CN104611024A - Process method for producing lubricating oil base oil through poor-quality heavy distillate oil - Google Patents
Process method for producing lubricating oil base oil through poor-quality heavy distillate oil Download PDFInfo
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Abstract
The present invention discloses a process method for producing lubricating oil base oil through poor-quality heavy distillate oil. According to the method, poor-quality heavy distillate oil and hydrogen gas enter a first-stage reaction zone to carry out a hydrorefining reaction, the liquid obtained by separating the reaction effluent and hydrogen gas enter a second-stage reaction zone to carry out a hydrorefining reaction, the second-stage reaction effluent enters a third-stage reaction zone to carry out a hydrocracking reaction, the hydrocracking reaction effluent is separated to obtain tail oil, the tail oil is subjected to pre-fractionation to the obtained the suitable tail oil distillate, and the suitable tail oil distillate is sequentially subjected to isomerizing dewaxing and finishing to obtain the lubricating oil base oil. With the method of the present invention, the nitrogen-containing impurities in the poor-quality raw material can be subjected to hydrotreating under the relatively mild condition so as to make the poor-quality raw material meet the hydrocracking feeding requirement, such that the lubricating oil base oil raw material source is broadened; and the hydrorefining temperature is substantially reduced so as to increase the operation period of the device and process the poor-quality raw material, or increase the processing capacity of the device in the same operation period.
Description
Technical field
The invention discloses a kind of processing method of producing lubricant base, particularly a kind of processing method of processing inferior heavy distillate production lubricant base.
Background technology
Along with China's rapid development of economy, refining of petroleum ability increases fast.Meanwhile, domestic hydrocracking technology also obtain large-scale industrial application, and by the end of the year 2011, the hydroeracking unit that China is running will have cover more than 40, and total working ability is more than 50.0Mt/a, and working ability leaps to second place of the world.In addition, due to the variation year by year of domestic crude quality, the significantly increase of imported high sulfur crude oil amount of finish, the requirement of environmental protection to oil refining process and petroleum product-quality is increasingly strict, and market is to the continuous increase of clean fuel oil and industrial chemicals demand, especially as the clean intermediate oil of transportation fuel and the high-quality charging that provides for devices such as reformation, ethene, therefore the progress of market to hydrocracking technology level is had higher requirement.The wide scope of material that hydrocracking is processed, products scheme is flexible, and liquid product yield is high, can obtain high-quality power fuel and industrial chemicals, and hydrocracking process and technology are more and more subject to the most attention of each major oil companies of the world.
The production technique of base oil mainly comprises tradition " old three covers " lubricating oil complete processing and the hydrogenation method technique that is representative with hydrotreatment, hydrocracking, catalytic dewaxing/isomerization dewaxing.And II/III class High Quality Lube Base Oils especially III class lubricating oil base oil there is the features such as saturated hydrocarbon content is high, sulphur content is extremely low, property of viscosity versus temperature is good, be the main raw material producing top-grade lubricating oil, with traditional solvent method be difficult to produce.Producing the state-of-the-art technology of high-quality lubricant base outside Present Domestic is adopt hydrogenation method technique, and especially hydrocracking-isomerization dewaxing combination process route is comparatively ripe, has been widely used in and has produced top-grade lubricating oil base oil.Utilize hydrocracking tail oil to have the advantages such as low-sulfur, low nitrogen, low arene content, excellent heat-resistant quality and oxidation stability, lower volatility, excellent viscosity temperature characteristic and good additive response by the lubricant base that isomerization dewaxing pour point depression technology is produced, the requirement of modern top-grade lubricating oil to API II/III class base oil can be met.
US6,676,827 disclose a kind of method that isomerization dewaxing produces low solidifying lubricant base.Adopt hydrocracking-isomerization dewaxing two-stage hydrogenation operational path, hydrocracking and isomerization dewaxing all have respective hydrogen gas circulating system, and this is that current hydrogenation method produces lubricant base main processes.Owing to using two-stage process, therefore technical process is complicated, equipment is many, operating cost is high.
CN200710011927.5 discloses a kind of production method of lubricant base, the tail oil of Hydrocracking unit directly supplies tail oil isomerization dewaxing unit and does raw material, new hydrogen is once by tail oil isomerization dewaxing unit, and its tail hydrogen then directly returns to Hydrocracking unit and does hydrogen make-up.The method is only the combination of two unit, and reduce investment and the process cost of device, the quality product of Hydrocracking unit does not improve.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of hydrocracking-isomerization dewaxing combined method of improvement, for processing the very high inferior feedstock oil of nitrogen content to produce lubricant base.Compared with the existing technology, the inventive method can improve quality product and the working ability of device greatly, or at same quality product and working ability condition decline low operating pressure, reduces process cost.
The processing method of lubricant base produced by a kind of inferior heavy distillate of the present invention, comprises following content:
(1) under hydrofining technology condition, enter first paragraph reaction zone after inferior heavy distillate mixes with hydrogen and carry out hydrofining reaction, first paragraph reaction zone comprises Hydrobon catalyst, and the denitrification percent of first paragraph reaction zone controls as 60wt% ~ 95wt%;
(2) first paragraph reaction zone effluent enters separator and is separated, and obtains gas phase and liquid phase; Gas phase (is mainly NH through imurity-removal
3and H
2s) can recycle after;
(3) step (2) obtains entering second segment reaction zone after liquid phase mixes with hydrogen, carries out hydrofining reaction, and second segment reaction zone uses Hydrobon catalyst;
(4) enter the 3rd section of reaction zone after the hydrogenation reaction effluent that step (3) obtains mixes with hydrogen, carry out hydrocracking reaction, the 3rd section of reaction zone uses hydrocracking catalyst;
(5) step (4) obtains hydrocracking reaction effluent and enters separation system, through being separated to obtain one or more and tail oil of gas, petroleum naphtha, kerosene and diesel oil;
(6) the tail oil preliminary fractionator that enters at least partially that step (5) obtains tail oil carries out fractionation, obtains lighter hydrocarbons and two or more tail oil fraction; The tail oil of remainder can loop back the reactor inlet of first paragraph or second segment reaction zone;
(7) at least one of step (6) gained tail oil fraction, enters isomerization dewaxing reaction zone with hydrogen after mixing, and carries out isomerization dewaxing reaction; Isomerization dewaxing reaction effluent enters post-refining conversion zone and carries out post-refining reaction;
(8) reaction product that step (7) obtains carries out gas-liquid separation, and product liquid obtains the lube base oil production of different size through distillation.
In processing method of the present invention, the nitrogen content of the inferior heavy distillate described in step (1) is generally 1500 more than μ g/g, is preferably 2000 more than μ g/g, most preferably is 2500 ~ 15000 μ g/g.The initial boiling point of inferior heavy distillate feedstock is generally 220 ~ 450 DEG C, is preferably 300 ~ 420 DEG C; Final boiling point is generally 470 ~ 550 DEG C, is preferably 500 ~ 550 DEG C.What described inferior heavy distillate was typically used as the raw material of catalytic cracking unit or hydroeracking unit mixes refining raw material.
In processing method of the present invention, wherein first paragraph reaction zone and second segment reaction zone are the downward fixed bed hydrogenation refining reaction of gas and liquid flowing.
Separator described in step (2) can be high pressure hot separator or cold high pressure separator.In step (2), gas-liquid separation is operating as routine operation well known to those skilled in the art.
According to processing method of the present invention, wherein in step (3), preferably the liquid phase after first paragraph reaction zone gas-liquid separation in step (2) is first washed with water, generate dissolved ammonia (NH in oil to reduce first paragraph hydrofining
3) content, through washing after liquid phase enter second segment reaction zone with hydrogen again.Described water washing operations is the routine operation of those skilled in the art.
In the inventive method, the separation system described in step (5) generally includes high-pressure separator, light pressure separator and separation column.The operation of described separation system is the routine operation of the art.
In the inventive method, wherein the denitrification percent general control of first paragraph reaction zone is 60wt% ~ 95wt%, preferably controls as 70wt% ~ 90wt%.The processing condition of first paragraph reaction zone are generally: average reaction temperature is 330 ~ 480 DEG C, are preferably 350 ~ 450 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 0.2 ~ 4.0h
-1, be preferably 0.5 ~ 3.0h
-1.
In the inventive method, the processing condition of second segment reaction zone are generally: average reaction temperature is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 0.2 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.
In the inventive method, the processing condition of wherein the 3rd section of reaction zone hydrocracking are generally: average reaction temperature is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 1.0 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.
In the inventive method, according to the scale of device, first paragraph reaction zone can arrange one or several reactors; Second segment reaction zone also can arrange one or several reactors; Same three-zone hydrocracking reaction zone can also arrange one or several reactors.
In the inventive method, after first paragraph reaction zone reaction effluent carries out gas-liquid separation, gas phase can through removing hydrogen sulfide and the use of ammonia Posterior circle, and liquid phase enters second segment reaction zone after washing hydrogen sulfide and ammonia off preferably through washing again, carries out deep hydrogenation denitrogenation and hydrofining reaction with hydrogen.
In the inventive method, mainly there is partial desulfurization and the part denitrification reaction of raw material in first paragraph reaction zone; The Hydrobon catalyst of second segment reaction zone proceeds the reactions such as deep hydrodesulfurizationof, denitrogenation, aromatic saturation.
In the inventive method, the processing condition of described hydroisomerization dewax reaction zone are: average reaction temperature is 220 ~ 380 DEG C, preferably 280 ~ 350 DEG C; Reaction pressure is 4.0 ~ 20.0 MPa, is preferably 6.0 ~ 17.0 MPa; Volume space velocity is 0.6 ~ 1.8 h
-1, be preferably 0.8 ~ 1.5 h
-1; Hydrogen to oil volume ratio 100:1 ~ 1500:1, is preferably 300:1 ~ 800:1.
Post-refining section uses the Hydrobon catalyst of this area routine, can be non-noble metal type catalyzer, and also can be noble metal type catalyzer, post-refining support of the catalyst be generally the porous refractory such as aluminum oxide or silicon-containing alumina material.Precious metal post-refining catalyzer uses after reduction, and base metal type catalyzer can use after reduction, also can use after sulfuration, preferably uses the post-refining catalyzer of reduction-state.If use sulphided state post-refining catalyzer, need in the material entering post-refining reaction zone, to supplement appropriate sulphur or sulfocompound, to keep catalyst activity.
The processing condition of described post-refining conversion zone are: average reaction temperature is 220 ~ 380 DEG C, preferably 280 ~ 350 DEG C; Reaction pressure is 4.0 ~ 20.0MPa, preferably 6.0 ~ 17.0MPa; Volume space velocity is 0.6 ~ 6.0h
-1, preferably 0.8 ~ 3.0h
-1; Hydrogen to oil volume ratio 100:1 ~ 1500:1, preferred 300:1 ~ 800:1.
In the inventive method, the Hydrobon catalyst that first paragraph and second segment use can be the arbitrary Hydrobon catalyst product in this area, hydrocracking catalyst can select suitable product according to the Spreading requirements of reaction product, as can be the middle oil type hydrocracking catalyst of voluminous intermediate oil (kerosene and diesel oil), or it be the mobile type hydrocracking catalyst producing petroleum naphtha and intermediate oil flexibly.Above-mentioned selection is content well-known to those skilled in the art.Hydrobon catalyst and hydrocracking catalyst are under response behaviour, and hydrogenation active component is sulphided state.
Compared with prior art, processing method of the present invention has following outstanding effect:
1, when processing the very high inferior heavy distillate feedstock oil of nitrogen content, the present invention can hydrogen sulfide in obviously reduction system and ammonia content, improves hydrogen dividing potential drop, effectively plays the activity of Hydrobon catalyst and hydrocracking catalyst.Current hydroeracking unit charging generally includes vacuum distillate, solvent treatment deasphalted oil or Fischer-Tropsch synthesis oil, wherein can mix refining part inferior distillate oil.And after in the inventive method, inferior distillate oil raw material carries out the reactions such as desulfurization, denitrogenation, deoxidation, aromatic saturation through the first reaction zone, second reaction zone feedstock quality reaches general hydrocrack charge specification of quality, directly as hydrocrack charge instead of as mixing refining raw material, thus the raw material sources of hydroeracking unit can be expanded.
2, those skilled in the art it is generally acknowledged, Hydrobon catalyst has resistance to nitrogen, and the hydrogen sulfide in recycle hydrogen and ammonia do not have restraining effect to catalyzer.But by learning the in-depth analysis of existing hydroprocessing technique, when the stock oil that processing nitrogen content is very high, because the foreign matter contents such as sulphur nitrogen are very high, reaction process generates a large amount of hydrogen sulfide and ammonia, produces very strong restraining effect to the nitrogen removal performance of Hydrobon catalyst.If adopt the ordinary method of this area, need the denitrification effect needed for could obtaining under higher temperature of reaction.And the present invention is by optimizing hydrofining technology flow process, identical or different Hydrobon catalyst is assigned in different refining reaction districts by suitable proportion; And achieve while the identical hydrogenation removing impurities matter degree of depth at second segment refining reaction device, significantly reduce temperature of reaction, improve hydrofining effluent quality, and extend running period.Meanwhile, the temperature that second segment is lower also can promote that aromatic saturation reacts, and denitrification reaction is generally ring-opening reaction, thus temperature of reaction is reduced further.That is, when processing same inferior raw material under identical air speed, because two-stage reaction has higher hydrogen dividing potential drop and aromatic saturation reaction faster, using two reactors to be removed to <10 μ g/g needs lower average reaction temperature by than use reactor.
3, the feature that the present invention is high according to stock oil nitrogen content, in first paragraph reaction zone, preferably adopt the Hydrobon catalyst being prepared carrier production by chloride process, be characterized in that duct is large and concentrated, foreign matter content is low, the effect of carrier and metal is strong, more effectively can reduce the restraining effect of ammonia to catalyzer, especially to processing inferior raw material, there is better activity stability; And in second segment reactor, preferably use the Hydrobon catalyst being prepared carrier production by sulphate method, be characterized in that duct is relatively little and disperse, the effect of carrier and metal is relatively weak.Catalyst for refining in second segment has higher activity and better activity stability for the raw material being stripped of most of the nitrogen impurity.Thus the grating of these two kinds of catalyzer can better play the activity of catalyzer.
4, first paragraph reaction effluent liquid phase preferably first enters second segment hydrofining reactor again after washing hydrogen sulfide and ammonia off, more can reduce the ammonia content in second segment reactor further, more effectively plays the activity of second segment Hydrobon catalyst.
5, the tail oil that three-zone hydrocracking obtains partly can return the hydrofining reactor of first paragraph or second segment, carries out deep refining, thus reduces the nitrogen content generating oil further, improves the feedstock quality of isomerization dewaxing unit.
Accompanying drawing explanation
Fig. 1 is a kind of principle process flow sheet of the present invention.
Embodiment
The present invention's inferior heavy distillate used can be one or more in the wax tailings of crude oil, deasphalted oil, shale oil and coal synthetic oil, crude oil deep vacuum distillation cut wet goods cut.Doing of described inferior heavy distillate is generally 470 ~ 550 DEG C.
The Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone can be conventional heavy distillate Hydrobon catalyst.Conventional hydro catalyst for refining generally comprises carrier and is loaded in the hydrogenation metal component on carrier.Catalyzer to generally include in the periodic table of elements group VIB active metal component as tungsten and/or molybdenum, in oxide weight 8% ~ 35%, and preferably 12% ~ 30%; And the VIIIth race's active metal component as nickel and/or cobalt, in oxide weight 1% ~ 7%, preferably 1.5% ~ 6%.The carrier that Hydrobon catalyst uses is inorganic refractory oxide, as aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc.Can also containing suitable adjuvant component in conventional hydro catalyst for refining, as one or more in the elements such as phosphorus, boron and fluorine, the content of auxiliary agent is generally 0.1wt% ~ 5wt%.In the inventive method, special recommendation uses the catalyzer with following character in first paragraph reaction zone: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, preferably 8 ~ 9nm; The volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is 70% ~ 90%, is preferably 75% ~ 85%; The pore volume in <4nm hole accounts for less than 5% of total pore volume.
The Hydrobon catalyst that first paragraph reaction zone uses, be generally the catalyzer being prepared carrier production by chloride process, the maturing temperature in catalyst preparation process is generally at about 480 DEG C.The catalyzer used in first paragraph reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyzer according to the method for this area.
Because the nitrogen content of stock oil is removed to relatively low level by first paragraph reaction zone, the Hydrobon catalyst that second segment reaction zone can use first paragraph reaction zone to use.The present invention preferably uses in second segment reaction zone has the catalyzer of following character: the average pore diameter of catalyzer is 4 to being less than 7.5nm, preferably 5 ~ 7nm; Its median pore diameter is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 50% ~ 75%, preferably 55% ~ 65%; The pore volume in the hole of <4nm accounts for the volume fraction of total pore volume generally lower than 10%.Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants little 0.5 ~ 3nm, preferably little 1.0 ~ 2.5nm; The hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percentage ratios of volume fraction of total pore volume, preferably little 15 ~ 25 percentage ratios.
Catalyzer in second segment reaction zone be generally by sulphate as Tai-Ace S 150 method prepare carrier produce catalyzer, the maturing temperature of catalyst preparation process is generally at about 450 DEG C.The catalyzer used in second segment reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyzer according to the method for this area.
Or body phase hydrogenation catalyst can also be used in second segment reaction zone in the inventive method, to improve the hydrogenation temperature of second segment reaction zone further.Body phase hydrogenation catalyst contains Mo, W, Ni tri-kinds of metal components, and in oxidized catalyst, W, Ni exist with composite oxides form: Ni
xw
yo
z, z=x+3y, Mo exist with oxide form: MoO
3; Composite oxides Ni
xw
yo
zthe ratio of middle x and y is 1:8 ~ 8:1, composite oxides Ni
xw
yo
zwith oxide M oO
3weight ratio be 1:10 ~ 10:1; Composite oxides Ni in bulk phase catalyst
xw
yo
zwith oxide M oO
3gross weight content be 40% ~ 100%.One or more in the components such as aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve can be contained as required in bulk phase catalyst, these components weight content is in the catalyst 0 ~ 60%, is preferably 20% ~ 50%.The specific surface area of bulk phase catalyst is 120 ~ 400m
2/ g, pore volume is 0.10 ~ 0.50mL/g.The commercial catalysts that body phase hydrogenation catalyst can select Fushun Petrochemical Research Institute to develop, or be prepared according to the Conventional wisdom of this area.
The hydrocracking reaction district of the 3rd section can use routine business hydrocracking catalyst, owing to can the foreign matter content of charging be taken off lower, the hydrocracking catalyst of resistance to nitrogen need not be adopted, operable business hydrocracking catalyst is except selecting the business Catalyst For Single-stage Hydrocracking with resistance to organonitrogen function, as ZHC-01, ZHC-02, ZHC-04, FC-14, FC-28 that Fushun Petrochemical Research Institute develops, the ICR126 etc. that FC-34, CHEVRON company develops.Can also use as DHC-32, DHC-39, HC-43, HC-115 etc. of Uop Inc., Fushun Petrochemical Research Institute develop 3971,3974,3976, FC-12, FC-16, FC-26 etc.
The present invention adopts the high-quality lubricant base of hydroisomerization dewax explained hereafter.Described hydroisomerization dewax catalyzer can the conventional lube oil hydrogenation heterogeneous catalyst in anthology field, can commodity in use hydroisomerization catalyst, also can prepare by this area general knowledge.Hydroisomerization catalyst carrier is generally the NU-10 molecular sieve of aluminum oxide and TON structure or ZSM-22 molecular sieve etc., and molecular sieve content is in the catalyst 30wt% ~ 80wt%, is preferably 40wt% ~ 70wt%, also can adds partial oxidation silicon in carrier; Active metal component be in Pt, Pd, Ru, Rh and Ni one or more, content is in the catalyst 0.1wt% ~ 30.0wt%.Selectable adjuvant component is one or more in boron, fluorine, chlorine and phosphorus, and content is in the catalyst 0.1wt% ~ 5.0wt%; The specific surface of hydroisomerization catalyst is 150 ~ 500m
2/ g, pore volume is 0.15 ~ 0.60mL/g.Before using, reduction treatment is carried out to catalyzer, make hydrogenation active metals be in reduction-state in reaction process.
Post-refining unit uses this area conventional hydro catalyst for refining, can be non-noble metal type catalyzer, and also can be noble metal type catalyzer, post-refining support of the catalyst be generally the porous refractory such as aluminum oxide or silicon-containing alumina material.Precious metal post-refining catalyzer uses after reduction, and base metal type catalyzer can use after reduction, also can use after sulfuration, preferably uses the post-refining catalyzer of reduction-state.If use sulphided state post-refining catalyzer, need in the material entering post-refining reaction zone, to supplement appropriate sulphur or sulfocompound, to keep catalyst activity.
Method for hydrogen cracking of the present invention is explained further below in conjunction with drawings and Examples.
Inferior heavy distillate feedstock through pipeline 1 with after the recycle hydrogen of pipeline 2 mixes, enter first paragraph hydrofining reactor (first paragraph reaction zone) 3, carry out hydrofining reaction; First paragraph reaction effluent enters separator 5 along pipeline 4 and is separated, and isolated gas goes out device through pipeline 6, can use through imurity-removal Posterior circle; The liquid phase that separator 5 obtains, through pipeline 7 after mixing through the hydrogen of pipeline 8, enters second segment hydrofining reactor (second segment reaction zone) 9, removes the impurity such as sulphur, nitrogen further; Second segment reaction zone effluent, through pipeline 10, after can mixing, enters hydrocracking reactor 12(the 3rd section of reaction zone with the hydrogen make-up of pipeline 11) carry out hydrocracking reaction.Hydrocracking reaction effluent enters the first separation system 14 through pipeline 13 and is separated, and is isolated to gas 15, petroleum naphtha 16, kerosene 17, diesel oil 18 and tail oil 19.The first described separation system 14 generally includes high-pressure separator, light pressure separator and separation column.Tail oil 19 enters tail oil preliminary fractionator 20, obtain light tail oil and heavy-tailed oil (for two kinds) is discharged from pipeline 21, pipeline 22 respectively, heavy-tailed oil through pipeline 22, after mixing with the hydrogen of pipeline 23, enter hydroisomerization dewax reactor 24, carry out isomerization dewaxing reaction; Isomerization dewaxing reaction effluent enters post-refining reactor 26 through pipeline 25 and carries out post-refining reaction.Post-refining effluent enters the second separation system 28 through pipeline 27 and is separated, and obtains gas and discharges through pipeline 29, and various lubricant base leaves from pipeline 30,31 and 32 respectively.The second described separation system 29 generally includes high-pressure separator, light pressure separator and separation column.
Below by embodiment, the present invention program and effect are described.Hydrocracking catalyst, hydroisomerization dewax catalyzer and post-refining catalyzer are the commercial catalyst of Fushun Petrochemical Research Institute's development and production.Stock oil character lists in table 1, Hydrobon catalyst character lists in table 2.In the present invention, wt% is weight percentage.
Table 1 stock oil.
| Wax oil | |
| Density/kgm -3 | 950.1 |
| Boiling range/DEG C | 236~544 |
| Sulphur content/wt% | 2.03 |
| Nitrogen content/μ gg -1 | 6127 |
Table 2 Hydrobon catalyst.
| Numbering | Catalyst A | Catalyst B |
| Carrier | Aluminum oxide | Aluminum oxide |
| MoO 3，wt% | 24.9 | 24.5 |
| NiO，wt% | 4.12 | 4.26 |
| P，wt% | 2.67 | 2.71 |
| Average pore diameter, nm | 8.4 | 6.5 |
| 4 ~ 10nm hole accounts for the ratio of total pore volume, volume % | 85 | 61 |
Embodiment 1
Adopt technical process shown in Fig. 1, first paragraph loading catalyst A, second segment loading catalyst A, the 3rd section of filling FC-50 catalyzer.Three-zone hydrocracking be one way by flow process, controlling second segment, to refine nitrogen content be 15 ~ 25 μ g/g, and controlling cracking zone >370 DEG C of per pass conversion is ~ 70wt%.
Hydrocracking tail oil all carries out prefractionation, obtains light tail oil and heavy-tailed oil; Light tail oil be 450 DEG C with the cutting temperature of heavy-tailed oil.Heavy-tailed oil carries out isomerization dewaxing reaction and post-refining reaction.
Embodiment 2
Adopt technical process shown in Fig. 1.First paragraph and the equal loading catalyst B of second segment.Other are with embodiment 1.
Embodiment 3
Adopt technical process shown in Fig. 1.First paragraph uses Hydrobon catalyst A, and second segment uses Hydrobon catalyst B.Other are with embodiment 1.
Comparative example 1
Adopt prior art, refining stage only comprises a conversion zone, wherein uses Hydrobon catalyst A, and cracking zone uses FC-50 catalyzer.Other are with embodiment 1.
Comparative example 2
Adopt prior art, refining stage only comprises a conversion zone, wherein uses Hydrobon catalyst B, and cracking zone uses FC-50 catalyzer.Other are with embodiment 1.
Table 3 test-results (running 500h).
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Hydrocracking segment process condition | |||
| Catalyzer | A/A/FC-50 | B/B/FC-50 | A/B/FC-50 |
| First paragraph denitrification percent, wt% | 80 | 80 | 80 |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Volume space velocity/h -1 | 1.0/1.0/1.8 | 1.0/1.0/1.8 | 1.0/1.0/1.8 |
| Hydrogen to oil volume ratio | 900/900/1300 | 900/900/1300 | 900/900/1300 |
| Temperature of reaction/DEG C | 380/390/386 | 375/385/386 | 380/385/386 |
| > 370 DEG C of tail oil viscosity indexs | 143 | 142 | 142 |
| Hydroisomerization dewax/post-refining process condition | |||
| Catalyzer | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 |
| Temperature of reaction/DEG C | 330/250 | 330/250 | 330/250 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 800 |
| Cumulative volume air speed/h -1 | 1.0 | 1.0 | 1.0 |
| > 320 DEG C of lubricating oil distillate character | |||
| Yield (* *), wt% | 77.35 | 77.47 | 78.11 |
| Pour point/DEG C | -21 | -21 | -21 |
| Viscosity (40 DEG C), mm/s 2 | 28.65 | 28.71 | 28.58 |
| Viscosity (100 DEG C), mm/s 2 | 5.316 | 5.301 | 5.297 |
| Viscosity index | 120 | 119 | 119 |
Table 3-continues test-results (running 5000h).
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Hydrocracking segment process condition | |||
| Catalyzer | A/A/FC-50 | B/B/FC-50 | A/B/FC-50 |
| First paragraph denitrification percent, wt% | 80 | 80 | 80 |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Volume space velocity/h -1 | 1.0/1.0/1.8 | 1.0/1.0/1.8 | 1.0/1.0/1.8 |
| Hydrogen to oil volume ratio | 900/900/1300 | 900/900/1300 | 900/900/1300 |
| Temperature of reaction/DEG C | 385/395/389 | 388/391/389 | 385/391/389 |
| > 370 DEG C of tail oil viscosity indexs | 142 | 141 | 141 |
| Hydroisomerization dewax/post-refining process condition | |||
| Catalyzer | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 |
| Temperature of reaction/DEG C | 335/255 | 335/255 | 335/255 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 800 |
| Cumulative volume air speed/h -1 | 1.0 | 1.0 | 1.0 |
| > 320 DEG C of lubricating oil distillate character | |||
| Yield (* *), wt% | 76.93 | 76.87 | 77.12 |
| Pour point/DEG C | -21 | -21 | -21 |
| Viscosity (40 DEG C), mm/s 2 | 28.47 | 28.66 | 28.61 |
| Viscosity (100 DEG C), mm/s 2 | 5.287 | 5.300 | 5.281 |
| Viscosity index | 119 | 119 | 118 |
Table 4 comparative example test-results (operating 500 hours).
| Comparative example 1 | Comparative example 2 | |
| Hydrocracking segment process condition | ||
| Catalyzer | A/FC-50 | B/FC-50 |
| First paragraph denitrification percent, wt% | 80 | 80 |
| Reaction pressure/MPa | 15.7 | 15.7 |
| Volume space velocity/h -1 | 0.5/1.8 | 0.5/1.8 |
| Hydrogen to oil volume ratio | 900/1300 | 900/1300 |
| Temperature of reaction/DEG C | 403/386 | 397/386 |
| > 370 DEG C of tail oil viscosity indexs | 141 | 140 |
| Hydroisomerization dewax/post-refining process condition | ||
| Catalyzer | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 |
| Temperature of reaction/DEG C | 330/251 | 330/251 |
| Reaction pressure/MPa | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 800 |
| Cumulative volume air speed/h -1 | 1.0 | 1.0 |
| > 320 DEG C of lubricating oil distillate character | ||
| Yield (* *), wt% | 76.87 | 76.95 |
| Pour point/DEG C | -21 | -21 |
| Viscosity (40 DEG C), mm/s 2 | 28.97 | 28.83 |
| Viscosity (100 DEG C), mm/s 2 | 5.316 | 5.321 |
| Viscosity index | 118 | 119 |
Above embodiment shows, adopt method for hydrogen cracking of the present invention, hydrofining comprises two conversion zones, when the inferior heavy distillate feedstock that processing nitrogen content is higher, more effectively can play the activity of Hydrobon catalyst, inferior heavy distillate is converted into qualified hydrocrack charge, thus provides qualified raw material for isomerization dewaxing.Hydrocracking tail oil as isomerization dewaxing charging, has increased substantially the yield of lubricant base after prefractionation.
Because hydrofining reaction temperature reduces greatly, thus the running period of device can be improved, or improve the working ability of device under same running period, or reduce working pressure when keeping same denitrification percent.
Claims (16)
1. a processing method for lubricant base produced by inferior heavy distillate, comprises following content:
(1) under hydrofining technology condition, enter first paragraph reaction zone after inferior heavy distillate mixes with hydrogen and carry out hydrofining reaction, first paragraph reaction zone comprises Hydrobon catalyst, and the denitrification percent of first paragraph reaction zone controls as 60wt% ~ 95wt%;
(2) first paragraph reaction zone effluent enters separator and is separated, and obtains gas phase and liquid phase;
(3) step (2) obtains entering second segment reaction zone after liquid phase mixes with hydrogen, carries out hydrofining reaction, and second segment reaction zone uses Hydrobon catalyst;
(4) enter the 3rd section of reaction zone after the hydrogenation reaction effluent that step (3) obtains mixes with hydrogen, carry out hydrocracking reaction, the 3rd section of reaction zone uses hydrocracking catalyst;
(5) step (4) obtains hydrocracking reaction effluent and enters separation system, through being separated to obtain one or more and tail oil of gas, petroleum naphtha, kerosene and diesel oil;
(6) the tail oil preliminary fractionator that enters at least partially that step (5) obtains tail oil carries out fractionation, obtains lighter hydrocarbons and two or more tail oil fraction;
(7) at least one of step (6) gained tail oil fraction, enters isomerization dewaxing reaction zone with hydrogen after mixing, and carries out isomerization dewaxing reaction; Isomerization dewaxing reaction effluent enters post-refining conversion zone and carries out post-refining reaction;
(8) reaction product that step (7) obtains carries out gas-liquid separation, and product liquid obtains the lube base oil production of different size through distillation.
2. in accordance with the method for claim 1, it is characterized in that, the nitrogen content of described inferior heavy distillate is 1500 more than μ g/g.
3. in accordance with the method for claim 2, it is characterized in that, the nitrogen content of described inferior heavy distillate is 2000 more than μ g/g.
4. in accordance with the method for claim 3, it is characterized in that, the nitrogen content of described inferior heavy distillate is 2500 ~ 15000 μ g/g.
5. in accordance with the method for claim 2, it is characterized in that, the final boiling point of described inferior heavy distillate is 470 ~ 550 DEG C.
6. in accordance with the method for claim 1, it is characterized in that, the denitrification percent of first paragraph reaction zone controls to be 70% ~ 90%.
7. in accordance with the method for claim 1, it is characterized in that, the processing condition of first paragraph reaction zone are: average reaction temperature is 300 ~ 480 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 0.2 ~ 4.0h
-1; Processing condition in second segment reaction zone are: average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h
-1; The processing condition of the 3rd section of reaction zone are: average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h
-1.
8. in accordance with the method for claim 1, it is characterized in that, in described step (3), the liquid phase in step (2) after the gas-liquid separation of first paragraph reaction zone is first washed with water, and then enters second segment reaction zone with hydrogen.
9. in accordance with the method for claim 1, it is characterized in that, the Hydrobon catalyst used in first paragraph reaction zone has following character: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, the volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is that the pore volume in 70% ~ 90%, <4nm hole accounts for less than 5% of total pore volume.
10. in accordance with the method for claim 9, it is characterized in that, the Hydrobon catalyst used in second segment reaction zone has following character, the average pore diameter of catalyzer is 4 to being less than 7.5nm, the pore volume in its median pore diameter to be volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume be hole of 50 ~ 75%, <4nm accounts for the volume fraction of total pore volume lower than 10%; Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants the hole of little 0.5 ~ 3nm, aperture 4 ~ 10nm to account for little 10 ~ 30 percentage ratios of volume fraction of total pore volume.
11. in accordance with the method for claim 9, it is characterized in that, the catalyzer used in first paragraph reaction zone has following character: the average pore diameter of catalyzer is 8 ~ 9nm, and the volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is 75% ~ 85%.
12. in accordance with the method for claim 10, it is characterized in that, the catalyzer used in second segment reaction zone has following character: the average pore diameter of catalyzer is 5 ~ 7nm, and its median pore diameter is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 55 ~ 65%.
13. in accordance with the method for claim 10, it is characterized in that, compared with the Hydrobon catalyst in first paragraph reaction zone, the hole of the little 1.0 ~ 2.5nm of average pore diameter of second segment Hydrobon catalyst, aperture 4 ~ 10nm accounts for little 15 ~ 25 percentage ratios of volume fraction of total pore volume.
14. according to the method described in claim 9 or 10, it is characterized in that, the Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone is made up of carrier and the hydrogenation metal component be loaded on carrier, catalyzer to comprise in the periodic table of elements group VIB active metal component in oxide weight 8% ~ 35%, VIIIth race's active metal component is in oxide weight 1% ~ 7%, and carrier is inorganic refractory oxide.
15. in accordance with the method for claim 10, it is characterized in that, use body phase hydrogenation catalyst in second segment reaction zone, described body phase hydrogenation catalyst contains Mo, W, Ni tri-kinds of metal components, and in oxidized catalyst, W, Ni exist with composite oxides form: Ni
xw
yo
z, z=x+3y, Mo exist with oxide form: MoO
3; Composite oxides Ni
xw
yo
zthe ratio of middle x and y is 1:8 ~ 8:1, composite oxides Ni
xw
yo
zwith oxide M oO
3weight ratio be 1:10 ~ 10:1; Composite oxides Ni in bulk phase catalyst
xw
yo
zwith oxide M oO
3gross weight content be 40% ~ 100%.
16. in accordance with the method for claim 15, it is characterized in that, also containing one or more in aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide and molecular sieve in bulk phase catalyst, these components weight content is in the catalyst 1 ~ 60%.
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| CN111454747A (en) * | 2020-04-23 | 2020-07-28 | 胜帮科技股份有限公司 | Shale oil grading reverse-order hydrogenation process system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552812A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Deep desulphurizing and dearomating process for diesel oil |
| CN101333460A (en) * | 2007-06-26 | 2008-12-31 | 中国石油化工股份有限公司 | Combined technological process for producing lube oil base stock |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552812A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Deep desulphurizing and dearomating process for diesel oil |
| CN101333460A (en) * | 2007-06-26 | 2008-12-31 | 中国石油化工股份有限公司 | Combined technological process for producing lube oil base stock |
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|---|---|---|---|---|
| CN111454747A (en) * | 2020-04-23 | 2020-07-28 | 胜帮科技股份有限公司 | Shale oil grading reverse-order hydrogenation process system |
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