CN104611033B - The method producing hydrogenation low-coagulation diesel oil - Google Patents

The method producing hydrogenation low-coagulation diesel oil Download PDF

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CN104611033B
CN104611033B CN201310540344.7A CN201310540344A CN104611033B CN 104611033 B CN104611033 B CN 104611033B CN 201310540344 A CN201310540344 A CN 201310540344A CN 104611033 B CN104611033 B CN 104611033B
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catalyst
hydro
diesel
accordance
upgrading
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CN104611033A (en
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石友良
王仲义
彭冲
崔哲
孙士可
黄新露
吴子明
潘德满
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • 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 a kind of production method being hydrogenated with low-coagulation diesel oil.After diesel raw material mixes with hydrogen, passing sequentially through the hydroconversion reaction zone of at least two series connection, hydroconversion reaction zone as described in Flow of Goods and Materials direction includes the pour point depression modifying catalyst composite bed by Hydrodewaxing catalyst and catalyst for hydro-upgrading mixed packing and Hydrodewaxing catalyst bed successively；Last hydroconversion reaction zone gained reaction effluent is through separating and after fractionation, 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 reducing the consumption of cold hydrogen or the combustion gas loss of heating furnace, joint has also saved operating cost.

Description

The 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 a kind of by the compound filling of catalyst and grating technology, it 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, irreplaceable effect is played as non-renewable resources during the productive life of modernization, the delivery vehicles 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..Industry and the difference of environment is used according to it, user also has the biggest difference for the quality requirement of diesel product, for the people that extremely frigid zones or winter are lived, the demand of low freezing point diesel fuel remains high always, and traditional shape slective cracking technique can process the heavy diesel fuel cut of the content of wax, and pour point depression amplitude is up to 20～50 DEG C, while obtaining low freezing point diesel fuel, also can widen diesel oil distillate scope, improve productivity, be to solve low freezing point diesel fuel to produce the highly useful and advanced technology of problem.
The situation of China is also similar to, the most 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, in addition to 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 is paid close attention to.And select row cracking and combinations thereof technique as reducing one of Main Means of condensation point of diesel oil, can be used to produce low-sulfur low-coagulation diesel oil, be 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 reduces 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 the aromatic hydrocarbons contour condensation point compositional selecting of alkane, band short-side chain alkane, the cycloalkane of belt length side chain and belt length side chain in raw material, and other component does not changes, it is finally reached the purpose of the condensation point reducing oil product.Owing to it has, course of reaction hydrogen consumption is relatively low, adaptability to raw material is strong, energy consumption is relatively low, technological process is simple, can form the plurality of advantages such as process integration or independent use with other hydrogenation process, is therefore widely used.The a lot of oil refining enterprise of northern China Han Qu all have employed this technology and produces low-coagulation diesel oil at present.
CN98121075.9 discloses a kind of method being produced high-grade low-freezing diesel oil by distillate.The method uses hydrofinishing and hydro dewaxing one-stage serial flow process, and including Hydrobon catalyst and two beds of Hydrodewaxing catalyst, hydro dewaxing uses 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, by 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 using 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 refining agent, increase the utilization rate of pour point depression catalyst, but the reaction temperature of each bed outlet is the most 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 feedstock oil, hydrogen first to be contacted with catalyst for hydro-upgrading or hydrocracking catalyst, reaction effluent the most then contacts with Hydrodewaxing catalyst, reaction effluent cooled entrance high-pressure separator, isolated product liquid enters fractionating system, and the gas rich in hydrogen loops back reactor.The method can improve the Cetane number of diesel oil in same set of device simultaneously and reduce the condensation point of diesel oil, and the Cetane number of diesel product relatively feedstock 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, using the strong Hydrobon catalyst of anti-coking performance and have stronger anti-ammonia, the hydro-upgrading of capacity antacid and Hydrodewaxing catalyst, so that this technique has, refined/depression effeCt is good, diesel yield is high, adaptability to raw material is strong, diesel cetane-number is high, technological process is simple and products scheme feature flexibly.
Summary of the invention
The problem existed for prior art, the present invention provides the production method of a kind of low-coagulation diesel oil.Hydro dewaxing and hydro-upgrading are combined the mixed catalyst of filling and carry out grating with Hydrodewaxing catalyst 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 use 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 is 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 that the present invention provides, including herein below:
After diesel raw material mixes with hydrogen, passing sequentially through the hydroconversion reaction zone of at least two series connection, hydroconversion reaction zone as described in Flow of Goods and Materials direction includes successively by Hydrodewaxing catalyst and the composite catalyst bed of catalyst for hydro-upgrading mixed packing and Hydrodewaxing catalyst bed；Last hydroconversion reaction zone gained reaction effluent is through separating and after fractionation, 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 by Hydrodewaxing catalyst and the composite catalyst bed of catalyst for hydro-upgrading mixed packing, carry out that hydrodesulfurization, hydrodenitrogeneration, aromatic hydrocarbons is saturated, open loop and pour point depression reaction.Reaction effluent by Hydrodewaxing catalyst bed, carries out degree of depth pour point depression reaction again；
According to the method for hydrotreating of the present invention, described diesel raw material is conventional pour point depression raw material i.e. high freezing point diesel fuel, and condensation point is the most all more than 0 DEG C, and preferably condensation point is more than 5 DEG C.The nitrogen content of described diesel raw material at 1000 below μ g/g, generally 10～400 μ g/g, most preferably 40～150 μ g/g.If the organic nitrogen content in diesel raw material is too high, if nitrogen content is when 1000 more than μ g/g, beforehand through a hydrofinishing or hydrodenitrogenation catalyst bed, part denitrogenation can be carried out before diesel raw material is by the refining modification catalyst composite bed of the first hydroconversion reaction zone.Described diesel raw material can be to process various straight run or the diesel oil etc. of secondary operations that naphthene base crude, intermediate base crude or paraffinic base crude oil obtain, the said components that preferably processing paraffinic base crude oil obtains.Diesel raw material do generally 350～440 DEG C, preferably 370～400 DEG C.One or several in the various straight-run diesel oils that can obtain selected from processing Daqing crude oil such as described diesel raw material, coker gas oil, catalytic diesel oil etc..
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, prepares gained for the conventional hydro reforming catalyst in this area is modified.Described catalyst for hydro-upgrading is a kind of dual function hydrogenation catalyst, with aluminum oxide and Y type molecular sieve as 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 aluminum oxide 6w%～45w%, amorphous silica-alumina 0w%～60w%, molecular sieve 5w%～60w%, wherein pore volume 0.40～0.82 mL/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 aluminum oxide of boehmite, content is 40w%～80w%.According to the alumina support of this technology special preparation, containing macroporous aluminium oxide in catalyst for hydro-upgrading, macroporous aluminium oxide content is generally 5w%～45w%, preferably 10w%～40w%；The pore volume of described macroporous aluminium oxide is 1.0～1.7mL/g, and preferably > 1.2～1.7mL/g(more than 1.2 to 1.7 mL/g)；Specific surface area is 200～550m2/ g, preferably 300～500m2/g.Sieve and silica-sesquioxide weight ratio 1:2 of amorphous silicon aluminium contained by described carrier～2:1, content 0w%～20w%, best 10w%～20w%.
Described hydrogenation metal can be at least one VI B family metal oxide or sulfide and at least one VIII family metal oxide or the combination of sulfide, and VI B race metal can be Mo or W, preferably selects W；VIII race's metal can be Ni or Co, preferably selects 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, such as FRIPP develop 3963, prepared by the catalyst modification such as FC-18.Specific catalyst for hydro-upgrading can also be prepared by the general knowledge of this area as required, such as, be referred to CN1184843A, CN1178238A disclosure and prepare satisfactory hydro-upgrading (conversion) catalyst.
In the method for the present invention, selected catalyst for hydro-upgrading is when catalyst/support is molded, preferably especially it is suitable for the sour peptizing techniques of this technique, the mixed acid of inorganic acid Yu organic acid is 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, prepared catalyst/support is made to keep higher pore volume.This technology can be that gained is prepared in the modification when shaping of current industry-wide catalyst.Use catalyst prepared by this technology, on catalyst face shaping, be also carried out optimization process simultaneously, be preferably prepared as tooth ball shape catalyst, it is simple to transport, load and mix.
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 the catalyst for hydro-upgrading about 10 DEG C of routine, and normal use temperature range is increased to 380 DEG C～400 DEG C.This kind of modified catalyst is compared with Hydrodewaxing catalyst, and in mixed process, bulk density difference is preferably smaller than 0.05g cm-3。
Described Hydrodewaxing catalyst uses the catalyst containing shape slective cracking molecular sieve, including carrier and the metal component loaded.Described catalyst is typically with shape slective cracking molecular sieve and adhesive as 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, preferably ZSM-5 molecular sieve；The silica alumina ratio of described shape slective cracking molecular sieve is generally 10～150, preferably 20～120.
Described group VIB metal is Mo and/or W, and described group VIII metal is Co and/or Ni.On the basis of the weight of catalyst, hydrogenation active metals component content in terms of oxide is 1%～16%, and the content of shape slective cracking molecular sieve is 50%～85%, and the content of adhesive is 10%～40%.The bulk density of Hydrodewaxing catalyst is typically at 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, can also be prepared by the general knowledge of this area as required, such as, be referred to the content disclosed in CN1952074A, CN1352231A, CN101143333A, CN102451748A and prepare satisfactory Hydrodewaxing catalyst.
The operating condition of the pour point depression modification composite catalyst bed of described hydro dewaxing and catalyst for hydro-upgrading composition is: reaction pressure 6.0～20.0 MPa, hydrogen to oil volume ratio 200:1～1500:1, volume space velocity is 0.1～10.0 h-1, reaction temperature 270 DEG C～460 DEG C；Preferred operations condition is reaction pressure 7.0～15.0 MPa, hydrogen to oil volume ratio 300:1～1000:1, volume space velocity 0.3～8.0 h-1, reaction temperature 315 DEG C～415 DEG C.
The operating condition of described Hydrodewaxing catalyst bed is: reaction pressure 6.0～20.0 MPa, hydrogen to oil volume ratio 200:1～1500:1, and volume space velocity is 0.1～10.0 h-1, reaction temperature 260 DEG C～455 DEG C；Preferred operations condition is reaction pressure 7.0～15.0 MPa, hydrogen to oil volume ratio 300:1～1000:1, volume space velocity 0.3～8.0 h-1, reaction temperature 310 DEG C～410 DEG C.
The method according to the invention, wherein in each hydroconversion reaction zone, described is 1:10～10:1, preferably 1:5～5:1 with the composite catalyst bed of Hydrodewaxing catalyst mixed packing with the admission space ratio of Hydrodewaxing catalyst bed by catalyst for hydro-upgrading.
In described pour point depression modifying catalyst composite bed, the compound filling of Hydrodewaxing catalyst and catalyst for hydro-upgrading, admission space ratio is for 1:10～10:1, preferably 1:5～5:1.
For described at least two hydroconversion reaction zone, wherein said composite catalyst bed and Hydrodewaxing catalyst bed, can 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, feedstock oil first passes through pour point depression modification composite catalyst bed, processes diesel raw material, carrying out hydrodesulfurization, hydrodenitrogeneration, aromatic saturation and ring opening and pour point depression reaction, this reaction shows as the synergistic effect of heat absorption and heat release.Feedstock oil after pour point depression modifying process processes by Hydrodewaxing catalyst bed, carries out pour point depression reaction more further, and this reaction shows as the endothermic reaction, and 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, fuel factor shows as the endothermic reaction, and process produces temperature drop；These two kinds of catalyst are carried out the compound filling of grating, 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 more preferable depression effeCt.Owing to have employed diesel oil hydrogenation modification technique in the present invention, the Cetane number of diesel product has lifting by a relatively large margin, simultaneously significant desulfurization effect.In addition Hydrodewaxing catalyst is used to carry out grating, the advantage also with catalyst low cost.
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 on the basis of changing 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, owing to the heat of course of reaction has obtained more reasonably utilizing, 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 catalyst for hydro-upgrading and technique with the use of, there is the biggest adaptability and advantage.During by it with Hydrodewaxing catalyst mixed packing, can reach more excellent and load in mixture effect, when avoiding the catalyst mixed packing caused because density variation is excessive, in irregular shape, the problem that distribution of particles is uneven, the most suitable the most modified reactivity reducing catalyst for hydro-upgrading, so preferably can mate with Hydrodewaxing catalyst, make the two activity quite, to play its each maximum effect in same temperature ranges stated, while reducing product condensation point, it is also possible to 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 the accompanying drawings a kind of method producing hydrogenation low-coagulation diesel oil of the present invention is described in detail.
As shown in Figure 1, the method flow that the present invention a kind of produces hydrogenation low-coagulation diesel oil is as follows: feedstock oil 1 enters reactor 3 with hydrogen 2 after reactor inlet mixes, pass sequentially through the composite catalyst bed 4 of hydro dewaxing and the hydro-upgrading connected step by step from top to bottom, Hydrodewaxing catalyst bed 5, the composite bed 6 of hydro dewaxing and hydro-upgrading and Hydrodewaxing catalyst bed 7, obtain reaction effluent 8 and after water filling 9, enter into high-pressure separator 10 from reactor bottom discharge, high-pressure separator 10 top obtains gas 11 by circulating hydrogen compressor 12, obtain recycle hydrogen 14 with new hydrogen 13 after mixing to use as supplementary hydrogen or cold hydrogen；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 sour water processing means 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.Table 2 lists raw materials used oil properties.
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 W-Ni W-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 —
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 using hydro-upgrading, hydro dewaxing one-stage serial flow process to produce low freezing point diesel fuel.Including catalyst for hydro-upgrading bed and Hydrodewaxing catalyst bed.Comparative example 1 and embodiment 1 produce the low-coagulation diesel oil of the identical trade mark.The catalyst, feedstock oil and the diesel product condensation point that use are the most same as in Example 1.Operation result is listed in table 3.
Comparative example 2
Comparative example 2 is the device using hydro-upgrading, hydro dewaxing 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, feedstock oil and diesel product yield that comparative example uses are the most same as in Example 1, and Catalyst packing is with comparative example 1.Operation result is listed in table 3.
Embodiment 1
Use the technological process shown in Fig. 1, utilize and load in mixture and grating serial flow production low freezing point diesel fuel.Embodiment 1 includes two hydroconversion reaction zones connected, and in the pour point depression modifying catalyst composite bed of each reaction zone, the mixed volume of Hydrodewaxing catalyst and catalyst for hydro-upgrading is than for 1:2, and the total consumption of catalyst is the most identical with comparative example 1 and comparative example 2.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
Use 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 two hydroconversion reaction zones connected, and in the combination pour point depression catalyst composite bed of each reaction zone, the mixed volume of Hydrodewaxing catalyst and catalyst for hydro-upgrading is than for 1:2, and the total consumption of catalyst is the most identical with comparative example 1 and comparative example 2.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.
Table 2 feedstock oil property list.
Project Feedstock oil
Source Atmosphere 3rd side cut diesel oil
Density (20 DEG C)/g cm-3 0.8808
Boiling range scope/DEG C 270～390
Nitrogen/μ g g-1 96
Sulphur/μ g g-1 980
Condensation point/DEG C 13
Cetane number 37.7
Table 3 process condition and result.
Comparative example 1 Comparative example 2 Embodiment 1 Embodiment 2
Catalyst forms FC-18/FDW-3 FC-18/FDW-3 (FDW-3+FC-18)/FDW-3 (FDW-3+FC-18G)/FDW-3
Reaction pressure/MPa 9.0 9.0 9.0 9.0
Average reaction temperature/DEG C 382/380 382/372 381*/380/381*/380 384*/380/384*/380
LHSV/h-1 3.0/2.5 3.0/2.5 5.0**/6.0/5.0**/6.0 5.0**/6.0/5.0**/6.0
Entrance hydrogen to oil volume ratio 600:1 600:1 600:1 600:1
Diesel product condensation point/DEG C -37 -22 -35 -37
Diesel yield, wt% 67.5 76.0 75.7 77.9
Diesel oil sulfur content, ppm 17 21 16 26
Diesel cetane-number 42.2 44.9 42.1 41.8
Bed peak temperature/DEG C 391 389 389 386
Cold hydrogen consumption/benchmark 0.92 1.90 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.
From above embodiment it can be seen that the modified catalyst of embodiment 2 use, having mixed effect more excellent, hot(test)-spot temperature is lower, the feature that diesel yield is higher simultaneously.In addition, the maximum feature of the inventive method is, for producing low solidifying product for processing high freezing point diesel fuel raw material, product Cetane number can be improved, reduce sulfur content, save catalyst investment cost, the condensation point of raw material can be reduced simultaneously in the case of ensureing certain diesel yield to greatest extent and make up the drawback of conventional mixed packing；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 the biggest advantage.

Claims (15)

1. the production method being hydrogenated with 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, each described hydroconversion reaction zone includes the pour point depression modifying catalyst composite bed by Hydrodewaxing catalyst and catalyst for hydro-upgrading mixed packing and Hydrodewaxing catalyst bed successively；Last hydroconversion reaction zone gained reaction effluent is through separating and after fractionation, obtaining low freezing point diesel fuel product.
The most 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 1000 below μ g/g.
3. according to 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 40～150 μ g/g.
The most in accordance with the method for claim 1, it is characterized in that, the nitrogen content in described diesel raw material is at 1000 more than μ g/g, before diesel raw material is by the pour point depression modifying catalyst composite bed of the first hydroconversion reaction zone, beforehand through a Hydrobon catalyst bed, carry out part denitrogenation.
The most in accordance with the method for claim 1, it is characterised in that doing of described diesel raw material is 350～440 DEG C.
The most in accordance with the method for claim 1, it is characterised in that in described each hydroconversion reaction zone, catalyst for hydro-upgrading it is 1:10～10:1 with the composite bed of Hydrodewaxing catalyst mixed packing with the admission space ratio of Hydrodewaxing catalyst bed.
The most 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.
The most in accordance with the method for claim 1, it is characterized in that, described Hydrodewaxing catalyst is with shape slective cracking molecular sieve and adhesive as carrier, with group VIB and/or group VIII metal for hydrogenation active metals component, on the basis of the weight of catalyst, hydrogenation active metals component content in terms of oxide is 1%～16%, and the content of shape slective cracking molecular sieve is 50%～85%, and the content of adhesive is 10%～40%.
The most in accordance with the method for claim 8, it is characterized in that, one or more in Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve of described shape-selective molecular sieve, the silica alumina ratio of shape slective cracking molecular sieve is 10～150.
The most in accordance with the method for claim 1, it is characterized in that, described catalyst for hydro-upgrading is with aluminum oxide and Y type molecular sieve as carrier, containing at least one VI B race metal and at least one VIII race's metal, catalyst carrier consists of aluminum oxide 5w%～45w%, amorphous silica-alumina 0w%～60w%, molecular sieve 5w%～60w%, wherein pore volume 0.40～0.52 mL/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%.
11. in accordance with the method for claim 10, it is characterised in that described aluminum oxide is macroporous aluminium oxide, and macroporous aluminium oxide content is 10w%～40w%；The pore volume of macroporous aluminium oxide is 1.0～1.7mL/g.
12. in accordance with the method for claim 1, it is characterised in that the operating condition of described pour point depression modifying catalyst composite bed is: reaction pressure 6.0～20.0 MPa, hydrogen to oil volume ratio 200:1～1500:1, and volume space velocity is 0.1～10.0 h-1, reaction temperature 270 DEG C～460 DEG C.
13. in accordance with the method for claim 1, it is characterised in that the operating condition of described Hydrodewaxing catalyst bed is: reaction pressure 6.0～20.0 MPa, hydrogen to oil volume ratio 200:1～1500:1, and volume space velocity is 0.1～10.0 h-1, reaction temperature 260 DEG C～455 DEG C.
14. in accordance with the method for claim 5, it is characterised in that doing of described diesel raw material is 370～400 DEG C.
15. in accordance with the method for claim 11, it is characterised in that the pore volume of described macroporous aluminium oxide is more than 1.2 to 1.7mL/g.
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CN106675641B (en) * 2015-11-11 2018-03-16 中国石油化工股份有限公司 A kind of production method of high-grade low-freezing diesel oil
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