CN104611032A - Process method for producing lubricating oil base oil through high dry point raw material - Google Patents
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Abstract
The present invention discloses a process method for producing lubricating oil base oil through a high dry point raw material. According to the process method, a high dry point raw material firstly is subjected to a first-stage hydrorefining reaction, and the reaction effluent is separated; the liquid enters a second-stage refining stage to carry out a deep denitrogenation and aromatic hydrocarbon saturation reaction, a gas-liquid co-current flow process and a gas-liquid counter flow process are concurrently adopted in the second stage, and the refining generated oil is subjected to hydrocracking; and the cracking tail oils are subjected to pre-fractionation to obtain the suitable tail oil distillate, and the suitable tail oil distillate is subjected to an isomerizing dewaxing and finishing reaction to obtain the lubricating oil base oil distillate. With the method of the present invention, the difficultly-removed impurities in the high dry point raw material can be subjected to the treatment under the relatively mild condition so as to make the high dry point raw material meet the hydrocracking feeding requirement, such that the lubricating oil base oil raw material source is broadened; and the hydrorefining temperature is substantially reduced so as to increase the operation period of the device and process the poor-quality raw material, or increase the processing capacity of the device in the same operation period.
Description
Technical field
The invention discloses a kind of production technique of lubricant base, particularly a kind of hydrocracking-isomerization dewaxing combination process that adopts processes the high processing method doing raw material production lubricant base.
Background technology
Along with China's rapid development of economy, refining of petroleum ability increases fast.Meanwhile, domestic hydrocracking technology also obtain large-scale industrial application, and by the end of the year 2011, the hydroeracking unit that China is running will have cover more than 40, and total working ability is more than 50.0Mt/a, and working ability leaps to second place of the world.World's crude resources is day by day exhausted simultaneously, and international oil price is hovered in a high position always.China in 2011 is imported crude oil 2.54 hundred million tons altogether, and crude oil import dependency degree reaches 56.5%, and serious threat, to the health of national economy, fast development, makes full use of the vital task that crude resources has become oil refining industry.In addition, due to the variation year by year of domestic crude quality, the significantly increase of imported high sulfur crude oil amount of finish, the requirement of environmental protection to oil refining process and petroleum product-quality is increasingly strict, and market is to the continuous increase of clean fuel oil and industrial chemicals demand, especially as the clean intermediate oil of transportation fuel and the high-quality charging that provides for devices such as reformation, ethene, therefore the progress of market to hydrocracking technology level is had higher requirement.The wide scope of material that hydrocracking is processed, products scheme is flexible, and liquid product yield is high, can obtain high-quality power fuel and industrial chemicals, and hydrocracking process and technology are more and more subject to the most attention of each major oil companies of the world.In order to improve crude oil utilization ratio, improve the productive rate of high value added product, enterprise of each great oil refining adopts deep drawing technology one after another, and decompressed wax oil is done and reached more than 590 DEG C, even reaches 620 DEG C, and hydrocracking technology can meet this demand well.
The stock oil that tradition hydrocracking process is processed is done and is generally less than 530 DEG C.After underpressure distillation adopts deep drawing technology, doing of Hydrocracking Raw Oil significantly improves, and nitrogen content, sulphur content, bituminous matter, carbon residue and trace metal impurities content are obviously increased.Except causing the speed that stock oil spreads to catalytic inner to slow down because viscosity increases, thus outside reduction speed of response, also bring the impurity such as more, that structure is more complicated non-hydrocarbon compound and polycyclic aromatic hydrocarbons, colloid, bituminous matter, heavy metal, considerably increase hydrogenation difficulty.
The production technique of base oil mainly comprises tradition " old three covers " lubricating oil complete processing and the hydrogenation method technique that is representative with hydrotreatment, hydrocracking, catalytic dewaxing/isomerization dewaxing.And II/III class High Quality Lube Base Oils especially III class lubricating oil base oil there is the features such as saturated hydrocarbon content is high, sulphur content is extremely low, property of viscosity versus temperature is good, be the main raw material producing top-grade lubricating oil, with traditional solvent method be difficult to produce.Producing the state-of-the-art technology of high-quality lubricant base outside Present Domestic is adopt hydrogenation method technique, and especially hydrocracking-isomerization dewaxing combination process route is comparatively ripe, has been widely used in and has produced top-grade lubricating oil base oil.Utilize hydrocracking tail oil to have the advantages such as low-sulfur, low nitrogen, low arene content, excellent heat-resistant quality and oxidation stability, lower volatility, excellent viscosity temperature characteristic and good additive response by the lubricant base that isomerization dewaxing pour point depression technology is produced, the requirement of modern top-grade lubricating oil to API II/III class base oil can be met.
US6,676,827 disclose a kind of method that isomerization dewaxing produces low solidifying lubricant base.Adopt hydrocracking-isomerization dewaxing two-stage hydrogenation operational path, hydrocracking and isomerization dewaxing all have respective hydrogen gas circulating system, and this is that current hydrogenation method produces lubricant base main processes.Owing to using two-stage process, therefore technical process is complicated, equipment is many, operating cost is high.
CN200710011927.5 discloses a kind of production method of lubricant base, the tail oil of Hydrocracking unit directly supplies tail oil isomerization dewaxing unit and does raw material, new hydrogen is once by tail oil isomerization dewaxing unit, and its tail hydrogen then directly returns to Hydrocracking unit and does hydrogen make-up.The method is only the combination of two unit, the quality product of Hydrocracking unit does not improve, and hydrocracking tail oil is that mixed fraction enters isomerization dewaxing device, be used for production III class oil time, if when last running reaches the requirement of lubricant base pour point, lighting end dewaxing is serious, causes a large amount of yield losses and mass loss.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of hydrocracking-isomerization dewaxing combination process of improvement, Hydrocracking unit adopts three-zone hydrocracking technique, processes highly to do raw material, production high-quality industrial chemicals, clean automotive fuel and High Quality Lube Base Oils.
A kind of high processing method doing raw material production lubricant base of the present invention, comprises following content:
(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 separation 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 after the liquid phase in step (2) after gas-liquid separation mixes with hydrogen, 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 and enter gas-liquid separation zone and be separated, gas draws reactor; Liquid enters the beds of bottom, second segment reaction zone, and the hydrogen introduced with reactor bottom carries out counter current contact reaction, and reacted gas leaves reactor from gas-liquid separation zone;
(4) enter the 3rd section of reaction zone after the hydrofined oil that step (3) obtains mixes with hydrogen, the 3rd section of reaction zone uses hydrocracking catalyst;
(5) the 3rd sections of reaction zones obtain reaction effluent and enter separation system, are separated one or more and tail oil that obtain gasoline, kerosene and diesel oil;
(6) the tail oil preliminary fractionator that enters at least partially that step (5) obtains tail oil carries out fractionation, obtains lighter hydrocarbons and two or more tail oil fraction;
(7) at least one in the two or more tail oil fraction of step (6) gained, together with optional external isomerization dewaxing raw material, can enter isomerization dewaxing reaction zone, carry out isomerization dewaxing reaction with new hydrogen after mixing; 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 the reactor inlet of first paragraph or second segment reaction zone;
(8) reaction product that step (7) obtains carries out gas-liquid separation, and gas hydrogen and hydrocracking raw material can be mixed into hydrocracking reaction district as a supplement, and product liquid obtains the lube base oil production of different size through distillation.
According to method of 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 hydrofining generation oil
3) 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 loading volume ratio of gas-liquid counter-flow reaction zone specifically can be determined according to the hydrodenitrification rate of the character of raw material and first paragraph.
In processing method of the present invention, described height is done the final boiling point of raw material (or doing) and is generally more than 550 DEG C, is preferably more than 570 DEG C, most preferably is 580 ~ 620 DEG C.The nitrogen content that described height does raw material is generally 500 more than μ g/g, generally at 1000 more than μ g/g.
In the inventive method, the denitrification percent general control of first paragraph reaction zone is 60wt% ~ 95wt%, preferably controls as 70wt% ~ 90wt%.The processing condition of first paragraph reaction zone are generally: temperature of reaction 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.Preferred operational condition is: temperature of reaction 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 the processing condition flowing reaction zone are generally: temperature of reaction is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 1.0 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.In second segment reaction zone, the processing condition of counter-flow reaction zone are: temperature of reaction is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 2000:1, is preferably 400:1 ~ 1000:1; During liquid, volume space velocity is 1.0 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.
In the inventive method, the processing condition of three-zone hydrocracking reaction zone are generally: temperature of reaction is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 1.0 ~ 10.0h
-1, be preferably 1.0 ~ 4.0h
-1.
In the inventive method, according to the scale of device, first paragraph reaction zone can arrange one or several reactors, and second segment reaction zone also can arrange one or several reactors, and the hydrocracking reaction district of the 3rd section generally arranges a reactor.
In processing method of the present invention, the tail oil preliminary fractionator that enters at least partially that step (5) obtains tail oil carries out fractionation, obtains lighter hydrocarbons (being mainly non-condensable gas) and two or more tail oil fraction.In described tail oil preliminary fractionator, the cut point of tail oil fraction and tail oil fraction number are specifically determined according to the Property requirements of object product lubricant base.The cutting of tail oil fraction can adopt 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 through removing hydrogen sulfide and the use of ammonia Posterior circle, and liquid phase enters second segment reaction zone after washing hydrogen sulfide and ammonia off preferably through washing.First carry out in second segment reaction zone and flow hydrogenation reaction, reaction effluent carries out gas-liquid separation, and liquid carries out countercurrent hydrogenation reaction with hydrogen again.
In the inventive method, the reaction conditions of described hydroisomerization dewax reaction zone is: temperature of reaction 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, preferred 0.8h
-1~ 1.5h
-1; Hydrogen to oil volume ratio 100:1 ~ 1500:1, preferred 300:1 ~ 800:1.
Post-refining section uses the conventional hydro catalyst for refining of this area, can be non-noble metal type catalyzer, and also can be noble metal type catalyzer, post-refining support of the catalyst be generally the porous refractory such as aluminum oxide or silicon-containing alumina material.Precious metal post-refining catalyzer uses after reduction, and base metal type catalyzer can use after reduction, also can use after sulfuration, preferably uses the post-refining catalyzer of reduction-state.If use sulphided state post-refining catalyzer, need in the material entering post-refining reaction zone, to supplement appropriate sulphur or sulfocompound, to keep catalyst activity.
The reaction conditions of described post-refining section is: temperature of reaction 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, preferred 0.8h
-1~ 3.0h
-1, hydrogen to oil volume ratio 100:1 ~ 1500:1, preferred 300:1 ~ 800:1.
In the inventive method, after adopting deep vacuum distillation technology, the doing of wax oil stock oil that underpressure distillation obtains significantly improves, and nitrogen content, sulphur content, bituminous matter, carbon residue and trace metal impurities content are obviously increased.Except causing the speed that stock oil spreads to catalytic inner to slow down because viscosity increases, thus outside reduction speed of response, also bring the impurity such as more, that structure is more complicated non-hydrocarbon compound and polycyclic aromatic hydrocarbons, colloid, bituminous matter, heavy metal, considerably increase hydrogenation difficulty.
Hydrocracking catalyst can select suitable product according to the Spreading requirements of reaction product, as oil type hydrocracking catalyst in then selecting for voluminous intermediate oil (kerosene and diesel oil), as then selected mobile type hydrocracking catalyst for voluminous petroleum naphtha and intermediate oil.Above-mentioned selection is content well-known to those skilled in the art.Hydrobon catalyst and hydrocracking catalyst are under response behaviour, and hydrogenation active component is sulphided state.
In the inventive method, mainly there is the reaction such as hydrogenating desulfurization, denitrogenation, deoxidation, aromatic saturation of raw material in first paragraph reaction zone; The Hydrobon catalyst of second segment reaction zone proceeds the reactions such as hydrogenating desulfurization, denitrogenation, deoxidation, aromatic saturation occur, the hydrocracking catalyst of the 3rd section carries out hydrocracking reaction.
Compared with prior art, method of the present invention has the following advantages:
1, those skilled in the art know, the height being representative for deep drawing wax oil does raw material, although its nitrogen content may not be certain very high, because the structure of nitrogenous compound is very complicated, the nitrogen in high boiling fraction is but difficult to be removed by conventional hydro method.In the inventive method, first by first paragraph hydrofining, remove most nitrogen impurity; Then in second segment reaction zone, under the atmosphere of low ammonia, further hydrofining is carried out to the wax oil being stripped of most of the nitrogen impurity, lower ammonia dividing potential drop greatly slow down the restraining effect of ammonia for advanced nitrogen and aromatic saturation, thus can under the condition comparing mitigation, the nitrogen impurity of this part stubbornness is removed, thus is provided qualified raw material for the hydrocracking in downstream.
2, in second segment reaction zone, in the beds on top, one section of generation oil obtained carries out deep hydrofinishing reaction with hydrogen, and effluent is separated in gas-liquid separation zone; Liquid then carries out hydrogenation reaction by counter current contact with hydrogen again in lower catalyst bed layer, and the ammonia that reaction process generates leaves reactor through gas-liquid separation zone.Take gas and liquid flowing and gas-liquid countercurrent flow, what further provide a kind of especially applicable advanced nitrogen adds hydrogen atmosphere simultaneously.And the restraining effect of ammonia to Hydrobon catalyst is reduced to minimum, more can give full play to the activity of Hydrobon catalyst, thus advanced nitrogen can be carried out under the condition relaxed.
3, the present invention does height according to stock oil, the feature that nitride difficulty removes, in first paragraph reaction zone, preferably adopt the Hydrobon catalyst being prepared carrier production by chloride process, be characterized in that duct is large and concentrated, foreign matter content is low, the effect of carrier and metal is strong, more effectively can reduce the restraining effect of ammonia to catalyzer, especially has better activity stability to processing high raw material of doing inferior; And in second segment reactor, preferably use the Hydrobon catalyst being prepared carrier production by sulphate method, be characterized in that duct is relatively little and disperse, the effect of carrier and metal is relatively weak.Hydrobon catalyst in second segment has higher activity and better activity stability for the raw material being stripped of most of the nitrogen impurity.Thus the grating of these two kinds of catalyzer can better play the activity of catalyzer, the running period of also extension fixture effectively while realizing advanced nitrogen.
4, first paragraph reaction effluent liquid phase preferably first enters second segment hydrofining reactor again after washing hydrogen sulfide and ammonia off, more can reduce the ammonia content in second segment reactor further, the advanced nitrogen more effectively playing second segment Hydrobon catalyst is active.
5, the hydrocracking tail oil component loops of the 3rd section returns the hydrofining reactor of first paragraph or second segment, carries out deep refining, can reduce the high viscosity doing raw material on the one hand, greatly improves stock oil velocity of diffusion on a catalyst, improves reaction efficiency.
6, because hydrofining reaction temperature reduces greatly, thus the running period of device can be improved, process raw material more inferior or under same running period, improve the working ability of device.
7, hydrocracking tail oil enters preliminary fractionator and carries out fractionation, the yield of object product isomerization dewaxing raw material can be substantially increased, avoid Hydrocracking unit lighting end qualified time last running pour point not enough and last running is qualified time lighting end yield losses and the generation of mass loss.
Accompanying drawing explanation
Fig. 1 is a kind of principle process flow sheet of the present invention.
Embodiment
Technical process of the present invention is: adopt hydrocracking-isomerization dewaxing combination process, Hydrocracking unit adopts three segment process flow processs, under suitable hydroconversion condition, height does stock oil and hydrogen and first paragraph catalyst exposure, reaction effluent enters separation system, isolated liquid as second segment charging, second segment charging and hydrogen and second segment catalyst exposure, the refining oil that generates enters the 3rd section of reaction zone with hydrogen and carries out hydrocracking reaction; Reaction effluent enters separation system.First paragraph and three-zone hydrocracking adopt different separation systems respectively.After hydrocracking tail oil cutting, appropriate fractions and the new hydrogen of new hydrogen are mixed into isomerization dewaxing unit, and other cut and the tail oil that can't meet the quality requirement loop back Hydrocracking unit.
The present invention's height used does one or more in deasphalted oil that stock oil can be crude oil, shale oil, coal synthetic oil, crude oil deep vacuum distillation cut wet goods cut, the heavy distillate that preferred crude oil deep vacuum distillation obtains.
The Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone can be conventional heavy distillate Hydrobon catalyst.Conventional hydro catalyst for refining is generally made up of carrier and the hydrogenation metal component be loaded on carrier, generally includes group VIB active metal component in the periodic table of elements, if tungsten and/or molybdenum are in metal oxide weight 8% ~ 35%, and preferably 12% ~ 30%; And the VIIIth race's active metal component, if nickel and/or cobalt are in metal oxide weight 1% ~ 7%, preferably 1.5% ~ 6%.The carrier of Hydrobon catalyst is inorganic refractory oxide, as aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc.In the inventive method, special recommendation uses the catalyzer with following pore structure character in first paragraph reaction zone: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, preferably 8 ~ 9nm; The volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is 70% ~ 90%, is preferably 75% ~ 85%; The pore volume in <4nm hole accounts for less than 5% of total pore volume.The Hydrobon catalyst that first paragraph reaction zone uses, be generally the catalyzer being prepared carrier production by chloride process, the maturing temperature of catalyzer is generally at about 480 DEG C.The catalyzer used in first paragraph reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyzer according to the method for this area.
Because the nitrogen content of stock oil is removed to relatively low level by first paragraph reaction zone, the Hydrobon catalyst that second segment reaction zone can use first paragraph reaction zone to use, the present invention preferably uses in second segment reaction zone has the catalyzer of following character: the average pore diameter of catalyzer is 4 to being less than 7.5nm, preferably 5 ~ 7nm; Its median pore diameter is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 50 ~ 75%, preferably 55 ~ 65%; The pore volume in the hole of <4nm accounts for the volume fraction of total pore volume generally lower than 10%.Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants little 0.5 ~ 3nm, preferably little 1.0 ~ 2.5nm; The hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percentage ratios of volume fraction of total pore volume, preferably little 15 ~ 25 percentage ratios.The catalyzer used in second segment reaction zone can select existing business Hydrobon catalyst, or prepares satisfactory catalyzer according to the method for this area.
Or body phase hydrogenation catalyst can also be used in second segment reaction zone in the present invention, to improve the hydrogenation temperature of second segment reaction zone further.Body phase hydrogenation catalyst contains Mo, W, Ni tri-kinds of metal components, and in oxidized catalyst, W, Ni exist with composite oxides form: Ni
xw
yo
z, z=x+3y, Mo exist with oxide form: MoO
3; Composite oxides Ni
xw
yo
zthe ratio of middle x and y is 1:8 ~ 8:1, composite oxides Ni
xw
yo
zwith oxide M oO
3weight ratio be 1:10 ~ 10:1; Composite oxides Ni in bulk phase catalyst
xw
yo
zwith oxide M oO
3gross weight content be 40% ~ 100%.One or more in the components such as aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve can be contained as required in bulk phase catalyst, these components weight content is in the catalyst 0 ~ 60%, is preferably 20% ~ 50%.The specific surface area of bulk phase catalyst is 120 ~ 400m
2/ g, pore volume is 0.10 ~ 0.50mL/g.The commercial catalysts that body phase hydrogenation catalyst can select Fushun Petrochemical Research Institute to develop, or be prepared according to the Conventional wisdom of this area.
The hydrocracking reaction district of the 3rd section can use routine business hydrocracking catalyst, owing to can the foreign matter content of charging be taken off lower, the hydrocracking catalyst of resistance to nitrogen need not be adopted, operable business hydrocracking catalyst is except selecting the business Catalyst For Single-stage Hydrocracking with resistance to organonitrogen function, as ZHC-01, ZHC-02, ZHC-04, FC-14, FC-28 that Fushun Petrochemical Research Institute develops, the ICR126 etc. that FC-34, CHEVRON company develops.Can also use as DHC-32, DHC-39, HC-43, HC-115 etc. of Uop Inc., Fushun Petrochemical Research Institute develop 3971,3974,3976, FC-12, FC-16, FC-26 etc.
The inventive method adopts the high-quality lubricant base of hydroisomerization dewax explained hereafter.Described hydroisomerization dewax catalyzer can the conventional lube oil hydrogenation heterogeneous catalyst in anthology field, as commodity in use hydroisomerization catalyst, and also can by the suitable catalyzer of this area general knowledge preparation.Hydroisomerization catalyst carrier generally comprises the NU-10 molecular sieve of aluminum oxide and TON structure or ZSM-22 molecular sieve etc., and molecular sieve content is in the catalyst 30wt% ~ 80wt%, is preferably 40wt% ~ 70wt%, also can adds partial oxidation silicon in carrier; Active metal component be in Pt, Pd, Ru, Rh and Ni one or more, content is in the catalyst 0.1wt% ~ 30.0wt%.Selectable adjuvant component is one or more in boron, fluorine, chlorine and phosphorus, and content is in the catalyst 0.1wt% ~ 5.0wt%; The specific surface of hydroisomerization catalyst is 150 ~ 500m
2/ g, pore volume is 0.15 ~ 0.60mL/g.Before using, reduction treatment is carried out to catalyzer, make hydrogenation active metals be in reduction-state in reaction process.
Post-refining unit uses the conventional hydro catalyst for refining of this area, can be non-noble metal type catalyzer, and also can be noble metal type catalyzer, post-refining support of the catalyst be generally the porous refractory such as aluminum oxide or silicon-containing alumina material.Precious metal post-refining catalyzer uses after reduction, and base metal type catalyzer can use after reduction, also can use after sulfuration, preferably uses the post-refining catalyzer of reduction-state.If use sulphided state post-refining catalyzer, need in the material entering post-refining reaction zone, to supplement appropriate sulphur or sulfocompound, to keep catalyst activity.
The present invention is explained further below in conjunction with drawings and Examples.
As shown in Figure 1: enter first paragraph hydrofining reactor R1 after the stock oil of pipeline 1 mixes with the recycle hydrogen of pipeline 2, remove most of impurity; Reaction effluent enters separator 4 along pipeline 3 and is separated; 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 and enter gas-liquid separation zone C and be separated, gas enters after water wash column 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; B district obtain gas and A distinguish from gas and vapor permeation after leave R2 from pipeline 9, B district obtains liquid phase through pipeline 12, with mix after the replenishment cycles hydrogen of pipeline 13 after enter hydrocracking reactor R3 and carry out hydrocracking reaction, second segment reaction zone effluent enters separation system 15 through pipeline 14 and is separated, be separated into gas 16, petroleum naphtha 17, kerosene 18, diesel oil 19 and tail oil 20, separation system 15 generally includes high-pressure separator, light pressure separator and separation column.At least part of tail oil 20 enters tail oil preliminary fractionator 22 along pipeline 21 and isolates lighter hydrocarbons (non-condensable gas) 23, light tail oil fraction 24, object cut 25 and heavy-tailed oil distillate 26(to be cut into three kinds of tail oil fraction), carry out hydrofining reaction along entering first paragraph hydrofining reactor R1 after pipeline 27 mixes with pipeline 1 stock oil after lighting end 24, last running 26 and part tail oil 20 mix.Preliminary fractionator 22 is separated and enters hydroisomerization dewax unit pour point depression reaction zone R4 after the object tail oil fraction 25 obtained mixes with new hydrogen 28 and carry out pour point depression reaction, pour point depression reaction product is mixed into post-refining reactor R5 along pipeline 29 without separation and new hydrogen 30, the gas 32 that reaction product obtains after fractionating system 31 is separated returns to hydrocracking reaction district, and the hydrogen make-up as process uses.The product liquid of hydroisomerization dewax can obtain the lube base oil production of different viscosity through fractionation, respectively through pipeline 33,34 and 35 separating device.Also the raw material of the satisfactory quality in other source can be mixed in isomerization dewaxing raw material.New hydrogen needed for reactive system can all enter hydroisomerizing reaction zone, and also can require only to need the new hydrogen of part according to reaction conditions, remainder can enter post-refining reaction zone or hydrocracking reaction district.Wherein fractionating system 31 also comprises high-pressure separator, light pressure separator and separation column usually.
Also the raw material of the satisfactory quality in other source can be mixed in isomerization dewaxing raw material.New hydrogen needed for reactive system can all enter hydroisomerizing reaction zone, and also can require only to need the new hydrogen of part according to reaction conditions, 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 lists in table 1.Use the character of Hydrobon catalyst to list in table 2.In the present invention, wt% is weight percentage or weight content.
Embodiment 1
Adopt the technical process shown in Fig. 1, three-zone hydrocracking adopts 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 refining reaction device top adopts gas and liquid flowing flow process, and bottom adopts gas-liquid counter current flow process, and the section of stream is 1:1 with the catalyst loading volume ratio of adverse current section.
In the operation of hydrocracking tail oil preliminary fractionator, tail oil fractionation 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 the equal loading catalyst B of second segment, other are with embodiment 1.
Comparative example 1
Technique basic procedure, with embodiment 1, only adopts in second segment reaction zone and flows technical process, not comprising counter-current process.The hydrocracking of the 3rd section be one way by flow process, hydrocracking tail oil fractionation 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
Adopt conventional two-stage hydrocracking flow process, hydrofining reaction only comprises one section of reaction zone, does not comprise second segment reaction zone, and the effluent of one section of reaction zone carries out gas-liquid separation, the liquid that gas-liquid separation obtains generates oil and carries out hydrocracking, and hydrocracking adopts one way to pass 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 test-results that embodiment 1-2 and comparative example 1-2 operates 500 hours lists in table 3, and the test-results that embodiment 1-2 and comparative example 1-2 operates 6000 hours is listed in table and only gived hydrofining data in 5(6000 hour).
Table 1 stock oil
| Density (20 DEG C)/kgm -3 | 929.3 |
| Boiling range scope/DEG C | 367～600 |
| Sulphur content, wt% | 2.99 |
| Nitrogen content/μ gg -1 | 1073 |
| Condensation point/DEG C | 28 |
| BMCI value | 50.7 |
Table 2 Hydrobon catalyst
| Numbering | A | B |
| Carrier | Aluminum oxide | Aluminum oxide |
| MoO 3，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 test-results (for the running result of 500 hours)
| Embodiment | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Processing condition | ||||
| Catalyzer | 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 |
| Temperature of reaction/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 | Refining N, 10 μ g/g |
| Cracking zone > 370 DEG C of per pass conversion, wt% | 72.1 | 72.3 | 72.0 | 71.9 |
| > 370 DEG C of tail oil viscosity indexs | 144 | 142 | 141 | 137 |
| Hydroisomerization dewax/post-refining process condition | ||||
| Isomerization dewaxing/post-refining catalyzer | 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 |
| Temperature of reaction/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 lubricating oil distillate character | ||||
| Yield (* *), wt% | 75.32 | 75.35 | 75.83 | 76.55 |
| Pour point/DEG C | -21 | -20 | -20 | -18 |
| Viscosity (40 DEG C), mm/s 2 | 28.51 | 28.63 | 28.72 | 28.77 |
| Viscosity (100 DEG C), mm/s 2 | 5.316 | 5.322 | 5.314 | 5.231 |
| Viscosity index | 121 | 120 | 119 | 113 |
* the catalyzer used in first paragraph, second segment and the 3rd section is respectively; # is respectively the catalyzer of refining stage and cracking zone use; * in isomerization dewaxing inlet amount for 100%.
Embodiment 3
As shown in Figure 1, wherein >370 DEG C of ends fraction is recycled to second segment hydrofining reactor entrance to main flow, and internal circulating load is 25% of tail oil.The denitrification percent controlling first paragraph reaction zone is 75wt%.Test-results lists in table 3.
Embodiment 4
As shown in Figure 1, wherein >370 DEG C of ends fraction is recycled to second segment hydrofining reactor entrance to main flow, and internal circulating load is 25% of tail oil.The denitrification percent controlling first paragraph reaction zone is 87wt%.Test-results lists in table 3.
Comparative example 3
Adopt two-stage hydrocracking flow process of the prior art, hydrofining reaction only comprises one section of reaction zone, do not comprise 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 carries out hydrocracking, >370 DEG C of hydrocracking tail oil component loops returns hydrofining reactor entrance, and tail oil internal circulating load is 25%, and residue tail oil carries out isomerization dewaxing reaction.
The test-results of embodiment 3-4 and comparative example 3 lists in table 4.
Table 4 test-results
| Numbering | Embodiment 3 | Embodiment 4 | Comparative example 3 |
| Hydrocracking segment process condition | |||
| Catalyzer | 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 |
| Temperature of reaction/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 per pass conversion, wt% | 60 | 60 | 60 |
| Cracking zone > 370 DEG C of total conversion rates, wt% | 70.0 | 70.0 | 70.0 |
| Hydroisomerization dewax/post-refining process condition | |||
| Hydroisomerization catalyst/post-refining catalyzer | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 3:1 |
| Temperature of reaction/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 lubricating oil distillate character | |||
| Yield (* *), wt% | 75.41 | 75.73 | 74.68 |
| Pour point/DEG C | -20 | -20 | -18 |
| Viscosity (40 DEG C), mm/s 2 | 27.93 | 27.62 | 28.13 |
| Viscosity (100 DEG C), mm/s 2 | 5.269 | 5.207 | 5.136 |
| Viscosity index | 122 | 121 | 112 |
* the catalyzer used in first paragraph, second segment and the 3rd section is respectively; # is respectively the catalyzer used in refining stage and cracking zone.* in isomerization dewaxing inlet amount for 100%.
Table 5 test-results (operating 6000 hours)
| Embodiment | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Hydrofining technology condition | ||||
| Catalyzer | 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 |
| Temperature of reaction/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 | Refining N, 10 μ g/g |
* be first paragraph, second segment and the 3rd section of catalyzer used; # is respectively the catalyzer that refining stage and cracking zone use; * with isomerization dewaxing inlet amount for benchmark.
Shown by above embodiment, adopt processing method of the present invention, first paragraph reactor adopts Hydrobon catalyst, second segment reactor adopts Hydrobon catalyst, second segment hydrofining top adopts gas and liquid flowing flow process, bottom adopts gas-liquid counter current flow process, process high do raw material as deep drawing wax oil time, more effectively can play the activity of Hydrobon catalyst and hydrocracking catalyst.
Because hydrofining and hydrocracking reaction temperature reduce greatly, thus the running period of device can be improved, or improve the working ability of device under same running period.
Claims (20)
1. the high processing method doing raw material production lubricant base, comprises following content:
(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 separation system, obtains gas phase and liquid phase;
(3) second segment reaction zone is entered after the liquid phase in step (2) after gas-liquid separation mixes with hydrogen, 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 and enter gas-liquid separation zone and be separated, gas draws reactor; Liquid enters the beds of bottom, second segment reaction zone, and the hydrogen introduced with reactor bottom carries out counter current contact reaction, and reacted gas leaves reactor from gas-liquid separation zone;
(4) enter the 3rd section of reaction zone after the hydrofined oil that step (3) obtains mixes with hydrogen, the 3rd section of reaction zone uses hydrocracking catalyst;
(5) the 3rd sections of reaction zones obtain reaction effluent and enter separation system, are separated one or more and tail oil that obtain gasoline, kerosene and diesel oil;
(6) the tail oil preliminary fractionator that enters at least partially that step (5) obtains tail oil carries out fractionation, obtains lighter hydrocarbons and two or more tail oil fraction;
(7) at least one in the two or more tail oil fraction of step (6) gained, enters isomerization dewaxing reaction zone, carry out isomerization dewaxing reaction with new hydrogen after mixing; Isomerization dewaxing reaction effluent enters post-refining conversion zone and carries out post-refining reaction, with further imurity-removal;
(8) reaction product that step (7) obtains carries out gas-liquid separation, and product liquid obtains the lube base oil production of different size through distillation.
2. in accordance with the method for claim 1, it is characterized in that, described height does the final boiling point 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 characterized in that, the final boiling point that described height does raw material is more than 570 DEG C.
4. in accordance with the method for claim 3, it is characterized in that, the final boiling point that described height does raw material is 580 ~ 620 DEG C.
5. in accordance with the method for claim 2, it is characterized in that, the nitrogen content that described height does raw material is 500 more than μ g/g.
6. in accordance with the method for claim 1, it is characterized in that, the remainder of step (5) gained tail oil loops back the reactor inlet of first paragraph or second segment reaction zone.
7. in accordance with the method for claim 1, it is characterized in that, the denitrification percent of the first paragraph reaction zone described in step (1) controls as 70wt% ~ 90wt%.
8. in accordance with the method for claim 1, it is characterized in that, step (1) and the Hydrobon catalyst described in step (3) are made up of carrier and the hydrogenation metal component be loaded on carrier, catalyzer to comprise in the periodic table of elements group VIB active metal component in oxide weight 8% ~ 35%, and the VIIIth race's active metal component is in oxide weight 1% ~ 7%.
9. in accordance with the method for claim 8, it is characterized in that, the Hydrobon catalyst described in step (1) also has following character: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, and aperture is the volume fraction that the hole of 4 ~ 10nm accounts for total pore volume is 70 ~ 90%.
10. according to the method described in claim 1,8 or 9, it is characterized in that, Hydrobon catalyst described in step (3) has following character: the average pore diameter of catalyzer is 4 to being less than 7.5nm, and aperture is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 50 ~ 75%; Wherein compared with the Hydrobon catalyst in first paragraph, the average pore diameter of second segment Hydrobon catalyst wants the hole of little 0.5 ~ 3nm, aperture 4 ~ 10nm to account for little 10 ~ 30 percentage ratios of volume fraction of total pore volume.
11. in accordance with the method for claim 10, it is characterized in that, compared with the Hydrobon catalyst in first paragraph, the hole of the little 1.0 ~ 2.5nm of average pore diameter of second segment Hydrobon catalyst, aperture 4 ~ 10nm accounts for little 15 ~ 25 percentage ratios of volume fraction of total pore volume.
12. in accordance with the method for claim 9, it is characterized in that, the average pore diameter of the Hydrobon catalyst described in step (1) is 8 ~ 9nm, and the volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is 75% ~ 85%.
13. according to the method described in claim 10 or 11, it is characterized in that, the average pore diameter of the Hydrobon catalyst described in step (3) is 5 ~ 7nm, and its median pore diameter is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 55% ~ 65%.
14. in accordance with the method for claim 1, it is characterized in that, the processing condition of first paragraph reaction zone are: temperature of reaction 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.
15. in accordance with the method for claim 1, it is characterized in that, in second segment reaction zone described in step (3), and the processing condition flowing reaction zone are: temperature of reaction 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 processing condition of counter-flow reaction zone are: temperature of reaction 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.
16. in accordance with the method for claim 1, it is characterized in that, the processing condition of three-zone hydrocracking reaction zone are: temperature of reaction 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.
17. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the hydroisomerization dewax reaction zone described in step (6) is: temperature of reaction 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: temperature of reaction 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.
18. in accordance with the method for claim 1, it is characterized in that, the carrier of described hydroisomerization dewax catalyzer comprises NU-10 molecular sieve or the ZSM-22 molecular sieve of aluminum oxide and TON structure, molecular sieve content is in the catalyst 30wt% ~ 80wt%, active metal component be in Pt, Pd, Ru, Rh and Ni one or more, content is in the catalyst 0.1wt% ~ 30.0wt%.
19. in accordance with the method for claim 16, it is characterized in that, containing adjuvant component in hydroisomerization dewax catalyzer, adjuvant component is one or more in boron, fluorine, chlorine and phosphorus, and content is in the catalyst 0.1wt% ~ 5.0wt%.
20. 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 Mo, W, Ni tri-kinds of metal components, and in oxidized catalyst, W, Ni exist with composite oxides form: Ni
xw
yo
z, z=x+3y, Mo exist with oxide form: MoO
3; Composite oxides Ni
xw
yo
zthe ratio of middle x and y is 1:8 ~ 8:1, composite oxides Ni
xw
yo
zwith oxide M oO
3weight ratio be 1:10 ~ 10:1; Composite oxides Ni in bulk phase catalyst
xw
yo
zwith oxide M oO
3gross weight content be 40% ~ 100%.
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| CN109852465A (en) * | 2018-12-31 | 2019-06-07 | 盘锦北方沥青股份有限公司 | A kind of production technology of naphthenic base lubricating oil |
| CN110938463A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Method for producing lubricating oil base oil raw material |
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| CN110938463B (en) * | 2018-09-25 | 2021-10-08 | 中国石油化工股份有限公司 | Method for producing lubricating oil base oil raw material |
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