CN104611032B - A kind of high process doing raw material production lube base oil - Google Patents
A kind of high process doing raw material production lube base oil Download PDFInfo
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Abstract
The invention discloses a kind of high process doing raw material production lube base oil.Height is done raw material and is first carried out one stage hydrofining reaction, and reaction effluent separates；Liquid enters two-section refinement section and carries out advanced nitrogen and aromatic hydrocarbons saturated reaction, uses gas and liquid flowing and countercurrent flow in two-stage nitration simultaneously, and the refined oil that generates is hydrocracked；Cracking tail oil carries out prefractionation, obtains suitable tail oil fraction and carries out isomerization dewaxing and post-refining reaction, it is thus achieved that lubricant base oil fraction.The difficult imurity-removal that height can be done in raw material under the conditions of relatively relaxing by the inventive method processes so that it is meets and is hydrocracked feed needs, thus has widened the raw material sources of lube base oil；Simultaneously because hydrofinishing temperature is substantially reduced, can improve the service cycle of device, process raw material more inferior or under same service cycle, improve the working ability of device.
Description
Technical field
The invention discloses the production technology of a kind of lube base oil, a kind of employing is hydrocracked the-high process doing raw material production lube base oil of isomerization dewaxing group technology processing.
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.World's crude resources is day by day exhausted simultaneously, and international oil price is hovered in a high position always.China in 2011 imported crude oil 2.54 hundred million tons altogether, crude oil import dependency degree has reached 56.5%, and the health of serious threat to national economy, fast development make full use of crude resources and have become as the vital task of oil refining industry.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.In order to improve crude oil utilization rate, improving the productivity of high value added product, enterprise of each great oil refining uses deep drawing technology one after another, and decompressed wax oil is done and reached more than 590 DEG C, even up to 620 DEG C, and hydrocracking technology can meet this demand well.
The raw oil that tradition hydrocracking process is processed does generally less than 530 DEG C.After decompression distillation uses deep drawing technology, doing of Hydrocracking Raw Oil significantly improves so that nitrogen content, sulfur content, asphalitine, carbon residue and trace metal impurities content substantially increase.Except because viscosity increases the speed causing raw oil to spread to catalytic inner and slows down, thus reduce outside response speed, also bring the impurity such as non-hydrocarbon compound more, that structure is increasingly complex and polycyclic aromatic hydrocarbon, colloid, asphalitine, heavy metal, considerably increase hydrogenation difficulty.
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.
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, the product quality of Hydrocracking unit does not improve, and hydrocracking tail oil is mixed fraction enters isomerization dewaxing device, when being used for producing III class oil, if heavy distillat reaches lube base oil pour point requirement, light fraction dewaxing is serious, causes a large amount of yield losses and mass loss.
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 three-zone hydrocracking technique, processing height to do raw material, produces high-quality industrial chemicals, cleaning automotive fuel and High Quality Lube Base Oils.
A kind of high process doing raw material production lube base oil of the present invention, including herein below:
(1) under Hydrofinishing conditions, height does raw material and hydrogen is mixed into first paragraph reaction zone, and first paragraph reaction zone uses Hydrobon catalyst, and the denitrification percent general control of first paragraph reaction zone is 60wt%～95wt%；
(2) first paragraph reaction zone effluent enters piece-rate system, obtains gas phase and liquid phase, and the gas phase after gas-liquid separation uses through removing impurities matter Posterior circle；
(3) second segment reaction zone is entered with hydrogen after liquid phase after gas-liquid separation mixes in step (2), second segment reaction zone uses Hydrobon catalyst, the top of second segment reaction zone is gas and liquid flowing reaction zone, and flow reaction effluent enter gas-liquid separation zone separate, gas draw reactor；Liquid enters the beds of bottom, second segment reaction zone, and the hydrogen introduced with reactor bottom carries out counter current contacting reaction, and reacted gas leaves reactor from gas-liquid separation zone；
(4) entering the 3rd section of reaction zone with hydrogen after the hydrofined oil that step (3) obtains mixes, the 3rd section of reaction zone uses hydrocracking catalyst；
(5) the 3rd sections of reaction zones obtain reaction effluent and enter piece-rate system, one or more and tail oil of isolated gasoline, kerosene and diesel oil；
(6) step (5) obtains at least some of tail oil prefractionator that enters of tail oil and carries out fractional distillation, obtains lighter hydrocarbons and two or more tail oil fraction；
(7) at least one in the two or more tail oil fraction of step (6) gained, can enter isomerization dewaxing reaction zone, carries out isomerization dewaxing reaction together with optional external isomerization dewaxing raw material after mixing with new hydrogen；Isomerization dewaxing reaction effluent enters post-refining conversion zone and carries out post-refining reaction, with further imurity-removal；The tail oil of step (6) remainder can loop back first paragraph or the reactor inlet of second segment reaction zone；
(8) product that step (7) obtains carries out gas-liquid separation, and gas can be mixed into hydrocracking reaction district as supplementary hydrogen and hydrocracking raw material, and product liquid obtains the lube base oil product of different size through distillation.
According to the method for hydrotreating of the present invention, wherein in step (2), preferably the liquid phase after gas-liquid separation is first washed with water, to reduce the ammonia (NH in first paragraph hydrofinishing generation oil3) content, the liquid phase after washing enters second segment reaction zone with hydrogen again.Water washing operations described herein is the routine operation of those skilled in the art.
Wherein in the second segment reaction zone of step (3), 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 raw material and first paragraph.
In the process of the present invention, described height is done the end point of distillation of raw material (or doing) and is generally more than 550 DEG C, preferably more than 570 DEG C, most preferably 580～620 DEG C.Described height is done the nitrogen content of raw material and is usually 500 more than μ g/g, typically at 1000 more than μ g/g.
In the inventive method, the denitrification percent general control of first paragraph reaction zone is 60wt%～95wt%, is preferably controlled to 70wt%～90wt%.The process conditions of first paragraph reaction zone are generally: reaction temperature is 330～480, 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 8.0～17.0MPa, 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, in the second segment reaction zone described in step (3), and flow the process conditions of reaction zone generally: 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 second segment reaction zone, the process conditions of counter-flow reaction zone are: 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 three-zone hydrocracking reaction zone are generally: 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 can arrange 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 process of the present invention, step (5) obtains at least some of tail oil prefractionator that enters of tail oil and carries out fractional distillation, obtains lighter hydrocarbons (predominantly fixed gas) and two or more tail oil fraction.In described tail oil prefractionator, cut point and the tail oil fraction number of tail oil fraction specifically determine according to the Property requirements of purpose product lube base oil.The cutting of tail oil fraction can use routine operation well known to those skilled in the art.
In the inventive method, after first paragraph reaction zone reaction effluent carries out gas-liquid separation, gas phase can use through removing hydrogen sulfide and ammonia Posterior circle, and liquid phase enters second segment reaction zone after washing hydrogen sulfide and ammonia off preferably through washing.First carrying out and flow hydrogenation reaction in second segment reaction zone, reaction effluent carries out gas-liquid separation, and liquid carries out countercurrent hydrogenation reaction with hydrogen again.
In the inventive method, the reaction condition of described hydroisomerizing dewaxing reaction zone is: reaction temperature is 220 DEG C～380 DEG C, preferably 280 DEG C～350 DEG C；Reaction pressure is 4.0MPa～20.0MPa, preferably 6.0～17.0MPa；Volume space velocity is 0.6h-1～1.8h-1, preferably 0.8h-1～1.5h-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 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 material entering post-refining reaction zone, to keep catalyst activity.
The reaction condition of described post-refining section is: reaction temperature is 220 DEG C～380 DEG C, preferably 280 DEG C～350 DEG C, and reaction pressure is 4.0MPa～20.0MPa, preferably 6.0～17.0MPa, and volume space velocity is 0.6h-1～6.0h-1, preferably 0.8h-1～3.0h-1, hydrogen to oil volume ratio 100:1～1500:1, preferably 300:1～800:1.
In the inventive method, after using deep vacuum distillation technology, the doing of wax oil raw oil that decompression distillation obtains significantly improves so that nitrogen content, sulfur content, asphalitine, carbon residue and trace metal impurities content substantially increase.Except because viscosity increases the speed causing raw oil to spread to catalytic inner and slows down, thus reduce outside response speed, also bring the impurity such as non-hydrocarbon compound more, that structure is increasingly complex and polycyclic aromatic hydrocarbon, colloid, asphalitine, heavy metal, considerably increase hydrogenation difficulty.
Hydrocracking catalyst can select suitable product according to the Spreading requirements of product, such as oil type hydrocracking catalyst in then selecting for fecund intermediate oil (kerosene and diesel oil), as then selected mobile type hydrocracking catalyst for voluminous Petroleum and 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, the reaction such as mainly occur the hydrodesulfurization of raw material, denitrogenation, deoxidation, aromatic hydrocarbons saturated of first paragraph reaction zone；The reaction such as proceed to occur hydrodesulfurization, denitrogenation, deoxidation, aromatic hydrocarbons saturated on the Hydrobon catalyst of second segment reaction zone, carries out hydrocracking reaction on the hydrocracking catalyst of the 3rd section.
Compared with prior art, the method have the advantages that:
1, those skilled in the art know, raw material is done for the height that deep drawing wax oil is representative, although its nitrogen content may not be certain the highest, but owing to the structure of nitrogen-containing compound is extremely complex, the nitrogen in high boiling fraction is difficult to be removed by conventional hydro method.In the inventive method, first pass through first paragraph hydrofinishing, remove most nitrogen impurity；Then in second segment reaction zone, under the atmosphere of low ammonia, the wax oil being stripped of most of the nitrogen impurity is carried out further hydrofinishing, lower ammonia dividing potential drop greatly slow down ammonia for the saturated inhibitory action of advanced nitrogen and aromatic hydrocarbons, it is thus possible under conditions of comparing mitigation, the nitrogen impurity that this part is obstinate is removed, thus is hydrocracked, for downstream, the raw material providing qualified.
2, in second segment reaction zone, in the beds on top, the generation oil that one section obtains carries out deep hydrofinishing reaction with hydrogen, and effluent separates in gas-liquid separation zone；Liquid then carries out hydrogenation reaction by counter current contacting with hydrogen in lower catalyst bed layer again, and the ammonia that course of reaction generates leaves reactor through gas-liquid separation zone.Take gas and liquid flowing and gas-liquid countercurrent flow simultaneously, further provide a kind of be especially suitable for advanced nitrogen add hydrogen atmosphere.And ammonia is reduced to minimum to the inhibitory action of Hydrobon catalyst, more can give full play to the activity of Hydrobon catalyst such that it is able under conditions of relaxing, carry out advanced nitrogen.
3, the present invention does height according to raw oil, the feature of nitride difficulty removing, 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 concentrates, impurity content is low, the effect of carrier and metal is strong, can more effectively reduce the ammonia inhibitory action to catalyst, and height especially inferior to processing is done raw material and 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.Hydrobon catalyst 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, the service cycle of extension fixture the most effectively while realizing advanced nitrogen.
4, first paragraph reaction effluent liquid phase preferably first passes through after hydrogen sulfide and ammonia are washed in washing off and enters back into second segment hydrofining reactor, more can reduce the ammonia content in second segment reactor further, more effectively play the advanced nitrogen activity of second segment Hydrobon catalyst.
5, the hydrocracking tail oil part of the 3rd section loops back the hydrofining reactor of first paragraph or second segment, carries out deep refining, and on the one hand can reduce height does the viscosity of raw material, is greatly improved raw oil diffusion velocity on a catalyst, improves reaction efficiency.
6, it is substantially reduced due to hydrofining reaction temperature, such that it is able to improve the service cycle of device, processes raw material more inferior or under same service cycle, improve the working ability of device.
7, hydrocracking tail oil enters prefractionator and carries out fractional distillation, the yield of purpose product isomerization dewaxing raw material can be substantially increased, it is to avoid when Hydrocracking unit light fraction is qualified heavy distillat pour point is not enough and light fraction yield losses and the generation of mass loss time heavy distillat is qualified.
Accompanying drawing explanation
Fig. 1 is a kind of principle process chart of the present invention.
Detailed description of the invention
The technological process of the present invention is: uses and is hydrocracked-isomerization dewaxing group technology, Hydrocracking unit uses three segment process flow processs, under suitable hydroconversion condition, height is done raw oil and is contacted with first paragraph catalyst with hydrogen, reaction effluent enters piece-rate system, isolated liquid feeds as second segment, and second segment charging contacts with second segment catalyst with hydrogen, and refined generation oil enters the 3rd section of reaction zone with hydrogen and carries out hydrocracking reaction；Reaction effluent enters piece-rate system.First paragraph and three-zone hydrocracking are respectively adopted different piece-rate systems.After hydrocracking tail oil cutting, appropriate fractions is mixed into isomerization dewaxing unit with the new hydrogen of new hydrogen, and other fraction and the tail oil that can't meet the quality requirement loop back Hydrocracking unit.
It can be one or more in the fractions such as the deasphalted oil of crude oil, shale oil, coal artificial oil, crude oil deep vacuum distillation distillate that height used by the present invention does raw oil, the heavy distillate that preferably crude oil deep vacuum distillation obtains.
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 is typically made up of carrier and the hydrogenation metal component being loaded on carrier, generally includes group VIB active metal component in the periodic table of elements, such as tungsten and/or molybdenum in terms of metal oxide weight 8% ~ 35%, and preferably 12% ~ 30%；And the VIIIth race's active metal component, such as nickel and/or cobalt in terms of metal oxide weight 1% ~ 7%, preferably 1.5% ~ 6%.The carrier of Hydrobon catalyst is inorganic refractory oxide, such as aluminium oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc..In the inventive method, special recommendation uses the catalyst with following pore structure character 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 is removed to relatively low level by 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.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 such 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 inventive method uses hydroisomerizing dewaxing technique to produce high-quality lube base oil.Described hydroisomerizing dewaxing catalyst can select lube oil hydrogenation heterogeneous catalyst commonly used in the art, such as commodity in use hydroisomerization catalyst, it is also possible to prepares suitable catalyst by this area general knowledge.Hydroisomerization catalyst carrier generally comprises 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%.Selectable adjuvant component 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.Before using, catalyst is carried out reduction treatment, make hydrogenation active metals be in reduction-state in course of reaction.
Post-refining unit 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 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 material entering post-refining reaction zone, to keep catalyst activity.
The present invention is explained further below in conjunction with drawings and Examples.
As shown in Figure 1: the raw oil of pipeline 1 enters first paragraph hydrofining reactor R1, removing major part impurity with the recycle hydrogen of pipeline 2 after mixing；Reaction effluent enters separator 4 along pipeline 3 and separates；Isolated gas goes out device through pipeline 5, first paragraph reaction zone generates oil and mixes with the hydrogen through pipeline 7 through pipeline 6, the A district entering second segment hydrofining reactor R2 removes the impurity such as S, N, O further, the A district of reactor R2 is gas and liquid flowing flow process, and flow reaction effluent enter gas-liquid separation zone C separate, gas enters after water scrubber 10 washes hydrogen sulfide and ammonia off through pipeline 9 and enters recycle hydrogen system through pipeline 11；The new hydrogen that C district obtains introducing through pipeline 8 bottom liquid phase and B district proceeds deep hydrofinishing in B district and reacts, and B district is gas-liquid counter current technique；R2 leaves from pipeline 9 after obtaining the gas mixing that gas separates with A district in B district, B district obtains liquid phase through pipeline 12, with mix after the replenishment cycles hydrogen of pipeline 13 after enter hydrocracking reactor R3 carry out hydrocracking reaction, second segment reaction zone effluent enters piece-rate system 15 through pipeline 14 and separates, being separated into gas 16, Petroleum 17, kerosene 18, diesel oil 19 and tail oil 20, piece-rate system 15 generally includes high-pressure separator, low pressure separator and fractionating column.At least partly tail oil 20 enters tail oil prefractionator 22 along pipeline 21 and isolates lighter hydrocarbons (fixed gas) 23, light tail oil fraction 24, purpose fraction 25 and heavy-tailed oil distillate 26(as a example by being cut into three kinds of tail oil fraction), light fraction 24, heavy distillat 26 and part tail oil 20 mix entrance first paragraph hydrofining reactor R1 after tailing edge pipeline 27 mixes with pipeline 1 raw oil and carry out hydrofining reaction.The purpose tail oil fraction 25 of prefractionator 22 isolated enters hydroisomerizing dewaxing unit pour point depression reaction zone R4 after mixing with new hydrogen 28 and carries out pour point depression reaction, pour point depression product is mixed into post-refining reactor R5 with new hydrogen 30 without isolation along pipeline 29, the gas 32 that product is fractionated into obtaining after system 31 separates returns to hydrocracking reaction district, and the supplementary hydrogen as process uses.The product liquid of hydroisomerizing dewaxing is fractionated into the lube base oil product of available different viscosities, respectively through pipeline 33,34 and 35 separating device.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.Wherein fractionating system 31 generally also includes high-pressure separator, low pressure separator and fractionating column.
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 embodiment, the present invention program and effect are described.Used catalyst 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 uses one way to pass through flow process；Hydrocracking tail oil all carries out isomerization dewaxing reaction.Loading catalyst A in first paragraph, second segment loading catalyst B.Second segment finishing reactor top uses gas and liquid flowing flow process, and bottom uses gas-liquid counter current flow process, and the Catalyst packing volume ratio of the section of stream and adverse current section is 1:1.
In the operation of hydrocracking tail oil prefractionator, tail oil fractional distillation obtains lightweight tail oil, middle tail oil and heavy tail oil, and cutting temperature is respectively 400 DEG C and 450 DEG C, and heavy tail oil all carries out isomerization dewaxing reaction.
Embodiment 2
First paragraph and second segment equal loading catalyst B, other are with embodiment 1.
Comparative example 1
Technique basic procedure with embodiment 1, in second segment reaction zone only with and flow technological process, including counter-current process.3rd section be hydrocracked as one way by flow process, hydrocracking tail oil fractional distillation obtains lightweight tail oil, middle tail oil and heavy tail oil, and cutting temperature is respectively 400 DEG C and 450 DEG C, and heavy tail oil all carries out isomerization dewaxing reaction.
Comparative example 2
Use conventional two-stage reforming flow process, hydrofining reaction only includes one section of reaction zone, and including second segment reaction zone, the effluent of one section of reaction zone carries out gas-liquid separation, the liquid that gas-liquid separation obtains generates oil and is hydrocracked, and is hydrocracked employing one way and passes through flow process.The cutting temperature of hydrocracking tail oil is with embodiment 1, and heavy tail oil fraction all carries out isomerization dewaxing reaction.
The result of the test that embodiment 1-2 and comparative example 1-2 operate 500 hours is listed in table 3, embodiment 1-2 and the comparative example 1-2 operating result of the test of 6000 hours and is listed in table and within 5(6000 hour, only gives hydrofinishing data).
Table 1 raw oil
| Density (20 DEG C)/kg m-3 | 929.3 |
| Boiling range scope/DEG C | 367～600 |
| Sulfur content, wt% | 2.99 |
| Nitrogen content/μ g g-1 | 1073 |
| Condensation point/DEG C | 28 |
| BMCI value | 50.7 |
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 | 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 (for the operating result of 500 hours)
| Embodiment | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Process conditions | ||||
| Catalyst | A/(B/B)/FC-46* | B/(B/B)/FC-46* | B/B/FC-46* | B/FC-46# |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 | 15.7 |
| Reaction temperature/DEG C | 375/(375/375)/380 | 372/(375/375)/380 | 372/381/381 | 391/382 |
| Volume space velocity/h-1 | 1.2/(2.4/2.4)/1.8 | 1.2/(2.4/2.4)/1.8 | 1.2/1.2/1.8 | 0.6/1.8 |
| Hydrogen to oil volume ratio | 900/(900/900)/1300 | 900/(900/900)/1300 | 900/900/1300 | 900/1300 |
| First paragraph denitrification percent, wt% | 82 | 82 | 82 | Refined N, 10 μ g/g |
| Cracking zone > 370 DEG C of conversion per pass, wt% | 72.1 | 72.3 | 72.0 | 71.9 |
| > 370 DEG C of tail oil viscosity index (VI)s | 144 | 142 | 141 | 137 |
| Hydroisomerizing dewaxing/post-refining process condition | ||||
| Isomerization dewaxing/post-refining catalyst | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 | 2:1 |
| Reaction temperature/DEG C | 330/250 | 330/250 | 330/260 | 320/280 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 800 | 800 |
| Cumulative volume air speed/h-1 | 1.0 | 1.0 | 1.0 | 1.0 |
| > 320 DEG C of lube cut character | ||||
| Yield (* *), wt% | 75.32 | 75.35 | 75.83 | 76.55 |
| Pour point/DEG C | -21 | -20 | -20 | -18 |
| Viscosity (40 DEG C), mm/s2 | 28.51 | 28.63 | 28.72 | 28.77 |
| Viscosity (100 DEG C), mm/s2 | 5.316 | 5.322 | 5.314 | 5.231 |
| Viscosity index (VI) | 121 | 120 | 119 | 113 |
* 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.
Embodiment 3
Main flow is as it is shown in figure 1, wherein > 370 DEG C of ends fraction are recycled to second segment hydrofining reactor entrance, and circulating load is the 25% of tail oil.The denitrification percent controlling first paragraph reaction zone is 75wt%.Result of the test is listed in table 3.
Embodiment 4
Main flow is as it is shown in figure 1, wherein > 370 DEG C of ends fraction are recycled to second segment hydrofining reactor entrance, and circulating load is the 25% of tail oil.The denitrification percent controlling first paragraph reaction zone is 87wt%.Result of the test is listed in table 3.
Comparative example 3
Use two-stage reforming flow process of the prior art, hydrofining reaction only includes one section of reaction zone, including second segment reaction zone, the effluent of one section of reaction zone carries out gas-liquid separation, the liquid that gas-liquid separation obtains generates oil and is hydrocracked, > 370 DEG C of hydrocracking tail oil parts loop back hydrofining reactor entrance, tail oil circulating load is 25%, and residue tail oil carries out isomerization dewaxing reaction.
The result of the test of embodiment 3-4 and comparative example 3 is listed in table 4.
Table 4 result of the test
| Numbering | Embodiment 3 | Embodiment 4 | Comparative example 3 |
| It is hydrocracked segment process condition | |||
| Catalyst | A/(B/B)/FC-50* | A/(B/B)/FC-50* | B/FC-50# |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Hydrogen to oil volume ratio | 900/(900/900)/1300 | 900/(900/900)/1300 | 900/1300 |
| Volume space velocity/h-1 | 1.2/(2.4/2.4)/1.8 | 1.2/(2.4/2.4)/1.8 | 0.6/1.8 |
| Reaction temperature/DEG C | 368/(380/380)/383 | 376/(372/372)/383 | 390/386 |
| First paragraph denitrification percent, wt% | 75 | 87 | — |
| Cracking zone > 370 DEG C of conversion per pass, wt% | 60 | 60 | 60 |
| Cracking zone > 370 DEG C of total conversions, wt% | 70.0 | 70.0 | 70.0 |
| 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 | 3:1 |
| Reaction temperature/DEG C | 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% | 75.41 | 75.73 | 74.68 |
| Pour point/DEG C | -20 | -20 | -18 |
| Viscosity (40 DEG C), mm/s2 | 27.93 | 27.62 | 28.13 |
| Viscosity (100 DEG C), mm/s2 | 5.269 | 5.207 | 5.136 |
| Viscosity index (VI) | 122 | 121 | 112 |
* the catalyst used it is respectively in first paragraph, second segment and the 3rd section；# is respectively in refining stage and cracking zone the catalyst used.* is in terms of 100% by isomerization dewaxing inlet amount.
Table 5 result of the test (operates 6000 hours)
| Embodiment | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Hydrofining technology condition | ||||
| Catalyst | A/B/FC-32* | B/B/FC-32* | B/B/FC-32* | B/FC-32# |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 | 15.7 |
| Reaction temperature/DEG C | 379/(378/378)/383 | 382/(378/378)/383 | 382/384/383 | 411/385 |
| Volume space velocity/h-1 | 1.2/(2.4/2.4)/1.8 | 1.2/(2.4/2.4)/1.8 | 1.2/1.2/1.8 | 0.6/1.8 |
| Hydrogen to oil volume ratio | 900/(900/900)/1300 | 900/(900/900)/1300 | 900/900/1300 | 900/1300 |
| First paragraph denitrification percent, wt% | 82 | 82 | 82 | Refined N, 10 μ g/g |
* it is first paragraph, second segment and the catalyst of the 3rd section of use；# is the catalyst that respectively refining stage uses with cracking zone；* is on the basis of isomerization dewaxing inlet amount.
Shown by above embodiment, use the process of the present invention, first paragraph reactor uses Hydrobon catalyst, second segment reactor uses Hydrobon catalyst, second segment hydrofinishing top uses gas and liquid flowing flow process, bottom uses gas-liquid counter current flow process, when processing height and doing raw material such as deep drawing wax oil, can more effectively play the activity of Hydrobon catalyst and hydrocracking catalyst.
Owing to hydrofinishing and hydrocracking reaction temperature are substantially reduced, such that it is able to improve the service cycle of device, or under same service cycle, improve the working ability of device.
Claims (18)
1. the high process doing raw material production lube base oil, including herein below:
(1) under Hydrofinishing conditions, height does raw material and hydrogen is mixed into first paragraph reaction zone, and first paragraph reaction zone uses Hydrobon catalyst, and the denitrification percent of first paragraph reaction zone controls as 60wt%～95wt%；
(2) first paragraph reaction zone effluent enters piece-rate system, obtains gas phase and liquid phase；
(3) second segment reaction zone is entered with hydrogen after liquid phase after gas-liquid separation mixes in step (2), second segment reaction zone uses Hydrobon catalyst, the top of second segment reaction zone is gas and liquid flowing reaction zone, and flow reaction effluent enter gas-liquid separation zone separate, gas draw reactor；Liquid enters the beds of bottom, second segment reaction zone, and the hydrogen introduced with reactor bottom carries out counter current contacting reaction, and reacted gas leaves reactor from gas-liquid separation zone；
(4) entering the 3rd section of reaction zone with hydrogen after the hydrofined oil that step (3) obtains mixes, the 3rd section of reaction zone uses hydrocracking catalyst；
(5) the 3rd sections of reaction zones obtain reaction effluent and enter piece-rate system, one or more and tail oil of isolated gasoline, kerosene and diesel oil；
(6) step (5) obtains at least some of tail oil prefractionator that enters of tail oil and carries out fractional distillation, obtains lighter hydrocarbons and two or more tail oil fraction；
(7) at least one in the two or more tail oil fraction of step (6) gained, enters isomerization dewaxing reaction zone, carries out isomerization dewaxing reaction after mixing with new hydrogen；Isomerization dewaxing reaction effluent enters post-refining conversion zone and carries out post-refining reaction, with further imurity-removal；
(8) product that step (7) obtains carries out gas-liquid separation, and product liquid obtains the lube base oil product of different size 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 used in second segment reaction zone 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 described height does the end point of distillation of raw material or to do be more than 550 DEG C.
3. according to the method described in claim 1 or 2, it is characterised in that it is more than 570 DEG C that described height does the end point of distillation of raw material.
The most in accordance with the method for claim 3, it is characterised in that it is 580～620 DEG C that described height does the end point of distillation of raw material.
The most in accordance with the method for claim 2, it is characterised in that it is 500 more than μ g/g that described height does the nitrogen content of raw material.
The most in accordance with the method for claim 1, it is characterised in that the remainder of step (5) gained tail oil 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 the denitrification percent of the first paragraph reaction zone described in step (1) 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 (3) is made up of carrier and the hydrogenation metal component being loaded on carrier, catalyst includes group VIB active metal component in terms of oxide weight 8% ~ 35% in the periodic table of elements, and the VIIIth race's active metal component in terms of 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.
11. 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, and 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.
12. in accordance with the method for claim 1, it is characterised in that the process conditions of first paragraph reaction zone are: reaction temperature is 330 ~ 480 DEG C, and reaction pressure is 5.0MPa ~ 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, in second segment reaction zone described in step (3), and the process conditions flowing reaction zone are: 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；In second segment reaction zone, the process conditions of counter-flow reaction zone are: 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。
14. in accordance with the method for claim 1, it is characterized in that, the process conditions of three-zone hydrocracking reaction zone are: 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。
15. in accordance with the method for claim 1, it is characterised in that the reaction condition of the hydroisomerizing dewaxing reaction zone described in step (7) is: reaction temperature is 220 DEG C ~ 380 DEG C, and reaction pressure is 4.0MPa ~ 20.0MPa, and volume space velocity is 0.6h-1~1.8h-1, hydrogen to oil volume ratio is 100:1 ~ 1500:1；The condition of described post-refining conversion zone is: reaction temperature is 220 DEG C ~ 380 DEG C, and hydrogen dividing potential drop is 4.0MPa ~ 20.0MPa, and volume space velocity is 0.6h-1~6.0h-1, hydrogen to oil volume ratio 100:1 ~ 1500:1.
16. in accordance with the method for claim 1, it is characterized in that, the carrier of described hydroisomerizing dewaxing catalyst 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%.
17. in accordance with the method for claim 16, 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%.
18. in accordance with the method for claim 1, it is characterized in that, the Hydrobon catalyst used in 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 |
| CN102041081A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Combined method of hydrocracking and producing lubricant oil base oil |
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| US5183556A (en) * | 1991-03-13 | 1993-02-02 | Abb Lummus Crest Inc. | Production of diesel fuel by hydrogenation of a diesel feed |
| 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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