CN106675643B - A kind of poor ignition quality fuel pour point depression method for modifying - Google Patents
A kind of poor ignition quality fuel pour point depression method for modifying Download PDFInfo
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- CN106675643B CN106675643B CN201510761644.7A CN201510761644A CN106675643B CN 106675643 B CN106675643 B CN 106675643B CN 201510761644 A CN201510761644 A CN 201510761644A CN 106675643 B CN106675643 B CN 106675643B
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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 pour point depression method for modifying, including herein below：（1）Poor ignition quality fuel raw material is sufficiently mixed in a mixer with powdered 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；（3）Logistics, into reactor is stablized, carries out supplement hydrofinishing through being discharged at the top of fluidized bed reactor after reaction；（4）For material through separation of solid and liquid, liquid phase enters fractionating system, obtains high-grade low-freezing, low-sulfur, high cetane number diesel 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 of hydro-upgrading process are rationally utilized, while low condensation point, ultra-low-sulphur diesel is produced, improve Cetane number, reduce the hot(test)-spot temperature of device, extend service cycle, save operating cost.
Description
Technical field
It is especially a kind of to be produced by fluidized bed reactor the present invention relates to a kind of pour point depression method for modifying of poor ignition quality fuel
The production method of high-grade low-freezing, low-sulfur 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 pour point depression method for modifying.The inventive method
The characteristics of making full use of fluidized bed reactor back-mixing, by the temperature drop of hydro dewaxing process and hydrofinishing and hydro-upgrading process
Temperature rise carries out rational combination and utilized, and can improve Cetane number while low condensation point, ultra-low-sulphur diesel is produced, reduce
The hot(test)-spot temperature of device, extend service cycle；In addition the combustion gas loss of the consumption or heating furnace of cold hydrogen is reduced, is saved
Operating cost.
The poor ignition quality fuel pour point depression method for modifying of the present invention, including herein below：（1）Poor ignition quality fuel raw material and powdered hydrogenation
Catalyst for refining is sufficiently mixed in a mixer, obtains the mixed feeding of catalyst and feedstock oil；
（2）Mixed feeding and hydrogen are from mixed packing Hydrodewaxing catalyst and the reactor bottom of catalyst for hydro-upgrading
Into fluidized bed reactor, hydrogenation reaction is carried out；Wherein described hydrogenation reaction includes hydro dewaxing reaction, hydroisomerizing reaction
With hydrofining reaction etc.；（3）Logistics at the top of fluidized bed reactor through arranging after reaction comprising powdered Hydrobon catalyst
Go out, into reactor is stablized, carry out supplement hydrofinishing；（4）Step（3）Through separation of solid and liquid, liquid phase enters divides the material of acquisition
System is evaporated, obtains high-grade low-freezing, low-sulfur, high 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%~15 with oxide
wt%。
The inventive method step（1）Mixed feeding in, powdered Hydrobon catalyst addition is calculated as 20 with metal
~200 μ g/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.
Described hydro-upgrading isomerization-visbreaking catalyst is conventional catalyst in the art.The hydro-upgrading drop
Solidifying catalyst generally comprise amorphous silica-alumina, modified beta molecular sieve, refractory porous oxide,B races andRace's metal oxidation
Thing.On the basis of the weight ratio of catalyst, the content of each component is generally in catalyst：Amorphous silica-alumina 29w%~50w%, changes
Property beta-molecular sieve 1w%~9%, vib metals 15w%~35w% in terms of oxide, group VIII metal are calculated as 3w% with oxide
~9w%, refractory porous oxide 0w%~45w%.Described refractory porous oxide, aluminum oxide, titanium oxide, oxidation can be selected from
Zirconium, boron oxide and above-mentioned element（Aluminium, titanium, zirconium, boron）One or more in composite oxides etc., preferably aluminum oxide.Such as may be used
To be generally 0w%~22w% containing macroporous aluminium oxide and aperture alumina adhesive, macroporous aluminium oxide；Small porous aluminum oxide is general
For 0w%~23w%.The specific surface area of catalyst is generally 160~230m2/ g, pore volume are 0.32~0.45mL/g.The modified β
The property of molecular sieve is generally：Its SiO2With Al2O3Mol ratio is generally 30~150, and crystallinity is generally 90~110, and crystal grain is put down
Equal size is generally 0.1~0.5 micron, 400~750m of specific surface area2/ g, pore volume 0.25~0.50mL/g, Na2O content is less than
0.10w%, infrared 0.1~0.4mmol/g of acidity, 2~10nm secondary pore pore volume account for the 30%~60% of total pore volume.Described
SiO in amorphous silica-alumina2Content be generally 20w%~75w%, preferably 35w%~60w%.The pore volume of amorphous silica-alumina is 0.5
~1.1mL/g, preferably 0.6~0.8mL/g；Specific surface area is 200~500m2/ g, preferably 280~500m2/g.Macropore oxygen
It is 0.6~1.2mL/g, preferably 0.8~1.2mL/g to change aluminium pore volume, and 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, group VIII metal are generally Ni and/or Co.Conventional hydro modification isomerization-visbreaking catalyst can select existing
Various commercial catalysts, such as the catalyst such as FC-14, FC-20 of FRIPP developments.This area can also be pressed as needed
General knowledge prepare specific hydro-upgrading isomerization-visbreaking catalyst, such as be referred to content disclosed in CN1712498A and prepare
Satisfactory hydro-upgrading isomerization-visbreaking catalyst.
In the inventive method, in described fluidized bed reactor, powdered Hydrobon catalyst is catalyzed with hydro dewaxing
The volume ratio of agent and hydro-upgrading isomerization-visbreaking catalyst is 1：5~5：1, preferably 1：3~3：1.Wherein Hydrodewaxing catalyst
Volume ratio with hydro-upgrading isomerization-visbreaking catalyst is 1：3~3：1, preferably 1：2~2：1.
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 ~ 5h-1, hydrogen to oil volume ratio is 400 ~ 2000.
In the inventive method, in boiling bed hydrogenation reactor, diesel raw material, hydrogen and powdered hydrofinishing are catalyzed
Agent, diesel oil hydrogenation modification catalyst and Hydrodewaxing catalyst contact, carry out hydrodesulfurization, denitrogenation, hydroisomerizing, are hydrocracked
And pour point depression 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 the inventive method, described stable reactor exit sets separating and filtering equipment, for powdered hydrogenation essence
The separation of solid and liquid of catalyst processed and generation oil product, the solid phase powder shape Hydrobon catalyst for separating acquisition recycle.
In the inventive method, described fractionating system separates fractionation train for conventional oil product 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 hydro-upgrading isomerization-visbreaking catalyst and Hydrodewaxing catalyst, together
When catalyst particles intergranular be mixed with powdered 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.The combination of two kinds of different type pour point depression catalyst, is enhanced
Pour-point depressing process, there is the characteristics of adaptability to raw material is strong, and desulfurized effect is preferable, and pour point depression condition relaxes.
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, area's liquid in the case of without Hydrodewaxing catalyst and/or hydro-upgrading isomerization-visbreaking catalyst can be prevented
The generation of the polycondensation coking reaction of body under the high temperature conditions.
Brief description of the drawings
Fig. 1 is a kind of schematic flow sheet of poor ignition quality fuel pour point depression method for modifying of the present invention.
Embodiment
A kind of poor ignition quality fuel pour point depression 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 pour point depression method for modifying flow of the present invention is as follows：Poor ignition quality fuel 1 is added with powdered
Hydrogen catalyst for refining（Including supplementing new agent 2 and recycling catalyst 13）It is sufficiently mixed in blender 3, obtains uniform charging 4,
Enter fluidized bed reactor through delivery pump, high pressure hydrogen 8 enters mixing from the bottom of fluidized bed reactor 5 in a manner of upper feeding and filled
There is the fluidized bed reactor of Hydrodewaxing catalyst 6 and diesel oil hydrogenation modification isomerization-visbreaking catalyst 7 catalyst is kept boiling
Shape, under suitable reaction condition, with Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst and powdered hydrogenation
Catalyst for refining contacts, and carries out catalytic hydrogenation reaction, and reacted logistics 9 is discharged into stable reactor at the top of reactor
10, supplement hydrofinishing is carried out using the hydrogen partial and logistics self heat that wherein dissolve, oil will be generated by separator 11
12 separate with powdered Hydrobon catalyst 13, and powdered Hydrobon catalyst recycles, and generate oil and enter separation point
System 14 is evaporated, fractionates out gas, light distillate and high-grade low-freezing, low-sulfur, high cetane number diesel product 15.
The poor ignition quality fuel pour point depression method for modifying of the present invention is further described followed by specific embodiment.
Embodiment 1~4
The present embodiment is using Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst and powdered hydrogenation essence
The boiling bed hydrogenation experiment of catalyst processed.Concrete operations flow is shown in accompanying drawing 1.Powdered Hydrobon catalyst in embodiment 1~2
Volume ratio with Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst is 1：4, wherein Hydrodewaxing catalyst,
The volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst is 1：1；Powdered Hydrobon catalyst is with facing hydrogen drop in embodiment 3
Solidifying catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 3：1, wherein Hydrodewaxing catalyst, diesel oil hydrogenation
The volume ratio for modifying isomerization-visbreaking catalyst is 2：1；Powdered Hydrobon catalyst is catalyzed with hydro dewaxing in embodiment 4
Agent, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 1：3, wherein Hydrodewaxing catalyst, diesel oil hydrogenation modification is different
The volume ratio of structure pour point depression catalyst is 1：3.Poor ignition quality fuel and powdered Hydrobon catalyst are sufficiently mixed in a mixer,
Uniform charging is obtained, enters fluidized bed reactor through delivery pump, high pressure hydrogen is in a manner of upper feeding from fluidized bed reactor
Bottom, which enters the fluidized bed reactor equipped with Hydrodewaxing catalyst and diesel oil hydrogenation modification isomerization-visbreaking catalyst, makes catalyst
Boiling-like is kept, under suitable reaction condition, while and/or priority and Hydrodewaxing catalyst, diesel oil hydrogenation modification isomery
Pour point depression catalyst and the contact of powdered Hydrobon catalyst, carry out catalytic hydrogenation reaction, reacted logistics is from reactor
Top is discharged into stable reactor, and supplement hydrofinishing is carried out using the hydrogen partial of dissolving and the self heat of material, after
Through separator will generate it is oily separated with powdered Hydrobon catalyst, powdered Hydrobon catalyst recycles, generation
Oil enters separation fractionating system, fractionates out gas, light distillate and high-grade low-freezing, low-sulfur, high cetane number diesel product.Implement
The Hydrodewaxing catalyst C used in example is the spheric catalyst of special preparation, the catalyst component property and Fushun oil
The commercial catalyst FDW-3 of chemical research institute's development and production is consistent.The diesel oil hydrogenation modification isomerization-visbreaking catalyst D used is spy
The spheric catalyst very prepared, the catalyst component property and the commercial catalyst of Fushun Petrochemical Research Institute's development and production
FC-14 is consistent.The powder catalyst A used is alumina load Mo-Ni type catalyst, and its granularity is 1000~1200 μm,
Contain active component in catalyst（In terms of metal）Molybdenum 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.
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, diesel oil hydrogenation
It is same as Example 1 to modify isomerization-visbreaking catalyst, feedstock oil.The product property of comparative example 1 ~ 2 is shown in Table 4.Comparative example 1 is hydrogenated with
The volume ratio of catalyst for refining and Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst is 1：4, wherein facing hydrogen drop
Solidifying catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 1：1；The Hydrobon catalyst of comparative example 2 is with facing hydrogen
Pour point depression catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 3：1, wherein Hydrodewaxing catalyst, diesel oil adds
The volume ratio of hydrogen modification isomerization-visbreaking catalyst is 2：1.
The raw material oil nature 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 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 (10)
1. a kind of poor ignition quality fuel pour point depression method for modifying, it is characterised in that including herein below：（1）Poor ignition quality fuel raw material with it is powdered
Hydrobon catalyst is sufficiently mixed in a mixer, obtains the mixed feeding of catalyst and feedstock oil；（2）Mixed feeding and hydrogen
Gas enters ebullating bed reactor from the reactor bottom of mixed packing Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst
Device, carry out hydrogenation reaction；It is anti-that wherein described hydrogenation reaction includes hydro dewaxing reaction, hydroisomerizing reaction and hydrofinishing
Should；（3）Logistics is reacted through being discharged at the top of fluidized bed reactor into stable after reaction comprising powdered Hydrobon catalyst
Device, 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-quality
Low solidifying, low-sulfur, high cetane number diesel product.
2. in accordance with the method for claim 1, it is characterised in that：Described poor ignition quality fuel raw material condensation point is selected from more than 0 DEG C
The one kind processed in naphthene base crude, the various straight-run diesel oils that intermediate base crude or paraffinic base crude oil obtain, secondary processing diesel oil
It is or 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.
4. in accordance with the method for claim 3, it is characterised in that：Described powdered Hydrobon catalyst is with vib
And/or group VIII metal is active component, using aluminum oxide or silicon-containing alumina as carrier, vib metals are Mo and/or W,
Group VIII metal is Co and/or Ni；On the basis of the weight of catalyst, vib metals content is calculated as 8wt% with oxide
~28wt%, group VIII tenor are calculated as the wt% of 2wt%~15 with oxide.
5. 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 20~200 μ g/g with metal.
6. 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.
7. in accordance with the method for claim 1, it is characterised in that：The hydro-upgrading isomerization-visbreaking catalyst includes amorphous
Sial, modified beta molecular sieve, refractory porous oxide,B races andFamily metal oxide；Using the weight ratio of catalyst as
Benchmark, amorphous silica-alumina 29w%~50w%, modified beta molecular sieve 1w%~9%, vib metals 15w%~35w% in terms of oxide,
Group VIII metal is calculated as 3w%~9w%, refractory porous oxide 0w%~45w% with oxide；The specific surface area of catalyst is
160~230m2/ g, pore volume are 0.32~0.45mL/g；The property of the modified beta molecular sieve is：SiO2With Al2O3Mol ratio is
30~150, crystallinity is 90~110, and average grain size is 0.1~0.5 micron, 400~750m of specific surface area2/ g, pore volume
0.25~0.50mL/g, Na2O content is less than 0.10w%, infrared 0.1~0.4mmol/g of acidity, 2~10nm secondary pore pore volume
Product accounts for the 30%~60% of total pore volume；SiO in described amorphous silica-alumina2Content be 20w%~75w%, the hole of amorphous silica-alumina
It is 200~500m to hold for 0.5~1.1mL/g, specific surface area2/g；Vib metals are W and/or Mo, and group VIII metal is
Ni and/or Co.
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 and hydro-upgrading isomerization-visbreaking catalyst of catalyst and mixed packing is 1：5~5：1；Its
The volume ratio of middle Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst is 1：3~3：1.
9. 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 is 400 ~ 2000.
10. 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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| CN111378495B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil |
| CN111378494B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Processing method of Fischer-Tropsch synthetic oil |
| CN111378493B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Hydrogenation process for producing API III + base oil from Fischer-Tropsch synthetic oil |
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| CN1326495A (en) * | 1998-11-13 | 2001-12-12 | 埃克森研究工程公司 | Small catalyst particle addition to slurry reaction |
| CN102264871A (en) * | 2008-12-31 | 2011-11-30 | 埃克森美孚研究工程公司 | Integrated hydrocracking and dewaxing of hydrocarbons |
| CN104611033A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low freezing point |
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| US9650312B2 (en) * | 2013-03-14 | 2017-05-16 | Lummus Technology Inc. | Integration of residue hydrocracking and hydrotreating |
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| CN1326495A (en) * | 1998-11-13 | 2001-12-12 | 埃克森研究工程公司 | Small catalyst particle addition to slurry reaction |
| CN102264871A (en) * | 2008-12-31 | 2011-11-30 | 埃克森美孚研究工程公司 | Integrated hydrocracking and dewaxing of hydrocarbons |
| CN104611033A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing hydrogenated diesel oil with low freezing point |
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