CN104611024B - A kind of inferior heavy distillate produces the process of lube base oil - Google Patents
A kind of inferior heavy distillate produces the process of lube base oil Download PDFInfo
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Abstract
The invention discloses a kind of inferior heavy distillate and produce the process of lube base oil。Inferior heavy distillate and hydrogen enter first paragraph reaction zone and carry out hydrofining reaction；The separated gained liquid of reaction effluent and hydrogen enter second segment reaction zone and carry out hydrofining reaction；Second segment reaction effluent enters the 3rd section of reaction zone, carries out hydrocracking reaction；Hydrocracking reaction effluent separates the tail oil obtained and carries out prefractionation, obtains suitable tail oil fraction and is sequentially carried out isomerization dewaxing and post-refining reaction, obtains lube base oil。Nitrogen-containing impurity in inferior raw material can be carried out hydrotreatment when relatively relaxing by the inventive method so that it is meet hydrogenation cracked charge requirement, thus having expanded the raw material sources of lube base oil；Simultaneously because hydrofinishing temperature is substantially reduced such that it is able to process more inferior raw material and improve the service cycle of device, or improving the working ability of device under same service cycle。
Description
Technical field
The invention discloses a kind of process producing lube base oil, particularly a kind of inferior heavy distillate of processing produces the process of lube base oil。
Background technology
Along with China's rapid development of economy, PETROLEUM PROCESSING ability quickly increases。Meanwhile, domestic hydrocracking technology also obtain large-scale commercial Application, and by the end of the year 2011, the hydrocracking unit that China is currently running has set more than 40, and total working ability alreadys more than 50.0Mt/a, and working ability leaps to second place of the world。Additionally, variation year by year due to domestic crude quality, being significantly increased of imported high sulfur crude oil processing capacity, environmental protection is increasingly strict to the requirement of oil refining process and petroleum product-quality, and market being continuously increased clean fuel oil and industrial chemicals demand, cleaning intermediate oil especially as transportation fuel and the high-quality charging for device offers such as reformation, ethylene, therefore the progress of hydrocracking technology level is had higher requirement by market。The wide scope of material that hydrogenation cracking is machined, products scheme is flexible, and liquid product yield is high, can obtain high-quality power fuel and industrial chemicals, hydrocracking process and technology and increasingly be subject to the most attention of each major oil companies of the world。
The production technology of base oil mainly includes tradition " old three sets " lubricating oil processing technique and the hydrogenation method technique being representative with hydrotreatment, hydrogenation cracking, catalytic dewaxing/isomerization dewaxing。And II/III class High Quality Lube Base Oils especially III class lubricating oil base oil has the features such as saturated hydrocarbon content height, 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 adopt hydrogenation method technique, is especially hydrogenated with cracking-isomerization dewaxing group technology route comparatively ripe, is widely used in production top-grade lubricating oil base oil。Hydrocracking tail oil is utilized 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, it is possible to meet the modern top-grade lubricating oil requirement to API II/III class base oil。
US6,676,827 discloses a kind of method that isomerization dewaxing produces low solidifying lube base oil。Adopting hydrogenation cracking-isomerization dewaxing two-stage hydrogenation process route, hydrogenation cracking and isomerization dewaxing all have respective hydrogen gas circulating system, and this is that current hydrogenation method produces lube base oil main processes。Owing to using two-stage process, therefore technological process is complicated, equipment is many, operating cost is high。
CN200710011927.5 discloses the production method of a kind of lube base oil, the tail oil of Hydrocracking unit directly feeds tail oil isomerization dewaxing unit and does raw material, new hydrogen is once by tail oil isomerization dewaxing unit, and its tail hydrogen is then directly returned to Hydrocracking unit and does supplementary hydrogen。The method is only the combination of two unit, reduces investment and the operating cost of device, and the product quality of Hydrocracking unit does not improve。
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide the hydrogenation of a kind of improvement cracking-isomerization dewaxing combined method, for processing the significantly high inferior feedstock oil of nitrogen content to produce lube base oil。Compared with the existing technology, the inventive method is greatly improved product quality and the working ability of device, or at same product quality and working ability condition decline low operating pressure, reduces operating cost。
A kind of inferior heavy distillate of the present invention produces the process of lube base oil, including herein below:
(1) when hydrofining technology, inferior heavy distillate enters first paragraph reaction zone after mixing with hydrogen and carries out hydrofining reaction, and first paragraph reaction zone includes Hydrobon catalyst, and the denitrification percent of first paragraph reaction zone controls as 60wt% ~ 95wt%；
(2) first paragraph reaction zone effluent entrance separator is easily separated, and obtains gas phase and liquid phase；Gas phase (is mainly NH through imurity-removal3And H2S) can recycle after；
(3) step (2) obtains entrance second segment reaction zone after liquid phase mixes with hydrogen, carries out hydrofining reaction, and second segment reaction zone uses Hydrobon catalyst；
(4) hydrogenation reaction effluent that step (3) obtains enters the 3rd section of reaction zone after mixing with hydrogen, carries out hydrocracking reaction, and the 3rd section of reaction zone uses hydrocracking catalyst；
(5) step (4) obtains hydrocracking reaction effluent and enters piece-rate system, one or more and tail oil of separated gas, Petroleum, 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；The tail oil of remainder can loop back first paragraph or the reactor inlet of second segment reaction zone；
(7) at least one of step (6) gained tail oil fraction, enters isomerization dewaxing reaction zone, carries out isomerization dewaxing reaction after mixing with hydrogen；Isomerization dewaxing reaction effluent enters post-refining conversion zone and carries out post-refining reaction；
(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。
In the process of the present invention, the nitrogen content of the inferior heavy distillate described in step (1) is generally 1500 more than μ g/g, it is preferred to 2000 more than μ g/g, it is most preferred that be 2500～15000 μ g/g。The initial boiling point of inferior heavy distillate feedstock is generally 220～450 DEG C, it is preferred to 300～420 DEG C；The end point of distillation is generally 470～550 DEG C, it is preferred to 500～550 DEG C。What described inferior heavy distillate was typically used as the raw material of catalytic cracking unit or hydrocracking unit mixes refining raw material。
In the process of the present invention, wherein first paragraph reaction zone and second segment reaction zone are the fixed bed hydrogenation refining reaction that gas and liquid flowing is downward。
Separator described in step (2) can be high pressure hot separator or cold high pressure separator。In step (2), the operation of gas-liquid separation is routine operation well known to those skilled in the art。
Process according to the invention method, wherein in step (3), it is preferable that the liquid phase after first paragraph reaction zone gas-liquid separation in step (2) is first washed with water, to reduce dissolved ammonia (NH in first paragraph hydrofinishing generation oil3) content, through washing after liquid phase again with hydrogen enter second segment reaction zone。Described water washing operations is the routine operation of those skilled in the art。
In the inventive method, the piece-rate system described in step (5) generally includes high-pressure separator, low pressure separator and fractionating column。The operation of described piece-rate system is the routine operation of the art。
In the inventive method, wherein the denitrification percent general control of first paragraph reaction zone is 60wt% ~ 95wt%, it is preferable that control as 70wt% ~ 90wt%。The process conditions of first paragraph reaction zone are generally: average reaction temperature is 330 ~ 480 DEG C, it is preferred to 350 ~ 450 DEG C；Reaction pressure is 5.0 ~ 20.0MPa, it is preferred to 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1 ~ 4000:1, it is preferred to 400:1 ~ 2000:1；During liquid, volume space velocity is 0.2 ~ 4.0h-1, it is preferred to 0.5 ~ 3.0h-1。
In the inventive method, the process conditions of second segment reaction zone are generally: average reaction temperature is 250 ~ 500 DEG C, it is preferred to 300 ~ 440 DEG C；Reaction pressure is 5.0 ~ 20.0MPa, it is preferred to 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1 ~ 4000:1, it is preferred to 400:1 ~ 2000:1；During liquid, volume space velocity is 0.2 ~ 10.0h-1, it is preferred to 1.0 ~ 4.0h-1。
In the inventive method, wherein the process conditions of the 3rd section of reaction zone hydrogenation cracking are generally: average reaction temperature is 250 ~ 500 DEG C, it is preferred to 300 ~ 440 DEG C；Reaction pressure is 5.0 ~ 20.0MPa, it is preferred to 8.0 ~ 17.0MPa；Hydrogen to oil volume ratio is 100:1 ~ 4000:1, it is preferred to 400:1 ~ 2000:1；During liquid, volume space velocity is 1.0 ~ 10.0h-1, it is preferred to 1.0 ~ 4.0h-1。
In the inventive method, the scale according to device, first paragraph reaction zone can arrange one or several reactors；Second segment reaction zone can also arrange one or several reactors；Same three-zone hydrocracking reaction zone can also arrange one or several reactors。
In the inventive method, after first paragraph reaction zone reaction effluent carries out gas-liquid separation, gas phase can use through elimination hydrogen sulfide and ammonia Posterior circle, and liquid phase enters back into second segment reaction zone after washing hydrogen sulfide and ammonia off preferably through washing, carry out deep hydrogenation denitrogenation and hydrofining reaction with hydrogen。
In the inventive method, mainly there is partial desulfurization and the part denitrification reaction of raw material in first paragraph reaction zone；The Hydrobon catalyst of second segment reaction zone proceeds the reactions such as deep hydrodesulfurizationof, denitrogenation, aromatic hydrocarbons are saturated。
In the inventive method, the process conditions of described hydroisomerizing dewaxing reaction zone are: average reaction temperature is 220 ~ 380 DEG C, it is preferable that 280 ~ 350 DEG C；Reaction pressure is 4.0 ~ 20.0MPa, it is preferred to 6.0 ~ 17.0MPa；Volume space velocity is 0.6 ~ 1.8h-1, it is preferred to 0.8 ~ 1.5h-1；Hydrogen to oil volume ratio 100:1 ~ 1500:1, it is preferred to 300:1 ~ 800:1。
Post-refining section uses the Hydrobon catalyst that this area is conventional, it is possible to being non-noble metal type catalyst, it is also possible to be noble metal type catalyst, 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, it is preferred to use the post-refining catalyst of reduction-state。If using sulphided state post-refining catalyst, it is necessary to supplement appropriate sulfur or sulfur-containing compound in the material entering post-refining reaction zone, to keep catalyst activity。
The process conditions of described post-refining conversion zone are: average reaction temperature is 220 ~ 380 DEG C, it is preferable that 280 ~ 350 DEG C；Reaction pressure is 4.0 ~ 20.0MPa, it is preferable that 6.0 ~ 17.0MPa；Volume space velocity is 0.6 ~ 6.0h-1, it is preferable that 0.8 ~ 3.0h-1；Hydrogen to oil volume ratio 100:1 ~ 1500:1, it is preferable that 300:1 ~ 800:1。
In the inventive method, the Hydrobon catalyst that first paragraph and second segment use can be the arbitrary Hydrobon catalyst product in this area, hydrocracking catalyst can select suitable product according to the Spreading requirements of product, as can be the middle oil type hydrocracking catalyst of fecund intermediate oil (kerosene and diesel oil), or it be the mobile type hydrocracking catalyst of flexibly production 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。
Compared with prior art, the process of the present invention has effect highlighted below:
1, when processing the significantly high inferior heavy distillate feedstock oil of nitrogen content, the present invention can hydrogen sulfide in substantially reduction system and ammonia content, improve hydrogen dividing potential drop, effectively play the activity of Hydrobon catalyst and hydrocracking catalyst。Current hydrocracking unit charging generally includes vacuum distillate, solvent refining deasphalted oil or Fischer-Tropsch synthesis oil, wherein can mix refining part inferior distillate oil。And inferior distillate oil raw material carries out after the reactions such as desulfurization, denitrogenation, deoxidation, aromatic hydrocarbons are saturated through the first reaction zone in the inventive method, second reaction zone feedstock quality reaches generally hydrogenation cracked charge prescription, can directly as hydrogenation cracked charge not as mixing refining raw material, thus expanding the raw material sources of hydrocracking unit。
2, those skilled in the art are it is generally believed that Hydrobon catalyst has resistance to nitrogen, and catalyst is not had inhibitory action by hydrogen sulfide and ammonia in recycle hydrogen。But by the in-depth analysis of existing hydroprocessing technique is learnt, when the raw oil that processing nitrogen content is significantly high, owing to the impurity contents such as sulfur nitrogen are significantly high, course of reaction generates substantial amounts of hydrogen sulfide and ammonia, and the nitrogen removal performance of Hydrobon catalyst is produced very strong inhibitory action。If adopting the conventional method of this area, it is necessary to required denitrification effect could be obtained under higher reaction temperature。And the present invention is by optimizing hydrofining technology flow process, identical or different Hydrobon catalyst is assigned in different refining reaction districts by suitable proportion；And achieve while the identical hydrogenation removing impurities matter degree of depth at second segment refining reaction device, significantly reduce reaction temperature, improve hydrofinishing effluent quality, and extend service cycle。Meanwhile, the relatively low temperature of second segment also can promote aromatic hydrocarbons saturated reaction, and denitrification reaction is generally ring-opening reaction, so that reaction temperature reduces further。That is, when processing same inferior raw material under identical air speed, have higher hydrogen dividing potential drop and aromatic hydrocarbons saturated reaction faster due to two-stage reaction, < ratio is used a reactor to need less average reaction temperature by 10 μ g/g to use two reactors to be removed to。
3, the present invention is according to the high feature of raw oil nitrogen content, prepared, by chloride process, the Hydrobon catalyst that carrier produces preferably in first paragraph reaction zone adopts, 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, especially processing inferior raw material be had better activity stability；And be preferably used in second segment reactor and prepared, by sulphate method, the Hydrobon catalyst that carrier produces, it being characterized in that duct is relatively small and disperses, the effect of carrier and metal is relatively weak。Catalyst for refining in second segment has higher activity and better activity stability for the raw material being stripped of most of the nitrogen impurity。Thus, the grating of both catalyst can better play the activity of catalyst。
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 plays the activity of second segment Hydrobon catalyst。
5, the tail oil that three-zone hydrocracking obtains can partly return the hydrofining reactor of first paragraph or second segment, carries out deep refining, thus reducing the nitrogen content generating oil further, improves the feedstock quality of isomerization dewaxing unit。
Accompanying drawing explanation
Fig. 1 is a kind of principle process chart of the present invention。
Detailed description of the invention
Inferior heavy distillate used by the present invention can be one or more in the wax tailings of crude oil, deasphalted oil, shale oil and coal artificial oil, crude oil deep vacuum distillation fraction wet goods fraction。Doing of described inferior heavy distillate is generally 470 ~ 550 DEG C。
The Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone can be conventional heavy distillate Hydrobon catalyst。Conventional hydro catalyst for refining generally comprises carrier and the hydrogenation metal component being loaded on carrier。Catalyst generally includes group VIB active metal component such as tungsten and/or molybdenum in the periodic table of elements, in oxide weight 8% ~ 35%, it is preferable that 12% ~ 30%；And the VIIIth race's active metal component such as nickel and/or cobalt, in oxide weight 1% ~ 7%, it is preferable that 1.5% ~ 6%。The carrier that Hydrobon catalyst uses is inorganic refractory oxide, such as aluminium oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc.。Can also containing suitable adjuvant component in conventional hydro catalyst for refining, one or more in the elements such as phosphorus, boron and fluorine, the content of auxiliary agent is generally 0.1wt% ~ 5wt%。In the inventive method, special recommendation uses the catalyst having the following properties that in first paragraph reaction zone: the average pore diameter of catalyst is 7.5 ~ 9.5nm, it is preferable that 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, it is preferred to 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 generally and is prepared, by chloride process, the catalyst that carrier produces, and the sintering temperature in catalyst preparation process is typically in about 480 DEG C。The catalyst used in first paragraph reaction zone can select existing business Hydrobon catalyst, or the method according to this area prepares satisfactory catalyst。
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 uses, preferably in second segment reaction zone, the catalyst that has the following properties that: the average pore diameter of catalyst is 4 to less than 7.5nm, it is preferable that 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, it is preferable that 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, it is preferable that little 1.0 ~ 2.5nm；The hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percents of volume fraction of total pore volume, it is preferable that little 15 ~ 25 percents。
Catalyst in second segment reaction zone is generally is prepared, by sulphate such as aluminum sulfate method, the catalyst that carrier produces, and the sintering temperature of catalyst preparation process is typically in about 450 DEG C。The catalyst used in second segment reaction zone can select existing business Hydrobon catalyst, or the method according to this area prepares satisfactory catalyst。
Or the inventive method can also use body phase hydrogenation catalyst in second segment reaction zone, to improve the hydrogenation temperature of second segment reaction zone further。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 exists with oxide form: 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%, it is preferred to 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 the Conventional wisdom according to this area is prepared。
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 adopted, operable business hydrocracking catalyst is except selecting the business Catalyst For Single-stage Hydrocracking with resistance to organic nitrogen function, such 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 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 present invention adopts 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, it is possible to use commodity hydroisomerization catalyst, it is also possible to prepares by this area general knowledge。Hydroisomerization catalyst carrier is generally NU-10 molecular sieve or the ZSM-22 molecular sieve etc. of aluminium oxide and TON structure, and molecular sieve content in the catalyst is 30wt% ~ 80wt%, it is preferred to 40wt% ~ 70wt%, also can add partial oxidation silicon in carrier；Active metal component be in Pt, Pd, Ru, Rh and Ni one or more, 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 this area conventional hydro catalyst for refining, it is possible to being non-noble metal type catalyst, it is also possible to be noble metal type catalyst, 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, it is preferred to use the post-refining catalyst of reduction-state。If using sulphided state post-refining catalyst, it is necessary to supplement appropriate sulfur or sulfur-containing compound in the material entering post-refining reaction zone, to keep catalyst activity。
The method for hydrogen cracking of the present invention is explained further below in conjunction with drawings and Examples。
Inferior heavy distillate feedstock, through pipeline 1 and entrance first paragraph hydrofining reactor (first paragraph reaction zone) 3 after the recycle hydrogen of pipeline 2 mixes, carries out hydrofining reaction；First paragraph reaction effluent enters separator 5 along pipeline 4 and is easily separated, and isolated gas goes out device through pipeline 6, it is possible to use through imurity-removal Posterior circle；The liquid phase that separator 5 obtains, through pipeline 7 with after the hydrogen of pipeline 8 mixes, enter second segment hydrofining reactor (second segment reaction zone) 9, remove the impurity such as sulfur, nitrogen further；Second segment reaction zone effluent is through pipeline 10, it is possible to after mixing with the hydrogen make-up of pipeline 11, enters the 3rd section of reaction zone of hydrocracking reactor 12() carry out hydrocracking reaction。Hydrocracking reaction effluent enters the first piece-rate system 14 through pipeline 13 and is easily separated, and is isolated to gas 15, Petroleum 16, kerosene 17, diesel oil 18 and tail oil 19。The first described piece-rate system 14 generally includes high-pressure separator, low pressure separator and fractionating column。Tail oil 19 enters tail oil prefractionator 20, obtains light tail oil and heavy-tailed oil (for two kinds) is discharged from pipeline 21, pipeline 22 respectively, and heavy-tailed oil is through pipeline 22, after mixing with the hydrogen of pipeline 23, enters hydroisomerizing dewaxing reactor 24, carries out isomerization dewaxing reaction；Isomerization dewaxing reaction effluent enters post-refining reactor 26 through pipeline 25 and carries out post-refining reaction。Post-refining effluent enters the second piece-rate system 28 through pipeline 27 and is easily separated, and obtains gas and discharges through pipeline 29, and various lube base oils leave from pipeline 30,31 and 32 respectively。The second described piece-rate system 29 generally includes high-pressure separator, low pressure separator and fractionating column。
The present invention program and effect are described by the examples below。Hydrocracking catalyst, hydroisomerizing dewaxing catalyst and post-refining catalyst are the commercial catalyst of Fushun Petrochemical Research Institute's development and production。Raw oil character is listed in table 1, Hydrobon catalyst character is listed in table 2。In the present invention, wt% is weight percentage。
Table 1 raw oil。
| Wax oil | |
| Density/kg m-3 | 950.1 |
| Boiling range/DEG C | 236~544 |
| Sulfur content/wt% | 2.03 |
| Nitrogen content/μ g g-1 | 6127 |
Table 2 Hydrobon catalyst。
| Numbering | Catalyst A | Catalyst B |
| Carrier | Aluminium oxide | Aluminium oxide |
| MoO3, wt% | 24.9 | 24.5 |
| NiO, wt% | 4.12 | 4.26 |
| P, wt% | 2.67 | 2.71 |
| Average pore diameter, nm | 8.4 | 6.5 |
| 4 ~ 10nm hole accounts for the ratio of total pore volume, volume % | 85 | 61 |
Embodiment 1
Adopt technological process shown in Fig. 1, first paragraph loading catalyst A, second segment loading catalyst A, the 3rd section of filling FC-50 catalyst。Three-zone hydrocracking is that one way passes through flow process, and controlling the refining nitrogen content of second segment is 15 ~ 25 μ g/g, controls cracking zone > 370 DEG C of conversion per pass are ~ 70wt%。
Hydrocracking tail oil all carries out prefractionation, obtains light tail oil and heavy-tailed oil；Light tail oil is 450 DEG C with the cutting temperature with heavy-tailed oil。Heavy-tailed oil carries out isomerization dewaxing reaction and post-refining reaction。
Embodiment 2
Adopt technological process shown in Fig. 1。First paragraph and the equal loading catalyst B of second segment。Other are with embodiment 1。
Embodiment 3
Adopt technological process shown in Fig. 1。First paragraph uses Hydrobon catalyst A, and second segment uses Hydrobon catalyst B。Other are with embodiment 1。
Comparative example 1
Adopting prior art, refining stage only includes a conversion zone, wherein uses Hydrobon catalyst A, and cracking zone uses FC-50 catalyst。Other are with embodiment 1。
Comparative example 2
Adopting prior art, refining stage only includes a conversion zone, wherein uses Hydrobon catalyst B, and cracking zone uses FC-50 catalyst。Other are with embodiment 1。
Table 3 result of the test (operating 500h)。
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Hydrogenation cracking zone process conditions | |||
| Catalyst | A/A/FC-50 | B/B/FC-50 | A/B/FC-50 |
| First paragraph denitrification percent, wt% | 80 | 80 | 80 |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Volume space velocity/h-1 | 1.0/1.0/1.8 | 1.0/1.0/1.8 | 1.0/1.0/1.8 |
| Hydrogen to oil volume ratio | 900/900/1300 | 900/900/1300 | 900/900/1300 |
| Reaction temperature/DEG C | 380/390/386 | 375/385/386 | 380/385/386 |
| > 370 DEG C of tail oil viscosity index (VI)s | 143 | 142 | 142 |
| Hydroisomerizing dewaxing/post-refining process condition | |||
| Catalyst | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 |
| Reaction temperature/DEG C | 330/250 | 330/250 | 330/250 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 800 |
| Cumulative volume air speed/h-1 | 1.0 | 1.0 | 1.0 |
| > 320 DEG C of lube cut character | |||
| Yield (* *), wt% | 77.35 | 77.47 | 78.11 |
| Pour point/DEG C | -21 | -21 | -21 |
| Viscosity (40 DEG C), mm/s2 | 28.65 | 28.71 | 28.58 |
| Viscosity (100 DEG C), mm/s2 | 5.316 | 5.301 | 5.297 |
| Viscosity index (VI) | 120 | 119 | 119 |
Table 3-continues result of the test (operating 5000h)。
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Hydrogenation cracking zone process conditions | |||
| Catalyst | A/A/FC-50 | B/B/FC-50 | A/B/FC-50 |
| First paragraph denitrification percent, wt% | 80 | 80 | 80 |
| Reaction pressure/MPa | 15.7 | 15.7 | 15.7 |
| Volume space velocity/h-1 | 1.0/1.0/1.8 | 1.0/1.0/1.8 | 1.0/1.0/1.8 |
| Hydrogen to oil volume ratio | 900/900/1300 | 900/900/1300 | 900/900/1300 |
| Reaction temperature/DEG C | 385/395/389 | 388/391/389 | 385/391/389 |
| > 370 DEG C of tail oil viscosity index (VI)s | 142 | 141 | 141 |
| Hydroisomerizing dewaxing/post-refining process condition | |||
| Catalyst | FIW-1/FHDA-1 | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 | 2:1 |
| Reaction temperature/DEG C | 335/255 | 335/255 | 335/255 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 800 |
| Cumulative volume air speed/h-1 | 1.0 | 1.0 | 1.0 |
| > 320 DEG C of lube cut character | |||
| Yield (* *), wt% | 76.93 | 76.87 | 77.12 |
| Pour point/DEG C | -21 | -21 | -21 |
| Viscosity (40 DEG C), mm/s2 | 28.47 | 28.66 | 28.61 |
| Viscosity (100 DEG C), mm/s2 | 5.287 | 5.300 | 5.281 |
| Viscosity index (VI) | 119 | 119 | 118 |
Table 4 comparative example result of the test (operates 500 hours)。
| Comparative example 1 | Comparative example 2 | |
| Hydrogenation cracking zone process conditions | ||
| Catalyst | A/FC-50 | B/FC-50 |
| First paragraph denitrification percent, wt% | 80 | 80 |
| Reaction pressure/MPa | 15.7 | 15.7 |
| Volume space velocity/h-1 | 0.5/1.8 | 0.5/1.8 |
| Hydrogen to oil volume ratio | 900/1300 | 900/1300 |
| Reaction temperature/DEG C | 403/386 | 397/386 |
| > 370 DEG C of tail oil viscosity index (VI)s | 141 | 140 |
| Hydroisomerizing dewaxing/post-refining process condition | ||
| Catalyst | FIW-1/FHDA-1 | FIW-1/FHDA-1 |
| Catalyst volume ratio | 2:1 | 2:1 |
| Reaction temperature/DEG C | 330/251 | 330/251 |
| Reaction pressure/MPa | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 800 | 800 |
| Cumulative volume air speed/h-1 | 1.0 | 1.0 |
| > 320 DEG C of lube cut character | ||
| Yield (* *), wt% | 76.87 | 76.95 |
| Pour point/DEG C | -21 | -21 |
| Viscosity (40 DEG C), mm/s2 | 28.97 | 28.83 |
| Viscosity (100 DEG C), mm/s2 | 5.316 | 5.321 |
| Viscosity index (VI) | 118 | 119 |
Above example shows, adopt the method for hydrogen cracking of the present invention, hydrofinishing includes two conversion zones, when the inferior heavy distillate feedstock that processing nitrogen content is higher, the activity of the more effective performance Hydrobon catalyst of energy, inferior heavy distillate is converted into qualified hydrogenation cracked charge, thus providing qualified raw material for isomerization dewaxing。Hydrocracking tail oil as isomerization dewaxing charging, is greatly improved the yield of lube base oil after prefractionation。
Owing to hydrofining reaction temperature is 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, or drop low operating pressure when maintaining like denitrification percent。
Claims (15)
1. inferior heavy distillate produces a process for lube base oil, including herein below:
(1) when hydrofining technology, inferior heavy distillate enters first paragraph reaction zone after mixing with hydrogen and carries out hydrofining reaction, and first paragraph reaction zone includes Hydrobon catalyst, and the denitrification percent of first paragraph reaction zone controls as 60wt% ~ 95wt%；
(2) first paragraph reaction zone effluent entrance separator is easily separated, and obtains gas phase and liquid phase；
(3) step (2) obtains entrance second segment reaction zone after liquid phase mixes with hydrogen, carries out hydrofining reaction, and second segment reaction zone uses Hydrobon catalyst；
(4) hydrogenation reaction effluent that step (3) obtains enters the 3rd section of reaction zone after mixing with hydrogen, carries out hydrocracking reaction, and the 3rd section of reaction zone uses hydrocracking catalyst；
(5) step (4) obtains hydrocracking reaction effluent and enters piece-rate system, one or more and tail oil of separated gas, Petroleum, 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 of step (6) gained tail oil fraction, enters isomerization dewaxing reaction zone, carries out isomerization dewaxing reaction after mixing with hydrogen；Isomerization dewaxing reaction effluent enters post-refining conversion zone and carries out post-refining reaction；
(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 used in first paragraph reaction zone has the property that the average pore diameter of catalyst is 7.5 ~ 9.5nm, 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, and < pore volume in 4nm hole accounts for less than the 5% of total pore volume；The Hydrobon catalyst used in second segment reaction zone has the following properties that, the average pore diameter of catalyst is 4 to less than 7.5nm, 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, and < pore volume in the hole of 4nm accounts for the volume fraction of total pore volume lower than 10%。
2. in accordance with the method for claim 1, it is characterised in that the nitrogen content of described inferior heavy distillate is 1500 more than μ g/g。
3. in accordance with the method for claim 2, it is characterised in that the nitrogen content of described inferior heavy distillate is 2000 more than μ g/g。
4. in accordance with the method for claim 3, it is characterised in that the nitrogen content of described inferior heavy distillate is 2500 ~ 15000 μ g/g。
5. in accordance with the method for claim 2, it is characterised in that the end point of distillation of described inferior heavy distillate is 470～550 DEG C。
6. in accordance with the method for claim 1, it is characterised in that it is 70%～90% that the denitrification percent of first paragraph reaction zone controls。
7. in accordance with the method for claim 1, it is characterized in that, the process conditions of first paragraph reaction zone are: average reaction temperature is 300～480 DEG C, and reaction pressure is 5.0～20.0MPa, hydrogen to oil volume ratio is 100:1～4000:1, and during liquid, volume space velocity is 0.2～4.0h-1；Process conditions in second segment reaction zone are: average reaction temperature is 250～500 DEG C, and reaction pressure is 5.0～20.0MPa, and hydrogen to oil volume ratio is 100:1～4000:1, and during liquid, volume space velocity is 1.0～10.0h-1；The process conditions of the 3rd section of reaction zone are: average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1 ~ 4000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h-1。
8. in accordance with the method for claim 1, it is characterised in that in described step (3), in step (2), the liquid phase after the gas-liquid separation of first paragraph reaction zone is first washed with water, then enter second segment reaction zone with hydrogen again。
9. in accordance with the method for claim 1, it is characterized in that, 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。
10. in accordance with the method for claim 1, it is characterised in that the catalyst used in first paragraph reaction zone has the property that the average pore diameter of catalyst 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 catalyst used in second segment reaction zone has the property that the average pore diameter of catalyst is 5 ~ 7nm, its median pore diameter is that to account for the volume fraction of total pore volume be 55 ~ 65% for the pore volume in the hole of 4 ~ 10nm。
12. the method described in claim 1 or 9, it is characterized in that, compared with the Hydrobon catalyst in first paragraph reaction zone, 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。
13. in accordance with the method for claim 1, it is characterized in that, the Hydrobon catalyst used in first paragraph reaction zone and second segment reaction zone is made up of carrier and the hydrogenation metal component being loaded on carrier, catalyst includes in the periodic table of elements group VIB active metal component in oxide weight 8% ~ 35%, VIIIth race's active metal component is in oxide weight 1% ~ 7%, and carrier is inorganic refractory oxide。
14. in accordance with the method for claim 1, it is characterized in that, using body phase hydrogenation catalyst in second segment reaction zone, described 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 exists with oxide form: 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%。
15. in accordance with the method for claim 14, it is characterized in that, possibly together with one or more in aluminium oxide, silicon oxide, amorphous silica-alumina, phosphorous oxides, titanium oxide, Zirconium oxide and molecular sieve in described bulk phase catalyst, these components weight content in the catalyst is 1 ~ 60%。
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| CN101333460A (en) * | 2007-06-26 | 2008-12-31 | 中国石油化工股份有限公司 | Combined technological process for producing lube oil base stock |
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| 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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