CN103805270A - Production method of low-condensation point diesel oil - Google Patents
Production method of low-condensation point diesel oil Download PDFInfo
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- CN103805270A CN103805270A CN201210440716.4A CN201210440716A CN103805270A CN 103805270 A CN103805270 A CN 103805270A CN 201210440716 A CN201210440716 A CN 201210440716A CN 103805270 A CN103805270 A CN 103805270A
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Abstract
The invention discloses a production method of low-condensation point diesel oil. The production method comprises following steps: diesel oil raw material and hydrogen are mixed, an obtained mixture is delivered through at least two hydrogenation reaction zones in series connection successively, wherein along a material flowing direction, each hydrogenation reaction zone comprises a hydrogenation modification catalyst bed layer, and a condensation point reducing catalyst composite bed layer filled with a hydrogenation modification isomerization condensation point reducing catalyst and a hydrodewaxing catalyst; a reaction effluent obtained from the last hydrogenation reaction zone is subjected to separation and fractionation so as to obtain low-condensation point diesel oil. According to the production method, temperature reducing of hydrodewaxing processes and temperature increasing of hydrogenation modification processes are combined reasonably, low-condensation point diesel oil is produced, and yield and cetane value of diesel oil are increased at the same time, equipment hot-spot temperature is reduced, running period is prolonged, consumption of cold hydrogen or combustion gas loss of a heating furnace is reduced, and operation cost is reduced.
Description
Technical field
The present invention relates to a kind of production method of low-coagulation diesel oil, especially a kind of by catalyzer grating technology and compound filling technology, be used for producing the method for hydrotreating of low-coagulation diesel oil.
Background technology
Diesel oil is as the fuel of self-igniton engine, in modern productive life process, play irreplaceable effect as Nonrenewable resources, the fuel of the launch vehicles such as automobile, tank, aircraft, tractor, rail vehicle or other mechanical use be can be used as, generating, heating etc. also can be used to.According to the difference of its use industry and environment, user also has very large difference for the specification of quality of diesel product, for the people in extremely frigid zones or life in winter, the demand of low freezing point diesel fuel is always high, and traditional shape slective cracking technique can be processed the heavy gas oil cut of the content of wax, and pour point depression amplitude can reach 20～50 ℃, when obtaining low freezing point diesel fuel, also can widen diesel oil distillate scope, improve productive rate, be the very useful and advanced technology that solves low freezing point diesel fuel production 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 diesel oil routine is refined the requirement of character, condensation point becomes requisite one of the index that requires, and therefore can improve output and the quality of low-coagulation diesel oil, meets the need of market and becomes the major issue that Han Qu oil refining enterprise pays close attention to.And select row cracking and combination process thereof as reducing one of Main Means of condensation point of diesel oil, and can be used for producing low-sulfur low-coagulation diesel oil, be conducive to improve the economic benefit of oil refining enterprise.
Diesel oil shape slective cracking technology claims again hydrodewaxing, refers in the situation that hydrogen exists, and the diesel raw material of the content of wax is by the dual-function catalyst surface of containing active metal and molecular sieve, thus reduction wax molecule content wherein.Its dewaxing principle is under certain operational condition, make raw material mix and contact with Hydrodewaxing catalyst with hydrogen, be cracked into small molecules the contour condensation point compositional selecting of aromatic hydrocarbons of the paraffinic hydrocarbons in raw material, the naphthenic hydrocarbon with short-side chain alkane, belt length side chain and belt length side chain, and other component does not change substantially, finally reach the object of the condensation point that reduces oil product.Because it has, reaction process hydrogen consumption is lower, adaptability to raw material strong, energy consumption is lower, technical 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 have all adopted this technology to produce low-coagulation diesel oil at present.
CN1257107A discloses a kind of method of being produced high-grade low-freezing diesel oil by distillate.The method adopts hydrofining and hydrodewaxing one-stage serial flow process, and comprising Hydrobon catalyst and two beds of Hydrodewaxing catalyst, hydrodewaxing adopts Ni/ZSM-5 catalyzer.The method is larger at the temperature drop of Hydrodewaxing catalyst bed, and the raising of the yield of diesel oil distillate and pour point depression effect is subject to certain limitation, has reduced the work-ing life of Hydrodewaxing catalyst.
CN102051232A discloses a kind of method of diesel oil hydrogenation pour point depression.Thereby the method is that to have diesel oil pour point depression effective by adjusting the character of catalyzer, the feature that diesel oil distillate yield is high, but owing to still adopting the combination process of hydrofining and hydrodewaxing series connection, the contradiction between pour point depression effect and diesel oil distillate yield is existence still.
CN102453531A discloses a kind of method of diesel hydro-pour-reducing.Although the method has improved the average reaction temperature of Hydrodewaxing catalyst, utilize the temperature rise of finishing agent, strengthen the utilization ratio of pour point depression catalyzer, the temperature of reaction of each bed outlet is still relatively high, has been subject to certain restriction running period.
CN01134271.4 discloses a kind of combined hydrogenation method of producing high hexadecane value, low-coagulation diesel oil.The method is that stock oil, hydrogen are first contacted with catalyst for hydro-upgrading or hydrocracking catalyst, reaction effluent then contacts with Hydrodewaxing catalyst without separating, reaction effluent is through the cooling high-pressure separator that enters, isolated product liquid enters fractionating system, and the gas circulation that is rich in hydrogen is returned reactor.The method can improve diesel-fuel cetane number simultaneously and reduce the condensation point of diesel oil in same set of device, and the cetane value of diesel product improves 6 more than unit compared with stock oil.
CN99113293.9 discloses a kind of method of being produced high-quality low-coagulation diesel oil with high hexadecane value by distillate.The method is directly connected hydrodewaxing with hydrofining, hydro-upgrading, realize hydrofining-hydro-upgrading-hydrodewaxing-section serial flow, what adopt is Hydrobon catalyst that anti-coking performance is strong and has hydro-upgrading and the Hydrodewaxing catalyst of stronger anti-ammonia, capacity antacid, thereby this technique is had, and refining/pour point depression is effective, diesel yield is high, adaptability to raw material is strong, diesel cetane-number is high, technical process is simple and products scheme feature flexibly.
Summary of the invention
For the problem of prior art existence, the invention provides a kind of production method of low-coagulation diesel oil.The mixed catalyst of compound to catalyst for hydro-upgrading and hydro-upgrading isomerization-visbreaking and hydrodewaxing (mixing) filling is carried out grating by the inventive method, temperature rise in the temperature drop of hydrodewaxing process and hydrogenation process is carried out to reasonably combination to be utilized, yield and the cetane value of diesel oil in producing low condensation point low-sulfur diesel-oil, are improved, the hot(test)-spot temperature that has reduced device, has extended running period; In addition reduce the combustion gas loss of consumption or the process furnace of cold hydrogen, saved process cost.
The invention provides a kind of low-coagulation diesel oil production method, comprise following content:
After diesel raw material is mixed with hydrogen, by the hydroconversion reaction zone of at least two series connection, comprise successively catalyst for hydro-upgrading bed and the pour point depression catalyzer composite bed by hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst mixed packing by the each hydroconversion reaction zone of Flow of Goods and Materials direction successively; The reaction effluent that last hydroconversion reaction zone obtains, after separation and fractionation, obtains low freezing point diesel fuel product.
According to method of the present invention, wherein, in each described hydroconversion reaction zone, first diesel raw material and hydrogen by catalyst for hydro-upgrading bed, carry out hydrogenating desulfurization, hydrodenitrification and aromatic saturation and ring-opening reaction; Reaction effluent, again by the pour point depression catalyzer composite bed by hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst mixed packing, carries out isomery upgrading and pour point depression reaction.
According to method for hydrogen cracking of the present invention, described diesel raw material is that conventional pour point depression raw material is high freezing point diesel fuel, and condensation point is generally all more than 0 ℃, and preferably condensation point is more than 5 ℃.The nitrogen content of described diesel raw material, below 1000 μ g/g, is generally 10～400 μ g/g, most preferably is 40～150 μ g/g.If the organonitrogen too high levels in diesel raw material, if nitrogen content is at 1000 μ g/g when above, can, in diesel raw material by before the catalyst for hydro-upgrading bed of the first hydroconversion reaction zone, by a hydrofining or hydrodenitrogenation catalyst bed, carry out part denitrogenation in advance.Various straight-run diesel oil or secondary processing diesel oil that described diesel raw material can obtain for processing naphthenic base crude, intermediate base crude oil or paraffinic crude, preferably process the said components that paraffinic crude obtains.The boiling range scope of diesel raw material is generally 350～440 ℃, preferably 370～400 ℃.As described in diesel raw material can be selected from one or several in the various straight-run diesel oils that obtain of processing Daqing crude oil, coker gas oil, catalytic diesel oil etc.
Catalyst for hydro-upgrading described in the present invention is the hydrogenation conversion catalyst containing molecular sieve, refers to a kind of hydrogenation catalyst that is exclusively used in diesel modifying, is the conventional hydrogenation conversion catalyst in this area.Described catalyst for hydro-upgrading is a kind of dual function hydrogenation catalyst, take aluminum oxide and Y zeolite as carrier, contain at least one VI B family metal and at least one VIII family metal, it is characterized in that support of the catalyst consists of aluminum oxide 40w%～80w%, amorphous aluminum silicide 0w%～20w%, molecular sieve 5w%～30w%, wherein pore volume 0.40～0.52 mL/g of Y molecular sieve, specific surface 750～900m
2/ g, lattice constant 2.420～2.500nm, SiO
2/ Al
2o
3molecular ratio 7～15, in catalyzer, VI B family metal oxide content is 10w%～30w%, VIII family metal oxide content is 2w%～15w%.
Described catalyst for hydro-upgrading salic be that a kind of crystalline phase is the aluminum oxide of pseudo-boehmite, content is 40w%～80w%.The sieve and silica-sesquioxide weight ratio 1:2～2:1 of contained amorphous silicon aluminium in described carrier, content 0w%～20w%, preferably 10w%～20w%.
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, VI B family metal can be Mo or W, preferably select W, content 10w%～30w%, VIII family metal can be Ni or Co, preferably select Ni, content 2w%～15w%.Conventional catalyst for hydro-upgrading can be selected existing various commercial catalysts, such as FRIPP develop 3963, the catalyzer such as FC-18.Also can prepare specific catalyst for hydro-upgrading by the general knowledge of this area as required, for example, can prepare satisfactory hydro-upgrading (conversion) catalyzer with reference to the disclosed content of CN1184843A, CN1178238A.
Described hydro-upgrading isomerization-visbreaking catalyzer is conventional catalyst in the art.Described hydro-upgrading pour point depression catalyzer generally comprises beta-molecular sieve, refractory porous oxide, VI B family and the VIII family metal oxide of amorphous aluminum silicide, modification.Take the weight ratio of catalyzer as benchmark, in catalyzer, the content of each component is generally: amorphous aluminum silicide 29w%～50w%, modified beta molecular sieve 1w%～9%, group VIB metal is in oxide compound 15w%～35w%, group VIII metal is counted 3w%～9w% with oxide compound, porous refractory oxide 0w%～45w%; The wherein SiO of modified beta molecular sieve
2/ Al
2o
3weight ratio is 50～90, and average grain size is 0.1～0.5 micron, and infrared acidity is 0.1～0.4 mmol/g.
Described porous refractory oxide, can be selected from one or more in aluminum oxide, titanium oxide, zirconium white, boron oxide and above-mentioned element (aluminium, titanium, zirconium, boron) composite oxides etc., preferential oxidation aluminium.As contained macroporous aluminium oxide and aperture alumina adhesive, macroporous aluminium oxide is generally 0w%～22w%; Little porous aluminum oxide is generally 0w%～23w%.The specific surface area of catalyzer is generally 160～230m
2/ g, pore volume is 0.32～0.45mL/g.The character of described modified beta molecular sieve is generally: its SiO
2/ Al
2o
3weight ratio is generally 50～90, and degree of crystallinity is generally 90～110, and average grain size is generally 0.1～0.5 micron, specific surface area 400～750m
2/ g, pore volume 0.25～0.50mL/g, Na
2o content is less than 0.10w%, infrared acidity 0.1～0.4mmol/g, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume.
SiO in described amorphous aluminum silicide
2content be generally 20w%～75w%, be preferably 35w%～60w%.The pore volume of amorphous aluminum silicide is 0.5～1.1mL/g, is preferably 0.6～0.8mL/g; Specific surface area is 200～500m
2/ g, is preferably 280～500m
2/ g.
Macroporous aluminium oxide pore volume is 0.6～1.2mL/g, is preferably 0.8～1.2mL/g, and specific surface area is 200～550m
2/ g, is preferably 300～500m
2/ g.Aperture aluminum oxide pore volume is 0.3～0.5mL/g, and specific surface area is 180～350m
2/ g.Group VIB metal is generally W and/or Mo, and group VIII metal is generally Ni and/or Co.
Conventional hydro-upgrading isomerization-visbreaking catalyzer can be selected existing various commercial catalysts, the catalyzer such as FC-14, FC-20 that such as FRIPP develops.Also can prepare specific hydro-upgrading isomerization-visbreaking catalyzer by the general knowledge of this area as required, for example, can prepare satisfactory hydro-upgrading isomerization-visbreaking catalyzer with reference to disclosed content in CN1712498A.
Described Hydrodewaxing catalyst adopts the catalyzer containing shape slective cracking molecular sieve, comprises the metal component of carrier and institute's load.Described catalyzer is generally take shape slective cracking molecular sieve and tackiness agent as carrier, take group vib and/or group VIII metal as 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, is preferably 20～120.
Described group VIB metal is Mo and/or W, and described group VIII metal is Co and/or Ni.Take the weight of catalyzer as benchmark, hydrogenation active metals component is take the content of oxide compound as 1%～16%, and the content of shape slective cracking molecular sieve is 50%～85%, and the content of tackiness agent is 10%～40%.Described Hydrodewaxing catalyst can be selected existing various commercial catalysts, the Hydrodewaxing catalyst such as FDW-1, FDW-3 that such as Fushun Petrochemical Research Institute (FRIPP) develops; Also can be prepared by the general knowledge of this area as required, for example, can prepare satisfactory Hydrodewaxing catalyst with reference to disclosed content in CN1952074A, CN1352231A, CN101143333A, CN102451748A.
The operational condition of described catalyst for hydro-upgrading bed is: reaction pressure 6.0～20.0 MPa, and hydrogen to oil volume ratio 200:1～1500:1, volume space velocity is 0.1～10.0 h
-1, 260 ℃～455 ℃ of temperature of reaction; 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, 310 ℃～410 ℃ of temperature of reaction.
The operational condition of the pour point depression catalyzer composite bed of described hydro-upgrading isomerization-visbreaking and Hydrodewaxing catalyst composition is: reaction pressure 6.0～20.0 MPa, and hydrogen to oil volume ratio 200:1～1500:1, volume space velocity is 0.1～10.0 h
-1, 270 ℃～460 ℃ of temperature of reaction; 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, 315 ℃～415 ℃ of temperature of reaction.
The method according to this invention, wherein, in each hydroconversion reaction zone, described catalyst for hydro-upgrading bed than for 1:10～10:1, is preferably 1:10～10:1 with the admission space of pour point depression catalyzer composite bed.
And in described pour point depression catalyzer composite bed, the compound filling of hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst, admission space ratio is 1:10～10:1, preferably 1:5～5:1.
For at least two described hydroconversion reaction zones, wherein said catalyst for hydro-upgrading bed and pour point depression catalyzer composite bed, can be separately positioned in two or more beds of a reactor; Or can be separately positioned in the hydrogenator of two or more series connection.
Compared with prior art, the inventive method has the following advantages:
1,, in the inventive method, in each hydroconversion reaction zone, stock oil, first by catalyst for hydro-upgrading bed, carries out hydrogenating desulfurization, hydrodenitrification and aromatic saturation and ring opening reaction, and diesel raw material is carried out to pre-treatment.This hydro-upgrading reaction shows as exothermic effect.Stock oil after MCI art breading is again by compound pour point depression beds, and because the reaction of hydro-upgrading isomerization-visbreaking shows as thermopositive reaction, this process produces temperature rise; And hydrodewaxing reaction is reacted for selecting type molecular sieve cracking, heat effect shows as thermo-negative reaction, and process produces temperature drop; These two kinds of pour point depression catalyzer are carried out to grating mixed packing, can make full use of its heat release and endothermic effect separately, the comprehensive utilization of the heat of realization response process, can not produce obvious temperature rise and temperature drop effect, and affect pour point depression effect, thereby make the reaction of compound pour point depression beds substantially realize the reaction process of isothermal, both can guarantee the yield of diesel oil, also obtained better pour point depression effect; In addition owing to having adopted in the present invention MCI technique, the cetane value of diesel product has lifting by a relatively large margin, simultaneously significant desulfurization effect.
2,, at process aspect, in each hydroconversion reaction zone, all show essentially identical effect.Thereby at least two hydroconversion reaction zones 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 grading composition and the compound filling of catalyzer, effectively rationally utilize from part by the high temperature dot of device and low warm spot, reduce the hot(test)-spot temperature of device, reasonably reduce the bulk temperature gradient of device, extended the work-ing life of catalyzer.In addition this combination is compared with conventional hydrodewaxing combination process, because the heat of reaction process has obtained more reasonably utilizing, between two reaction zones, can beat less or liquid hydrogen injection not, therefore also reduce the combustion gas loss of consumption and the process furnace of cold hydrogen, save process cost.
Accompanying drawing explanation
Fig. 1 is the grading loading schematic diagram of a kind of embodiment of the inventive method; Select single reactor layering filling to there is the operating method of two hydroconversion reaction zones.
Embodiment
Below in conjunction with accompanying drawing, low-coagulation diesel oil production method of the present invention is elaborated.
As shown in Figure 1, low-coagulation diesel oil production method flow process of the present invention is as follows:
Stock oil 1 enters reactor 3 with hydrogen 2 after reactor inlet mixes, the composite bed 7 of composite catalyst bed 5, catalyst for hydro-upgrading bed 6 and hydro-upgrading isomerization-visbreaking and the hydrodewaxing by catalyst for hydro-upgrading bed 4, hydro-upgrading isomerization-visbreaking and the hydrodewaxing of connecting step by step successively from top to bottom, obtaining reaction effluent 8 discharges and after water filling 9, enters into high-pressure separator 10 from reactor bottom, top obtains gas 11 by circulating hydrogen compressor 12, obtains recycle hydrogen 14 hydrogen or the use of cold hydrogen as a supplement with new hydrogen 13 after mixing; The liquid phase that middle and lower part obtains enters light pressure separator 17, and top is discharged low point of gas 18 and gone subsequent disposal, and middle and lower part obtains liquid phase 20 and enters follow-up fractionating system; After the sour water 19 that the sour water 15 that discharge high-pressure separator 10 bottoms is discharged with light pressure separator 17 bottoms mixes, disacidify water treatment device carries out following process.
Next by specific embodiment, low-coagulation diesel oil production method of the present invention is further described.
Comparative example 1
Comparative example 1 is for adopting hydro-upgrading, hydro-upgrading isomerization-visbreaking and hydrodewaxing one-stage serial flow process to produce the device of low freezing point diesel fuel.Comparative example 1 comprises two reaction zones, each reaction zone includes catalyst for hydro-upgrading bed and the pour point depression beds by hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst layering filling, the catalyst loading ratio of two reaction zones is identical, and the catalyzer of single reaction zone forms in table 2.Comparative example 1 and embodiment 1 produce the low-coagulation diesel oil of the identical trade mark.The catalyzer, stock oil and the diesel product condensation point that use are all identical with embodiment 1.Operation result is listed in table 2.
Comparative example 2
Comparative example 2 is for adopting hydro-upgrading, hydro-upgrading isomerization-visbreaking and hydrodewaxing one-stage serial flow process to produce the device of low freezing point diesel fuel.Control essentially identical diesel yield with embodiment 1, produce the low-coagulation diesel oil of the different trades mark.Catalyzer, stock oil and diesel product yield that comparative example uses are all identical with embodiment 1, and catalyst loading is with comparative example 1.Operation result is listed in table 2.
Embodiment 1
Adopt the technical process shown in Fig. 1, utilize grating series connection and load in mixture flow process and produce low freezing point diesel fuel.Embodiment 1 comprises the hydroconversion reaction zone of two series connection, and in the pour point depression catalyzer composite bed of each reaction zone, the agent of hydro-upgrading isomerization-visbreaking catalyzer is 1:4 with the mixed volume ratio of Hydrodewaxing catalyst.The catalyst for hydro-upgrading agent using in embodiment 1 is FC-18 catalyzer, hydro-upgrading isomerization-visbreaking catalyzer is FC-14 catalyzer, Hydrodewaxing catalyst is FDW-3 catalyzer, and described catalyzer is the commercial catalyst of Fushun Petrochemical Research Institute's development and production.
Operational condition and test-results are listed in table 2.
Table 1 stock oil property list.
| Project | Stock oil |
| Source | Atmosphere 3rd side cut straight-run diesel oil |
| Density (20 ℃)/gcm -3 | 0.8708 |
| Boiling range scope/℃ | 270～390 |
| Nitrogen/μ gg -1 | 126 |
| Sulphur/μ gg -1 | 980 |
| Condensation point/ |
13 |
| Cetane value | 39.7 |
Table 2 process conditions and result.
| ? | Comparative example 1 | Comparative example 2 | Embodiment 1 |
| Catalyzer composition | FC-18/(FC-14/FDW-3) | FC-18/(FC-14/FDW-3) | FC-18/(FC-14+FDW-3) |
| Reaction pressure/MPa | 9.0 | 9.0 | 9.0 |
| Average reaction temperature/℃ | 379/387*/380/388* | 379/376*/380/377* | 379/388*/380/389* |
| LHSV/h -1 | 6.0/5.0**/6.0/5.0** | 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 |
| Diesel product condensation point/℃ | -37 | -22 | -35 |
| Diesel yield/wt% | 71.7 | 81.2 | 80.8 |
| Diesel oil sulphur content/μ gg -1 | 4 | 7 | 4 |
| Diesel cetane-number | 48 | 50.1 | 48 |
| Bed vertex temperature/℃ | 399 | 390 | 392 |
| Cold hydrogen consumption/benchmark | 0.95 | 1.9 | 1.0 |
* average reaction temperature is the weighted mean temperature of pour point depression beds;
* volume space velocity is the volume space velocity of pour point depression beds.
Can find out from above embodiment, the maximum feature of the inventive method is, produces low solidifying product for processing diesel raw material, can improve product cetane value, reduce sulphur content, in the situation that guaranteeing certain diesel yield, can reduce to greatest extent the condensation point of raw material simultaneously; In addition also to have hot(test)-spot temperature low for the inventive method, and running period is long, the low feature of cold hydrogen consumption; For enterprise, in completing quality products production task, in human and material resources and energy consumption, there is very large advantage.
Claims (11)
1. a low-coagulation diesel oil production method, comprises following content:
After diesel raw material is mixed with hydrogen, by the hydroconversion reaction zone of at least two series connection, comprise successively catalyst for hydro-upgrading bed and the pour point depression catalyzer composite bed by hydro-upgrading isomerization-visbreaking catalyzer and Hydrodewaxing catalyst mixed packing by the each hydroconversion reaction zone of Flow of Goods and Materials direction successively; The reaction effluent that last hydroconversion reaction zone obtains, after separation and fractionation, obtains low freezing point diesel fuel product.
2. in accordance with the method for claim 1, it is characterized in that, the condensation point of described diesel raw material is more than 0 ℃, and nitrogen content is below 1000 μ g/g.
3. in accordance with the method for claim 2, it is characterized in that, the nitrogen content of described diesel raw material is 10～400 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that, the condensation point of described diesel raw material is more than 0 ℃, and nitrogen content is more than 1000 μ g/g, before the hydroconversion reaction zone of series connection, is also provided with Hydrobon catalyst bed or hydrodenitrogenation catalyst bed.
5. in accordance with the method for claim 1, it is characterized in that, in each hydroconversion reaction zone, described catalyst for hydro-upgrading bed is 1:10～10:1 with the admission space ratio of pour point depression catalyzer composite bed.
6. according to the method described in claim 1 or 5, it is characterized in that, in described pour point depression catalyzer composite bed, hydro-upgrading isomerization-visbreaking catalyzer is 1:10～10:1 with the admission space ratio of Hydrodewaxing catalyst.
7. in accordance with the method for claim 1, it is characterized in that, the operational condition of described catalyst for hydro-upgrading bed is: reaction pressure 6.0～20.0 MPa, and hydrogen to oil volume ratio 200:1～1500:1, volume space velocity is 0.1～10.0 h
-1, 260 ℃～455 ℃ of temperature of reaction; The operational condition of described pour point depression catalyzer composite bed is: reaction pressure 6.0～20.0 MPa, and hydrogen to oil volume ratio 200:1～1500:1, volume space velocity is 0.1～10.0 h
-1, 270 ℃～460 ℃ of temperature of reaction.
8. in accordance with the method for claim 1, it is characterized in that, described catalyst for hydro-upgrading is take aluminum oxide and Y zeolite as carrier, contain at least one VI B family metal and at least one VIII family metal, VI B family metal is take oxide compound content as 10w%～30w%, and VIII family metal is take oxide compound content as 2w%～15w%; Described vehicle group becomes aluminum oxide 40w%～80w%, amorphous aluminum silicide 0w%～20w%, molecular sieve 5w%～30w%, wherein pore volume 0.40～0.52 mL/g of Y molecular sieve, specific surface 750～900m
2/ g, lattice constant 2.420～2.500nm, SiO
2/ Al
2o
3molecular ratio is 7～15.
9. in accordance with the method for claim 1, it is characterized in that, described hydro-upgrading pour point depression catalyzer comprises amorphous aluminum silicide, modified beta molecular sieve, refractory porous oxide, VI B family and VIII family metal oxide, take the weight ratio of catalyzer as benchmark, the content of each component is: amorphous aluminum silicide 29w%～50w%, and modified beta molecular sieve 1w%～9%, group VIB metal is in oxide compound 15w%～35w%, group VIII metal is counted 3w%～9w% with oxide compound, porous refractory oxide 0w%～45w%; The wherein SiO of modified beta molecular sieve
2/ Al
2o
3weight ratio is 50～90, and average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.
10. in accordance with the method for claim 1, it is characterized in that, described Hydrodewaxing catalyst is take shape slective cracking molecular sieve and tackiness agent as carrier, take group VIB and/or group VIII metal as hydrogenation active metals component, take the weight of catalyzer as benchmark, hydrogenation active metals is take the content of oxide compound as 1% ~ 16%, and the content of shape slective cracking molecular sieve is 50% ~ 85%, and the content of tackiness agent is 10% ~ 40%.
11. in accordance with the method for claim 10, it is characterized in that, described shape slective cracking molecular sieve is one or more in Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38, and the silica alumina ratio of shape slective cracking molecular sieve is 10～150.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109988638A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | The flexibly hydrogenation technique of production low freezing point diesel fuel |
| CN109988601A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of hydrogenation technique of flexible production low freezing point diesel fuel |
| CN109988612A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible diesel oil hydrogenation modification technique |
| CN109988613A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible diesel oil hydrogenation modification pour point depression technique |
| CN109988598A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible diesel oil hydrogenation modification technique |
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| CN109988622A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible diesel oil hydrogenation modification pour point depression technique |
| CN109988638A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | The flexibly hydrogenation technique of production low freezing point diesel fuel |
| CN109988601A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of hydrogenation technique of flexible production low freezing point diesel fuel |
| CN109988612A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible diesel oil hydrogenation modification technique |
| CN109988613A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible diesel oil hydrogenation modification pour point depression technique |
| CN109988598A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible diesel oil hydrogenation modification technique |
| CN109988612B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Flexible diesel hydro-upgrading process |
| CN109988613B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Flexible diesel hydro-upgrading pour point depressing process |
| CN109988622B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible diesel hydro-upgrading pour point depressing process |
| CN109988601B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Hydrogenation process for flexibly producing low-condensation-point diesel oil |
| CN109988638B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Hydrogenation process for flexibly producing low-condensation-point diesel oil |
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