CN106675640B - A kind of poor ignition quality fuel highly effective hydrogenation method for modifying - Google Patents
A kind of poor ignition quality fuel highly effective hydrogenation method for modifying Download PDFInfo
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- CN106675640B CN106675640B CN201510761518.1A CN201510761518A CN106675640B CN 106675640 B CN106675640 B CN 106675640B CN 201510761518 A CN201510761518 A CN 201510761518A CN 106675640 B CN106675640 B CN 106675640B
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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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a kind of poor ignition quality fuel highly effective hydrogenation method for modifying, including herein below：（1）Poor ignition quality fuel raw material is sufficiently mixed in a mixer with powdered Hydrobon catalyst, obtains mixed feeding；（2）Mixed feeding enters fluidized bed reactor with hydrogen from the reactor bottom equipped with Hydrodewaxing catalyst, catalyst for hydro-upgrading and isomerization-visbreaking catalyst is mixed, and carries out hydrogenation reaction；（3）Logistics, into reactor is stablized, carries out supplement hydrofinishing through being discharged at the top of fluidized bed reactor after reaction comprising powdered Hydrobon catalyst；（4）For material through separation of solid and liquid, liquid phase enters fractionating system, obtains fine-quality diesel oil product.The inventive method makes full use of the characteristics of fluidized bed reactor back-mixing, the temperature drop of hydro dewaxing process and hydrofinishing and the temperature rise in hydroconversion process are rationally utilized, while ensureing diesel oil in high yield, produce low condensation point, super-low sulfur, high cetane number diesel oil, the hot(test)-spot temperature of device is reduced, extends service cycle.
Description
Technical field
The present invention relates to a kind of highly effective hydrogenation method for modifying of poor ignition quality fuel, it is especially a kind of by fluidized bed reactor come
Produce the production method of high-grade low-freezing high cetane number diesel oil.
Background technology
Fuel of the diesel oil as compression ignition engine, risen during the production and living of modernization as non-renewable resources
Irreplaceable effect, the delivery vehicles such as automobile, tank, aircraft, tractor, rolling stock or other can be used as
The fuel of machinery, it is also possible to generate electricity, warm oneself.According to it using industry and the difference of environment, user is for diesel product
Quality requirement also have very big difference, for extremely frigid zones or winter life people for, low freezing point diesel fuel
Demand remains high always, and traditional shape slective cracking technique can process the heavy diesel fuel cut of the content of wax, pour point depression amplitude up to 20~
50 DEG C, while obtaining low freezing point diesel fuel, diesel oil distillate scope can be also widened, improves yield, be to solve low freezing point diesel fuel production
The highly useful and advanced technology of problem.
The situation in China is also similar, particularly in recent years, right with the national economic development and the continuous improvement of environmental consciousness
In 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, except normal to diesel oil
Outside the requirement of the refined property of rule, condensation point becomes one of essential requirement index, therefore can improve the production of low-coagulation diesel oil
Amount and quality, meet that the market demand has turned into Han Qu oil refining enterprise major issue of interest.And shape slective cracking and combinations thereof work
Skill can be used for producing low-sulfur low-coagulation diesel oil, be advantageous to improve oil refining enterprise as one of Main Means for reducing condensation point of diesel oil
Economic benefit.
Diesel oil shape slective cracking technology is also known as hydro dewaxing, refers in the presence of hydrogen, and the diesel raw material of the content of wax is led to
The bifunctional catalyst surface containing active metal and molecular sieve is crossed, so as to reduce wax molecule content therein.Its principle that dewaxes
It is under certain operating conditions, to mix raw material and hydrogen and contacted with Hydrodewaxing catalyst, alkane in raw material, with short
It is cracked into small molecule the aromatic hydrocarbons of side chain alkane, the cycloalkane of belt length side chain and belt length side chain grade high condensation point compositional selecting, and
Other components do not change substantially, are finally reached the purpose for the condensation point for reducing oil product.Due to its have course of reaction hydrogen consumption compared with
It is low, adaptability to raw material is strong, energy consumption is relatively low, technological process is simple, can form and process integration or independently makes with other hydrogenation processes
With many advantages, such as, therefore be widely used.The many oil refining enterprise of northern China Han Qu employ this technology at present
Produce low-coagulation diesel oil.
CN1257107A describes a kind of method that high-grade low-freezing diesel oil is produced by distillate.This method uses hydrofinishing
With hydro dewaxing one-stage serial flow, including two beds of Hydrobon catalyst and Hydrodewaxing catalyst,
Hydro dewaxing uses Ni/ZSM-5 catalyst.This method is larger in the temperature drop of Hydrodewaxing catalyst bed, the receipts of diesel oil distillate
The raising of rate and depression effeCt is reduced the service life of Hydrodewaxing catalyst by a definite limitation.
CN102051232A describes a kind of method of diesel oil hydrogenation pour point depression, this method by adjust the property of catalyst from
And there is the characteristics of diesel oil depression effeCt is good, diesel oil distillate high income, but due to still using hydrofinishing and hydro dewaxing to connect
Group technology, between depression effeCt and diesel oil distillate yield contradiction still exist.
CN102453531A describes a kind of method of diesel hydro-pour-reducing, although improving the flat of Hydrodewaxing catalyst
Equal reaction temperature, using the temperature rise of refining agent, the utilization rate of pour point depression catalyst is increased, still
The reaction temperature of each bed outlet is still of a relatively high, and the cycle receives certain limitation.
CN01134271.4 discloses a kind of combined hydrogenation method for producing high cetane number, low-coagulation diesel oil.This method is
Feedstock oil, hydrogen are first contacted with catalyst for hydro-upgrading or hydrocracking catalyst, reaction effluent without isolation then with
Hydrodewaxing catalyst contacts, and reaction effluent enters high-pressure separator through cooling, and the product liquid isolated enters fractionation train
System, the gas circulation rich in hydrogen return reactor.This method can improve the Cetane number and drop of diesel oil simultaneously in same covering device
The condensation point of low diesel oil, the Cetane number of diesel product improve more than 6 units compared with feedstock oil.
CN99113293.9 discloses a kind of method that high-quality low-coagulation diesel oil with high hexadecane value is produced by distillate.This method
Hydro dewaxing is directly connected with hydrofinishing, hydro-upgrading, realizes hydrofinishing-hydro-upgrading-hydro dewaxing-section series connection
Flow, using the strong Hydrobon catalyst of anti-coking performance and with relatively strong anti-ammonia, capacity antacid hydro-upgrading 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 oil
The characteristics of Cetane number is high, technological process is simple and products scheme is flexible.
The content of the invention
The problem of existing for prior art, the present invention provide a kind of poor ignition quality fuel highly effective hydrogenation method for modifying.The present invention
Method makes full use of the characteristics of fluidized bed reactor back-mixing, by the temperature drop of hydro dewaxing process and hydrofinishing and hydro-conversion mistake
Temperature rise in journey carries out rational combination and utilized, and while ensureing diesel oil in high yield, produces low condensation point, super-low sulfur, Gao Shiliu
Alkane value diesel oil, the hot(test)-spot temperature of device is reduced, extend service cycle.
A kind of poor ignition quality fuel highly effective hydrogenation method for modifying provided by the invention, including herein below：
（1）Poor ignition quality fuel raw material is sufficiently mixed in a mixer with powdered Hydrobon catalyst, obtain catalyst with
The mixed feeding of feedstock oil；
（2）Mixed feeding is urged with hydrogen from mixed packing Hydrodewaxing catalyst, catalyst for hydro-upgrading and isomerization-visbreaking
The reactor bottom of agent enters fluidized bed reactor, carries out hydrogenation reaction；Wherein described hydrogenation reaction includes hydro dewaxing
Reaction, selective opening（Continuous side chain）Reaction, isomerization-visbreaking reaction and hydrofining reaction etc.；
（3）Logistics is through discharging at the top of fluidized bed reactor after reaction comprising powdered Hydrobon catalyst, into steady
Determine reactor, carry out supplement hydrofinishing；
（4）Step（3）For the material of acquisition through separation of solid and liquid, liquid phase enters fractionating system, obtains high-grade low-freezing, low-sulfur, height
Cetane number diesel product.
In the inventive method, described poor ignition quality fuel raw material is high freezing point diesel fuel for conventional pour point depression raw material inferior, condensation point
Typically all more than 0 DEG C, preferably condensation point is more than 5 DEG C.Can be processing naphthene base crude, intermediate base crude or paraffinic base crude oil
Obtained various straight-run diesel oils, secondary processing diesel oil（Coker gas oil, catalytic diesel oil etc.）In one or several kinds, preferably process
The said components that paraffinic base crude oil obtains.The diesel raw material does generally 350~440 DEG C, preferably 370~400 DEG C.
In the inventive method, described powdered Hydrobon catalyst can be it is commonly used in the art it is powdered plus
Hydrogen catalyst for refining, its granularity are generally 50~2000 μm, preferably 500~1500 μm, and described powder catalyst can be with
Flowed with oil product.Typically using group vib and/or group VIII metal as active component, using 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, the
Group vib tenor is calculated as 8wt%~28wt% with oxide, and group VIII tenor is calculated as 2wt%~15wt% with oxide.
The inventive method step（1）Mixed feeding in, powdered Hydrobon catalyst addition is calculated as 20 with metal
~200mg/g.
In the inventive method, described blender can use multistage shear pump, can also use static mixer, ultrasound
The mixing arrangement commonly used in the art such as wave oscillator.
In the inventive method, described Hydrodewaxing catalyst is the conventional pour point depression catalyst in this area.Described urges
Agent includes silica-alumina supports and hydrogenation active metals containing shape slective cracking molecular sieve.Described shape slective cracking molecular sieve is Hydrogen
Molecular sieve, the molecular sieve can be selected from Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38
One or more in molecular sieve, preferably 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 in the periodic table of elements
VIII and/or group vi metallic element, wherein group VIII active metal can be Ni and/or Co, group vi active metal
It is W and/or Mo.On the basis of the weight of catalyst, hydrogenation active metal component contains using the content that oxide is counted as 10%~30%
It is 70%~90% to have shape slective cracking molecular sieve silica-alumina supports content, and wherein shape slective cracking molecular sieve content in silica-alumina supports is
10%~40%, remaining is aluminum oxide.Described Hydrodewaxing catalyst can select existing various commercial catalysts, such as comfort
Along Petroleum Chemical Engineering Institute（FRIPP）The Hydrodewaxing catalysts such as FDW-1, FDW-3 of development；It can also press as needed
It is prepared by the general knowledge of this area, for example, be referred to CN1952074A, CN1352231A, CN101143333A,
Content disclosed in CN102451748A prepares satisfactory Hydrodewaxing catalyst.
Catalyst for hydro-upgrading described in the inventive method is the hydrogenation conversion catalyst containing molecular sieve, is referred to a kind of special
For the hydrogenation catalyst of diesel modifying, there is aromatic hydrocarbons open loop（Continuous side chain）The characteristics of selectivity is high.Described hydro-upgrading
Catalyst includes catalyst carrier and active component, and active component is selected from least one group vib metal and at least one VIII
Metal, group vib metal oxide content are 10w%~30wt%, and group VIII metal oxide content is 2wt%~15wt%.；Catalysis
Agent carrier composition is aluminum oxide 40wt%~80wt%, amorphous silica-alumina 0wt%~20wt%, Y molecular sieve 5wt%~30wt%, wherein Y
0.40~0.52mL/g of pore volume of molecular sieve, than 750~900m of surface2/ g, lattice constant 2.420~2.500nm, SiO2/
Al2O3Molecular proportion 7~15, described catalyst for hydro-upgrading it is salic be a kind of crystalline phase be boehmite aluminum oxide,
Content is 40wt%~80wt%.The sieve and silica-sesquioxide weight of contained amorphous silicon aluminium is than 1 in the carrier:2~2:1, content
0wt%~20wt%, best 10wt%~20wt%.The hydrogenation metal can be at least one group vib metal oxide or vulcanization
The combination of thing and at least one group VIII metal oxide or sulfide, group vib metal can be Mo or W, preferably from W, contain
10wt%~30wt% is measured, group VIII metal can be Ni or Co, preferably from Ni, content 2wt%~15wt%.Conventional hydro modifies
Catalyst can select existing various commercial catalysts, for example, FRIPP develop 3963, the catalyst such as FC-18.Also may be used
With as needed press this area general knowledge prepare specific catalyst for hydro-upgrading, such as be referred to CN1184843A,
CN1178238A disclosures prepare satisfactory hydro-upgrading（Conversion）Catalyst.
Described isomerization-visbreaking catalyst is conventional catalyst in the art.The isomerization-visbreaking catalyst is general
Including following component：Amorphous silica-alumina, modified beta molecular sieve, refractory porous oxide,B races andFamily metal oxide.
On the basis of the weight ratio of catalyst, the content of each component is generally in catalyst：Amorphous silica-alumina 29wt%~50wt%, it is modified
Beta-molecular sieve 1wt%~9%, vib metals 15wt%~35wt% in terms of oxide, group VIII metal are calculated as with oxide
3wt%~9wt%, refractory porous oxide 0wt%~45wt%.Described refractory porous oxide, aluminum oxide, oxidation can be selected from
Titanium, zirconium oxide, boron oxide and above-mentioned element（Aluminium, titanium, zirconium, boron）One or more in composite oxides etc., are preferably aoxidized
Aluminium.Can such as macroporous aluminium oxide be contained and aperture alumina adhesive, macroporous aluminium oxide are generally 0wt%~22wt%；Aperture
Aluminum oxide is generally 0wt%~23wt%.The specific surface area of catalyst is generally 160~230m2/ g, pore volume is 0.32~
0.45mL/g.The property of the modified beta molecular sieve is generally：Its SiO2/Al2O3Mol ratio is 50~90, and crystallinity is generally 90
~110, average grain size is generally 0.1~0.5 micron, 400~750m of specific surface area2/ g, 0.25~0.50mL/g of pore volume,
Na2O content is less than 0.10wt%, infrared 0.1~0.4mmol/g of acidity, and 2~10nm secondary pore pore volume accounts for the 30% of total pore volume
~60%.SiO in described amorphous silica-alumina2Content be generally 20wt%~75wt%, preferably 35wt%~60wt%.Without fixed
The pore volume of shape sial is 0.5~1.1mL/g, preferably 0.6~0.8mL/g；Specific surface area is 200~500m2/ g, preferably
280~500m2/g.Macroporous aluminium oxide pore volume is 0.6~1.2mL/g, preferably 0.8~1.2mL/g, specific surface area is 200~
550m2/ g, preferably 300~500m2/g.Aperture aluminum oxide pore volume is 0.3~0.5mL/g, and specific surface area is 180~350m2/
g.Vib metals are generally W and/or Mo, and group VIII metal is generally Ni and/or Co.Conventional hydro modifies isomerization-visbreaking
Catalyst can select existing various commercial catalysts, such as the catalyst such as FC-14, FC-20 of FRIPP developments.
Specific hydro-upgrading isomerization-visbreaking catalyst can be prepared by the general knowledge of this area as needed, such as be referred to
Content disclosed in CN1712498A prepares satisfactory isomerization-visbreaking catalyst.
In the inventive method, in described fluidized bed reactor, powdered Hydrobon catalyst and mixed packing face
The volume ratio of hydrogen pour point depression catalyst, catalyst for hydro-upgrading and isomerization-visbreaking catalyst is 1：5~5：1, preferably 1：3~3：1；
Wherein Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst account for the volume hundred of catalyst in reactor total amount
Divide than being not less than 10% respectively, the volume ratio of three kinds of catalyst is preferably 1~3：1~3：1~3.
In the inventive method, the hydrogenation conditions in described fluidized bed reactor are：6 ~ 30MPa of reaction pressure, instead
It is 270 ~ 500 DEG C to answer temperature, and air speed is 0.1 ~ 5.0h-1, hydrogen to oil volume ratio 400：1~2000:1.
In the inventive method, in boiling bed hydrogenation reactor, diesel raw material, hydrogen and powdered hydrofinishing are catalyzed
Agent, diesel oil hydrogenation modification catalyst, hydroisomerizing pour point depression catalyst and Hydrodewaxing catalyst contact, carry out hydrodesulfurization, take off
The continuous side chain reaction of nitrogen, aromatic hydrocarbons open loop, it is hydrocracked and isomery, hydro dewaxing reaction etc..
In the inventive method, described stable reactor is used for the post-refining of upper reaction member generation oil, due to facing
The characteristics of hydrogen pour point depression catalyst is selectively strong to linear paraffin hydrocracking, and the hydrocracking processes of linear paraffin follow just
Carbon ion reaction mechanism, the unsaturated hydro carbons such as generating portion alkene during the course of the reaction, reduce the stability of oil product.The present invention
The hydrogen partial dissolved in the reaction heat and generation oil of last action unit is made full use of, supplement is carried out in reactor is stablized and is added
Hydrogen refines, 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 sets separating and filtering equipment, adds for powdered
The separation of solid and liquid of hydrogen catalyst for refining and generation oil product, the solid phase powder shape Hydrobon catalyst for separating acquisition recycle.
In production method of the present invention, described fractionating system is conventional oil product separation fractionation well known to those skilled in the art
System, 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 and hydrofinishing, the hydro-upgrading reaction of fluidized bed reactor
Exothermic effect and hydro dewaxing reaction endothermic effect, 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 hydrofinishing, hydro-upgrading and pour point depression reaction, so as to improve hydro-upgrading drop
Solidifying effect, can both ensure the quality and yield of diesel oil, the depression effeCt achieved again.
2nd, mixed class is equipped in fluidized bed reactor fills out catalyst for hydro-upgrading, isomerization-visbreaking catalyst and hydro dewaxing and urges
Agent, while catalyst particles intergranular is mixed with powdered Hydrobon catalyst again, can give full play to the coupling advantage of catalyst, carry
High yield quality, and utilization of Heat of Reaction efficiency can be improved, reduce plant energy consumption.The diesel modifying catalyst virtue used in the present invention
The continuous side chain reaction selectivity of hydrocarbon open loop is strong, can improve diesel fuel cetane to greatest extent while high diesel yield is ensured
Value.The isomerization-visbreaking catalyst used can strengthen pour point depression and hydro-upgrading effect.
3rd, temperature and the hydrogen partial that wherein dissolves of the present invention using fluidized bed reactor reaction effluent, it is and powdered
Hydrobon catalyst carries out supplement hydrofinishing in reactor is stablized, and reduces unsaturated hydrocarbons content and sulphur in generation oil product
Content, improves the stability and quality of diesel product, while improves the utilization rate of hydrogen resources.
4th, the present invention is by the motion violent in reactor of reactant, from part by the high temperature dot of device and low temperature point
Effectively eliminate, reduce the hot(test)-spot temperature of device, extend the service life of catalyst.
5th, the powdered Hydrobon catalyst in the present invention travels up to fluidized bed reactor without catalysis with generation oil
The fluid zone of agent, it can prevent that area's liquid is in high temperature in the case of without isomerization-visbreaking catalyst and/or catalyst for hydro-upgrading
Under the conditions of polycondensation coking reaction generation.
Brief description of the drawings
Fig. 1 is a kind of schematic flow sheet of poor ignition quality fuel highly effective hydrogenation method for modifying of the present invention.
Embodiment
A kind of poor ignition quality fuel highly effective hydrogenation method for modifying of the present invention is described in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the poor ignition quality fuel highly effective hydrogenation method for modifying flow of the present invention is as follows：By poor ignition quality fuel 1 and powder
Shape Hydrobon catalyst（Including supplementing new agent 2 and recycling catalyst 14）It is sufficiently mixed in blender 3, acquisition is uniformly entered
Material 4, enter fluidized bed reactor through delivery pump, high pressure hydrogen 9 enters mixed in a manner of upper feeding from the bottom of fluidized bed reactor 5
Attaching together the fluidized bed reactor of Hydrodewaxing catalyst 6, catalyst for hydro-upgrading 7 and isomerization-visbreaking catalyst 8 makes catalyst
Boiling-like is kept, under suitable reaction condition, is catalyzed with Hydrodewaxing catalyst 6, catalyst for hydro-upgrading 7, isomerization-visbreaking
Agent 8 and the contact of powdered Hydrobon catalyst, carry out catalytic hydrogenation reaction, and reacted logistics 10 is arranged from the top of reactor
Go out to enter and stablize reactor 11, supplement hydrofinishing is carried out using the hydrogen partial and logistics self heat that wherein dissolve, by
Separator 12 separates oil 13 is generated with powdered Hydrobon catalyst 14, and powdered Hydrobon catalyst recycles,
Generation oil enters separation fractionating system 15, fractionates out gas, light distillate and high-grade low-freezing, low-sulfur, the production of high cetane number diesel oil
Product 16.
The poor ignition quality fuel highly effective hydrogenation method for modifying of the present invention is further described followed by specific embodiment.
Embodiment 1~3
The present embodiment is to use Hydrodewaxing catalyst, catalyst for hydro-upgrading, hydroisomerizing pour point depression catalyst and powder
The boiling bed hydrogenation experiment of shape Hydrobon catalyst.Concrete operations flow is shown in accompanying drawing 1.Powdered hydrogenation essence in embodiment 1~2
The volume ratio of catalyst processed and Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst is 1：5, wherein facing hydrogen
Pour point depression catalyst, catalyst for hydro-upgrading, the volume ratio of isomerization-visbreaking catalyst are 1：1：1.Powdered hydrogenation essence in embodiment 3
The volume ratio of catalyst processed and Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst is 3：1, wherein facing hydrogen
Pour point depression catalyst, catalyst for hydro-upgrading, the volume ratio of isomerization-visbreaking catalyst are 1：2：1, poor ignition quality fuel is added with powdered
Hydrogen catalyst for refining is sufficiently mixed in a mixer, is obtained uniform charging, is entered fluidized bed reactor, High Pressure Hydrogen through delivery pump
Gas is entered in a manner of upper feeding from fluidized bed reactor bottom is equipped with Hydrodewaxing catalyst, catalyst for hydro-upgrading and isomery
The fluidized bed reactor of pour point depression catalyst make catalyst keep boiling-like, under suitable reaction condition, while and/or successively with
Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst and the contact of powdered Hydrobon catalyst, are urged
Change hydrogenation reaction, reacted logistics is discharged into stable reactor at the top of reactor, using dissolving hydrogen partial and
The self heat of material carries out supplement hydrofinishing, by separator will generate it is oily separated with powdered Hydrobon catalyst,
Powdered Hydrobon catalyst recycles, and generates oil and enters separation fractionating system, fractionates out gas, light distillate and high-quality
Low solidifying, low-sulfur, high cetane number diesel product.The Hydrodewaxing catalyst C used in embodiment is that the spherical of special preparation is urged
Agent, the catalyst component property are consistent with the commercial catalyst FDW-3 of Fushun Petrochemical Research Institute's development and production.Use
Catalyst for hydro-upgrading D be special preparation spheric catalyst, the catalyst component property and Fushun petrochemical industry research
The commercial catalyst FC-18 of institute's development and production is consistent.The isomerization-visbreaking catalyst E used is the spheric catalyst of special preparation,
The catalyst component property is consistent with the commercial catalyst FC-14 of Fushun Petrochemical Research Institute's development and production.The powder used
Last shape catalyst A is the catalyst of alumina load Mo-Ni active metals, and its granularity is 1000~1200 μm, is contained in catalyst
Active component（In terms of metal）Molybdenum is 20%, nickel 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, table 4.
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,
Hydrobon catalyst and Hydrodewaxing catalyst are passed sequentially through, the oil product of generation obtains corresponding product through separating fractionating system.
The Hydrobon catalyst used is that shape size is different with embodiment 1（It is shown in Table 2）, Hydrodewaxing catalyst, hydro-upgrading
Catalyst, isomerization-visbreaking catalyst, feedstock oil are same as Example 1.The product property of comparative example 1 ~ 2 is shown in Table 4.Comparative example 1
The volume ratio of Hydrobon catalyst and Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst is 1：5, its
Middle Hydrodewaxing catalyst, catalyst for hydro-upgrading, the volume ratio of isomerization-visbreaking catalyst are 1：1：1, the hydrofinishing of comparative example 2
The volume ratio of catalyst and Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst is 3：1, wherein facing hydrogen drop
Solidifying catalyst, catalyst for hydro-upgrading, the volume ratio of isomerization-visbreaking catalyst are 1：2：1.
The feedstock oil property list of table 1.
| Project | Feedstock oil |
| Density (20 DEG C)/gcm-3 | 0.8688 |
| Boiling range scope/DEG C | 270~380 |
| Nitrogen/mgg-1 | 86 |
| Sulphur/mgg-1 | 900 |
| Condensation point/DEG C | 12 |
| Cetane number | 27 |
The catalyst fundamental property of table 2.
| Embodiment hydrofinishing agent A | Comparative example hydrofinishing agent B | Hydro dewaxing agent C | Catalyst for hydro-upgrading D | Isomerization-visbreaking catalyst E | |
| Shape | It is powdered | Clover | It is spherical | It is spherical | It is spherical |
| Diameter, mm | --- | 1.1~1.3 | 1.3~1.6 | 1.3~1.6 | 1.3~1.6 |
| Length, mm | --- | 2~8 | --- | --- | --- |
| Intensity, N.cm-1 | ≮200 | ≮150 | ≮100 | ≮100 | ≮100 |
| Active component | Mo-Ni | Mo-Ni | Ni | W-Ni | W-Ni |
The embodiment process condition of table 3 and result.
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Reaction temperature, DEG C | 360 | 360 | 355 |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 |
| Hydrogen to oil volume ratio | 500 | 800 | 800 |
| Reaction velocity, h- 1 | 1.5 | 1.0 | 1.5 |
| Powder catalyst addition（Based on metal）, mg/g | 200 | 80 | 100 |
| Diesel product condensation point/DEG C | -48 | -46 | -44 |
| Diesel yield, wt% | 90.02 | 91.37 | 91.86 |
| Diesel cetane-number | 63 | 57 | 55 |
| Diesel oil sulfur content, ppm | 3 | 5 | 6 |
The comparative example process condition of table 4 and result.
| Numbering | Comparative example 1 | Comparative example 2 |
| Finishing reactor average reaction temperature, DEG C | 353 | 350 |
| Pour point depression reactor average reaction temperature, DEG C | 357 | 353 |
| Reaction pressure, MPa | 8.0 | 8.0 |
| Hydrogen to oil volume ratio | 500/500 | 500/500 |
| Reaction velocity, h- 1 | 1.0/1.0 | 0.8/0.8 |
| Diesel product condensation point/DEG C | -43 | -41 |
| Diesel yield, wt% | 84.23 | 85.17 |
| Diesel cetane-number | 45 | 46 |
| Diesel oil sulfur content, ppm | 17 | 21 |
Embodiment is compared with comparative example, in catalyst proportion under the same conditions, product quality be improved significantly, technology
It is with the obvious advantage.
Claims (11)
- A kind of 1. poor ignition quality fuel highly effective hydrogenation method for modifying, it is characterised in that：Including herein below：（1）Poor ignition quality fuel raw material with Powdered Hydrobon catalyst is sufficiently mixed in a mixer, obtains the mixed feeding of catalyst and feedstock oil；（2）It is mixed into Expect to enter with the reactor bottom of hydrogen from mixed packing Hydrodewaxing catalyst, catalyst for hydro-upgrading and isomerization-visbreaking catalyst Enter fluidized bed reactor, carry out hydrogenation reaction；Wherein described hydrogenation reaction is anti-including hydro dewaxing reaction, selective opening Answer, isomerization-visbreaking reacts and hydrofining reaction；（3）Logistics is through ebullated bed after reaction comprising powdered Hydrobon catalyst Reactor head is discharged, and into reactor is stablized, carries out supplement hydrofinishing；（4）Step（3）The material of acquisition is through solid-liquid point From 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 is more than 0 DEG C, choosing One in the various straight-run diesel oils that are obtained from processing naphthene base crude, intermediate base crude or paraffinic base crude oil, secondary processing diesel oil Kind is several.
- 3. in accordance with the method for claim 1, it is characterised in that：The granularity of described powdered Hydrobon catalyst is 50 ~2000 μm；Using vib and/or group VIII metal as active component, using aluminum oxide or silicon-containing alumina as carrier, the Group vib metal is 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 the wt% of 2wt%~15 with oxide.
- 4. in accordance with the method for claim 1, it is characterised in that：Step（1）Mixed feeding in, powdered hydrofinishing is urged Agent addition is calculated as 20~200mg/g with metal.
- 5. in accordance with the method for claim 1, it is characterised in that：Described Hydrodewaxing catalyst includes containing shape slective cracking The silica-alumina supports and hydrogenation active metals of molecular sieve；Described shape slective cracking molecular sieve is hydrogen type molecular sieve, the molecule screening One or more from Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve；Institute The silica alumina ratio for stating shape slective cracking molecular sieve is 10~150；Described hydrogenation active metals are the in the periodic table of elements VIII and/or vib metals element, wherein group VIII active metal are Ni and/or Co, and vib active metal is W And/or Mo；On the basis of the weight of catalyst, hydrogenation active metal component contains using the content that oxide is counted as 10%~30% Shape slective cracking molecular sieve silica-alumina supports content is 70%~90%, and wherein shape slective cracking molecular sieve content in silica-alumina supports is 10% ~40%, remaining is aluminum oxide.
- 6. in accordance with the method for claim 1, it is characterised in that：Described catalyst for hydro-upgrading include catalyst carrier and Active component, active component are selected from least one vib metals and at least one group VIII metal, vib metals oxygen Compound content is 10wt%~30wt%, and group VIII metal oxide content is 2wt%~15wt%；Catalyst carrier composition is oxygen Change aluminium 40wt%~80wt%, amorphous silica-alumina 0wt%~20wt%, Y molecular sieve 5wt%~30wt%；The wherein pore volume of Y molecular sieve 0.40~0.52mL/g, than 750~900m of surface2/ g, lattice constant 2.420~2.500nm, SiO2/Al2O3Molecular proportion 7~ 15。
- 7. in accordance with the method for claim 1, it is characterised in that：The isomerization-visbreaking catalyst includes following component：Without fixed Shape sial, modified beta molecular sieve, refractory porous oxide,B races andFamily metal oxide；With the weight of catalyst Than on the basis of, the content of each component is in catalyst：Amorphous silica-alumina 29wt%~50wt%, modified beta molecular sieve 1wt%~9wt%, Vib metals 15wt%~35wt% in terms of oxide, group VIII metal are calculated as 3wt%~9wt%, porous refractory with oxide Oxide 0wt%~45wt%；The wherein SiO of modified beta molecular sieve2/Al2O3Mol ratio is 50~90, average grain size 0.1 ~0.5 micron, infrared acidity is 0.1~0.4mmol/g.
- 8. in accordance with the method for claim 1, it is characterised in that：In described fluidized bed reactor, powdered hydrofinishing The volume ratio of the Hydrodewaxing catalyst of catalyst and mixed packing, catalyst for hydro-upgrading and isomerization-visbreaking catalyst is 1：5 ~5：1；Wherein Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst account for catalyst in reactor total amount Percent by volume is not less than 10% respectively.
- 9. in accordance with the method for claim 1, it is characterised in that：In described fluidized bed reactor, powdered hydrofinishing The volume ratio of the Hydrodewaxing catalyst of catalyst and mixed packing, catalyst for hydro-upgrading and isomerization-visbreaking catalyst is 1：3 ~3：1；Wherein Hydrodewaxing catalyst, catalyst for hydro-upgrading, isomerization-visbreaking catalyst account for reactor inner volume ratio as 1~3： 1~3：1~3.
- 10. in accordance with the method for claim 1, it is characterised in that：Hydrogenation conditions in described fluidized bed reactor For：6 ~ 30MPa of reaction pressure, reaction temperature are 270 ~ 500 DEG C, and air speed is 0.1 ~ 5h-1, hydrogen to oil volume ratio 400：1~2000: 1。
- 11. in accordance with the method for claim 1, it is characterised in that：Described stable reactor exit sets separating and filtering Equipment, for the separation of solid and liquid of powdered Hydrobon catalyst and generation oil product, the solid phase powder shape hydrogenation for separating acquisition is smart Catalyst processed recycles.
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