of aluminum oxide that crystalline phase is boehmite, content is 40wt%～80wt%.The sieve and silica-sesquioxide weight of contained amorphous silicon aluminium compares 1 in the carrier:2～2:1, content 0wt%～20wt%, best 10wt%～20wt%.The hydrogenation metal can be the combination of at least one group vib metal oxide or sulfide and at least one group VIII metal oxide or sulfide, group vib metal can be Mo or W, preferably select W, content 10wt%～30wt%, group VIII metal can be Ni or Co, preferably select Ni, content 2wt%～15wt%.Conventional hydro modifying catalyst can select existing various commercial catalysts, such as FRIPP develop 3963, the catalyst such as FC-18.As needed specific catalyst for hydro-upgrading can also be prepared by the general knowledge of this area, for example, be referred to CN1184843A, CN1178238A disclosure and prepare satisfactory hydro-upgrading（Conversion）Catalyst.
In production method of the present invention, in described fluidized bed reactor, powder Hydrobon catalyst is 1 with the volume ratio of Hydrodewaxing catalyst and catalyst for hydro-upgrading：10～10：1, preferably 1：5～5：1.Wherein the volume ratio of Hydrodewaxing catalyst and catalyst for hydro-upgrading is 1：5～5：1, preferably 1：2～2：1.
In production method of the present invention, the hydrogenation conditions in described fluidized bed reactor are：6.0 ~ 30.0MPa of reaction pressure, reaction temperature is 270 ~ 500 DEG C, and air speed is 0.1 ~ 5.0h-1, hydrogen to oil volume ratio is 400：1~2000：1.
In production method of the present invention, in boiling bed hydrogenation reactor, diesel raw material, hydrogen are contacted with powder Hydrobon catalyst, diesel oil hydrogenation modification catalyst and Hydrodewaxing catalyst, carry out hydrodesulfurization, denitrogenation, aromatic hydrocarbons open loop（Continuous side chain）Reaction, be hydrocracked and pour point depression reaction etc..
In production method of the present invention, described stable reactor is used for the post-refining that a upper reaction member generates oil, the characteristics of due to Hydrodewaxing catalyst is selective to linear paraffin hydrocracking strong, and the hydrocracking processes of linear paraffin follow carbonium ion reaction mechanism, during the course of the reaction the unsaturation such as generating portion alkene hydro carbons, reduces the stability of oil product.The present invention makes full use of the reaction heat of last action unit and generates the hydrogen partial dissolved in oil, carries out supplementing hydrofinishing in reactor is stablized, and while unsaturated hydro carbons is removed, further reduces the sulfur content of oil product.
In production method of the present invention, described stable reactor exit arranges separating and filtering equipment, for powder Hydrobon catalyst and the separation of solid and liquid of generation oil product, separates the solid phase powder shape Hydrobon catalyst for obtaining and recycles.
In production method of the present invention, described fractionating system separates fractionating system for conventional oil product well known to those skilled in the art, for obtaining the purpose product of appropriate cut.
Compared with prior art, the inventive method has advantages below：
1st, the present invention makes full use of back-mixing " boiling " feature of fluidized bed reactor and the endothermic effect of hydrofinishing, the exothermic effect of hydro-upgrading reaction and hydro dewaxing reaction, realize the comprehensive utilization of course of reaction heat, at utmost reduce temperature rise and temperature drop effect, so that isothermal operation is realized in the reaction of hydrofinishing, hydro-upgrading and pour point depression, so as to improve hydro-upgrading depression effeCt, both the quality and yield of diesel oil, the depression effeCt for achieving again can ensure that.
2nd, mixed class is equipped in fluidized bed reactor fills out catalyst for hydro-upgrading and Hydrodewaxing catalyst, simultaneously catalyst particles intergranular is mixed with powder Hydrobon catalyst again, can give full play to the coupling advantage of catalyst, improve product quality, and utilization of Heat of Reaction efficiency can be improved, reduce plant energy consumption.Diesel modifying catalyst aromatic hydrocarbons open loop used in the present invention（Continuous side chain）Reaction selectivity is strong, can to greatest extent improve diesel cetane-number while high diesel yield is ensured.
3rd, the temperature for utilizing fluidized bed reactor reaction effluent of the invention and the hydrogen partial for wherein dissolving, carry out supplementing hydrofinishing in reactor is stablized with powder Hydrobon catalyst, reduce generating the unsaturated hydrocarbons content and sulfur content in oil product, the stability and quality of diesel product are improve, while improve the utilization rate of hydrogen resources.
4th, the violent motion in reactor that the present invention passes through reactant, effectively eliminates the high temperature dot of device from local with low temperature point, reduces the hot(test)-spot temperature of device, extends the service life of catalyst.
5th, the powder Hydrobon catalyst in the present invention travels up to fluid zone of the fluidized bed reactor without catalyst with oil is generated, and can prevent the generation of area's liquid polycondensation coking reaction under the high temperature conditions in the case of without Hydrodewaxing catalyst and/or catalyst for hydro-upgrading.
Description of the drawings
Fig. 1 is a kind of schematic flow sheet of hydro-upgrading of inferior diesel method of the invention.
Specific embodiment
A kind of hydro-upgrading of inferior diesel method of the present invention is described in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the hydro-upgrading of inferior diesel method flow of the present invention is as follows：By poor ignition quality fuel 1 and powder Hydrobon catalyst（Including the new agent 2 of supplement and recycling catalyst 13）It is sufficiently mixed in blender 3, obtain uniform charging 4, Jing delivery pumps enter fluidized bed reactor, high pressure hydrogen 8 enters fluidized bed reactor of the mixing equipped with Hydrodewaxing catalyst 6 and diesel oil hydrogenation modification catalyst 7 in the way of upper feeding from the bottom of fluidized bed reactor 5 makes catalyst keep boiling-like, under suitable reaction condition, with Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst and powder Hydrobon catalyst are contacted, carry out catalytic hydrogenation reaction, reacted logistics 9 is discharged into stablizing reactor 10 from the top of reactor, carry out supplementing hydrofinishing using the hydrogen partial and logistics self heat that wherein dissolve, separate oil 12 is generated with powder Hydrobon catalyst 13 by separator 11, powder Hydrobon catalyst is recycled, generate oil and enter separation fractionating system 14, fractionate out gas, light distillate and high-grade low-freezing, low-sulfur, high cetane number diesel product 15.
The hydro-upgrading of inferior diesel method of the present invention is further described followed by specific embodiment.
Embodiment 1～4
The present embodiment is to be tested using the boiling bed hydrogenation of Hydrodewaxing catalyst, diesel oil hydrogenation modification and powder Hydrobon catalyst.Concrete operations flow process is shown in accompanying drawing 1.Powder Hydrobon catalyst and the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst are 1 in embodiment 1～2：9, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 1：4；Powder Hydrobon catalyst and the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst are 8 in embodiment 3：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 5：1；Powder Hydrobon catalyst and the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst are 1 in embodiment 4：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 1：2.Poor ignition quality fuel is sufficiently mixed in a mixer with powder Hydrobon catalyst, obtain uniform charging, Jing delivery pumps enter fluidized bed reactor, high pressure hydrogen enters the fluidized bed reactor equipped with Hydrodewaxing catalyst and diesel oil hydrogenation modification catalyst in the way of upper feeding from fluidized bed reactor bottom makes catalyst keep boiling-like, under suitable reaction condition, simultaneously and/or priority and Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst and powder Hydrobon catalyst are contacted, carry out catalytic hydrogenation reaction, reacted logistics is discharged into stablizing reactor from the top of reactor, carry out supplementing hydrofinishing using the hydrogen partial of dissolving and the self heat of material, separate oil is generated with powder Hydrobon catalyst by separator, powder Hydrobon catalyst is recycled, generate oil and enter separation fractionating system, fractionate out gas, light distillate and high-grade low-freezing, low-sulfur, high cetane number diesel product.Hydrodewaxing catalyst C used in embodiment is the spheric catalyst of special preparation, and the catalyst component property is consistent with the commercial catalyst FDW-3 of Fushun Petrochemical Research Institute's development and production.The diesel oil hydrogenation modification catalyst D for using is the spheric catalyst of special preparation, and the catalyst component property is consistent with the commercial catalyst FC-18 of Fushun Petrochemical Research Institute's development and production.The powder catalyst A for using is alumina load Mo-Ni type catalyst, and its granularity is 1000～1200 μm, and active component is contained in catalyst（In terms of metal）Molybdenum 20%, nickel is 8%.
Raw material oil nature is shown in Table 1, and catalyst fundamental property is shown in Table 2, process condition and the results are shown in Table 3.
Comparative example 1-2
Comparative example 1-2 is conventional hydro dewaxing technological process, and reactor types are fixed bed, after feedstock oil is heated, passes sequentially through Hydrobon catalyst and Hydrodewaxing catalyst, and the separated fractionating system of oil product of generation obtains corresponding product.The Hydrobon catalyst for using is that shape size is different with embodiment 1（It is shown in Table 2）, Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst, feedstock oil are same as Example 1.The product property of comparative example 1 ~ 2 is shown in Table 4.The Hydrobon catalyst of comparative example 1 is 1 with the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 1：2；The Hydrobon catalyst of comparative example 2 is 8 with the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 5：1.
The feedstock oil property list of table 1
The catalyst fundamental property of table 2.
The embodiment process condition of table 3 and result.
The comparative example process condition of table 4 and result.
Embodiment compared with comparative example, under the conditions of catalyst proportion identical, product quality be improved significantly, technical advantage is obvious.

Claims (10)

1. it is a kind of to improve cetane number of inferior diesel oil method of hydrotreating, it is characterised in that including herein below：（1）Poor ignition quality fuel raw material is sufficiently mixed in a mixer with powder Hydrobon catalyst, obtains the mixed feeding of catalyst and feedstock oil；（2）Mixed feeding enters fluidized bed reactor with hydrogen from the reactor bottom equipped with Hydrodewaxing catalyst and catalyst for hydro-upgrading is mixed, and carries out hydrogenation reaction；Wherein described hydrogenation reaction includes the continuous side chain reaction of hydro dewaxing reaction, arenes selectivity open loop and hydrofining reaction；（3）Logistics Jing fluidized bed reactor top is discharged after reaction comprising powder Hydrobon catalyst, is entered and is stablized reactor, carries out supplementing hydrofinishing；（4）Step（3）The material Jing separation of solid and liquid of acquisition, liquid phase enters fractionating system, obtains high-grade low-freezing, low-sulfur, high cetane number diesel product.
2. in accordance with the method for claim 1, it is characterised in that：The condensation point of described poor ignition quality fuel raw material more than 0 DEG C, one or several in the various straight-run diesel oils, the secondary processing diesel oil that obtain selected from processing naphthene base crude, intermediate base crude or paraffinic base crude oil.
3. in accordance with the method for claim 1, it is characterised in that：The granularity of described powder Hydrobon catalyst is 50～2000 μm；With group vib and/or group VIII metal as active component, with aluminum oxide or silicon-containing alumina as carrier, vib metals are Mo and/or W, and group VIII metal is Co and/or Ni；On the basis of the weight of catalyst, vib metals content is calculated as 8wt%～28wt% with oxide, and group VIII tenor is calculated as 2wt%～15 wt% with oxide.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）Mixed feeding in, powder Hydrobon catalyst addition is calculated as 20～200 μ g/g with metal.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described blender is multistage shear pump, static mixer or ultrasonic oscillator.
6. in accordance with the method for claim 1, it is characterised in that：Described Hydrodewaxing catalyst includes the silica-alumina supports containing shape slective cracking molecular sieve and hydrogenation active metals；Described shape slective cracking molecular sieve is hydrogen type molecular sieve, and the molecular sieve is selected from one or more in Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve；The silica alumina ratio of the shape slective cracking molecular sieve is 10～150；Group VIII and/or group vi metallic element in the described hydrogenation active metals periodic table of elements, wherein group VIII active metal are Ni and/or Co, and group vi active metal is W and/or Mo；On the basis of the weight of catalyst, the content that hydrogenation active metals component is counted with oxide is as 10%～30%, it is 70%～90% containing shape slective cracking molecular sieve silica-alumina supports content, wherein shape slective cracking molecular sieve content in silica-alumina supports is 10%～40%, and remaining is aluminum oxide.
7. in accordance with the method for claim 1, it is characterised in that：Described catalyst for hydro-upgrading includes catalyst carrier and active component, active component is selected from least one group vib metal and at least one group VIII metal, group vib metal oxide content is 10w%～30wt%, and group VIII metal oxide content is 2wt%～15wt%；Catalyst carrier consists of aluminum oxide 40wt%～80wt%, amorphous silica-alumina 0wt%～20wt%, Y molecular sieve 5wt%～30wt%；Wherein 0.40～the 0.52mL/g of pore volume of Y molecular sieve, 750～900m of specific surface2/ g, 2.420～2.500nm of lattice constant, SiO2/Al2O3Molecular proportion 7～15.
8. in accordance with the method for claim 1, it is characterised in that：In described fluidized bed reactor, powder Hydrobon catalyst is 1 with the volume ratio equipped with Hydrodewaxing catalyst and catalyst for hydro-upgrading is mixed：10～10：1；Wherein the volume ratio of Hydrodewaxing catalyst and catalyst for hydro-upgrading is 1：5～5：1.
9. in accordance with the method for claim 1, it is characterised in that：Hydrogenation conditions in described fluidized bed reactor are：6.0 ~ 30.0MPa of reaction pressure, reaction temperature is 270 ~ 500 DEG C, and air speed is 0.1 ~ 5.0h-1, hydrogen to oil volume ratio is 400：1~2000：1.
10. in accordance with the method for claim 1, it is characterised in that：Described stable reactor exit arranges separating and filtering equipment, for powder Hydrobon catalyst and the separation of solid and liquid of generation oil product, separates the solid phase powder shape Hydrobon catalyst for obtaining and recycles.
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