CN104611045B - A kind of method producing hydrogenation low-coagulation diesel oil - Google Patents

A kind of method producing hydrogenation low-coagulation diesel oil Download PDF

Info

Publication number
CN104611045B
CN104611045B CN201310540390.7A CN201310540390A CN104611045B CN 104611045 B CN104611045 B CN 104611045B CN 201310540390 A CN201310540390 A CN 201310540390A CN 104611045 B CN104611045 B CN 104611045B
Authority
CN
China
Prior art keywords
catalyst
diesel
hydro
upgrading
accordance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310540390.7A
Other languages
Chinese (zh)
Other versions
CN104611045A (en
Inventor
王仲义
崔哲
彭冲
石友良
孙士可
黄新露
吴子明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201310540390.7A priority Critical patent/CN104611045B/en
Publication of CN104611045A publication Critical patent/CN104611045A/en
Application granted granted Critical
Publication of CN104611045B publication Critical patent/CN104611045B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C10G2300/20—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

Abstract

The invention discloses a kind of production method being hydrogenated with low-coagulation diesel oil.After diesel raw material mixes with hydrogen, pass sequentially through the hydroconversion reaction zone of at least two series connection, include Hydrodewaxing catalyst bed and the composite catalyst bed by Hydrodewaxing catalyst and catalyst for hydro-upgrading mixed packing successively by each described hydroconversion reaction zone, Flow of Goods and Materials direction；Last hydroconversion reaction zone gained reaction effluent is through separating and after fractional distillation, obtaining low freezing point diesel fuel product.The temperature rise of the temperature drop of hydro dewaxing process Yu hydro-upgrading process is reasonably combined utilization by the inventive method, improves yield and the Cetane number of diesel oil, reduce the hot(test)-spot temperature of device, extend service cycle while producing low solidifying low-sulfur diesel-oil；In addition reduce the consumption of cold hydrogen or the combustion gas loss of heating furnace, also save operating cost.

Description

A kind of method producing hydrogenation low-coagulation diesel oil
Technical field
The present invention relates to the production method of a kind of low-coagulation diesel oil, especially one is by catalyst grating technology and compound filling technology, is used for producing the method for hydrotreating of low-coagulation diesel oil.
Background technology
Diesel oil is as the fuel of compression ignition engine, modern productive life process plays irreplaceable effect as non-renewable resources, the vehicle such as automobile, tank, aircraft, tractor, rolling stock or the fuel of other machinery can be used as, it is possible to be used for generating electricity, heating etc..The difference of industry and environment is used according to it, user also has very big difference for the prescription of diesel product, for the people lived at extremely frigid zones or winter, the demand of low freezing point diesel fuel remains high always, and traditional shape slective cracking technique can process the heavy diesel fuel fraction 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 can widen diesel oil distillate scope, improve productivity, be solve low freezing point diesel fuel to produce being highly useful and advanced technology of problem.
The situation of China is also similar, particularly in recent years, along with improving constantly of the national economic development and environmental consciousness, requirement for diesel quality is more and more higher, and the popularity rate of diesel refining rises year by year, this external northern cold area, except the requirement to diesel oil regular refiner character, condensation point becomes and requisite requires one of index, therefore, it is possible to improve yield and the quality of low-coagulation diesel oil, meeting the market demand has become the major issue that Han Qu oil refining enterprise pays close attention to.And select row cracking and group technology thereof as one of Main Means reducing condensation point of diesel oil, it is possible to it is used for producing low-sulfur low-coagulation diesel oil, is conducive to improving the economic benefit of oil refining enterprise.
Diesel oil shape slective cracking technology, also known as hydro dewaxing, refers in the presence of hydrogen, and the diesel raw material of the content of wax is by the bifunctional catalyst surface containing active metal and molecular sieve, thus reducing wax molecule content therein.Its dewaxing principle is under certain operating conditions, raw material is made to contact with Hydrodewaxing catalyst with hydrogen mixing, it is cracked into little molecule alkane in raw material, aromatic hydrocarbons contour condensation point compositional selecting with short-side chain alkane, the cycloalkane of belt length side chain and belt length side chain, and other component does not change substantially, it is finally reached the purpose of the condensation point reducing oil product.Due to its have course of reaction hydrogen consumption relatively low, adaptability to raw material is strong, energy consumption is relatively low, technological process is simple, can with other hydrogenation process composition process integration or independently from etc. plurality of advantages, be therefore widely used.The a lot of oil refining enterprise of current northern China Han Qu all have employed this technology and produces low-coagulation diesel oil.
CN98121075.9 discloses a kind of method being produced high-grade low-freezing diesel oil by distillate.The method adopts hydrofinishing and hydro dewaxing one-stage serial flow process, and including Hydrobon catalyst and two beds of Hydrodewaxing catalyst, hydro dewaxing adopts Ni/ZSM-5 catalyst.The method is relatively big at 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.
CN200910188163.6 discloses a kind of method of diesel oil hydrogenation pour point depression.The method is by adjusting the character of catalyst thus to have diesel oil depression effeCt good, the feature that diesel oil distillate yield is high, but owing to still adopting hydrofinishing and the group technology of hydro dewaxing series connection, the contradiction between depression effeCt and diesel oil distillate yield still exists.
CN201010514141.7 discloses a kind of method of diesel hydro-pour-reducing.Although the method improves the average reaction temperature of Hydrodewaxing catalyst, utilize the temperature rise of finishing agent, increase the utilization rate of pour point depression catalyst, but the reaction temperature of each bed outlet is still of a relatively high, receives certain restriction service cycle.
CN01134271.4 discloses a kind of combined hydrogenation method producing high cetane number, low-coagulation diesel oil.The method is raw oil, hydrogen first to be contacted with catalyst for hydro-upgrading or hydrocracking catalyst, reaction effluent is not separated then to be contacted with Hydrodewaxing catalyst, the cooled entrance high-pressure separator of reaction effluent, isolated product liquid enters fractionating system, and the gas rich in hydrogen loops back reactor.The method can improve diesel-fuel cetane number in same set of device simultaneously and reduce the condensation point of diesel oil, and the Cetane number of diesel product relatively raw oil improves more than 6 units.
CN99113293.9 discloses a kind of method being produced high-quality low-coagulation diesel oil with high hexadecane value by distillate.Hydro dewaxing is directly connected by the method with hydrofinishing, hydro-upgrading, realize hydrofinishing-hydro-upgrading-hydro dewaxing-section serial flow, what adopt is Hydrobon catalyst that anti-coking performance is strong and has stronger anti-ammonia, the hydro-upgrading of capacity antacid and Hydrodewaxing catalyst, so that this technique has, refining/depression effeCt is good, diesel yield is high, adaptability to raw material is strong, diesel cetane-number is high, technological process is simple and products scheme feature flexibly.
Summary of the invention
For prior art Problems existing, the present invention provides the production method of a kind of low-coagulation diesel oil.The mixed catalyst of Hydrodewaxing catalyst with hydro dewaxing and the filling of hydro-upgrading compound is carried out grating by the inventive method, the temperature drop of hydro dewaxing process is reasonably combined utilization with the temperature rise in hydrogenation process, yield and the Cetane number of diesel oil is improve while producing low condensation point low-sulfur diesel-oil, reduce the hot(test)-spot temperature of device, extend service cycle, additionally adopt the art of this patent can also make up conventional compound filling process problem encountered, optimize the effect of mixed packing, fully different types of catalyst has been mated；In addition reduce the consumption of cold hydrogen or the combustion gas loss of heating furnace, save operating cost.
The production method of a kind of low-coagulation diesel oil provided by the invention, including herein below:
After diesel raw material mixes with hydrogen, pass sequentially through the hydroconversion reaction zone of at least two series connection, by Flow of Goods and Materials direction, each described hydroconversion reaction zone includes Hydrodewaxing catalyst bed and the composite catalyst bed by Hydrodewaxing catalyst and catalyst for hydro-upgrading mixed packing successively；Last hydroconversion reaction zone gained reaction effluent is through separating and after fractional distillation, obtaining low freezing point diesel fuel product.
According to method of the present invention, wherein in each described hydroconversion reaction zone, diesel raw material and hydrogen first pass through Hydrodewaxing catalyst bed, carry out pour point depression reaction；Reaction effluent, again through the composite catalyst bed by Hydrodewaxing catalyst and catalyst for hydro-upgrading mixed packing, carries out that hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbons is saturated, open loop and the reaction of degree of depth pour point depression.
Method of hydrotreating according to the present invention, described diesel raw material is conventional pour point depression raw material and high freezing point diesel fuel, and condensation point is generally all more than 0 DEG C, it is preferable that condensation point is more than 5 DEG C.The nitrogen content of described diesel raw material, at 2000 below μ g/g, is generally 50～1200 μ g/g, it is most preferred that be 100～500 μ g/g.If the organic nitrogen content in diesel raw material is too high, if nitrogen content is when 2000 more than μ g/g, before diesel raw material is by the Hydrodewaxing catalyst bed of the first hydroconversion reaction zone, beforehand through a hydrofinishing or hydrodenitrogenation catalyst bed, part denitrogenation can be carried out.Described diesel raw material can be processing naphthene base crude, intermediate base crude or paraffinic base crude oil obtain various straight run or the diesel oil etc. of secondary operations, it is preferable that the said components that processing paraffinic base crude oil obtains.Doing of diesel raw material is generally 350～440 DEG C, it is preferable that 370～400 DEG C.As described diesel raw material can be selected from one or several in various straight-run diesel oils that processing Daqing crude oil obtains, coker gas oil, catalytic diesel oil etc..
Described Hydrodewaxing catalyst adopts the catalyst containing shape slective cracking molecular sieve, including the metal component of carrier and institute's load.Described catalyst is generally with shape slective cracking molecular sieve and binding agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component.Described shape slective cracking molecular sieve is hydrogen type molecular sieve, and described 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, it is preferable that ZSM-5 molecular sieve；The silica alumina ratio of described shape slective cracking molecular sieve is generally 10～150, it is preferred to 20～120.
Described group VIB metal is Mo and/or W, and described group VIII metal is Co and/or Ni.With the weight of catalyst for benchmark, the content that hydrogenation active metals component is counted with oxide is for 1%～16%, and the content of shape slective cracking molecular sieve is 50%～85%, and the content of binding agent is 10%～40%.The bulk density of Hydrodewaxing catalyst is typically in 0.65～0.75g cm-3, it uses temperature range to be 380 DEG C～400 DEG C normally.Described Hydrodewaxing catalyst can select existing various commercial catalysts, for instance the Hydrodewaxing catalysts such as FDW-1, FDW-3 that Fushun Petrochemical Research Institute (FRIPP) develops；Can also be prepared by the general knowledge of this area as required, for instance be referred to the content disclosed in CN1952074A, CN1352231A, CN101143333A, CN102451748A and prepare satisfactory Hydrodewaxing catalyst.
Heretofore described catalyst for hydro-upgrading is the hydrogenation conversion catalyst containing molecular sieve, refers to a kind of hydrogenation catalyst being exclusively used in diesel modifying, for the conventional hydro reforming catalyst in this area.Described catalyst for hydro-upgrading is a kind of dual function hydrogenation catalyst, with aluminium oxide and Y type molecular sieve for carrier, containing at least one VI B race metal and at least one VIII race's metal, it is characterized in that catalyst carrier consists of aluminium oxide 5w%～45w%, amorphous silica-alumina 0w%～60w%, molecular sieve 5w%～60w%, the wherein pore volume 0.40～0.52mL/g of Y molecular sieve, specific surface 750～900m2/ g, lattice constant 2.420～2.500nm, SiO2/Al2O3Molecular proportion 7～15.
Described catalyst for hydro-upgrading salic be a kind of crystalline phase be the aluminium oxide of boehmite, content is 40w%～80w%.Alumina support according to the special preparation of this technology, containing macroporous aluminium oxide in catalyst for hydro-upgrading, macroporous aluminium oxide content (with carrier for benchmark) is generally 5w%～45w%, it is preferable that 10w%～40w%；The pore volume of described macroporous aluminium oxide is 1.0～1.7mL/g, it is preferred to > 1.2～1.7mL/g(is more than 1.2 to 1.7mL/g)；Specific surface area is 200～550m2/ g, it is desirable to be 300～500m2/ g.The sieve and silica-sesquioxide weight ratio 1:2～2:1, content 0w%～20w%, it is desirable to 10w%～20w% of contained amorphous silicon aluminium in described carrier.
Described hydrogenation metal can be the combination of at least one VI B family metal oxide or sulfide and at least one VIII family metal oxide or sulfide, and VI B race metal can be Mo or W, it is desirable to select W.VIII race's metal can be Ni or Co, it is desirable to select Ni.In catalyst, VI B family metal oxide content is 10w%～30w%, and VIII family metal oxide content is 2w%～15w%.Catalyst for hydro-upgrading can select the existing modified acquisition of various commercial catalysts, for instance FRIPP develop 3963, prepared by the catalyst modification such as FC-18.Specific catalyst for hydro-upgrading can also be prepared as required, for instance be referred to CN1184843A, CN1178238A disclosure and prepare satisfactory hydro-upgrading (conversion) catalyst by the general knowledge of this area.
In the method for the present invention, selected catalyst for hydro-upgrading is when catalyst/support molding, preferably especially it is suitable for the sour peptizing techniques of this technique, mineral acid and organic acid mixed acid are joined in forming process, enhance the character such as the specific surface area of catalyst, intensity, also simplify the production procedure of catalyst in addition, reduce production cost, simultaneously it is also ensured that the stability of macroporous aluminium oxide, make the pore volume that prepared catalyst/support maintenance is higher.This technology can be that current industry-wide catalyst is modified when molding prepares gained.Adopt catalyst prepared by this technology, on catalyst face shaping, be also carried out optimization process, it is desirable to prepare into tooth ball shape catalyst simultaneously, it is simple to transport, filling and mixing.
Catalyst for hydro-upgrading after modified recited above, due to the change of carrying alumina volume property, when reaching the same reaction degree of depth, its activity to be weaker than about 10 DEG C of the catalyst for hydro-upgrading of routine, and normal use temperature range is increased to 380 DEG C～400 DEG C.This kind of modified catalyst is compared with above-mentioned Hydrodewaxing catalyst, and in mixed process, bulk density difference is preferably smaller than 0.05g cm-3。
The operating condition of described Hydrodewaxing catalyst bed is: reaction pressure 6.0～20.0MPa, hydrogen to oil volume ratio 200:1～1500:1, and volume space velocity is 0.1～10.0h-1, reaction temperature 260 DEG C～455 DEG C；Preferred operations condition is reaction pressure 7.0～15.0MPa, hydrogen to oil volume ratio 300:1～1000:1, volume space velocity 0.3～8.0h-1, reaction temperature 310 DEG C～410 DEG C.
The operating condition of the composite catalyst composite bed of described hydro dewaxing and catalyst for hydro-upgrading composition is: reaction pressure 6.0～20.0MPa, hydrogen to oil volume ratio 200:1～1500:1, volume space velocity is 0.1～10.0h-1, reaction temperature 270 DEG C～460 DEG C；Preferred operations condition is reaction pressure 7.0～15.0MPa, hydrogen to oil volume ratio 300:1～1000:1, volume space velocity 0.3～8.0h-1, reaction temperature 315 DEG C～415 DEG C.
The method according to the invention, wherein in each hydroconversion reaction zone, described Hydrodewaxing catalyst bed is 1:10～10:1 with the admission space ratio by catalyst for hydro-upgrading with the composite catalyst bed of Hydrodewaxing catalyst mixed packing, it is preferred to 1:5～5:1.
In described pour point depression modifying catalyst composite bed, the filling of Hydrodewaxing catalyst and catalyst for hydro-upgrading compound, admission space ratio is for 1:10～10:1, it is preferable that 1:5～5:1.
For described at least two hydroconversion reaction zone, wherein said Hydrodewaxing catalyst bed and pour point depression modifying catalyst composite bed, it is possible to be separately positioned in two or more beds of a reactor；Or can be separately positioned in the hydrogenation reactor of two or more series connection.
Compared with prior art, the inventive method has the advantage that
1, in the inventive method, in each hydroconversion reaction zone, raw oil first passes through Hydrodewaxing catalyst bed, carry out pour point depression reaction, diesel raw material is processed, and this reaction shows as the endothermic reaction, and the raw oil after hydro dewaxing PROCESS FOR TREATMENT is again through compound pour point depression modifying catalyst bed, carrying out hydrodesulfurization, hydrodenitrogeneration, aromatic saturation and ring opening and the reaction of degree of depth pour point depression, this reaction shows as the synergistic effect of heat absorption and heat release.All in all, owing to hydrogenation reaction shows as exothermic reaction, this process produces temperature rise；And hydro dewaxing reaction is shape-selective molecular sieve cracking reaction, heat effect shows as the endothermic reaction, and process produces temperature drop；These two kinds of catalyst are carried out grating compound filling, its respective heat release and endothermic effect can be made full use of, realize the comprehensive utilization of the heat of course of reaction, excessive temperature rise and temperature drop effect will not be produced, and affect depression effeCt, so that the hot(test)-spot temperature of whole beds reduces, both can ensure that the yield of diesel oil, also achieved better depression effeCt.Owing to have employed MCI technique in the present invention, the Cetane number of diesel product has lifting by a relatively large margin, significant desulfurization effect simultaneously, diesel raw material first contacts with Hydrodewaxing catalyst, adaptability to raw material is stronger, in addition adopt Hydrodewaxing catalyst to carry out grating, also there is the advantage that catalyst cost is low.
2, at process aspect, essentially identical effect in each hydroconversion reaction zone, is all shown.Thus at least two hydroconversion reaction zone of series connection, described hydrogenation reaction shows as comprehensive cumulative effect of optimization.Compared with prior art, the present invention is not changing on the basis of device flow process, only by the grading composition of catalyst and compound filling, from local by the high temperature dot of device and the effective Appropriate application of low warm spot, reduce the hot(test)-spot temperature of device, reasonably decrease the bulk temperature gradient of device, extend the service life of catalyst.In addition this combination is compared with conventional hydro dewaxing group technology, more reasonably utilize owing to the heat of course of reaction obtains, can beat less between two reaction zones or not liquid hydrogen injection, therefore also reduce the consumption of cold hydrogen and the combustion gas loss of heating furnace, save operating cost.
3, the present invention selects especially suitable modifying catalyst and technique with the use of, there is very big adaptability and advantage.During by it with Hydrodewaxing catalyst mixed packing, can reach more excellent to load in mixture effect, when avoiding the catalyst mix filling caused because density variation is excessive, in irregular shape, the problem that distribution of particles is uneven, the simultaneously modified also suitable reactivity reducing catalyst for hydro-upgrading, so better can mate with Hydrodewaxing catalyst, make the two activity quite, to play its each maximum effect in same temperature ranges stated, reduce product condensation point at the same time it can also be improve product quality.If additionally, be provided with hydrodenitrogeneration reactor before mixing bed, it is also possible to reduce denitrification reactor outlet and the temperature difference mixing bed inlet, decrease the consumption of cold hydrogen, improve the safety coefficient of plant running, reached more excellent Temperature Matching effect.
Accompanying drawing explanation
Fig. 1 is the grading loading schematic diagram of a kind of embodiment of the inventive method；Single reactor layering filling is selected to have the mode of operation of two hydroconversion reaction zones.
Detailed description of the invention
Below in conjunction with accompanying drawing, the production method of a kind of low-coagulation diesel oil of the present invention is described in detail.
As it is shown in figure 1, the low-coagulation diesel oil production method flow process of the present invention is as follows:
Raw oil 1 enters reactor 3 with hydrogen 2 after reactor inlet mixes, pass sequentially through the Hydrodewaxing catalyst bed 4 connected step by step from top to bottom, composite catalyst bed 5 by Hydrodewaxing catalyst Yu catalyst for hydro-upgrading mixed packing, Hydrodewaxing catalyst bed 6 and the composite catalyst bed 7 by Hydrodewaxing catalyst Yu catalyst for hydro-upgrading mixed packing, obtain reaction effluent 8 and after water filling 9, enter into high-pressure separator 10 from reactor bottom discharge, the top of high-pressure separator 10 obtains gas 11 by circulating hydrogen compressor 12, obtain recycle hydrogen 14 hydrogen as a supplement after mixing with new hydrogen 13 or cold hydrogen uses；Liquid phase that high-pressure separator 10 middle and lower part obtains enters low pressure separator 17, and low pressure separator 17 top is discharged low point of gas 18 and gone subsequent treatment, low pressure separator 17 middle and lower part to obtain liquid phase 20 to enter subsequent fractionation system；The acid water 15 discharged bottom high-pressure separator 10 goes acid water treatment facilities to carry out following process after mixing with the acid water 19 discharged bottom low pressure separator 17.
Followed by specific embodiment, the low-coagulation diesel oil production method of the present invention is further described.Table 1 lists the character of used catalyst in embodiment 1 and comparative example 1.Table 2 lists the main character of raw oil.
The main physico-chemical property of table 1 catalyst and activity contrast.
Catalyst FC-18 FC-18G FDW-3
Catalyst type Hydro-upgrading Hydro-upgrading Hydro dewaxing
Wherein macroporous aluminium oxide, % 8 32
Pore volume, cm3/g 0.68 1.28 —
Specific surface area, m2/g 365 351 —
Catalyst physical properties
Shape Tooth ball Tooth ball Tooth ball
Diameter, mm 2.5 2.5 2.5
Mechanical strength, N/cm ≮150 ≮130 ≮100
Active component Mo-Ni Mo-Ni Ni
Tenor, % 29.2 24 2.1
Natural loading density, t/m3 0.77～0.87 0.65～0.75 0.65～0.75
Average pore size/nm 5.14 7.75 —
Pore-size distribution/nm 5-9 7-12 —
Temperature when reaching the same reaction degree of depth/DEG C 374 383 —
Normally use temperature (just-latter stage)/DEG C 370～390 380～400 380～400
Comparative example 1
Comparative example 1 is the device adopting hydro dewaxing, hydro-upgrading one-stage serial flow process to produce low freezing point diesel fuel.Including Hydrodewaxing catalyst bed and catalyst for hydro-upgrading bed.Comparative example 1 and embodiment 1 produce the low-coagulation diesel oil of the identical trade mark.The catalyst, raw oil and the diesel product condensation point that use are all identical with embodiment 1.Operation result is listed in table 3.
Comparative example 2
Comparative example 2 is the device adopting hydro dewaxing, hydro-upgrading one-stage serial flow process to produce low freezing point diesel fuel.Control essentially identical diesel yield with embodiment 1, produce the low-coagulation diesel oil of the different trade mark.Catalyst, raw oil and diesel product yield that comparative example 2 uses are all identical with embodiment 1, and Catalyst packing is with comparative example 1.Operation result is listed in table 3.
Embodiment 1
Adopt the technological process shown in Fig. 1, utilize grating series connection and load in mixture flow process production low freezing point diesel fuel.Embodiment 1 includes the hydroconversion reaction zone of two series connection, and in the pour point depression modifying catalyst composite bed of each reaction zone, Hydrodewaxing catalyst is all more identical than for 1:2, the total consumption of catalyst and comparative example 1 and comparative example 2 with the mixed volume of catalyst for hydro-upgrading.The catalyst for hydro-upgrading used in embodiment 1 is FC-18 catalyst, and Hydrodewaxing catalyst is FDW-3 catalyst, and described catalyst is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operating condition and result of the test are listed in table 3.
Embodiment 2
Adopt the technological process shown in Fig. 1, utilize grating series connection and load in mixture flow process production low freezing point diesel fuel.Embodiment 1 includes the hydroconversion reaction zone of two series connection, and in the combination pour point depression catalyst composite bed of each reaction zone, Hydrodewaxing catalyst is all more identical than for 1:2, the total consumption of catalyst and comparative example 1 and comparative example 2 with the mixed volume of catalyst for hydro-upgrading.The hydro-upgrading isomerization-visbreaking catalyst used in embodiment 2 is FC-18G catalyst, and Hydrodewaxing catalyst is FDW-3 catalyst, and described catalyst is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operating condition and result of the test are listed in table 3.
Table 2 raw oil property list.
Project Raw oil
Source Atmosphere 3rd side cut diesel oil
Density (20 DEG C)/g cm-3 0.8810
Boiling range scope/DEG C 280～400
Nitrogen/μ g g-1 120
Sulfur/μ g g-1 1200
Condensation point/DEG C 13
Cetane number 38.0
Table 3 process condition and result.
Comparative example 1 Comparative example 2 Embodiment 1 Embodiment 3
Catalyst forms FDW-3/FC-18 FDW-3/FC-18 FDW-3/(FDW-3+FC-18) FDW-3/(FDW-3+FC-18G)
Reaction pressure/MPa 9.0 9.0 9.0 9.0
Average reaction temperature/DEG C 380/382 372/382 380/381*/380/381* 380/382*/380/384*
LHSV/h-1 3.0/2.5 3.0/2.5 6.0/5.0**/6.0/5.0** 6.0/5.0**/6.0/5.0**
Entrance hydrogen to oil volume ratio 600:1 600:1 600:1 600:1
Diesel product condensation point/DEG C -36 -22 -35 -36
Diesel yield, wt% 67.7 76.0 75.8 77.8
Diesel oil sulfur content, ppm 17 23 19 16
Diesel cetane-number 42.1 44.9 42 42.8
Bed peak temperature/DEG C 392 390 386 384
Cold hydrogen consumption/benchmark 0.95 1.81 1.0 0.97
* average reaction temperature is the weighted mean of pour point depression modifying catalyst bed；
* volume space velocity is the volume space velocity of pour point depression modifying catalyst bed.
Can be seen that from above embodiments, the modified catalyst that embodiment 2 uses, there is mixed effect more excellent, hot(test)-spot temperature is lower, the feature that diesel yield is higher simultaneously, in addition, the maximum of the inventive method is characterized in that, low solidifying product is produced for processing diesel raw material, catalyst grade part cording has adaptability to raw material strong, and product Cetane number is high, and sulfur content is low, the feature that catalyst cost of investment is few, can reduce the condensation point of raw material simultaneously to greatest extent and make up the drawback of conventional mixed packing when ensureing certain diesel yield；In addition also to have hot(test)-spot temperature low for the inventive method, and service cycle is long, the feature that cold hydrogen consumption is low；For enterprise, while completing quality product production task, human and material resources and energy consumption have very big advantage.

Claims (12)

1. a production method for low-coagulation diesel oil, including herein below:
After diesel raw material mixes with hydrogen, pass sequentially through the hydroconversion reaction zone of at least two series connection, by Flow of Goods and Materials direction, described hydroconversion reaction zone includes Hydrodewaxing catalyst bed and successively by the pour point depression upgrading composite catalyst bed of Hydrodewaxing catalyst and catalyst for hydro-upgrading mixed packing；Last hydroconversion reaction zone gained reaction effluent is through separating and after fractional distillation, obtaining low freezing point diesel fuel product；
Wherein, described Hydrodewaxing catalyst is with shape-selective molecular sieve and binding agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component, with the weight of catalyst for benchmark, the content that hydrogenation active metals component is counted with oxide is for 1%～16%, the content of shape-selective molecular sieve is 50%～85%, and the content of binding agent is 10%～40%.
2. in accordance with the method for claim 1, it is characterised in that the condensation point of described diesel raw material is more than 0 DEG C, and nitrogen content is at 2000 below μ g/g.
3. the method described in claim 1 or 2, it is characterised in that the condensation point of described diesel raw material is more than 5 DEG C, and nitrogen content is 50～1200 μ g/g.
4. in accordance with the method for claim 1, it is characterised in that the nitrogen content of described diesel raw material is at 2000 more than μ g/g, before diesel raw material is by the Hydrodewaxing catalyst bed of the first hydroconversion reaction zone, beforehand through a Hydrobon catalyst bed.
5. in accordance with the method for claim 1, it is characterised in that doing of described diesel raw material is 350～440 DEG C.
6. in accordance with the method for claim 1, it is characterised in that in described each hydroconversion reaction zone, Hydrodewaxing catalyst bed is 1:10～10:1 with the admission space ratio by catalyst for hydro-upgrading with the composite bed of Hydrodewaxing catalyst mixed packing.
7. in accordance with the method for claim 1, it is characterised in that in described pour point depression modifying catalyst composite bed, Hydrodewaxing catalyst and catalyst for hydro-upgrading admission space are than for 1:10～10:1.
8. in accordance with the method for claim 1, it is characterized in that, described shape-selective 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, and the silica alumina ratio of shape-selective molecular sieve is 10～150.
9. in accordance with the method for claim 1, it is characterized in that, described catalyst for hydro-upgrading is with aluminium oxide and Y type molecular sieve for carrier, containing at least one VI B race metal and at least one VIII race's metal, catalyst carrier consists of aluminium oxide 5w%～45w%, amorphous silica-alumina 0w%～60w%, molecular sieve 5w%～60w%, wherein the pore volume 0.40～0.52mL/g of Y molecular sieve, specific surface 750～900m2/ g, lattice constant 2.420～2.500nm, SiO2/Al2O3Molecular proportion 7～15；In catalyst, VI B family metal oxide content is 10w%～30w%, and VIII family metal oxide content is 2w%～15w%.
10. in accordance with the method for claim 9, it is characterised in that described aluminium oxide is macroporous aluminium oxide, macroporous aluminium oxide content is 10w%～40w%, and the pore volume of macroporous aluminium oxide is 1.0～1.7mL/g.
11. in accordance with the method for claim 1, it is characterised in that the operating condition of described Hydrodewaxing catalyst bed is: reaction pressure 6.0～20.0MPa, hydrogen to oil volume ratio 200:1～1500:1, and volume space velocity is 0.1～10.0h-1, reaction temperature 260 DEG C～455 DEG C.
12. in accordance with the method for claim 1, it is characterised in that the operating condition of described pour point depression upgrading composite catalyst bed is: reaction pressure 6.0～20.0MPa, hydrogen to oil volume ratio 200:1～1500:1, volume space velocity is 0.1～10.0h-1, reaction temperature 270 DEG C～460 DEG C.
CN201310540390.7A 2013-11-05 2013-11-05 A kind of method producing hydrogenation low-coagulation diesel oil Active CN104611045B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310540390.7A CN104611045B (en) 2013-11-05 2013-11-05 A kind of method producing hydrogenation low-coagulation diesel oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310540390.7A CN104611045B (en) 2013-11-05 2013-11-05 A kind of method producing hydrogenation low-coagulation diesel oil

Publications (2)

Publication Number Publication Date
CN104611045A CN104611045A (en) 2015-05-13
CN104611045B true CN104611045B (en) 2016-06-29

Family

ID=53145699

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310540390.7A Active CN104611045B (en) 2013-11-05 2013-11-05 A kind of method producing hydrogenation low-coagulation diesel oil

Country Status (1)

Country Link
CN (1) CN104611045B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5593570A (en) * 1992-04-16 1997-01-14 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Catalyst system for combined hydrotreating and hydrocracking and a process for upgrading hydrocarbonaceous feedstocks
US6787022B1 (en) * 2000-05-02 2004-09-07 Exxonmobil Research And Engineering Company Winter diesel fuel production from a fischer-tropsch wax
CN103224810A (en) * 2012-01-31 2013-07-31 中国石油化工股份有限公司 Hydrogenation method for producing diesel oil with low pour point
CN103805250A (en) * 2012-11-07 2014-05-21 中国石油化工股份有限公司 Production method of hydrogenated diesel oil with low condensation point

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5593570A (en) * 1992-04-16 1997-01-14 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Catalyst system for combined hydrotreating and hydrocracking and a process for upgrading hydrocarbonaceous feedstocks
US6787022B1 (en) * 2000-05-02 2004-09-07 Exxonmobil Research And Engineering Company Winter diesel fuel production from a fischer-tropsch wax
CN103224810A (en) * 2012-01-31 2013-07-31 中国石油化工股份有限公司 Hydrogenation method for producing diesel oil with low pour point
CN103805250A (en) * 2012-11-07 2014-05-21 中国石油化工股份有限公司 Production method of hydrogenated diesel oil with low condensation point

Also Published As

Publication number Publication date
CN104611045A (en) 2015-05-13

Similar Documents

Publication Publication Date Title
CN103805257B (en) Catalyzer grating technology is utilized to produce the method for low-coagulation diesel oil
CN103805270B (en) A kind of production method of low-coagulation diesel oil
CN104611033B (en) The method producing hydrogenation low-coagulation diesel oil
CN103805251B (en) Grating technology produces the method for hydrogenation low-coagulation diesel oil
CN104611027B (en) Low freezing point diesel fuel production method
CN103805250B (en) A kind of production method of hydrogenation low-coagulation diesel oil
CN103805259B (en) A kind of grating technology produces the method for low-coagulation diesel oil
CN104611044B (en) The production method of lube base oil
CN103805244B (en) A kind of production method of clean low-coagulation diesel oil
CN105087064B (en) Method for producing clean low freezing point diesel oil by treating high nitrogen diesel oil
CN103805255B (en) Catalyzer grating technology is utilized to produce the method for hydrogenation low-coagulation diesel oil
CN103805237B (en) A kind of method utilizing catalyzer grating technology to produce low-coagulation diesel oil
CN104611045B (en) A kind of method producing hydrogenation low-coagulation diesel oil
CN105087063B (en) Hydroisomerization pour-point-depressing deep-coupling process for producing low-pour-point diesel oil
CN103805238B (en) A kind of grating technology produces the method for hydrogenation low-coagulation diesel oil
CN103805268B (en) A kind of poor ignition quality fuel that processes produces the method cleaning low-coagulation diesel oil
CN103805252B (en) The production method of hydrogenation low-coagulation diesel oil
CN103805239B (en) A kind of method utilizing catalyzer grating technology to produce hydrogenation low-coagulation diesel oil
CN104611035B (en) A kind of production method of lube base oil
CN103805263B (en) A kind of method of producing high-grade low-freezing diesel oil
CN103805260B (en) A kind of production method of low solidifying fine-quality diesel oil
CN104611043B (en) The production method of low-coagulation diesel oil
CN103805258B (en) A kind of combined technical method producing low freezing point diesel oil
CN103805254B (en) A kind of combined technical method of low freezing point diesel production
CN103805262B (en) The production method of low-coagulation diesel oil

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant