CN106675648B - A kind of method of hydrotreating for improving cetane number of inferior diesel oil - Google Patents
A kind of method of hydrotreating for improving cetane number of inferior diesel oil Download PDFInfo
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- CN106675648B CN106675648B CN201510761517.7A CN201510761517A CN106675648B CN 106675648 B CN106675648 B CN 106675648B CN 201510761517 A CN201510761517 A CN 201510761517A CN 106675648 B CN106675648 B CN 106675648B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses one kind to improve cetane number of inferior diesel oil method of hydrotreating, 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 comprising powdered Hydrobon catalyst；（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, high cetane number diesel product.The inventive method carries out the temperature drop of hydro dewaxing process with the temperature rise during hydro-upgrading reasonably to combine utilization, while ensureing diesel oil in high yield, produces low condensation point, high cetane number diesel oil, reduces the hot(test)-spot temperature of device, extend service cycle.
Description
Technical field
It is especially a kind of to be produced by fluidized bed reactor the present invention relates to a kind of hydrogenation modification method of poor ignition quality fuel
The production method of high-quality 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 method of hydrotreating for improving cetane number of inferior diesel oil.
The inventive method makes full use of the characteristics of fluidized bed reactor back-mixing, during the temperature drop and hydro-upgrading of hydro dewaxing process
Temperature rise carry out rational combination and utilize, while ensureing diesel oil in high yield, produce low condensation point, high cetane number diesel oil, drop
The low hot(test)-spot temperature of device, extend service cycle.
A kind of raising cetane number of inferior diesel oil method of hydrotreating 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 and hydrogen are from mixing the reactor bottom equipped with Hydrodewaxing catalyst and catalyst for hydro-upgrading
Into fluidized bed reactor, hydrogenation reaction is carried out；Wherein described hydrogenation reaction includes hydro dewaxing reaction, arenes selectivity is opened
Ring（Continuous side chain）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%~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.
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 10wt%~30wt%, and group VIII metal oxide content is 2wt%~15wt%.；Urge
Agent vehicle group turns into aluminum oxide 40wt%~80wt%, amorphous silica-alumina 0wt%~20wt%, Y molecular sieve 5wt%~30wt%, its
0.40~0.52mL/g of pore volume of middle Y 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.
In production method of the present invention, in described fluidized bed reactor, powdered Hydrobon catalyst and hydro dewaxing
The volume ratio of catalyst and catalyst for hydro-upgrading is 1：10~10：1, preferably 1：5~5：1.Wherein Hydrodewaxing catalyst and
The volume ratio of catalyst for hydro-upgrading is 1：5~5：1, preferably 1：2~2：1.
In production method of the present invention, the hydrogenation conditions in described fluidized bed reactor are：Reaction pressure 6.0 ~
30.0MPa, reaction temperature are 270 ~ 500 DEG C, and air speed is 0.1 ~ 5.0h-1, hydrogen to oil volume ratio 400：1~2000：1.
In production method of the present invention, in boiling bed hydrogenation reactor, diesel raw material, hydrogen and powdered hydrofinishing are urged
Agent, diesel oil hydrogenation modification catalyst and Hydrodewaxing catalyst contact, carry out hydrodesulfurization, denitrogenation, aromatic hydrocarbons open loop（Continuous side
Chain）React, be hydrocracked and pour point depression reaction etc..
In production method of the present invention, described stable reactor is used for the post-refining of upper reaction member generation oil, by
It is selectively strong to linear paraffin hydrocracking in the characteristics of Hydrodewaxing catalyst, and the hydrocracking processes of linear paraffin are abided by
Carbonium ion reaction mechanism is followed, during the course of the reaction the unsaturated hydro carbons such as generating portion alkene, reduce the stability of oil product.This
Invention makes full use of the hydrogen partial dissolved in the reaction heat and generation oil of last action unit, is mended in reactor is stablized
Hydrofinishing is filled, 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 and Hydrodewaxing catalyst, while catalyst
Powdered Hydrobon catalyst is mixed with again between particle, the coupling advantage of catalyst can be given full play to, improves product quality, and can
Utilization of Heat of Reaction efficiency is improved, reduces plant energy consumption.The diesel modifying catalyst aromatic hydrocarbons open loop used in the present invention（Continuous side
Chain）Reaction selectivity is strong, can improve diesel cetane-number to greatest extent while high diesel yield is ensured.
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 Hydrodewaxing 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 hydro-upgrading of inferior diesel method of the present invention.
Embodiment
A kind of hydro-upgrading of inferior diesel method of the present invention is described in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the hydro-upgrading of inferior diesel method flow of the present invention is as follows：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 catalyst 7 catalyst is kept boiling-like, suitable
Reaction condition under, contact, enter with Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst and powdered Hydrobon catalyst
Row catalytic hydrogenation reaction, reacted logistics 9 are discharged into stable reactor 10 at the top of reactor, utilize what is wherein dissolved
Hydrogen partial and logistics self heat carry out supplement hydrofinishing, and oil 12 and powdered hydrofinishing will be generated by separator 11
Catalyst 13 separates, and powdered Hydrobon catalyst recycles, and generates oil and enters separation fractionating system 14, is fractionated outlet
Body, light distillate and high-grade low-freezing, low-sulfur, high cetane number diesel product 15.
The hydro-upgrading of inferior diesel method of the present invention is further described followed by specific embodiment.
Embodiment 1~4
The present embodiment is the boiling using Hydrodewaxing catalyst, diesel oil hydrogenation modification and powdered Hydrobon catalyst
Bed hydroprocessing is tested.Concrete operations flow is shown in accompanying drawing 1.Powdered Hydrobon catalyst is catalyzed with hydro dewaxing in embodiment 1~2
Agent, the volume ratio of diesel oil hydrogenation modification catalyst are 1：9, wherein Hydrodewaxing catalyst, the body of diesel oil hydrogenation modification catalyst
Product is than being 1：4；Powdered Hydrobon catalyst and Hydrodewaxing catalyst in embodiment 3, diesel oil hydrogenation modification catalyst
Volume ratio is 8：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 5：1；Powder in embodiment 4
The volume ratio of shape Hydrobon catalyst and Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst is 1：1, wherein hydro dewaxing
Catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 1：2.Poor ignition quality fuel is being mixed with powdered Hydrobon catalyst
Be sufficiently mixed in device, obtain uniform charging, enter fluidized bed reactor through delivery pump, high pressure hydrogen in a manner of upper feeding from
Fluidized bed reactor bottom enters the fluidized bed reactor equipped with Hydrodewaxing catalyst and diesel oil hydrogenation modification catalyst and makes to urge
Agent keeps boiling-like, under suitable reaction condition, while and/or priority and Hydrodewaxing catalyst, diesel oil hydrogenation modification
Catalyst and the contact of powdered Hydrobon catalyst, carry out catalytic hydrogenation reaction, reacted logistics is from the top of reactor
Be discharged into stable reactor, supplement hydrofinishing carried out using the hydrogen partial of dissolving and the self heat of material, by point
From device will generate it is oily separated with powdered Hydrobon catalyst, powdered Hydrobon catalyst recycles, and generation oil enters
Enter to separate fractionating system, fractionate out gas, light distillate and high-grade low-freezing, low-sulfur, high cetane number diesel product.In embodiment
The Hydrodewaxing catalyst C used is the spheric catalyst of special preparation, the catalyst component property and Fushun petrochemical industry
The commercial catalyst FDW-3 of research institute's development and production is consistent.The diesel oil hydrogenation modification catalyst D used is the spherical of special preparation
Catalyst, the catalyst component property are consistent with the commercial catalyst FC-18 of Fushun Petrochemical Research Institute's development and production.Make
Powder catalyst A is alumina load Mo-Ni type catalyst, and its granularity is 1000~1200 μm, containing work in catalyst
Property component（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
Modifying catalyst, feedstock oil are same as Example 1.The product property of comparative example 1 ~ 2 is shown in Table 4.The hydrofinishing of comparative example 1 is catalyzed
The volume ratio of agent and Hydrodewaxing catalyst, diesel oil hydrogenation modification catalyst is 1：1, wherein Hydrodewaxing catalyst, diesel oil adds
The volume ratio of hydrogen modifying catalyst is 1：2；The Hydrobon catalyst of comparative example 2 and Hydrodewaxing catalyst, diesel oil hydrogenation modification
The volume ratio of catalyst is 8：1, wherein Hydrodewaxing catalyst, the volume ratio of diesel oil hydrogenation modification catalyst are 5：1.
The feedstock oil property list of table 1
The catalyst fundamental property of table 2.
The embodiment process condition of table 3 and result.
The comparative example process condition of table 4 and result.
Embodiment 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. one kind improves cetane number of inferior diesel oil method of hydrotreating, it is characterised in that including herein below：（1）Poor ignition quality fuel raw material
It is sufficiently mixed in a mixer with powdered Hydrobon catalyst, obtains the mixed feeding of catalyst and feedstock oil；（2）Mixing
Feed and enter ebullating bed reactor from the reactor bottom equipped with Hydrodewaxing catalyst and catalyst for hydro-upgrading is mixed with hydrogen
Device, carry out hydrogenation reaction；Wherein described hydrogenation reaction includes hydro dewaxing reaction, the continuous side chain reaction of arenes selectivity open loop
And hydrofining reaction；（3）Logistics is discharged through fluidized bed reactor top after reaction comprising powdered Hydrobon catalyst,
Into reactor is stablized, supplement hydrofinishing is carried out；（4）Step（3）The material of acquisition enters fractionation train through separation of solid and liquid, liquid phase
System, obtain 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 20~200 μ g/g with metal.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described blender is multistage shear pump, static state
Blender or ultrasonic oscillator.
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：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 10w%~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。
8. in accordance with the method for claim 1, it is characterised in that：In described fluidized bed reactor, powdered hydrofinishing
The volume ratio that catalyst is equipped with Hydrodewaxing catalyst and catalyst for hydro-upgrading with mixing is 1：10~10：1；Wherein face hydrogen drop
The volume ratio of solidifying catalyst and catalyst for hydro-upgrading is 1：5~5：1.
9. in accordance with the method for claim 1, it is characterised in that：Hydrogenation conditions in described fluidized bed reactor
For：6.0 ~ 30.0MPa of reaction pressure, reaction temperature are 270 ~ 500 DEG C, and air speed is 0.1 ~ 5.0h-1, hydrogen to oil volume ratio 400：1~
2000：1.
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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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289831A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing high-quality low-coagulation diesel oil with high hexadecane value |
| CN1326495A (en) * | 1998-11-13 | 2001-12-12 | 埃克森研究工程公司 | Small catalyst particle addition to slurry reaction |
| CN1743431A (en) * | 2004-08-31 | 2006-03-08 | 中国石油化工股份有限公司 | Pour-point depressing method for increasing diesel product yield and quality |
| CN101376834A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Bubbling bed combined process |
| CN104611027A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low freezing point diesel fuel production method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500329B2 (en) * | 1998-12-30 | 2002-12-31 | Exxonmobil Research And Engineering Company | Selective ring opening process for producing diesel fuel with increased cetane number |
| WO2011042617A2 (en) * | 2009-10-08 | 2011-04-14 | IFP Energies Nouvelles | Method for hydroconverting heavy carbonaceous loads, including a bubbling bed technology and slurry technology |
-
2015
- 2015-11-11 CN CN201510761517.7A patent/CN106675648B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326495A (en) * | 1998-11-13 | 2001-12-12 | 埃克森研究工程公司 | Small catalyst particle addition to slurry reaction |
| CN1289831A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing high-quality low-coagulation diesel oil with high hexadecane value |
| CN1743431A (en) * | 2004-08-31 | 2006-03-08 | 中国石油化工股份有限公司 | Pour-point depressing method for increasing diesel product yield and quality |
| CN101376834A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Bubbling bed combined process |
| CN104611027A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low freezing point diesel fuel production method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023137350A1 (en) * | 2022-01-13 | 2023-07-20 | Chevron U.S.A. Inc. | Improved ebullated bed reactor and process |
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