CN103805257A - Method for producing diesel oil with low condensation point by catalyst gradation technology - Google Patents
Method for producing diesel oil with low condensation point by catalyst gradation technology Download PDFInfo
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Abstract
The invention discloses a method for producing diesel oil with a low condensation point by catalyst gradation technology. The method comprises the following steps: mixing a diesel oil raw material with hydrogen, orderly passing through at least two hydrogenation reaction zones connected in series, wherein in the material flowing direction, each hydrogenation reaction zone orderly comprises a hydro-refining dewaxing catalyst composite bed layer filled with a mixture of a hydro-refining catalyst and a hydro-upgrading isodewaxing catalyst, and a hydrodewaxing catalyst bed layer; performing separation and fractionation of the reaction effluent from the last hydrogenation reaction zone to obtain the diesel oil product with a low condensation point. The method of the invention reasonably combines and utilizes the temperature increase of the hydro-refining and hydro-upgrading dewaxing process with the temperature decrease of the hydrodewaxing process, improves the diesel oil yield and the cetane value while producing diesel oil with a low condensation point and low sulfur, reduces the hot-spot temperature of the device, prolongs the running period, also reduces the cold hydrogen consumption or the combustion gas loss of a heating furnace, and saves operation cost.
Description
Technical field
The present invention relates to a kind of method of utilizing catalyzer grating technology to produce low-coagulation diesel oil, especially a kind of by the compound filling of catalyzer and grating 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 has introduced 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 has introduced a kind of method of diesel oil hydrogenation pour point depression, thereby the method is the character by adjusting catalyzer makes diesel oil pour point depression effective, 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 still exists.
CN102453531A has introduced a kind of method of diesel hydro-pour-reducing, although improved the average reaction temperature of Hydrodewaxing catalyst, utilizes the temperature rise of finishing agent, has strengthened the utilization ratio of pour point depression catalyzer,
The temperature of reaction of each bed outlet is still relatively high, and the cycle has been subject to certain restriction.
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.Mixed catalyst and the Hydrodewaxing catalyst of hydrofining and the compound filling of hydro-upgrading isomerization-visbreaking are 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, in producing low condensation point low-sulfur diesel-oil, improve the yield of diesel oil, 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.
A kind of method of utilizing catalyzer grating technology to produce low-coagulation diesel oil provided by the invention, comprises following content:
After diesel raw material is mixed with hydrogen, by the hydroconversion reaction zone of at least two series connection, comprise successively refining pour point depression catalyzer composite bed and the Hydrodewaxing catalyst bed by Hydrobon catalyst and the filling of hydro-upgrading isomerization-visbreaking catalyst mix by hydroconversion reaction zone described in Flow of Goods and Materials direction successively; Last hydroconversion reaction zone gained reaction effluent, 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, diesel raw material and hydrogen, first by the refining pour point depression catalyzer composite bed by Hydrobon catalyst and the filling of hydro-upgrading isomerization-visbreaking catalyst mix, carry out hydrogenating desulfurization, hydrodenitrification, aromatic saturation and pour point depression reaction.Reaction effluent by Hydrodewaxing catalyst bed, carries out pour point depression reaction again.
According to method of hydrotreating 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 1500 μ g/g, is generally 30～600 μ g/g, most preferably is 50～200 μ g/g.If the organonitrogen too high levels in diesel raw material, if nitrogen content is at 1500 μ g/g when above, can, in diesel raw material by before the refining pour point depression catalyzer composite bed of the first hydroconversion reaction zone, by a hydrofining or hydrodenitrogenation catalyst bed, carry out part denitrogenation in advance.Various straight run or the diesel oil of secondary processing etc. 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.Doing 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.
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 Hydrobon catalyst can adopt conventional diesel oil hydrofining catalyst, generally take VI B family and/or group VIII metal as active ingredient, take aluminum oxide or silicon-containing alumina as carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Take the weight of catalyzer as benchmark, group VIB metal content is counted 8wt%～28wt% with oxide compound, and group VIII metal content is counted 2wt%～15 wt% with oxide compound, and its character is as follows: specific surface is 100～650m
2/ g, pore volume is 0.15～0.8mL/g, alternative commercial catalysts is of a great variety, the Hydrobon catalyst such as FH-98, FH-UDS that such as Fushun Petrochemical Research Institute (FRIPP) develops; Also can prepare conventional hydrotreatment oxidized catalyst by the general knowledge of this area as required.
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 the refining pour point depression catalyzer composite bed of described hydrofining and hydro-upgrading isomerization-visbreaking catalyzer 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 operational condition of described Hydrodewaxing catalyst 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 method according to this invention, wherein in each hydroconversion reaction zone, the described refining pour point depression beds by Hydrobon catalyst and the filling of hydro-upgrading isomerization-visbreaking catalyst mix is 1:10～10:1 with the admission space ratio of Hydrodewaxing catalyst bed, is preferably 1:5～5:1.
In described refining pour point depression catalyzer composite bed, Hydrobon catalyst and the compound filling of hydro-upgrading isomerization-visbreaking catalyzer, admission space is than being 1:10～10:1, preferably 1:5～5:1.
For at least two described hydroconversion reaction zones, wherein said refining pour point depression catalyzer composite bed and Hydrodewaxing catalyst bed, can be separately positioned on two of a reactor with in upper bed layer; Or can be separately positioned in two hydrogenators of connecting above.
Compared with prior art, the inventive method has the following advantages:
1, in the inventive method, in each hydroconversion reaction zone, first stock oil by refining pour point depression catalyzer composite bed, processed diesel raw material, carry out hydrogenating desulfurization, hydrodenitrification, aromatic saturation and pour point depression reaction, this hydrogenation reaction shows as exothermic effect.Stock oil after refining pour point depression art breading, again by Hydrodewaxing catalyst bed, carries out pour point depression reaction, and this reaction shows as thermo-negative reaction, and all in all, because hydrogenation reaction shows as thermopositive reaction, this process produces temperature rise; And hydrodewaxing reaction is shape-selective molecular sieve cracking reaction, heat effect shows as thermo-negative reaction, and process produces temperature drop; These two kinds of catalyzer are carried out to grading loading, 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 excessive temperature rise and temperature drop effect, and affect pour point depression effect, thereby the hot(test)-spot temperature of whole beds is reduced, both can guarantee the yield of diesel oil, also obtained better pour point depression effect.In addition the present invention adopts Hydrobon catalyst to carry out grating, has adaptability to raw material strong, the feature that catalyzer cost is low.
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, a kind of method of utilizing catalyzer grating technology to produce low-coagulation diesel oil of the present invention is elaborated.
As shown in Figure 1, the flow process of a kind of method of utilizing catalyzer grating technology production low-coagulation diesel oil of the present invention is as follows:
Stock oil 1 enters reactor 3 with hydrogen 2 after reactor inlet mixes, from top to bottom successively by the hydrofining of connecting step by step and the composite catalyst bed 4 of hydro-upgrading isomerization-visbreaking, Hydrodewaxing catalyst bed 5, the composite bed 6 of hydrofining and hydro-upgrading isomerization-visbreaking and Hydrodewaxing catalyst bed 7, obtaining reaction effluent 8 discharges and after water filling 9, enters into high-pressure separator 10 from reactor bottom, high-pressure separator 10 tops obtain gas 11 by circulating hydrogen compressor 12, after mixing with new hydrogen 13, obtain recycle hydrogen 14 hydrogen or the use of cold hydrogen as a supplement, the liquid phase that high-pressure separator 10 middle and lower parts obtain enters light pressure separator 17, and light pressure separator 17 tops are discharged low point of gas 18 and gone subsequent disposal, and light pressure separator 17 middle and lower parts obtain liquid phase 20 and enter 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 hydrofining, hydro-upgrading isomerization-visbreaking and hydrodewaxing one-stage serial flow process to produce the device of low freezing point diesel fuel.Comprise refining pour point depression beds and Hydrodewaxing catalyst bed by Hydrobon catalyst and hydro-upgrading isomerization-visbreaking catalyzer layering filling.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 hydrofining, 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 and load in mixture and grating serial flow production low freezing point diesel fuel.Embodiment 1 comprises the hydroconversion reaction zone of two series connection, in the refining modification catalyzer composite bed of each reaction zone, Hydrobon catalyst is with the mixed volume of hydro-upgrading isomerization-visbreaking catalyzer than being 1:4, and the total consumption of catalyzer is all identical with comparative example 1 and comparative example 2.The hydro-upgrading isomerization-visbreaking catalyzer using in embodiment 1 is FC-14 catalyzer, Hydrobon catalyst is FH-98 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 diesel oil |
| Density (20 ℃)/gcm -3 | 0.8782 |
| Boiling range scope/℃ | 275～395 |
| Nitrogen/μ gg -1 | 151 |
| Sulphur/μ gg -1 | 1100 |
| Condensation point/ |
12 |
| Cetane value | 36.3 |
Table 2 process conditions and result.
| ? | Comparative example 1 | Comparative example 2 | Embodiment 1 |
| Catalyzer composition | (FH-98/FC-14)/FDW-3 | (FH-98/FC-14)/FDW-3 | (FH-98+FC-14)/FDW-3 |
| Reaction pressure/MPa | 9.0 | 9.0 | 9.0 |
| Average reaction temperature/℃ | 380*/375 | 380*/367 | 381*/375/380*/375 |
| LHSV/h -1 | 2.5**/3.0 | 2.5**/3.0 | 5.0**/6.0/5.0**/6.0 |
| Entrance hydrogen to oil volume ratio | 600:1 | 600:1 | 600:1 |
| Diesel product condensation point/℃ | -36 | -22 | -35 |
| Diesel yield, wt% | 73.6 | 82.1 | 82.0 |
| Diesel oil sulphur content/μ gg -1 | 28 | 32 | 28 |
| Diesel cetane-number | 39 | 41.9 | 39 |
| Bed vertex temperature/℃ | 391 | 378 | 379 |
| Cold hydrogen consumption/benchmark | 0.92 | 1.75 | 1.0 |
* average reaction temperature is the weighted mean temperature of refining pour point depression beds;
* volume space velocity is the volume space velocity of refining pour point depression beds.
Can find out from above embodiment, the maximum feature of the inventive method is, for processing diesel raw material, the strong adaptability of the catalyst system of choosing to raw material, catalyzer cost is low, the low solidifying product of producing can reduce foreign matter content, can reduce to greatest extent the condensation point of raw material in the situation that guaranteeing certain diesel yield 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 (12)
1. utilize catalyzer grating technology to produce a method for low-coagulation diesel oil, comprise following content:
After diesel raw material is mixed with hydrogen, by the hydroconversion reaction zone of at least two series connection, comprise successively refining pour point depression catalyzer composite bed and the Hydrodewaxing catalyst bed by Hydrobon catalyst and the filling of hydro-upgrading isomerization-visbreaking catalyst mix by hydroconversion reaction zone described in Flow of Goods and Materials direction successively; Last hydroconversion reaction zone gained reaction effluent, 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 1500 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that, the nitrogen content of described diesel raw material is 30～600 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that, the nitrogen content of described diesel raw material is more than 1500 μ g/g, diesel raw material is before passing through the refining pour point depression beds of the first hydroconversion reaction zone, by a hydrofining or hydrodenitrogenation catalyst bed, carry out part denitrogenation in advance.
5. in accordance with the method for claim 1, it is characterized in that, doing of described diesel raw material is 350～440 ℃.
6. in accordance with the method for claim 1, it is characterized in that, in described each hydroconversion reaction zone, the described refining pour point depression beds by Hydrobon catalyst and the filling of hydro-upgrading isomerization-visbreaking catalyst mix is 1:10～10:1 with the admission space ratio of Hydrodewaxing catalyst bed.
7. in accordance with the method for claim 1, it is characterized in that, in described refining pour point depression catalyzer composite bed, Hydrobon catalyst is 1:10～10:1 with the admission space ratio of hydroisomerizing upgrading and pour point reducing catalyzer.
8. in accordance with the method for claim 1, it is characterized in that, the operational condition of described Hydrodewaxing catalyst 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.
9. in accordance with the method for claim 1, it is characterized in that, the operational condition of the refining pour point depression catalyzer composite bed of described hydrofining and hydro-upgrading isomerization-visbreaking catalyzer 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, 270 ℃～460 ℃ of temperature of reaction.
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 1, it is characterized in that, described Hydrobon catalyst is take VI B family and/or group VIII metal as active ingredient, take aluminum oxide or silicon-containing alumina as carrier, take the weight of catalyzer as benchmark, group VIB metal content is counted 8wt%～28wt% with oxide compound, and group VIII metal content is counted 2wt%～15 wt% with oxide compound.
12. 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.
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| CN109988639A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Method of the catalyst grade with technology production gasoline and low solidifying oil |
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