CN103805244A - Production method of clean diesel oil with low condensation point - Google Patents
Production method of clean diesel oil with low condensation point Download PDFInfo
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- CN103805244A CN103805244A CN201210440421.7A CN201210440421A CN103805244A CN 103805244 A CN103805244 A CN 103805244A CN 201210440421 A CN201210440421 A CN 201210440421A CN 103805244 A CN103805244 A CN 103805244A
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Abstract
The invention discloses a production method of clean diesel oil with a low condensation point. The method comprises the following steps: mixing diesel oil 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 hydrodewaxing catalyst and a hydro-refining catalyst, and a hydro-upgrading catalyst bed layer; performing separation and fractionation of the reaction effluent from the last hydrogenation reaction zone to obtain the clean diesel oil product with a low condensation point, and a little light naphtha and liquefied gas. The method of the invention reasonably combines and utilizes the temperature decrease of the hydrodewaxing process with the temperature increase of the hydro-refining and hydro-upgrading process, improves the diesel oil yield 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 production method of clean 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 clean 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, utilize the temperature rise of finishing agent, strengthen the utilization ratio of pour point depression catalyzer, but 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 clean low-coagulation diesel oil.The mixed catalyst of hydrodewaxing and the compound filling of hydrofining and catalyst for hydro-upgrading are carried out grating by the inventive method, temperature rise in the temperature drop of hydrodewaxing process and unifining process is carried out to reasonably combination to be utilized, realize bed isothermal operation, 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 consumption or the process furnace load of cold hydrogen, saved process cost, reduced device comprehensive energy consumption.
The production method of a kind of clean 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 hydrodewaxing catalyzer composite bed and the catalyst for hydro-upgrading bed by Hydrodewaxing catalyst and Hydrobon catalyst mixed packing 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 clean low freezing point diesel fuel product, and a small amount of light naphthar and liquefied gas product.
According to method of the present invention, wherein in each described hydroconversion reaction zone, diesel raw material and hydrogen, first by the hydrodewaxing catalyzer composite bed by Hydrodewaxing catalyst and Hydrobon catalyst mixed packing, carry out hydrogenating desulfurization, hydrodenitrification, olefin saturated, aromatic saturation and hydroisomerizing and hydrodewaxing reaction; Reaction effluent by catalyst for hydro-upgrading bed, carries out deep hydrogenation saturated reaction and cyclic hydrocarbon ring-opening reaction etc. again.
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 2000 μ g/g, is generally 50～1200 μ g/g, most preferably is 100～1000 μ g/g.Various straight run or the diesel oil distillate 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.The boiling range scope of diesel raw material is generally 130～440 ℃, preferably 160～400 ℃.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 Hydrodewaxing catalyst is the conventional pour point depression catalyzer in this area.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.
Described Hydrobon catalyst, can be diesel oil hydrofining catalyst, can be also hydrocracking pre-refining catalyzer, also can use the highly effective hydrogenation catalyst for refining of the standby high metal content of body phase legal system.Described Hydrobon catalyst mainly comprises hydrogenation active metals and modified aluminium oxide supports component etc.General Hydrobon catalyst is made up of hydrogenation active metals component and various modified aluminium oxide supports etc. such as W, Mo, Co, Ni, Fe, and take the weight of catalyzer as benchmark, the content of hydrogenation component is 15%～80%.Conventional Hydrobon catalyst can be selected existing various commercial catalysts, the refining catalyst series of FHUDS diesel oil hydrofining catalyst series, FF hydrocracking pre-refining catalyst series and FTX body phase method highly effective hydrogenation that for example FRIPP develops, and the UF of the UOP of offshore company series hydrofining catalyzer, the diesel oil hydrofining catalysts such as the KF757 of Albemarle Corporation.Also can be that the general knowledge by this area is prepared the Hydrobon catalyst that selectivity is close as required.
Catalyst for hydro-upgrading described in the present invention is the hydrogenation conversion catalyst containing molecular sieve, and especially 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 0～20w%, 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, and in catalyzer, VI B family metal oxide content is 10w%～30w%, and VIII family metal oxide content is 2w%～15w%.
Wherein said VI B family metal can be Mo or W, preferably selects W, and VIII family metal can be Ni or Co, preferably selects Ni.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.
According to method of the present invention, in each hydroconversion reaction zone, described catalyst for hydro-upgrading bed is generally 1:10～10:1 with the admission space ratio of hydrodewaxing catalyzer composite bed, preferably 1:5～5:1.
The operational condition of the pour point depression catalyzer composite bed of described hydrodewaxing and Hydrobon 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 6.0～15.0 MPa, hydrogen to oil volume ratio 300:1～1000:1, volume space velocity 0.3～8.0 h
-1, 315 ℃～427 ℃ of temperature of reaction.
In described pour point depression catalyzer composite bed, the compound filling of Hydrodewaxing catalyst and Hydrobon catalyst, admission space is than being 1:10～10:1, preferably 1:5～5:1.
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.
For at least two described hydroconversion reaction zones, wherein said hydrodewaxing catalyzer composite bed and catalyst for hydro-upgrading 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, stock oil is first by hydrofining and Hydrodewaxing catalyst mixing bed, and because the saturated reaction of unsaturated hydrocarbons and the reaction of deviating from of impurity of hydrofining reaction all show as thermopositive reaction, this process beds produces temperature rise; And hydrodewaxing reacts for selecting type molecular sieve cracking and isomerization reaction, heat effect shows as thermo-negative reaction, and process produces temperature drop; These two kinds of catalyzer are carried out to grating mixed packing, can make full use of its heat release and thermo-negative reaction feature 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 composite catalyst bed can realize the reaction process of isothermal, obtain desirable reaction effect, both can guarantee the yield of diesel oil, also obtain better pour point depression effect, be more conducive to the long-term operation of device.After hydrofining and hydrodewaxing mixed catalyst bed, again by catalyst for hydro-upgrading bed, carry out aromatic saturation and cyclic hydrocarbon ring-opening reaction, diesel component is continued to advanced treatment, reaction process shows as exothermic effect, make the final temperature of charge of reaction outlet higher, thereby obtain good heat transfer effect, be conducive to save energy and reduce the cost.
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 the grading composition and even mixed packing 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, given full play of the catalytic performance of catalyzer the best, 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 consumption and the process furnace load of cold hydrogen have also been reduced, save process cost, reduced device comprehensive energy consumption.
Accompanying drawing explanation
Fig. 1 is the grading loading schematic diagram of a kind of embodiment of the inventive method; Select the operating method of two hydroconversion reaction zones of single reactor layering filling.
Embodiment
Below in conjunction with accompanying drawing, the production method of a kind of clean low-coagulation diesel oil of the present invention is elaborated.
As shown in Figure 1, the flow process of clean low-coagulation diesel oil production method 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 hydrodewaxing and hydrorefined composite catalyst bed 4, catalyst for hydro-upgrading bed 5, hydrodewaxing and hydrorefined composite bed 6 and the catalyst for hydro-upgrading bed 7 by connecting step by step, obtain reaction effluent 8 and discharge and after water filling 9, enter into high-pressure separator 10 from reactor bottom, high-pressure separator 10 tops obtain gas 11 by circulating hydrogen compressor 12, obtain recycle hydrogen 14 hydrogen or the use of cold hydrogen as a supplement with new hydrogen 13 after mixing; 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, clean low-coagulation diesel oil production method of the present invention is further described.
Comparative example 1
Comparative example 1 is for adopting hydrofining, hydrodewaxing and hydro-upgrading one-stage serial flow process to produce the device of clean low freezing point diesel fuel.Comparative example 1 comprises two reaction zones, each reaction zone includes pour point depression beds and the catalyst for hydro-upgrading bed by Hydrobon catalyst 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 hydrofining, hydrodewaxing and hydro-upgrading 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, Hydrodewaxing catalyst is 2:1 with the mixed volume ratio of Hydrobon catalyst.The Hydrobon catalyst using in embodiment 1 is FF-46 catalyzer, and Hydrodewaxing catalyst is FDW-3 catalyzer, and catalyst for hydro-upgrading agent is 3963 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+catalytic diesel oil |
| Ratio | 1:1 |
| Density (20 ℃)/gcm -3 | 0.8642 |
| Boiling range scope/℃ | 160～385 |
| Nitrogen/μ gg -1 | 241 |
| Sulphur/μ gg -1 | 3420 |
| Condensation point/℃ | 1 |
| Cetane index | 43 |
Table 2 process conditions and result.
| ? | Comparative example 1 | Comparative example 2 | Embodiment 1 |
| Catalyzer composition | (FDW-3/FF-46)/3963 | (FDW-3/FF-46)/3963 | (FDW-3+FF-46)/3963 |
| Reaction pressure/MPa | 9.0 | 9.0 | 9.0 |
| Average reaction temperature/℃ | 377*/379/378*/380 | 376*/385/377*/389 | 378*/379/379*/386 |
| LHSV/h -1 | 5.0**/6.0/5.0**/6.0 | 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 |
| Diesel product condensation point/℃ | -38 | -22 | -37 |
| Diesel yield, wt% | 73.9 | 81.2 | 80.8 |
| Bed vertex temperature/℃ | 399 | 390 | 389 |
| Cold hydrogen consumption/benchmark | 1.1 | 1.9 | 1.0 |
| Diesel oil density/gcm -3 | 0.8345 | 0.8364 | 0.8246 |
| Diesel oil cetane index | 49 | 48 | 52 |
| Diesel oil sulphur content/μ gg -1 | 34 | 24 | 12 |
* 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, produce low solidifying product for processing diesel raw material, can improve product cetane value, 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 (13)
1. a production method for clean low-coagulation diesel oil, comprises following content:
After diesel raw material is mixed with hydrogen, by the hydroconversion reaction zone of at least two series connection, comprise successively hydrodewaxing catalyzer composite bed and the catalyst for hydro-upgrading bed by Hydrodewaxing catalyst and Hydrobon catalyst mixed packing by the each hydroconversion reaction zone described in Flow of Goods and Materials direction successively; Last hydroconversion reaction zone gained reaction effluent, after separation and fractionation, obtains clean low freezing point diesel fuel product, and a small amount of light naphthar and liquefied gas 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 2000 μ g/g.
3. according to the method described in claim 1 or 2, it is characterized in that, the condensation point of described diesel raw material is more than 5 ℃, but content is 50～1200 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that, nitrogen content in described diesel raw material is more than 2000 μ g/g, diesel raw material is before passing through the hydrodewaxing catalyzer composite bed 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 each hydroconversion reaction zone, described catalyst for hydro-upgrading bed is 1:10～10:1 with the admission space ratio of hydrodewaxing catalyzer composite bed.
7. in accordance with the method for claim 1, it is characterized in that, in described hydrodewaxing catalyzer composite bed, Hydrobon catalyst is 1:10～10:1 with the admission space ratio of Hydrodewaxing catalyst.
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, 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%, and VIII family metal oxide content is 2w%～15w%.
9. 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 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%.
10. in accordance with the method for claim 9, it is characterized in that, described shape-selective molecular sieve is selected from one or more in Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve, and the silica alumina ratio of shape slective cracking molecular sieve is 10～150.
11. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst comprises hydrogenation active metals and modified aluminium oxide supports component, and take the weight of catalyzer as benchmark, the content of hydrogenation active metals counts 15%～80% with oxide compound.
12. 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.
13. in accordance with the method for claim 1, it is characterized in that, the operational condition of the described hydrodewaxing catalyzer composite bed being made up of hydrodewaxing and Hydrobon catalyst 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.
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| 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 |
| CN114196438A (en) * | 2020-09-17 | 2022-03-18 | 中国石油化工股份有限公司 | Hydrogenation process and hydrogenation system for treating high-nitrogen raw material |
| CN114196438B (en) * | 2020-09-17 | 2023-01-10 | 中国石油化工股份有限公司 | Hydrogenation process and hydrogenation system for treating high-nitrogen raw material |
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