CN106675641B - A kind of production method of high-grade low-freezing diesel oil - Google Patents
A kind of production method of high-grade low-freezing diesel oil Download PDFInfo
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- 239000002283 diesel fuel Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000007710 freezing Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 239000013589 supplement Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 22
- 239000002808 molecular sieve Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- 238000005336 cracking Methods 0.000 claims description 12
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 6
- 239000005864 Sulphur Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000000567 combustion gas Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000005345 coagulation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- -1 Carbonium ion Chemical class 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of production method of high-grade low-freezing diesel oil, 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, 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）After powdered Hydrobon catalyst is removed by filtration in the generation oil of acquisition, into fractionating system, high-grade low-freezing diesel product is obtained.The inventive method improves the yield and Cetane number of diesel oil while low condensation point, ultra-low-sulphur diesel is produced, and reduces the hot(test)-spot temperature of device, extends service cycle；In addition the combustion gas loss of the consumption or heating furnace of cold hydrogen is reduced, saves operating cost.
Description
Technical field
The present invention relates to a kind of production method of low-coagulation diesel oil, especially one kind to be produced high-quality by fluidized bed reactor
The production method of low-coagulation 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 production method of high-grade low-freezing diesel oil.Present invention side
Method makes full use of the characteristics of fluidized bed reactor back-mixing, and the temperature rise in the temperature drop and hydrogenation process of hydro dewaxing process is closed
The combination of reason is utilized, and the yield and Cetane number of diesel oil are improved while low condensation point, ultra-low-sulphur diesel is produced, is reduced
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.
A kind of production method of high-grade low-freezing diesel oil 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 enters fluidized bed reactor with hydrogen from the reactor bottom equipped with Hydrodewaxing catalyst, enters
Row hydrogenation reaction；Wherein described hydrogenation reaction includes hydro dewaxing reaction and hydrofining reaction；
（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 diesel product.
In production method of the present invention, described poor ignition quality fuel raw material is high freezing point diesel fuel for conventional pour point depression raw material inferior,
Condensation point is general all more than 0 DEG C, and preferably condensation point is more than 5 DEG C.Can be processing naphthene base crude, intermediate base crude or paraffinic base
Various straight-run diesel oils, the secondary processing diesel oil that crude oil obtains（Coker gas oil, catalytic diesel oil etc.）In one or several kinds, preferably
The said components that processing paraffinic base crude oil obtains.The diesel raw material does generally 350~440 DEG C, preferably 370~
400℃。
In production method of the present invention, described powdered Hydrobon catalyst can be powder commonly used in the art
Shape Hydrobon catalyst, its granularity are generally 50~2000 μm, preferably 500~1500 μm, described powder catalyst
It can be 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.Using the weight of catalyst as base
Standard, vib metals content are calculated as 8wt%~28wt% with oxide, group VIII tenor with oxide be calculated as 2wt%~
15 wt%。
Production method step of the present invention（1）Mixed feeding in, powdered Hydrobon catalyst addition is in terms of metal
For 20~200 μ g/g.
In production method of the present invention, described blender can use multistage shear pump, can also use static mixer,
The mixing arrangement commonly used in the art such as ultrasonic oscillator.
In production method of the present invention, described Hydrodewaxing catalyst is the conventional pour point depression catalyst in this area.It is described
Catalyst include silica-alumina supports and hydrogenation active metals containing shape slective cracking molecular sieve.Described shape slective cracking molecular sieve is
Hydrogen type molecular sieve, the molecular sieve can be selected from Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and
One or more in ZSM-38 molecular sieves, preferably ZSM-5 molecular sieve；The silica alumina ratio of the shape slective cracking molecular sieve is general
For 10~150, preferably 20~120.Hydrogenation active metals described in Hydrodewaxing catalyst can be in the periodic table of elements
Group VIII and/or group vi metallic element, wherein group VIII active metal can be Ni and/or Co, group vi activity
Metal is W and/or Mo.On the basis of the weight of catalyst, hydrogenation active metal component using the content that oxide is counted as 10%~
30%, it is 70%~90% containing shape slective cracking molecular sieve silica-alumina supports content, wherein shape slective cracking molecular sieve contains in silica-alumina supports
Measure as 10%~40%, remaining is aluminum oxide.Described Hydrodewaxing catalyst can select existing various commercial catalysts, example
Such as Fushun Petrochemical Research Institute（FRIPP）The Hydrodewaxing catalysts such as FDW-1, FDW-3 of development；Can also be according to need
To be prepared by the general knowledge of this area, for example, be referred to CN1952074A, CN1352231A, CN101143333A,
Content disclosed in CN102451748A prepares satisfactory Hydrodewaxing catalyst.
In production method of the present invention, in described fluidized bed reactor, powdered Hydrobon catalyst and hydro dewaxing
The volume ratio of catalyst is 1：3~3：1, preferably 1：2~2：1.
In production method of the present invention, the hydrogenation conditions in described fluidized bed reactor are：Reaction pressure 6 ~
30MPa, reaction temperature are 270 ~ 500 DEG C, and air speed is 0.1 ~ 5h-1, hydrogen to oil volume ratio is 400 ~ 2000.
In production method of the present invention, in boiling bed hydrogenation reactor, diesel raw material, hydrogen and powdered hydrofinishing are urged
Agent and Hydrodewaxing catalyst contact, carry out hydrodesulfurization, denitrogenation, aromatic hydrocarbons saturation 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 of fluidized bed reactor and the heat release effect of hydrofining reaction
The endothermic effect that should be reacted with hydro dewaxing, realizes the comprehensive utilization of course of reaction heat, at utmost reduces temperature rise and temperature
Effect is dropped so that isothermal operation is realized in hydrocracking pretreatment reaction, so as to improve hydro-upgrading depression effeCt, can both ensure bavin
The quality and yield of oil, the depression effeCt achieved again.
2nd, 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.
3rd, 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.
4th, the powdered Hydrobon catalyst in the present invention travels up to fluidized bed reactor without catalysis with generation oil
The fluid zone of agent, the polycondensation coking reaction of area's liquid under the high temperature conditions in the presence of without Hydrodewaxing catalyst can be prevented
Generation.
Brief description of the drawings
Fig. 1 is a kind of schematic flow sheet of the production method of high-grade low-freezing diesel oil of the present invention.
Embodiment
A kind of production method of high-grade low-freezing diesel oil of the present invention is described in detail below in conjunction with the accompanying drawings.
As shown in figure 1, the high-grade low-freezing diesel production 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 12）It is sufficiently mixed in blender 3, obtains uniform charging 4,
Enter fluidized bed reactor through delivery pump, high pressure hydrogen 7 enters to be equipped with and faced in a manner of upper feeding from the bottom of fluidized bed reactor 5
The fluidized bed reactor of hydrogen pour point depression catalyst 6 makes catalyst keep boiling-like, under suitable reaction condition, is urged with hydro dewaxing
Agent and the contact of powdered Hydrobon catalyst, carry out catalytic hydrogenation reaction, and reacted logistics 8 is arranged from the top of reactor
Go out enter stablize reactor 9, carry out supplement hydrofinishing using the hydrogen partial and logistics self heat that wherein dissolve, by point
Separated from device 10 by oil 11 is generated with powdered Hydrobon catalyst 12, powdered Hydrobon catalyst recycles, raw
Enter separation fractionating system 13 into oil, fractionate out gas, light distillate and high-grade low-freezing diesel product 14.
The high-grade low-freezing diesel production method of the present invention is further described followed by specific embodiment.
Embodiment 1~3
The present embodiment is to be tested using the boiling bed hydrogenation of Hydrodewaxing catalyst and powdered Hydrobon catalyst.Tool
Body operating process is shown in accompanying drawing 1.The volume ratio of powdered Hydrobon catalyst and Hydrodewaxing catalyst is 1 in embodiment 1:3,
The volume ratio of powdered Hydrobon catalyst and Hydrodewaxing catalyst is 2 in embodiment 2~3:1.By poor ignition quality fuel and powder
Last shape Hydrobon catalyst is sufficiently mixed in a mixer, is obtained uniform charging, is entered fluidized bed reactor through delivery pump,
High pressure hydrogen enters the fluidized bed reactor equipped with Hydrodewaxing catalyst in a manner of upper feeding from fluidized bed reactor bottom
Make catalyst keep boiling-like, under suitable reaction condition, while and/or successively with Hydrodewaxing catalyst and it is powdered plus
Hydrogen catalyst for refining contacts, and carries out catalytic hydrogenation reaction, and reacted logistics is discharged into stable reaction at the top of reactor
Device, supplement hydrofinishing is carried out using the hydrogen partial of dissolving and the self heat of material, oil and powder will be generated by separator
Last shape Hydrobon catalyst separation, powdered Hydrobon catalyst recycle, and generate oil and enter separation fractionating system, point
Distillate gas, light distillate and high-grade low-freezing diesel product.The Hydrodewaxing catalyst used in embodiment is special preparation
Spheric catalyst, the catalyst component property and the commercial catalyst FDW-3 mono- of Fushun Petrochemical Research Institute's development and production
Cause.The powdered Hydrobon catalyst used is Mo-Ni loaded catalysts, and its granularity is 1000~1200 μm, catalyst
In contain active component（In terms of metal）Molybdenum 20wt%, nickel 8wt%.
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, feedstock oil are equal
It is same as Example 1.The product property of comparative example 1 ~ 2 is shown in Table 4.The Hydrobon catalyst of comparative example 1 and Hydrodewaxing catalyst
Filling ratio 1:3, the filling ratio 2 of the Hydrobon catalyst of comparative example 2 and Hydrodewaxing catalyst: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. a kind of production method of high-grade low-freezing diesel oil, it is characterised in that including herein below：（1）Poor ignition quality fuel raw material and powder
Shape Hydrobon catalyst is sufficiently mixed in a mixer, obtains the mixed feeding of catalyst and feedstock oil；（2）Mixed feeding with
Hydrogen enters fluidized bed reactor from the reactor bottom equipped with Hydrodewaxing catalyst, carries out hydrogenation reaction；It is wherein described
Hydrogenation reaction includes hydro dewaxing reaction and hydrofining reaction；（3）Thing after reaction comprising powdered Hydrobon catalyst
Flow through and discharged at the top of fluidized bed reactor, into reactor is stablized, carry out supplement hydrofinishing；（4）Step（3）The material of acquisition
Through separation of solid and liquid, liquid phase enters fractionating system, obtains high-grade low-freezing diesel product.
2. according to the production method described in claim 1, it is characterised in that：The condensation point of described poor ignition quality fuel raw material 0 DEG C with
On.
3. according to the production method described in claim 1, it is characterised in that：The poor ignition quality fuel raw material is done as 350~440
℃。
4. according to the production method described in claim 1, it is characterised in that：The granularity of described powdered Hydrobon catalyst
For 50~2000 μm；Using vib and/or group VIII metal as active component, using aluminum oxide or silicon-containing alumina as carrier,
Vib metals are Mo and/or W, and group VIII metal is Co and/or Ni, on the basis of the weight of catalyst, vib gold
Category content is calculated as 8wt%~28wt% with oxide, and group VIII tenor is calculated as the wt% of 2wt%~15 with oxide.
5. according to the production method described in claim 1, it is characterised in that：Step（1）In mixed feeding, powdered hydrofinishing
Catalyst charge is calculated as 20~200 μ g/g with metal.
6. according to the production method described in claim 1, it is characterised in that：Described Hydrodewaxing catalyst is included containing shape-selective
The silica-alumina supports and hydrogenation active metals of cracking molecular sieve；Described shape slective cracking molecular sieve is hydrogen type molecular sieve, the molecule
Screened from one kind or more in Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve
Kind；The silica alumina ratio of the shape slective cracking molecular sieve is 10~150；Described hydrogenation active metals are in the periodic table of elements
Group VIII and/or vib metals element, wherein group VIII active metal are Ni and/or Co, vib 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.
7. according to the production method described in claim 1, it is characterised in that：In described fluidized bed reactor, powdered hydrogenation
The volume ratio of catalyst for refining and Hydrodewaxing catalyst is 1：3~3：1.
8. according to the production method described in claim 1, it is characterised in that：In described fluidized bed reactor, powdered hydrogenation
The volume ratio of catalyst for refining and Hydrodewaxing catalyst is 1：2~2：1.
9. according to the production method described in claim 1, it is characterised in that：Hydrogenation reaction bar in described fluidized bed reactor
Part is：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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Citations (3)
| 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 | Addition of small catalyst particles to the slurry reactor |
| 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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| US9243194B2 (en) * | 2009-10-08 | 2016-01-26 | IFP Energies Nouvelles | Process for hydroconversion of heavy carbon-containing feedstocks that integrate a boiling-bed technology and a slurry technology |
| US9650312B2 (en) * | 2013-03-14 | 2017-05-16 | Lummus Technology Inc. | Integration of residue hydrocracking and hydrotreating |
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| 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 | Addition of small catalyst particles to the slurry reactor |
| 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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