CN104611041B - Inferior raw material produces the method for hydrotreating of lube base oil - Google Patents
Inferior raw material produces the method for hydrotreating of lube base oil Download PDFInfo
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Abstract
The invention discloses a kind of inferior raw material and produce the method for hydrotreating of lube base oil.Inferior raw material initially enters first paragraph reaction zone and carries out hydrofining reaction, uses simultaneously and flow and countercurrent flow in first paragraph, and one section generates oil entrance second segment reaction zone and carries out hydrogenation reaction, and second-stage reaction effluent is hydrocracked；Cracking tail oil carries out isomerization dewaxing and post-refining reaction, it is thus achieved that lubricant base oil fraction.The inventive method can carry out hydrotreating to the nitrogen-containing impurity in inferior raw material under the conditions of relatively relaxing so that it is meets and is hydrocracked feed needs, thus has widened the raw material sources of lube base oil；The inventive method can improve the service cycle of device, processes more inferior raw material or improves the working ability of device under same service cycle.
Description
Technical field
The invention discloses a kind of method of hydrotreating producing lube base oil, a kind of employing is hydrocracked-and isomerization dewaxing group technology processing inferior raw material produces the method for hydrotreating of lube base oil.
Background technology
Along with China's rapid development of economy, PETROLEUM PROCESSING ability quickly increases.Meanwhile, domestic hydrocracking technology also obtain large-scale commercial Application, and by the end of the year 2011, the hydrocracking unit that China is currently running has set more than 40, and total working ability alreadys more than 50.0Mt/a, and working ability leaps to second place of the world.Additionally, variation year by year due to domestic crude quality, being significantly increased of imported high sulfur crude oil processing capacity, environmental protection is the strictest to the requirement of oil refining process and petroleum product-quality, and clean fuel oil and industrial chemicals demand are continuously increased by market, feeding especially as the cleaning intermediate oil of transportation fuel and the high-quality provided for devices such as reformation, ethylene, therefore the progress of hydrocracking technology level is had higher requirement by market.Being hydrocracked processed wide scope of material, products scheme is flexible, and liquid product yield is high, can obtain high-quality power fuel and industrial chemicals, hydrocracking process and technology increasingly by the most attention of each major oil companies of the world.
The production technology of base oil mainly include tradition " old three set " lubricating oil processing technique and with hydrotreating, be hydrocracked, the catalytic dewaxing/isomerization dewaxing hydrogenation method technique as representative.And II/III class High Quality Lube Base Oils especially III class lubricating oil base oil has the features such as saturated hydrocarbon content is high, sulfur content is extremely low, property of viscosity versus temperature is good, it is the primary raw material producing top-grade lubricating oil, is difficult to produce with traditional solvent method.Producing the state-of-the-art technology of high-quality lube base oil outside Present Domestic is to use hydrogenation method technique, be especially hydrocracked-isomerization dewaxing group technology route is the most ripe, is widely used in production top-grade lubricating oil base oil.Utilize hydrocracking tail oil to be had the advantages such as low-sulfur, low nitrogen, low arene content, excellent thermostability and oxidation stability, relatively low volatility, excellent viscosity temperature characteristic and good additive response by the lube base oil that isomerization dewaxing pour point depression technology produces, the modern top-grade lubricating oil requirement to API II/III class base oil can be met.Due to the restriction by hydrofinishing (or hydrotreating) catalyst technology, usually require that the feed properties of Hydrocracking unit is preferable, it is hydrocracked charging and includes vacuum distillate, solvent refining deasphalted oil or Fischer-Tropsch synthesis oil, nitrogen content is generally at 2000 below μ g/g, and the end point of distillation is generally below 550 DEG C.The nitrogen content vacuum distillate more than 2500 μ g/g or wax oil use the processing of existing hydrocracking technology to be not used as the raw material being hydrocracked owing to being not suitable for, let alone it being used for producing high tier lubricant base oil, the highest nitrogen inferior raw material produces high-grade lube base oil for oil refining enterprise and brings technological challenge.
US6,676,827 discloses a kind of method that isomerization dewaxing produces low solidifying lube base oil.Employing is hydrocracked-isomerization dewaxing two-stage hydrogenation process route, is hydrocracked and all has respective hydrogen gas circulating system with isomerization dewaxing, and this is that current hydrogenation method produces lube base oil main processes.Owing to using two-stage process, therefore technological process is complicated, equipment is many, operating cost is high.
CN200710011927.5 discloses the production method of a kind of lube base oil, the tail oil of Hydrocracking unit directly feeds tail oil isomerization dewaxing unit and does raw material, new hydrogen is once by tail oil isomerization dewaxing unit, and its tail hydrogen is then directly returned to Hydrocracking unit and does supplementary hydrogen.The method is only the combination of two unit, reduces investment and the operating cost of device, and the product quality of Hydrocracking unit does not improve.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of improvement is hydrocracked-isomerization dewaxing group technology, Hydrocracking unit uses the two-stage reforming technique improved, processing nitrogen-containing material inferior oil, produces high-quality industrial chemicals, cleaning automotive fuel and High Quality Lube Base Oils.
A kind of inferior raw material of the present invention produces the method for hydrotreating of lube base oil, including herein below:
(1) inferior feedstock oil initially enters first paragraph reaction zone and carries out hydrotreating reaction, and first paragraph reaction zone uses Hydrobon catalyst；The top of first paragraph reaction zone is gas and liquid flowing reaction zone, and the gas-liquid separation zone flowing reaction effluent entrance middle separates, and gas draws reactor；Liquid enters the beds of bottom, and the hydrogen introduced with reactor bottom carries out counter current contacting reaction, and reacted gas leaves reactor from gas-liquid separation zone；The denitrification percent of general control first paragraph reaction zone is 60wt% ~ 95wt%；
(2) the generation oil that step (1) obtains enters second segment reaction zone after mixing with hydrogen, carries out Deep Hydrotreating reaction, and second segment reaction zone uses Hydrobon catalyst；
(3) effluent that in step (2), second segment reaction zone obtains, enters the 3rd section of reaction zone together with hydrogen make-up, is filled with hydrocracking catalyst in the 3rd section of reaction zone；
(4) the 3rd sections of reaction effluents that reaction zone obtains enter separator, obtain gas and liquid；Gas after gas-liquid separation can recycle after removing impurities matter, and liquid is fractionated into obtaining one or more and tail oil of gasoline, kerosene and diesel oil；
(5) step (4) obtains entrance isomerization dewaxing reaction zone after tail oil at least some of mixes with hydrogen, carry out isomerization dewaxing reaction, isomerization dewaxing reaction effluent enters post-refining section and carries out post-refining reaction, with further imurity-removal, the tail oil of remainder can loop back first paragraph or the reactor inlet of second segment reaction zone；
(6) product that step (5) obtains can be mixed into hydrocracking reaction district as supplementary hydrogen and hydrocracking raw material through gas-liquid separation, gas, and product liquid obtains lube base oil product through distillation.
Wherein in the first paragraph reaction zone of step (1), the gas and liquid flowing reaction zone on top and the Catalyst packing volume ratio of gas-liquid counter-flow reaction zone specifically can determine according to the hydrodenitrogeneration rate of the character of inferior raw material and first paragraph.
In the inventive method, described inferior feedstock oil is the inferior heavy distillate that nitrogen content is higher.The nitrogen content of inferior feedstock oil is generally 1500 more than μ g/g, preferably 2000 more than μ g/g, most preferably 2500 ~ 15000 μ g/g.
In the inventive method, in step (1), the denitrification percent general control of first paragraph reaction zone is 60wt% ~ 95wt%, is preferably controlled to 70wt% ~ 90wt%.In first paragraph reaction zone described in step (1), and the process conditions flowing reaction zone are: average reaction temperature is 250 ~ 500 DEG C, preferably 300 ~ 440 DEG C；Reaction pressure is 5.0 ~ 20.0MPa, preferably 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1 ~ 4000:1, preferably 400:1 ~ 2000:1；During liquid, volume space velocity is 1.0 ~ 10.0h-1, preferably 1.0 ~ 4.0h-1.In first paragraph reaction zone, the process conditions of counter-flow reaction zone are: average reaction temperature is 250 ~ 500 DEG C, preferably 300 ~ 440 DEG C；Reaction pressure is 5.0 ~ 20.0MPa, preferably 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1 ~ 2000:1, preferably 400:1 ~ 1000:1；During liquid, volume space velocity is 1.0 ~ 10.0h-1, preferably 1.0 ~ 4.0h-1。
In the inventive method, the process conditions of second segment reaction zone are: average reaction temperature is 330 ~ 480 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 0.2 ~ 4.0h-1.Preferably operating condition is: reaction temperature is 350 ~ 450 DEG C, and reaction pressure is 8.0 ~ 17.0 MPa, and hydrogen to oil volume ratio is 400:1 ~ 2000:1, and during liquid, volume space velocity is 0.5 ~ 3.0h-1。
In the inventive method, the process conditions of three-zone hydrocracking reaction zone are: average reaction temperature is 250 ~ 500 DEG C, preferably 300 ~ 440 DEG C；Reaction pressure is 5.0 ~ 20.0MPa, preferably 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1 ~ 4000:1, preferably 400:1 ~ 2000:1；During liquid, volume space velocity is 1.0 ~ 10.0h-1, preferably 1.0 ~ 4.0h-1。
In the inventive method, according to the scale of device, first paragraph reaction zone typically arranges one or several reactors, and second segment reaction zone can also arrange one or several reactors, and the hydrocracking reaction district of the 3rd section typically arranges a reactor.
In the inventive method, the process conditions of described hydroisomerizing dewaxing reaction 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 ~ 1.8h-1, preferably 0.8 ~ 1.5h-1；Hydrogen to oil volume ratio 100:1 ~ 1500:1, preferably 300:1 ~ 800:1.
Post-refining section uses the Hydrobon catalyst that this area is conventional, can be with right and wrong noble metal type catalyst, it is also possible to be noble metal type catalyst, and post-refining catalyst carrier is generally the porous refractory material such as aluminium oxide or silicon-containing alumina.Noble metal post-refining catalyst uses after carrying out reduction, and base metal type catalyst can use after carrying out reduction, it is also possible to use after sulfuration, the post-refining catalyst of reduction-state is preferably used.If using sulphided state post-refining catalyst, need to supplement appropriate sulfur or sulfur-containing compound in the charging entering post-refining reaction zone, to keep catalyst activity.
The process conditions 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, preferably 300:1 ~ 800:1.
In the inventive method, the Hydrobon catalyst that first paragraph and second segment use can be this area arbitrary Hydrobon catalyst product.Hydrocracking catalyst can select suitable product according to the Spreading requirements of product, as can be the middle oil type hydrocracking catalyst of fecund intermediate oil (kerosene and diesel oil), or be flexibly production Petroleum and the mobile type hydrocracking catalyst of intermediate oil.Above-mentioned selection is content well-known to those skilled in the art.Hydrobon catalyst and hydrocracking catalyst are under reactive state, and hydrogenation active component is sulphided state.
In the inventive method, mainly there is the part denitrification reaction of raw material in first paragraph reaction zone；Proceed the reactions such as hydrodesulfurization, denitrogenation, deoxidation, aromatic hydrocarbons are saturated on the Hydrobon catalyst of second segment reaction zone, the hydrocracking catalyst of the 3rd section carries out hydrocracking reaction, isomerization dewaxing raw material is provided while obtaining hydrocracked product.
Compared with prior art, the process of the present invention has an effect highlighted below:
1, when processing the highest inferior feedstock oil of nitrogen content, the present invention can hydrogen sulfide in substantially reduction system and ammonia content, improve system hydrogen dividing potential drop, effectively play Hydrobon catalyst and the activity of hydrocracking catalyst.Be hydrocracked at present-isomerization dewaxing combined unit Hydrocracking unit charging generally comprise vacuum distillate, solvent refining deasphalted oil or Fischer-Tropsch synthesis oil, and inferior raw material is after the first reaction zone carries out the reactions such as desulfurization, denitrogenation, deoxidation, aromatic hydrocarbons are saturated in the present invention, second reaction zone feedstock quality reaches typically to be hydrocracked feedstock quality requirement, such that it is able to expand the source of Lube basic oil material feedstocks.
2, those skilled in the art are it is generally believed that Hydrobon catalyst has resistance to nitrogen, and hydrogen sulfide and ammonia in recycle hydrogen do not have inhibitory action to catalyst.But by the in-depth analysis of existing hydrocracking process is learnt, when the raw oil that processing nitrogen content is the highest, owing to the impurity contents such as sulfur nitrogen are the highest, course of reaction generates substantial amounts of hydrogen sulfide and ammonia, and the nitrogen removal performance of Hydrobon catalyst is produced the strongest inhibitory action.If using the conventional method of this area, need the denitrification effect needed for could obtaining under higher reaction temperature.And the present invention is by optimizing hydrofining technology flow process, Hydrobon catalyst is assigned in different refining reaction districts by suitable proportion；And use the flow process of top gas and liquid flowing, bottom gas-liquid counter current operation in first paragraph finishing reactor, it is achieved that while the identical hydrogenation removing impurities matter degree of depth, significantly reduce reaction temperature, improve hydrofinishing effluent quality, and extend service cycle.Meanwhile, the relatively low temperature of second segment also can promote aromatic hydrocarbons saturated reaction, and denitrification reaction is generally ring-opening reaction, so that reaction temperature reduces further.That is, when processing same inferior raw material under identical air speed, owing to two-stage reaction has higher hydrogen dividing potential drop and aromatic hydrocarbons saturated reaction faster, < ratio is used a reactor to need lower average reaction temperature by 10 μ g/g to use two reactors to be removed to.
3, the present invention is according to the high feature of raw oil nitrogen content, preferably use in first paragraph reaction zone and prepared, by chloride process, the Hydrobon catalyst that carrier produces, it is characterized in that duct is big and pore-size distribution is concentrated, impurity content is low, the effect of carrier and metal is strong, there is stronger resistant to ammonia ability, can more effectively reduce the ammonia inhibitory action to catalyst, especially processing inferior raw material be had more preferable activity stability；And be preferably used in second segment reactor and prepared, by sulphate method, the Hydrobon catalyst that carrier produces, it being characterized in that duct is relatively small and disperses, the effect of carrier and metal is relatively weak.Catalyst for refining in second segment has higher activity and more preferable activity stability for the raw material being stripped of most of the nitrogen impurity.Thus, the grating of both catalyst can preferably play the activity of catalyst.
4, the hydrocracking tail oil of the 3rd section can partly loop back the hydrofining reactor of first paragraph or second segment, carries out deep refining, such that it is able to reduce 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 chart of the inventive method.
Detailed description of the invention
Inferior feedstock oil used by the present invention can be one or more in the fraction such as the wax tailings of crude oil, deasphalted oil, shale oil and coal artificial oil, crude oil deep vacuum distillation distillate.Described inferior feedstock oil do generally 490 ~ 550 DEG C.
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 the hydrogenation metal component being loaded on carrier, generally includes group VIB active metal component such as tungsten and/or molybdenum in the periodic table of elements, and in terms of oxide weight 8% ~ 35%, preferably 12% ~ 30%；And the VIIIth race's active metal component such as nickel and/or cobalt, in terms of oxide weight 1% ~ 7%, preferably 1.5% ~ 6%.The carrier that Hydrobon catalyst uses is inorganic refractory oxide, such as aluminium oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc..Catalyst can also contain one or more in phosphorus, boron, fluorine and chlorine as adjuvant component.
In the inventive method, special recommendation uses the catalyst having the following properties that in first paragraph reaction zone: the average pore diameter of catalyst is 7.5 ~ 9.5nm, preferably 8 ~ 9nm；It is 70% ~ 90% that the pore volume in the hole of bore dia 4 ~ 10nm accounts for the volume fraction of total pore volume, preferably 75% ~ 85%；< pore volume in 4nm hole accounts for less than the 5% of total pore volume.The Hydrobon catalyst that first paragraph reaction zone uses, is usually prepared, by chloride process, the catalyst that carrier produces, and the sintering temperature of catalyst is typically at about 480 DEG C.The catalyst used in first paragraph reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyst according to the method for this area.
Owing to the nitrogen content of raw oil being removed to relatively low level in first paragraph reaction zone, second segment reaction zone can use the Hydrobon catalyst that first paragraph reaction zone uses, the present invention preferably uses the catalyst that has the following properties that in second segment reaction zone: the average pore diameter of catalyst is 4 to less than 7.5nm, preferably 5 ~ 7nm；Its median pore diameter is that to account for the volume fraction of total pore volume be 50% ~ 75% for the pore volume in the hole of 4 ~ 10nm, preferably 55% ~ 65%；< pore volume in the hole of 4nm accounts for the volume fraction of total pore volume and is generally below 10%.Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants little 0.5 ~ 3nm, the least 1.0 ~ 2.5nm；The hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percents of volume fraction of total pore volume, the least 15 ~ 25 percents.Catalyst in second segment reaction zone is usually prepared, by sulphate such as aluminum sulfate method, the catalyst that carrier produces, and the sintering temperature of catalyst is typically at about 450 DEG C.The catalyst used in second segment reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyst according to the method for this area.
Or the present invention can also use body phase hydrogenation catalyst, to improve the hydrogenation temperature of second segment reaction zone further in second segment reaction zone.Body phase hydrogenation catalyst contains tri-kinds of metal components of Mo, W, Ni, and in oxidized catalyst, W, Ni exist with composite oxides form: NixWyOz, z=x+3y, Mo are with oxide form existence: MoO3；Composite oxides NixWyOzThe ratio of middle x and y is 1:8 ~ 8:1, composite oxides NixWyOzWith oxide M oO3Weight ratio be 1:10 ~ 10:1；Composite oxides Ni in bulk phase catalystxWyOzWith oxide M oO3Gross weight content be 40% ~ 100%.Bulk phase catalyst can contain one or more in the components such as aluminium oxide, silicon oxide, amorphous silica-alumina, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve as required, these components weight content in the catalyst is 0 ~ 60%, preferably 20% ~ 50%.The specific surface area of bulk phase catalyst is 120 ~ 400m2/ g, pore volume is 0.10 ~ 0.50mL/g.Body phase hydrogenation catalyst can select the commercial catalysts that Fushun Petrochemical Research Institute develops, or is 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 impurity content of charging be taken off relatively low, the hydrocracking catalyst of resistance to nitrogen need not be used, the business hydrocracking catalyst that can use is except selecting the business Catalyst For Single-stage Hydrocracking with resistance to organic nitrogen function, ZHC-01, ZHC-02, ZHC-04, FC-14, the FC-28 developed such as Fushun Petrochemical Research Institute, the ICR126 etc. that FC-34, CHEVRON company develops；Can also use DHC-32, DHC-39, HC-43, HC-115 catalyst etc. such as Uop Inc., Fushun Petrochemical Research Institute develop 3971,3974,3976, FC-12, FC-16, FC-26 etc..
The present invention uses hydroisomerizing dewaxing technique to produce high-quality lube base oil.Hydroisomerizing dewaxing catalyst in described isomerization dewaxing reaction zone can select lube oil hydrogenation heterogeneous catalyst commonly used in the art, as can be with commodity in use hydroisomerization catalyst, it is also possible to prepares suitable catalyst by this area general knowledge.Hydroisomerization catalyst carrier is generally NU-10 molecular sieve or the ZSM-22 molecular sieve etc. of aluminium oxide and TON structure, and molecular sieve content in the catalyst is 30wt% ~ 80wt%, preferably 40wt% ~ 70wt%, also can add partial oxidation silicon in carrier；Active metal component is one or more in Pt, Pd, Ru, Rh and Ni, and content in the catalyst is 0.1wt% ~ 30.0wt%.The adjuvant component that can select is one or more in boron, fluorine, chlorine and phosphorus, and content in the catalyst is 0.1wt% ~ 5.0wt%；The specific surface of hydroisomerization catalyst is 150 ~ 500m2/ g, pore volume is 0.15 ~ 0.60mL/g.Need before using catalyst is carried out reduction treatment, so that hydrogenation active metals is in reduction-state in course of reaction.
The process conditions of described hydroisomerizing dewaxing 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 ~ 1.8h-1, preferably 0.8 ~ 1.5h-1；Hydrogen to oil volume ratio 100:1 ~ 1500:1, preferably 300:1 ~ 800:1.
Post-refining section uses the conventional hydro catalyst for refining of this area, can be with right and wrong noble metal type catalyst, it is also possible to be noble metal type catalyst, and post-refining catalyst carrier is generally the porous refractory oxide such as aluminium oxide or silicon-containing alumina.Noble metal post-refining catalyst need to use after carrying out reduction, and base metal type catalyst can use after carrying out reduction, it is also possible to use after sulfuration, the post-refining catalyst of reduction-state is preferably used.If using sulphided state post-refining catalyst, need to supplement appropriate sulfur or sulfur-containing compound in the material entering post-refining reaction zone, to keep catalyst activity.
The process conditions of described post-refining section 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, preferably 300:1 ~ 800:1.
Below in conjunction with the accompanying drawings and embodiment is explained further the process of the present invention.
As shown in Figure 1: inferior feedstock oil enters first paragraph hydrofining reactor 3(first paragraph reaction zone after the recycle hydrogen of pipeline 1 with pipeline 2 mixes), hydrotreating reaction is carried out in gas and liquid flowing section A district；And Liu Duan A district reaction effluent enters C district, gas-liquid separation zone and separates, obtain gas and draw reactor through pipeline 4；Obtain liquid and enter gas-liquid counter current section B district, react with the hydrogen counter current contacting introduced through pipeline 5.Countercurrently section B district obtains gas entrance C district, gas-liquid separation zone, draws reactor through pipeline 4；Countercurrently section B district obtains liquid and generates oil through pipeline 6, and after mix with the hydrogen of pipeline 7, entrance second segment hydrofining reactor 8(second segment reaction zone) carry out Deep Hydrotreating reaction.Second segment reaction effluent through pipeline 9 and with after the supplementary hydrogen of pipeline 10 mixes enter the 3rd section of reaction zone of hydrocracking reactor 11(), carry out hydrocracking reaction.Hydrocracking reaction effluent enters the first piece-rate system 13 through pipeline 12 to carry out separating (the first piece-rate system generally includes high-pressure separator, low pressure separator and fractionating column), obtain gas, Petroleum, boat coal and diesel oil, respectively through pipeline 14,15,16 and 17 separating device, obtain tail oil after pipeline 18 mixes with the new hydrogen of pipeline 19, enter isomerization dewaxing reactor 20 and carry out hydroisomerizing reaction, isomerization reaction effluent enters post-refining reactor 22 through pipeline 21, carries out post-refining reaction.Post-refining reaction effluent enters second piece-rate system 24(the second piece-rate system through pipeline 23 and generally includes high-pressure separator, low pressure separator and fractionating column), obtaining gas (including lighter hydrocarbons) to leave through pipeline 25, different oils base oil fractions is left through pipeline 26,27,28 and pipeline 29 respectively.
Isomerization dewaxing raw material can also mix the raw material of the satisfactory quality in other source.New hydrogen needed for response system can fully enter hydroisomerizing reaction zone, it is also possible to requiring only to need the new hydrogen of part according to reaction condition, remainder can enter post-refining reaction zone or hydrocracking reaction district.
Below by specific embodiment, the present invention program and effect are described.Hydrocracking catalyst used is the commercial catalyst of Fushun Petrochemical Research Institute's development and production, and raw materials used oil properties is listed in table 1.The character of used Hydrobon catalyst is listed in table 2.In the present invention, wt% is weight percentage or weight content.
Embodiment 1
Using the technological process shown in Fig. 1, three-zone hydrocracking is that one way passes through flow process, and hydrocracking tail oil all carries out isomerization dewaxing reaction.Loading catalyst A in first paragraph, second segment loading catalyst A.Top, first paragraph reaction zone uses gas and liquid flowing reaction, and bottom uses gas-liquid counter current reaction, and the Catalyst packing volume ratio of the section of stream and adverse current section is 1:1.
Embodiment 2
Using the technological process shown in Fig. 1, first paragraph and second segment equal loading catalyst B, other are with embodiment 1.
Embodiment 3
Using the technological process shown in Fig. 1, loading catalyst A in first paragraph, second segment loading catalyst B, other are with embodiment 1.
Comparative example 1
Hydrocracking unit includes a refining stage and a cracking zone, uses two-stage reforming technique.Refining stage uses catalyst A, and cracking zone uses FC-50 catalyst, and isomerization dewaxing and post-refining section are with embodiment 1.
Comparative example 2
Hydrocracking unit includes a refining stage and a cracking zone, uses two-stage reforming technique, and refining stage uses catalyst B, and cracking zone uses FC-50 catalyst, and isomerization dewaxing and post-refining section are with embodiment 2.
Comparative example 3
Technique basic procedure, with embodiment 1, includes that two refining reaction sections, first paragraph and second segment reaction zone all use and flow technological process equally, including counter-current process, carries out gas-liquid separation between first paragraph and second segment.3rd section be hydrocracked as one way by flow process, hydrocracking tail oil all carries out isomerization dewaxing reaction.
The result of the test that embodiment 1-3 operates 500 hours and 6000 hours is listed in table 3 and table 4 respectively.The result of the test that comparative example 1-3 operates 500 hours is listed in table 5.
Table 1 raw oil.
| Density (20 DEG C)/kg m-3 | 947.3 |
| Boiling range/DEG C | 275~548 |
| Sulfur content/wt% | 3.00 |
| Nitrogen content/μ g g-1 | 4453 |
| Condensation point/DEG C | 34 |
| BMCI value | 65.4 |
Table 2 Hydrobon catalyst.
| Numbering | A | B |
| Carrier | Aluminium oxide | Aluminium oxide |
| MoO3, 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, v% | 85 | 61 |
Table 3 result of the test (500 hours).
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Hydrocracking unit process conditions | |||
| Catalyst | (A/A)/A/FC-50* | (B/B)/B/FC-50* | (A/A)/B/FC-50* |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Reaction temperature/DEG C | (368/368)/373/386 | (365/365)/370/386 | (368/368)/370/386 |
| Volume space velocity/h-1 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 |
| Hydrogen to oil volume ratio | (900/900)/900/1300 | (900/900)/900/1300 | (900/900)/900/1300 |
| First paragraph denitrification percent, wt% | 82 | 82 | 82 |
| Cracking zone > 370 DEG C of conversion per pass, wt% | 71.7 | 71.9 | 72.1 |
| > 370 DEG C of tail oil viscosity index (VI)s | 144 | 144 | 143 |
| Hydroisomerizing dewaxing/post-refining process condition | |||
| Isomerization dewaxing/post-refining catalyst | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 |
| Reaction temperature/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 lube cut character | |||
| Yield**, wt% | 67.81 | 68.02 | 67.86 |
| Pour point/DEG C | -24 | -24 | -24 |
| Viscosity (40 DEG C), mm/s2 | 30.34 | 30.41 | 30.28 |
| Viscosity (100 DEG C), mm/s2 | 5.561 | 5.567 | 5.570 |
| Viscosity index (VI) | 123 | 123 | 124 |
* the catalyst used it is respectively in first paragraph, second segment and the 3rd section；* is in terms of 100% by isomerization dewaxing inlet amount.
Table 4 result of the test (6000 hours).
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Process conditions | |||
| Catalyst | (A/A)/A/FC-50* | (B/B)/B/FC-50* | (A/A)/B/FC-50* |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Reaction temperature/DEG C | (374/374)/378/389 | (377/377)/376/389 | (374/374)/376/389 |
| Volume space velocity/h-1 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 | (2.4/2.4)/1.2/1.8 |
| Hydrogen to oil volume ratio | (900/900)/900/1300 | (900/900)/900/1300 | (900/900)/900/1300 |
| First paragraph denitrification percent, wt% | 82 | 82 | 82 |
| Cracking zone > 370 DEG C of conversion per pass, wt% | 71.7 | 71.9 | 72.1 |
| > 370 DEG C of tail oil viscosity index (VI)s | 144 | 144 | 143 |
| Hydroisomerizing dewaxing/post-refining process condition | |||
| Isomerization dewaxing/post-refining catalyst | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 |
| Reaction temperature/DEG C | 334/253 | 334/253 | 334/253 |
| 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 lube cut character | |||
| Yield**, wt% | 67.11 | 67.23 | 67.40 |
| Pour point/DEG C | -24 | -24 | -24 |
| Viscosity (40 DEG C), mm/s2 | 30.27 | 30.13 | 30.30 |
| Viscosity (100 DEG C), mm/s2 | 5.527 | 5.531 | 5.561 |
| Viscosity index (VI) | 121 | 122 | 123 |
* the catalyst used it is respectively in first paragraph, second segment and the 3rd section；# is respectively refining stage and the catalyst of cracking zone use；* is in terms of 100% by isomerization dewaxing inlet amount.
Table 5 result of the test (500 hours).
| Numbering | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| It is hydrocracked segment process condition | |||
| Catalyst | A/FC-50 | B/FC-50 | A/B/FC-50 |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Hydrogen to oil volume ratio | 900/1300 | 900/1300 | 900/900/1300 |
| Volume space velocity/h-1 | 0.6/1.8 | 0.6/1.8 | 1.2/1.2/1.8 |
| Reaction temperature/DEG C | 393/386 | 387/386 | 377/373/387 |
| First paragraph denitrification percent, wt% | — | — | 82 |
| Cracking zone > 370 DEG C of conversion per pass, wt% | ~70 | ~70 | ~70 |
| Hydroisomerizing dewaxing/post-refining process condition | |||
| Hydroisomerization catalyst/post-refining catalyst | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 |
| Reaction temperature (R3/R4)/℃ | 330/250 | 330/260 | 330/260 |
| 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 lube cut character | |||
| Yield*, wt% | 67.31 | 67.44 | 66.93 |
| Pour point/DEG C | -24 | -23 | -24 |
| Viscosity (40 DEG C), mm/s2 | 29.66 | 29.71 | 30.26 |
| Viscosity (100 DEG C), mm/s2 | 5.433 | 5.419 | 5.547 |
| Viscosity index (VI) | 120 | 119 | 123 |
* by isomerization dewaxing inlet amount be in terms of 100%.
Being shown by above embodiment, using-isomerization dewaxing the group technology that is hydrocracked of the present invention, top, first paragraph reaction zone uses gas and liquid flowing, and bottom uses gas-liquid counter current technological process, and second segment uses gas and liquid flowing technological process；First paragraph and second segment use identical or different Hydrobon catalyst simultaneously, during for processing nitrogen content higher raw material, can hydrogen sulfide in substantially reduction system and ammonia content, the hydrogen dividing potential drop of raising system, more effectively play Hydrobon catalyst and the activity of hydrocracking catalyst, produce High Quality Lube Base Oils, and Hydrocracking unit raw material sources can be enriched.
Owing to hydrofinishing and hydrocracking reaction temperature are substantially reduced, thus improve the service cycle of device, or under same service cycle, improve the working ability of device.
Claims (17)
1. inferior raw material produces a method of hydrotreating for lube base oil, including following content:
(1) inferior feedstock oil initially enters first paragraph reaction zone and carries out hydrotreating reaction, and first paragraph reaction zone uses Hydrobon catalyst；The top of first paragraph reaction zone is gas and liquid flowing reaction zone, and the gas-liquid separation zone flowing reaction effluent entrance middle separates, and gas draws reactor；Liquid enters the beds of bottom, and the hydrogen introduced with reactor bottom carries out counter current contacting reaction, and reacted gas leaves reactor from gas-liquid separation zone；The denitrification percent controlling first paragraph reaction zone is 60wt% ~ 95wt%；
(2) the generation oil that step (1) obtains enters second segment reaction zone after mixing with hydrogen, carries out Deep Hydrotreating reaction, and second segment reaction zone uses Hydrobon catalyst；
(3) effluent that in step (2), second segment reaction zone obtains, enters the 3rd section of reaction zone together with hydrogen make-up, is filled with hydrocracking catalyst in the 3rd section of reaction zone；
(4) the 3rd sections of reaction effluents that reaction zone obtains enter separators, obtain gas and liquid, and liquid is fractionated into obtaining one or more and tail oil of gasoline, kerosene and diesel oil；
(5) step (4) obtains entrance isomerization dewaxing reaction zone after tail oil at least some of mix with hydrogen, carries out isomerization dewaxing reaction, and isomerization dewaxing reaction effluent entrance post-refining section carries out post-refining reaction, with further imurity-removal；
(6) product that step (5) obtains obtains lube base oil product through gas-liquid separation, product liquid through distillation；
Wherein, the Hydrobon catalyst that first paragraph reaction zone uses has the property that the average pore diameter of catalyst is 7.5 ~ 9.5nm, and aperture is that to account for the volume fraction of total pore volume be 70% ~ 90% for the hole of 4 ~ 10nm；The Hydrobon catalyst that second segment reaction zone uses has the property that the average pore diameter of catalyst is 4 to less than 7.5nm, and aperture is that to account for the volume fraction of total pore volume be 50% ~ 75% for the pore volume in the hole of 4 ~ 10nm；Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants little 0.5 ~ 3nm, and the hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percents of volume fraction of total pore volume.
The most in accordance with the method for claim 1, it is characterised in that the nitrogen content of described inferior feedstock oil is 1500 more than μ g/g.
The most in accordance with the method for claim 2, it is characterised in that the nitrogen content of described inferior feedstock oil is 2000 more than μ g/g.
The most in accordance with the method for claim 3, it is characterised in that the nitrogen content of described inferior feedstock oil is 2500 ~ 15000 μ g/g.
The most in accordance with the method for claim 1, it is characterised in that the tail oil of step (5) gained remainder loops back first paragraph or the reactor inlet of second segment reaction zone.
The most in accordance with the method for claim 1, it is characterised in that in step (1), the denitrification percent of first paragraph reaction zone controls as 70wt% ~ 90wt%.
The most in accordance with the method for claim 1, it is characterized in that, Hydrobon catalyst described in step (1) and step (2) includes carrier and the hydrogenation metal component being loaded on carrier, catalyst includes group VIB active metal component in terms of metal oxide weight 8% ~ 35% in the periodic table of elements, and the VIIIth race's active metal component in terms of metal oxide weight 1% ~ 7%.
The most in accordance with the method for claim 1, it is characterized in that, compared with the Hydrobon catalyst in first paragraph, the little 1.0 ~ 2.5nm of average pore diameter of second segment Hydrobon catalyst, the hole of aperture 4 ~ 10nm accounts for little 15 ~ 25 percents of volume fraction of total pore volume.
The most in accordance with the method for claim 1, it is characterised in that the average pore diameter of the Hydrobon catalyst that first paragraph reaction zone uses is 8 ~ 9nm, and it is 75% ~ 85% that the pore volume in the hole of bore dia 4 ~ 10nm accounts for the volume fraction of total pore volume.
The most in accordance with the method for claim 1, it is characterised in that the average pore diameter of Hydrobon catalyst that second segment reaction zone uses is 5 ~ 7nm, its median pore diameter is that to account for the volume fraction of total pore volume be 55% ~ 65% for the pore volume in the hole of 4 ~ 10nm.
11. in accordance with the method for claim 1, it is characterized in that, in first paragraph reaction zone described in step (1), and the process conditions flowing reaction zone are: average reaction temperature is 250 ~ 500 DEG C, reaction pressure is 5.0 ~ 20.0MPa, hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h-1；The process conditions of counter-flow 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 ~ 2000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h-1。
12. in accordance with the method for claim 1, it is characterised in that the process conditions of second segment reaction zone are: average reaction temperature is 330 ~ 480 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 0.2 ~ 4.0h-1。
13. in accordance with the method for claim 1, it is characterized in that, the process conditions of three-zone hydrocracking reaction zone are: average reaction temperature is 250 ~ 500 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 1.0 ~ 10.0h-1。
14. in accordance with the method for claim 1, it is characterised in that the process conditions of described hydroisomerizing dewaxing reaction zone are: average reaction temperature is 220 ~ 380 DEG C, and reaction pressure is 4.0 ~ 20.0MPa, and volume space velocity is 0.6 ~ 1.8h-1, hydrogen to oil volume ratio 100:1 ~ 1500:1；The process conditions of described post-refining section are: average reaction temperature is 220 ~ 380 DEG C, and reaction pressure is 4.0 ~ 12.0MPa, and volume space velocity is 0.6 ~ 6.0h-1, hydrogen to oil volume ratio 100:1 ~ 1500:1.
15. in accordance with the method for claim 1, it is characterized in that, the carrier of the hydroisomerizing dewaxing catalyst that described isomerization dewaxing reaction zone uses includes NU-10 molecular sieve or the ZSM-22 molecular sieve of aluminium oxide and TON structure, molecular sieve content in the catalyst is 30wt% ~ 80wt%, active metal component is one or more in Pt, Pd, Ru, Rh and Ni, and content in the catalyst is 0.1wt% ~ 30.0wt%.
16. in accordance with the method for claim 15, it is characterised in that containing adjuvant component in described hydroisomerizing dewaxing catalyst, adjuvant component is one or more in boron, fluorine, chlorine and phosphorus, and content in the catalyst is 0.1wt% ~ 5.0wt%.
17. in accordance with the method for claim 1, it is characterized in that, the Hydrobon catalyst used in described second segment reaction zone is body phase hydrogenation catalyst, and body phase hydrogenation catalyst contains tri-kinds of metal components of Mo, W, Ni, and in oxidized catalyst, W, Ni exist with composite oxides form: NixWyOz, z=x+3y, Mo are with oxide form existence: MoO3；Composite oxides NixWyOzThe ratio of middle x and y is 1:8 ~ 8:1, composite oxides NixWyOzWith oxide M oO3Weight ratio be 1:10 ~ 10:1；Composite oxides Ni in bulk phase catalystxWyOzWith oxide M oO3Gross weight content be 40% ~ 100%.
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| 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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| 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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