CN103805239B - A kind of method utilizing catalyzer grating technology to produce hydrogenation low-coagulation diesel oil - Google Patents
A kind of method utilizing catalyzer grating technology to produce hydrogenation low-coagulation diesel oil Download PDFInfo
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Abstract
The invention discloses a kind of method utilizing catalyzer grating technology to produce hydrogenation low-coagulation diesel oil.After diesel oil mixes with hydrogen, successively by the hydroconversion reaction zones of at least two series connection, comprise Hydrodewaxing catalyst bed and the pour point depression modifying catalyst composite bed by hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading mixed packing successively by each hydroconversion reaction zone, logistics direction; Last hydroconversion reaction zone gained reaction effluent is through being separated and after fractionation, obtaining low freezing point diesel fuel product.Hydrofining and the temperature rise of upgrading and pour point reducing process and the temperature drop of hydrodewaxing process are reasonably combined utilization by the inventive method, yield and the cetane value of diesel oil is improve while producing low solidifying low-sulfur diesel-oil, reduce the hot(test)-spot temperature of device, extend running period; In addition reduce the consumption of cold hydrogen or the combustion gas loss of process furnace, joint has also economized process cost.
Description
Technical field
The present invention relates to a kind of method utilizing catalyzer grating technology to produce hydrogenation 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, irreplaceable effect is played as Nonrenewable resources in modern productive life process, launch vehicle or other mechanical fuel such as automobile, tank, aircraft, tractor, rail vehicle can be used as, also can be used to generating, heating etc.The difference of industry and environment is used according to it, user also has very large difference for the specification of quality of diesel product, for the people at extremely frigid zones or life in winter, the demand of low freezing point diesel fuel remains high always, and traditional shape slective cracking technique can process the heavy gas oil cut of the content of wax, and pour point depression amplitude can reach 20 ~ 50 DEG C, while obtaining low freezing point diesel fuel, also can widen diesel oil distillate scope, improve productive rate, be the very useful and advanced technology solving 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 the requirement to diesel oil regular refiner character, condensation point becomes and requisitely requires one of index, therefore, it is possible to improve the seed output and quality of low-coagulation diesel oil, the major issue becoming and pay close attention to Han Qu oil refining enterprise of meeting the need of market.And select row cracking and combination process thereof as one of Main Means reducing condensation point of diesel oil, can be used for producing low-sulfur low-coagulation diesel oil, be conducive to the economic benefit improving oil refining enterprise.
Diesel oil shape slective cracking technology, also known as hydrodewaxing, refers in the presence of hydrogen, and the diesel raw material of the content of wax by the dual-function catalyst surface containing active metal and molecular sieve, thus reduces wax molecule content wherein.Its dewaxing principle is under certain operating conditions, raw material is mixed with hydrogen contact with Hydrodewaxing catalyst, be cracked into small molecules paraffinic hydrocarbons in raw material, band short-side chain alkane, the naphthenic hydrocarbon of belt length side chain and the contour condensation point compositional selecting of aromatic hydrocarbons of belt length side chain, and other component does not change substantially, finally reach the object of the condensation point reducing oil product.Because it has that lower, the adaptability to raw material of reaction process hydrogen consumption is strong, energy consumption is lower, technical process is simple, can form the plurality of advantages such as process integration or independence use with other hydrogenation process, be therefore widely used.The a lot of oil refining enterprise of current northern China Han Qu all have employed this technology and produces low-coagulation diesel oil.
CN1257107A describes 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 Hydrodewaxing catalyst two beds, hydrodewaxing adopts Ni/ZSM-5 catalyzer.The method is comparatively large at the temperature drop of Hydrodewaxing catalyst bed, and the yield of diesel oil distillate and the raising of depression effeCt are subject to a definite limitation, reduce the work-ing life of Hydrodewaxing catalyst.
CN102051232A describes a kind of method of diesel oil hydrogenation pour point depression, the method be by adjust catalyzer character thus make diesel oil depression effeCt good, 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 depression effeCt and diesel oil distillate yield still exists.
CN102453531A describes a kind of method of diesel hydro-pour-reducing, although improve the average reaction temperature of Hydrodewaxing catalyst, utilizes the temperature rise of finishing agent, increases the utilization ratio of pour point depression catalyzer,
The temperature of reaction of each bed outlet is still relatively high, and the cycle receives certain restriction.
CN01134271.4 discloses a kind of combined hydrogenation method producing high hexadecane value, low-coagulation diesel oil.The method is first contacted with catalyst for hydro-upgrading or hydrocracking catalyst stock oil, hydrogen, reaction effluent then contacts with Hydrodewaxing catalyst without separation, reaction effluent enters high-pressure separator through cooling, isolated product liquid enters fractionating system, and the gas circulation being rich in hydrogen returns 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 comparatively stock oil improves more than 6 units.
CN99113293.9 discloses a kind of method of being produced high-quality low-coagulation diesel oil with high hexadecane value by distillate.Hydrodewaxing is directly connected with hydrofining, hydro-upgrading by the method, realize hydrofining-hydro-upgrading-hydrodewaxing-section serial flow, what adopt is Hydrobon catalyst that anti-coking performance is strong and has stronger anti-ammonia, the hydro-upgrading of capacity antacid and Hydrodewaxing catalyst, and refining/depression effeCt is good, diesel yield is high, adaptability to raw material is strong, diesel cetane-number is high, technical process is simple and products scheme feature flexibly thus to make this technique have.
Summary of the invention
For prior art Problems existing, the invention provides a kind of production method of low-coagulation diesel oil.The mixed catalyst that Hydrodewaxing catalyst and hydro-upgrading isomerization-visbreaking and hydro-upgrading compound load is carried out grating by the inventive method, temperature rise in the temperature drop of hydrodewaxing process and hydrogenation process is reasonably combined utilization, yield and the cetane value of diesel oil is improve while producing low condensation point low-sulfur diesel-oil, reduce the hot(test)-spot temperature of device, extend running period; In addition reduce the consumption of cold hydrogen or the combustion gas loss of process furnace, save process cost.
The invention provides a kind of method utilizing catalyzer grating technology to produce hydrogenation low-coagulation diesel oil, comprise following content:
After diesel raw material mixes with hydrogen, successively by the hydroconversion reaction zones of at least two series connection, comprise Hydrodewaxing catalyst bed and the pour point depression modifying catalyst composite bed by hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading mixed packing successively by hydroconversion reaction zone described in Flow of Goods and Materials direction; Last hydroconversion reaction zone gained reaction effluent is through being separated and after fractionation, obtaining 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 Hydrodewaxing catalyst bed, carry out pour point depression reaction; Reaction effluent by the pour point depression modifying catalyst composite bed by hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading mixed packing, carries out hydrogenating desulfurization, hydrodenitrification, hydrodewaxing, aromatic saturation and ring-opening reaction again.
According to method of hydrotreating of the present invention, described diesel raw material is conventional pour point depression raw material and high freezing point diesel fuel, and condensation point is generally all more than 0 DEG C, and preferred condensation point is more than 5 DEG C.The nitrogen content of described diesel raw material, at 2000 below μ g/g, is generally 50 ~ 1200 μ g/g, most preferably is 100 ~ 500 μ g/g.If the organic nitrogen content in diesel raw material is too high, if nitrogen content is when 2000 more than μ g/g, before the Hydrodewaxing catalyst bed of diesel raw material by the first hydroconversion reaction zone, in advance by a hydrofining or hydrodenitrogenation catalyst bed, part denitrogenation can be carried out.The diesel oil etc. of the various straight run that described diesel raw material can obtain for processing naphthenic base crude, intermediate base crude oil or paraffinic crude or secondary processing, preferably processes the said components that paraffinic crude obtains.Doing of diesel raw material is generally 350 ~ 440 DEG C, preferably 370 ~ 400 DEG C.As described in diesel raw material can be selected from processing the Daqing crude oil various straight-run diesel oils, coker gas oil, catalytic diesel oil etc. that obtain one or several.
Described Hydrodewaxing catalyst adopts the catalyzer containing shape slective cracking molecular sieve, comprises the metal component of carrier and institute's load.Described catalyzer generally with shape slective cracking molecular sieve and tackiness agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component.Described shape slective cracking molecular sieve is hydrogen type molecular sieve, described molecular sieve can be selected from Hydrogen ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 molecular sieve one or more, preferred 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.With the weight of catalyzer for benchmark, hydrogenation active metals component is with the content of oxide basis for 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 select existing various commercial catalysts, the Hydrodewaxing catalysts 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, such as, can prepare satisfactory Hydrodewaxing catalyst with reference to content disclosed in CN1952074A, CN1352231A, CN101143333A, CN102451748A.
Catalyst for hydro-upgrading described in the present invention is the hydrogenation conversion catalyst containing molecular sieve, and especially a kind of hydrogenation catalyst being exclusively used in diesel modifying is the conventional hydro conversion catalyst in this area.Described catalyst for hydro-upgrading is a kind of dual function hydrogenation catalyst, with aluminum oxide and Y zeolite for carrier, containing at least one VI B race's metal and at least one VIII race 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%, the wherein pore volume 0.40 ~ 0.52mL/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%.
VI wherein said B race metal can be Mo or W, and preferably select W, VIII race's metal can be Ni or Co, preferably selects Ni.Conventional hydro modifying catalyst can select existing various commercial catalysts, such as FRIPP develop 3963, the catalyzer such as FC-18.Also specific catalyst for hydro-upgrading can be prepared by the general knowledge of this area as required, such as, satisfactory hydro-upgrading (conversion) catalyzer can be prepared with reference to content disclosed in CN1184843A, CN1178238A.
Described hydro-upgrading isomerization-visbreaking catalyzer is conventional catalyst in the art.Described hydro-upgrading pour point depression catalyzer generally comprises amorphous aluminum silicide, the beta-molecular sieve of modification, refractory porous oxide, VI B race and VIII family metal oxide.With the weight ratio of catalyzer for 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 with oxide basis 15w% ~ 35w%, group VIII metal take oxide basis as 3w% ~ 9w%, 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 ~ 0.4mmol/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%, and the secondary pore pore volume of infrared acidity 0.1 ~ 0.4mmol/g, 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 select existing various commercial catalysts, the catalyzer such as FC-14, FC-20 that such as FRIPP develops.Also specific hydro-upgrading isomerization-visbreaking catalyzer can be prepared by the general knowledge of this area as required, such as, satisfactory hydro-upgrading isomerization-visbreaking catalyzer can be prepared with reference to content disclosed in CN1712498A.
The operational condition of described Hydrodewaxing catalyst bed is: reaction pressure 6.0 ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 1500:1, and volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 260 DEG C ~ 455 DEG C; Preferred operations condition is reaction pressure 7.0 ~ 15.0MPa, hydrogen to oil volume ratio 300:1 ~ 1000:1, volume space velocity 0.3 ~ 8.0h
-1, temperature of reaction 310 DEG C ~ 410 DEG C.
The operational condition of the pour point depression modifying catalyst composite bed of described hydro-upgrading isomerization-visbreaking and catalyst for hydro-upgrading composition is: reaction pressure 6.0 ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 1500:1, volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 270 DEG C ~ 460 DEG C; Preferred operations condition is reaction pressure 7.0 ~ 15.0MPa, hydrogen to oil volume ratio 300:1 ~ 1000:1, volume space velocity 0.3 ~ 8.0h
-1, temperature of reaction 315 DEG C ~ 415 DEG C.
According to method of the present invention, wherein in each hydroconversion reaction zone, described Hydrodewaxing catalyst bed is 1:10 ~ 10:1 with the admission space ratio of the pour point depression modifying catalyst composite bed by hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading mixed packing, is preferably 1:5 ~ 5:1.
In described pour point depression modifying catalyst composite bed, hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading compound are loaded, and admission space is than being 1:10 ~ 10:1, preferred 1:5 ~ 5:1.
For described at least two hydroconversion reaction zones, wherein said Hydrodewaxing catalyst bed and pour point depression modifying catalyst composite bed, can be separately positioned in the two or more bed 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 is first by Hydrodewaxing catalyst bed, carry out pour point depression reaction, process diesel raw material, this reaction shows as thermo-negative reaction, and the stock oil after hydrodewaxing art breading is again by pour point depression modifying catalyst composite bed, carry out hydrogenating desulfurization, hydrodenitrification, hydrodewaxing and aromatic saturation and ring opening reaction, this hydrogenation reaction shows as exothermic effect.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 grading loading, its respective heat release and endothermic effect can be made full use of, the comprehensive utilization of the heat of realization response process, excessive temperature rise and temperature drop effect can not be produced, and affect depression effeCt, thus the hot(test)-spot temperature of whole beds is reduced, both can ensure the yield of diesel oil, also achieve better depression effeCt.Owing to have employed hydro-upgrading process, in the present invention, the cetane value of diesel product is having lifting by a relatively large margin, significant desulfurization effect, in addition because raw material is first and pour point depression catalyst exposure, also has the feature that adaptability to raw material is strong.
2, at process aspect, in each hydroconversion reaction zone, substantially identical effect is all shown.Thus 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 on the basis of not changing device flow process, load by means of only the grading composition of catalyzer and compound, from local by the high temperature dot of device and the effective Appropriate application of low warm spot, reduce the hot(test)-spot temperature of device, reasonably decrease the bulk temperature gradient of device, extend the work-ing life of catalyzer.In addition this combination is compared with the hydrodewaxing combination process of routine, heat due to reaction process obtains and more reasonably utilizes, can beat less between two reaction zones or not liquid hydrogen injection, therefore also reduce the consumption of cold hydrogen and the combustion gas loss of process furnace, save process cost.
Accompanying drawing explanation
Fig. 1 is the grading loading schematic diagram of a kind of embodiment of the inventive method; Single reactor layering is selected to load the operating method with two hydroconversion reaction zones.
Embodiment
Below in conjunction with accompanying drawing, a kind of method utilizing catalyzer grating technology to produce hydrogenation low-coagulation diesel oil of the present invention is described in detail.
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, Hydrodewaxing catalyst bed 4 from top to bottom successively by connecting step by step, the composite catalyst bed 5 of hydro-upgrading isomerization-visbreaking and hydro-upgrading, the composite bed 7 of Hydrodewaxing catalyst bed 6 and hydro-upgrading isomerization-visbreaking and hydro-upgrading, obtain reaction effluent 8 and after water filling 9, enter into high-pressure separator 10 from reactor bottom discharge, high-pressure separator 10 top obtains gas 11 by circulating hydrogen compressor 12, hydrogen or cold hydrogen use as a supplement to obtain recycle hydrogen 14 after mixing with new hydrogen 13, the liquid phase that high-pressure separator 10 middle and lower part obtains enters light pressure separator 17, and light pressure separator 17 top is discharged low point of gas 18 and gone subsequent disposal, and light pressure separator 17 middle and lower part obtains liquid phase 20 and enters subsequent fractionation system, the sour water 15 of discharging bottom high-pressure separator 10 mixes rear disacidify water treatment device with the sour water 19 of discharging bottom light pressure separator 17 and 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 the device adopting hydrodewaxing, hydro-upgrading isomerization-visbreaking and hydro-upgrading one-stage serial flow process to produce low freezing point diesel fuel.The pour point depression modifying catalyst bed comprising Hydrodewaxing catalyst bed and loaded by hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading layering.Comparative example 1 produces the low-coagulation diesel oil of the identical trade mark with embodiment 1.The catalyzer used, stock oil and diesel product condensation point are all identical with embodiment 1.Operation result lists in table 2.
Comparative example 2
Comparative example 2 is the device adopting hydrodewaxing, hydro-upgrading isomerization-visbreaking and hydro-upgrading one-stage serial flow process to produce low freezing point diesel fuel.Control substantially identical diesel yield with embodiment 1, produce the low-coagulation diesel oil of the different trade mark.The catalyzer that comparative example uses, stock oil and diesel product yield are all identical with embodiment 1, and catalyst loading is with comparative example 1.Operation result lists in table 2.
Embodiment 1
Adopt the technical process shown in Fig. 1, utilize grating to connect and load in mixture flow process and produce low freezing point diesel fuel.Embodiment 1 comprises the hydroconversion reaction zone of two series connection, in the pour point depression modifying catalyst composite bed of each reaction zone, hydro-upgrading isomerization-visbreaking catalyzer is 1:4 with the mixed volume ratio of catalyst for hydro-upgrading, and the total consumption of catalyzer is all identical with comparative example 2 with comparative example 1.The catalyst for hydro-upgrading used 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 list in table 2.
Table 1 stock oil property list.
| Project | Stock oil |
| Source | Atmosphere 3rd side cut diesel oil |
| Density (20 DEG C)/gcm -3 | 0.8810 |
| Boiling range scope/DEG C | 280～400 |
| Nitrogen/μ gg -1 | 220 |
| Sulphur/μ gg -1 | 1200 |
| Condensation point/DEG C | 13 |
| Cetane value | 35.0 |
Table 2 process conditions and result.
| Comparative example 1 | Comparative example 2 | Embodiment 1 | |
| Catalyzer forms | FDW-3/(FC-14/FC-18) | FDW-3/(FC-14/FC-18) | FDW-3/(FC-14+FC-18) |
| Reaction pressure/MPa | 9.0 | 9.0 | 9.0 |
| Average reaction temperature/DEG C | 378/387* | 370/387* | 378/388*/379/389* |
| LHSV/h -1 | 3.0/2.5** | 3.0/2.5** | 6.0/5.0**/6.0/5.0** |
| Entrance hydrogen to oil volume ratio | 600:1 | 600:1 | 600:1 |
| Diesel product condensation point/DEG C | -37 | -21 | -35 |
| Diesel yield, wt% | 71.9 | 81.5 | 81.3 |
| Diesel oil sulphur content/μ gg -1 | 17 | 21 | 18 |
| Diesel cetane-number | 43 | 45.9 | 43 |
| Bed vertex temperature/DEG C | 398 | 389 | 390 |
| Cold hydrogen consumption/benchmark | 0.97 | 1.88 | 1.0 |
* average reaction temperature is the weighted mean temperature of pour point depression modifying catalyst bed;
* volume space velocity is the volume space velocity of pour point depression modifying catalyst bed.
As can be seen from above embodiment, the maximum feature of the inventive method is, for processing diesel raw material, adaptability to raw material is very strong, the low solidifying product cetane value of producing is high, and sulphur content is low, can reduce the condensation point of raw material when ensureing certain diesel yield to greatest extent simultaneously; In addition also to have hot(test)-spot temperature low for the inventive method, and running period is long, the feature that cold hydrogen consumption is low; For enterprise, while completing quality products production task, human and material resources and energy consumption have very large advantage.
Claims (10)
1. utilize catalyzer grating technology to produce a method for hydrogenation low-coagulation diesel oil, comprise following content:
After diesel raw material mixes with hydrogen, successively by the hydroconversion reaction zone of at least two series connection, by Flow of Goods and Materials direction, each described hydroconversion reaction zone includes Hydrodewaxing catalyst bed and the pour point depression modifying catalyst composite bed by hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading mixed packing successively; Last hydroconversion reaction zone gained reaction effluent is through being separated and after fractionation, obtaining low freezing point diesel fuel product;
In each described hydroconversion reaction zone, described Hydrodewaxing catalyst bed is 1:10 ~ 10:1 with the admission space ratio of the pour point depression modifying catalyst composite bed by hydro-upgrading isomerization-visbreaking catalyzer and catalyst for hydro-upgrading mixed packing; In described pour point depression modifying catalyst composite bed, hydro-upgrading isomerization-visbreaking catalyzer is 1:10 ~ 10:1 with the admission space ratio of catalyst for hydro-upgrading.
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 DEG C, and nitrogen content is at 2000 below 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 50 ~ 1200 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 at 2000 more than μ g/g, and diesel raw material is before the Hydrodewaxing catalyst bed by the first hydroconversion reaction zone, in advance by a Hydrobon catalyst bed, carry out part denitrogenation.
5. in accordance with the method for claim 1, it is characterized in that, doing of described diesel raw material is 350 ~ 440 DEG C.
6. 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 ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 1500:1, and volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 260 DEG C ~ 455 DEG C.
7. in accordance with the method for claim 1, it is characterized in that, the operational condition of the pour point depression modifying catalyst composite bed of described hydro-upgrading isomerization-visbreaking and catalyst for hydro-upgrading composition is: reaction pressure 6.0 ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 1500:1, volume space velocity is 0.1 ~ 10.0h
-1, temperature of reaction 270 DEG C ~ 460 DEG C.
8. in accordance with the method for claim 1, it is characterized in that, described Hydrodewaxing catalyst with shape slective cracking molecular sieve and tackiness agent for carrier, with group VIB and/or group VIII metal for hydrogenation active metals component, with the weight of catalyzer for benchmark, hydrogenation active metals is with the content of oxide basis for 1% ~ 16%, and the content of shape slective cracking molecular sieve is 50% ~ 85%, and the content of tackiness agent is 10% ~ 40%.
9. in accordance with the method for claim 1, it is characterized in that, described hydro-upgrading isomerization-visbreaking catalyzer comprises amorphous aluminum silicide, modified beta molecular sieve, porous refractory oxide, VI B race and VIII family metal oxide, with the weight ratio of catalyzer for benchmark, the content of each component is: amorphous aluminum silicide 29w% ~ 50w%, modified beta molecular sieve 1w% ~ 9%, group VIB metal is with oxide basis 15w% ~ 35w%, group VIII metal take oxide basis as 3w% ~ 9w%, 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 catalyst for hydro-upgrading with aluminum oxide, amorphous aluminum silicide and Y zeolite for carrier, containing at least one VI B race's metal and at least one VIII race metal, VI B race metal with oxide basis content for 10w% ~ 30w%, VIII race's metal with oxide basis content for 2w% ~ 15w%; Described vehicle group becomes aluminum oxide 40w% ~ 80w%, amorphous aluminum silicide 0w% ~ 20w%, Y zeolite 5w% ~ 30w%, wherein the pore volume 0.40 ~ 0.52mL/g of Y zeolite, specific surface 750 ~ 900m
2/ g, lattice constant 2.420 ~ 2.500nm, SiO
2/ Al
2o
3molecular ratio is 7 ~ 15.
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