CN106675643A - Inferior diesel pour-point depressing modification method - Google Patents
Inferior diesel pour-point depressing modification method Download PDFInfo
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- CN106675643A CN106675643A CN201510761644.7A CN201510761644A CN106675643A CN 106675643 A CN106675643 A CN 106675643A CN 201510761644 A CN201510761644 A CN 201510761644A CN 106675643 A CN106675643 A CN 106675643A
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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 an inferior diesel pour-point depressing modification method, which comprises the following contents: (1) an inferior diesel material and a powdery hydrofining catalyst are fully mixed in a mixer to obtain a mixed feed of the catalyst and the raw oil; (2) the mixed feed and hydrogen enter a boiling-bed reactor from the bottom of a reactor filled with a mixture of a hydrodewaxing catalyst and a hydro-upgrading catalyst to undergo a hydrogenation reaction; (3) the reaction product is charged out of the top of the boiling-bed reactor and then enters a stable reactor to supplement hydrofining; and (4) the material undergoes solid-liquid separation, and a liquid phase enters a fractionating system so as to obtain a diesel product with high quality, low pour point, low sulfur content and high cetane number. According to the method, the backmixing characteristic of the boiling-bed reactor is fully utilized, and cooling and hydrofining of the hydrodewaxing process and temperature rising of the hydro-upgrading process are reasonably utilized. Therefore, the diesel with low pour point and ultra-low sulfur content is produced, cetane number is raised, hot-spot temperature of the device is reduced, running period is prolonged, and operation expenses are saved.
Description
Technical field
The present invention relates to a kind of pour point depression method for modifying of poor ignition quality fuel, especially a kind of production method that high-grade low-freezing, low-sulfur diesel-oil are 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 poor ignition quality fuel pour point depression method for modifying.The characteristics of the inventive method makes full use of fluidized bed reactor back-mixing, the temperature drop of hydro dewaxing process and hydrofinishing and the temperature rise of hydro-upgrading process are carried out reasonably to combine utilization, can be while low condensation point, ultra-low-sulphur diesel be produced, improve Cetane number, the hot(test)-spot temperature of device is reduced, extends service cycle；In addition the consumption of cold hydrogen or the combustion gas loss of heating furnace are reduced, operating cost is saved.
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 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 of mixed packing Hydrodewaxing catalyst and catalyst for hydro-upgrading, carries out hydrogenation reaction；Wherein described hydrogenation reaction includes hydro dewaxing reaction, hydroisomerizing 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.
Described hydro-upgrading isomerization-visbreaking catalyst is conventional catalyst in the art.The hydro-upgrading pour point depression catalyst generally comprise 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 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.Described refractory porous oxide, can be selected from aluminum oxide, titanium oxide, zirconium oxide, boron oxide and above-mentioned element（Aluminium, titanium, zirconium, boron）One or more in composite oxides etc., preferred aluminum oxide.Such as 0w%～22w% can be generally containing macroporous aluminium oxide and aperture alumina adhesive, macroporous aluminium oxide；Little porous aluminum oxide is generally 0w%～23w%.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 SiO2With Al2O3Mol ratio is generally 30～150, and degree of crystallinity is generally 90～110, and 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 0.10w%, and infrared 0.1～0.4mmol/g of acidity, the secondary pore pore volume of 2～10nm accounts for the 30%～60% of total pore volume.SiO in described 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.Macroporous aluminium oxide pore volume is 0.6～1.2mL/g, and 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 modification isomerization-visbreaking catalyst can select the catalyst such as existing various commercial catalysts, FC-14, FC-20 that such as FRIPP is developed.As needed specific hydro-upgrading isomerization-visbreaking catalyst can also be prepared by the general knowledge of this area, for example, be referred to the content disclosed in CN1712498A and prepare satisfactory hydro-upgrading isomerization-visbreaking catalyst.
In the inventive method, in described fluidized bed reactor, powder Hydrobon catalyst is 1 with the volume ratio of Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst：5～5：1, preferably 1：3～3：1.Wherein the volume ratio of Hydrodewaxing catalyst and 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, reaction temperature is 270 ~ 500 DEG C, 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 are contacted with powder Hydrobon catalyst, diesel oil hydrogenation modification catalyst and Hydrodewaxing catalyst, carry out hydrodesulfurization, denitrogenation, hydroisomerizing, be hydrocracked and pour point depression reaction etc..
In the inventive method, 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 the inventive method, 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 the inventive method, 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 hydro-upgrading isomerization-visbreaking catalyst and Hydrodewaxing catalyst, simultaneously catalyst particles intergranular is mixed with powder Hydrobon catalyst again, the coupling advantage of catalyst can be given full play to, 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, enhances pour-point depressing process, strong with adaptability to raw material, desulfurized effect preferably, the characteristics of pour point depression condition relaxes.
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 hydro-upgrading isomerization-visbreaking catalyst.
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 invention.
Specific 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 process 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 isomerization-visbreaking 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 isomerization-visbreaking 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 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 to be tested using the boiling bed hydrogenation of Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst 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 isomerization-visbreaking catalyst are 1 in embodiment 1～2：4, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 1：1；Powder Hydrobon catalyst and the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst are 3 in embodiment 3：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 2：1；Powder Hydrobon catalyst and the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst are 1 in embodiment 4：3, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 1：3.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 isomerization-visbreaking 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 isomerization-visbreaking 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 isomerization-visbreaking catalyst D for using is the spheric catalyst of special preparation, and the catalyst component property is consistent with the commercial catalyst FC-14 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 isomerization-visbreaking 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 isomerization-visbreaking catalyst：4, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 1：1；The Hydrobon catalyst of comparative example 2 is 3 with the volume ratio of Hydrodewaxing catalyst, diesel oil hydrogenation modification isomerization-visbreaking catalyst：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification isomerization-visbreaking catalyst are 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 compared with comparative example, under the conditions of catalyst proportion identical, product quality be improved significantly, technical advantage is obvious.
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 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 of mixed packing Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking catalyst, carries out hydrogenation reaction；Wherein described hydrogenation reaction includes hydro dewaxing reaction, hydroisomerizing reaction 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：Described poor ignition quality fuel raw material condensation point 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.
4. in accordance with the method for claim 3, it is characterised in that：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 to described powder Hydrobon catalyst, 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.
5. 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.
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：The hydro-upgrading pour point depression catalyst include amorphous silica-alumina, modified beta molecular sieve, refractory porous oxide,
B races andFamily metal oxide；On the basis of the weight ratio of catalyst, 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 is 0.32～0.45mL/g；The property of the modified beta molecular sieve is：SiO2With Al2O3Mol ratio is 30～150, and degree of crystallinity is 90～110, and average grain size is 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 0.10w%, and infrared 0.1～0.4mmol/g of acidity, the secondary pore pore volume of 2～10nm accounts for the 30%～60% of total pore volume；SiO in described amorphous silica-alumina2Content be 20w%～75w%, the pore volume of amorphous silica-alumina is 0.5～1.1mL/g, and specific surface area is 200～500m2/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, powder Hydrobon catalyst is 1 with the Hydrodewaxing catalyst of mixed packing and the volume ratio of hydro-upgrading isomerization-visbreaking catalyst：5～5：1；Wherein the volume ratio of 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 are：6 ~ 30MPa of reaction pressure, reaction temperature is 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 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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| CN111097513A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for restoring activity of low-activity pour point depressing catalyst |
| CN111378494A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Processing method of Fischer-Tropsch synthetic oil |
| CN111378495A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil |
| CN111378493A (en) * | 2018-12-31 | 2020-07-07 | 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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| CN111097513A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Method for restoring activity of low-activity pour point depressing catalyst |
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| 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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| 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 |
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