CN103773476A - Method for producing high-viscosity-index lubricant base oil by hydrocracking-isodewaxing combination - Google Patents
Method for producing high-viscosity-index lubricant base oil by hydrocracking-isodewaxing combination Download PDFInfo
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Abstract
The invention discloses a method for producing high-viscosity-index lubricant base oil by hydrocracking-isodewaxing combination. The method is as follows: after hydrocracking technology processing of raw oil, hydrocracking tail oil enters into a first hydroisodewaxing reaction zone, reaction products are separated to obtain light lubricant base oil fractions and heavy base oil fractions; the heavy base oil fractions are partly discharged as products, and the rest part of the heavy base oil fractions enters a second hydroisodewaxing reaction zone, the high-viscosity-index heavy lubricant base oil with the pour point meeting the requirements is obtained by control of the isomerization reaction depth. Compared with the prior art, according to the method, new hydrogen passes through an isodewaxing unit in one time, tail hydrogen directly returns back to a hydrocracking unit to be used as supplement hydrogen, two units have only one hydrogen circulation system, device construction investment and operation cost are obviously reduced, light and heavy lubricant base oil with the quality meeting the requirements are obtained, the process is simple, and the operation energy consumption is low.
Description
Technical field
The present invention relates to a kind of production method of lubricant base, particularly relate to a kind of combination process that adopts hydrocracking-isomerization dewaxing and produce light, heavy lubricating oil base oil.
Background technology
It is to adopt solvent process that traditional lubricant base is produced, and its main two steps are to adopt the undesirable components such as solvent treatment removal aromatic hydrocarbons and solvent dewaxing to guarantee the low temperature flowability of base oil.In addition, generally also to carry out carclazyte or hydrofinishing.
Due to worldwide crude oil in poor quality, the paraffinic crude quantity that is suitable for traditional technology production base oil of high viscosity index lubricant is reduced gradually, therefore, hydrogenation method is produced Lubricating Oil Technique and is developed very rapid.Hydrogenation method technique refers to the process that adopts hydrotreatment or hydrocracking process-hydrodewaxing or isomerization dewaxing-hydrofining process integration to produce lubricant base, and this technological advantage is that feed flexibility is large, base oil yield is high, by-product value is high.
Lubricating oil isomerization dewaxing is the new technology of the production high quality API II/III class lubricating oil base oil of the nineties exploitation in last century.Isomerization dewaxing is that straight-chain paraffin higher condensation point in oil product is generated to isoparaffin by isomerization reaction, reaches the technology that reduces product pour point and keep higher lubricant base yield.Compare with catalytic dewaxing with solvent dewaxing, isomerization dewaxing base oil yield is high, pour point is low, viscosity index is high, is the good blend component of modern high performance I. C. engine oil.
The key of lubricating oil Isodewaxing Technology is isomerization catalyst.According to the reaction mechanism of alkane isomerization, all isomerization dewaxing catalysts are all the dual-function catalysts that are made up of the noble metal component of high hydrogenation activity and the molecular sieve of acid active ingredient.This composition has determined that catalyzer is very responsive to the sulphur in isomerization dewaxing raw material, nitrogen impurity, raw material must be through the hydrotreatment of the degree of depth, or adopt sulphur, nitrogen impurity content little raw material as hydrocracking tail oil and Fischer-Tropsch synthetic wax etc., the raw material that enters isomerization reactor will be controlled sulphur content and be less than 10 μ g/g, and nitrogen content is less than 5 μ g/g.
US7,198,710 have proposed a kind of method of being produced base oil of high viscosity index lubricant by Fischer-Tropsch wax.First Fischer-Tropsch wax is carried out to fractionation and obtain light constituent and heavy constituent, then carry out respectively hydroisomerization dewax and reduce raw material pour point, can obtain the light lubricating oil base oil that pour point meets the demands.Hydroisomerization dewax heavy constituent, because pour point is defective, adopts the method for solvent dewaxing further to reduce the pour point of heavy constituent, finally obtains the satisfactory heavy grease base oil product of pour point.
US 6,676,827 discloses the method for the low solidifying lubricant base of a kind of isomerization dewaxing production.Adopt hydrocracking-isomerization dewaxing two-stage hydrogenation operational path, hydrocracking and isomerization dewaxing all have hydrogen gas circulating system separately, and this is that current hydrogenation method is produced the modal technological process of lubricant base.Owing to adopting two-stage process, therefore technical process complexity, equipment is many, operating cost is high.
US 4,283,272 discloses a kind of method that hydrocracking-Hydrodewaxing-post-refining one segment process is produced lubricant base.This technology has increased an absorbing unit behind hydrocracking unit, thereby can remove hydrogen sulfide and ammonia in isocrackate, then this logistics directly enters Hydrodewaxing and post-refining unit, is therefore only having a hydrogen gas circulating system to reach the object of producing lubricant base.But isocrackate is without fractionation by distillation, and lubricating oil component and light-end products all enter Hydrodewaxing and post-refining unit simultaneously, greatly reduces their reaction efficiency, has increased energy consumption and running cost.And must increase an absorbing unit and realize a segment process and produce the object of lubricating oil, increase plant investment, make process more complicated.
Summary of the invention
For the deficiencies in the prior art, a kind of method that the invention provides technical process and produce simply, flexibly lubricant base.
Hydrocracking of the present invention-isomerization dewaxing is produced base oil of high viscosity index lubricant method, comprises the steps:
(1) stock oil and hydrogen are mixed into hydrocracking reaction district, contact with hydrocracking catalyst, carry out hydrocracking reaction;
(2) step (1) gained hydrocracking effluent enters separation system, and separating obtained gas returns to hydrocracking reaction district as recycle hydrogen, and liquid product enters fractionating system;
(3) hydrocracking tail oil obtaining after step (2) fractionation is mixed into the first hydroisomerization dewax reaction zone with new hydrogen, contacts and reacts with hydroisomerization dewax catalyzer;
(4) step (3) hydroisomerization dewax reaction effluent enters separation system, separating obtained gas as a supplement hydrogen returns to hydrocracking reaction district, and liquid product obtains that pour point meets the demands after separation system separates, the light lubricating oil base oil fractions of high viscosity index (HVI) and heavy grease base oil fractions;
(5) the heavy grease base oil fractions part that step (4) obtains is discharged as product, remainder is mixed into the second hydroisomerization dewax reaction zone with new hydrogen, the second hydroisomerization dewax reaction zone reaction effluent and the first hydroisomerization dewax reaction zone reaction effluent enter same separation system jointly, by controlling the isomerization reaction degree of depth of the second hydroisomerization dewax reaction zone, make separation system discharge meet index request as the pour point of the heavy grease base oil of product, and keep higher viscosity index.
In the inventive method, stock oil is one or more in vacuum distillate, solvent treatment deasphalted oil and Fischer-Tropsch synthesis oil.
In the inventive method, only a hydrogen gas circulating system is set in hydrocracking reaction district, hydroisomerization dewax reaction zone hydrogen adopts one-pass mode.Hydrocracking method of the present invention can adopt single-stage hydrocracking technique, also can adopt serial hydrocracking technique.It is main (can have protective material etc.) that single-stage hydrocracking technique refers to use a kind of type catalyst.Series process flow refers to that dissimilar catalyzer has formed the two or several different reaction zone of order, can in a reactor, load dissimilar catalyzer, form cascade reaction district, also can use in two or more tandem reactors and use dissimilar catalyzer, form cascade reaction district.In serial hydrocracking technique, raw material is first by conventional Hydrobon catalyst bed, then by hydrocracking catalyst bed.
Hydrocracking reaction district catalyzer used is conventional Hydrobon catalyst and hydrocracking catalyst, its active metal is group vib or group VIII metal, use procatalyst should vulcanize, guarantee hydrogenation active metals in reaction process in sulphided state.Can select this field general goods catalyzer.
Hydrocracking process can be conventional hydroprocessing condition, and general reaction conditions is reaction pressure 0.5～18.0MPa, 230～430 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1500, volume space velocity 0.5～10.0h
-1.
The hydroisomerization dewax catalyzer that the inventive method is used can be selected the conventional lube oil hydrogenation heterogeneous catalyst in this area, can commodity in use hydroisomerization catalyst, also can prepare by this area general knowledge.Described hydroisomerization dewax catalyzer, carrier is NU-10 molecular sieve or the ZSM-22 molecular sieve of aluminum oxide and TON structure, the content of molecular sieve in catalyzer is 30wt%～80wt%, is preferably 40wt%～70wt%, also can add partial oxygen SiClx in carrier; Active metal component be in Pt, Pd, Ru, Rh and Ni one or more, the content in catalyzer is 0.1wt%～30.0wt%.Selectable adjuvant component is one or more in boron, fluorine, chlorine and phosphorus, and the content in catalyzer is 0.1wt%～5.0wt%; The specific surface of this catalyzer is 150～500m
2/ g, pore volume is 0.15～0.60ml/g.Use before catalyzer is reduced, make hydrogenation active metals in reaction process in reduction-state.The catalyzer that the first hydroisomerization dewax reaction zone and the second hydroisomerization dewax reaction zone are used can be selected in the hydroisomerization catalyst of foregoing description, two reaction zones can be used identical hydroisomerization catalyst, also can use different hydroisomerization catalysts.
In the inventive method, go into operation the initial stage at hydroisomerization dewaxing reaction unit, the pour point of the heavy grease base oil product that separation system obtains does not reach index request, whole heavy grease base oil product need to be entered to the second hydroisomerization dewax reaction zone, when after the steady running of hydroisomerization dewaxing reaction unit, maintain suitable heavy grease base oil circulation ratio, can obtain all qualified heavy grease base oil product of pour point and viscosity index, in general mass ratio (the heavy grease base oil fractions that separation system obtains circulates, circulation enters the amount of the second hydroisomerization dewax reaction zone and the ratio of amount that goes out device as product) be 0.2:1～5:1, be preferably 0.5:1～2:1, specifically can determine according to feedstock property and product quality indicator.
In the inventive method, the viscosity index of the light lubricating oil base oil fractions (1～2 sideline product that distillation obtains) obtaining and heavy grease base oil fractions (1 sideline product that distillation obtains and bottom product) is all greater than 120, is generally 120～170.The pour point of light lubricating oil base oil fractions and heavy grease base oil fractions is all lower than-10 ℃, preferably lower than-15 ℃.The pour point of light lubricating oil base oil fractions is generally-10～-30 ℃, is preferably-15～-27 ℃; The pour point of heavy grease base oil fractions is generally-10～-25 ℃, is preferably-12～-21 ℃.
The reaction conditions in the first described hydroisomerization dewax district is: temperature is 280 ℃～350 ℃, and preferably 300 ℃～330 ℃, hydrogen dividing potential drop is 2.0MPa～18.0MPa, preferably 10.0 MPa～15.0MPa, and when raw material fluid, volume space velocity is 0.4 h
-1～6.0h
-1, preferably 0.8 h
-1～1.8h
-1, hydrogen to oil volume ratio 400:1～1500:1, preferably 600:1～800:1.
The reaction conditions in the second described hydroisomerization dewax district is: temperature is 300 ℃～380 ℃, and preferably 310 ℃～340 ℃, hydrogen dividing potential drop is 2.0MPa～18.0MPa, preferably 10.0～15.0MPa, and when raw material fluid, volume space velocity is 0.2h
-1～6.0h
-1, preferably 0.4 h
-1～0.8h
-1, hydrogen to oil volume ratio 400:1～1500:1, preferably 600:1～800:1.
The reaction conditions in the first hydroisomerization dewax district and the second hydroisomerization dewax district can be identical, also can be different, specifically require to adjust according to quality product, the isomerization reaction degree of depth of the isomerization reaction degree of depth of the first hydroisomerization dewax reaction zone and the second hydroisomerization dewax reaction zone is mainly adjusted by temperature of reaction, temperature of reaction is higher, temperature of reaction is darker, and the pour point of reaction product is lower, but viscosity index reduces.Preferably the temperature of reaction in the second hydroisomerization dewax district is higher than 10～60 ℃, the first hydroisomerization dewax district.
In the inventive method, separation system generally comprises high-pressure separator, light pressure separator and separation column, and the liquid product that the liquid product that the first hydroisomerization dewax district obtains and the second hydroisomerization dewax district obtain carries out fractionation in same vacuum still.The underpressure distillation adopting is to well known to a person skilled in the art technology, can guarantee well product colour.As the condition of underpressure distillation is generally: vacuum still feeding temperature is 350 ℃～410 ℃, more suitable feeding temperature is 375 ℃～400 ℃; Vacuum still tower top pressure is 4KPa～10KPa, and more suitable tower top pressure is 5KPa～8KPa; Vacuum still tower top temperature is 110～180 ℃, can obtain some light-end products.The condition of underpressure distillation generally can be adjusted in above-mentioned scope, obtains required product.
In the inventive method, the cut-point temperature that obtains respectively light lubricating oil base oil fractions and heavy grease base oil fractions is 450～520 ℃, be in vacuum still, it is 450～520 ℃ that temperature (referring to true boiling point temperature) is cut apart in the distillation of light lubricating oil base oil fractions and heavy grease base oil fractions, boiling point is light lubricating oil base oil fractions lower than the lubricant base of cut-point, boiling point enters the second hydroisomerization dewax reaction zone higher than the heavy grease base oil fractions part of cut-point and further reacts, and remainder is discharged as product.
In the inventive method, vacuum still generally can arrange 2～3 side lines (according to raw material condition, 2 side lines can be set 3 side lines also can be set), correspondingly obtain 1～2 light lubricating oil base oil, 100 ℃ of viscosity of light lubricating oil base oil are 2.5-3.5mm
2/ s and 3.5-4.5mm
2/ s, the temperature of the side line that light lubricating oil base oil is corresponding is followed successively by 330 ℃～340 ℃ and 350 ℃～360 ℃ from low to high.Obtain 100 ℃ of viscosity simultaneously and be respectively 5.5-6.5mm
2/ s(sideline product) and 9.5-10.5mm
2/ s(bottom product) heavy grease base oil product, the temperature of side line is: 380 ℃～390 ℃.Vacuum still tower top temperature is 110～180 ℃, can obtain some light-end products.
In the inventive method, also can behind each hydroisomerization dewax reaction zone, increase hydrofinishing reaction zone, improve color and the stability of base oil product.Hydrofinishing catalyzer, for conventional reduced form Hydrobon catalyst, its active metal is that one or both or the active metal in Pt, Pd is reduced state nickel catalyzer, in noble metal catalyst, active metal is generally 0.05%～1% at the weight content of catalyzer, the active metal of reduced state nickel catalyzer counts 30%～80% with oxide weight, and support of the catalyst is generally Al
2o
3or Al
2o
3-SiO
2, can contain the auxiliary agents such as P, Ti, B, Zr.Use procatalyst carry out conventional reduction, guarantee hydrogenation active metals in reaction process in reduction-state.Can select this field general goods catalyzer, or by the preparation of this area usual way.
Described hydrofinishing reaction conditions is: temperature is 200 ℃～300 ℃, and preferably 210 ℃～280 ℃, hydrogen dividing potential drop is 6.0MPa～18.0MPa, preferably 10.0～15.0MPa, and volume space velocity is 0.3h
-1～3.0h
-1, be preferably 0.6h
-1～1.2h
-1, hydrogen to oil volume ratio 400:1～1500:1, preferably 600:1～800:1.
The inventive method by waxy oil hydroisomerization dewax process analysis know, under identical hydroisomerization dewax condition, the isomerization dewaxing degree of depth difference of weight component, for reaching identical pour point requirement, compare with light constituent, heavy constituent needs the higher isomerization dewaxing degree of depth.By controlling the depth of conversion of isomerization dewaxing process, make weight component in waxy oil in different isomerization dewaxing reaction zones, reach respectively the best dewaxing degree of depth, reach optimal balance point thereby realize between the pour point of light, heavy lubricating oil base oil product and viscosity index.
Compared with prior art, the inventive method is without waxy oil raw material is carried out to prefractionation, can solve the qualified lightweight of pour point and the method for heavy base oil of high viscosity index lubricant of producing, a head tank only need be set and a set ofly separate, Distallation systm, in actual production also without switching raw material and frequent adjusting process parameter, greatly reduce the construction investment of device and the operation easier of device, and significantly reduced the quantity of substandard product.
The present invention has that technical process is simple, process cost and invest the advantages such as low.Hydroisomerization dewax catalyzer is the dual-function catalyst being made up of the noble metal component of high hydrogenation activity and the molecular sieve of acid active ingredient.This composition has determined that sulphur, the nitrogen content in hydroisomerization dewax raw material is very low, in the hydrogen of charging, can not contain hydrogen sulfide and ammonia.According to this area general knowledge and prior art, hydroisomerization dewax product need to be obtained not containing H through high and low pressure separation and distillation
2s and NH
3hydrogen, as recycle hydrogen return hydroisomerization dewax reactor continue use.The present invention learns by the detailed analysis of the whole technological process to hydroisomerization dewax, the hydrogen consumption of hydroisomerization dewax process is not high, methane, ethane that process generates are little, so hydrogen purity is still very high in the gas that isomerization dewaxing generation oil obtains after separating, can once pass through the also direct use of the hydrogen make-up as hydrocracking process, thereby omit the hydrogen recycle of hydroisomerization dewax process.Two sections of combination process processes of whole hydrocracking-isomerization dewaxing, realize the mouth-to-mouth hot feed of hydrocracking and isomerization dewaxing Liang Ge workshop section, and the heavy basestock component temperature that isomerization dewaxing separation column bottom obtains is higher, a large amount of heats directly can be brought into the second hydroisomerizing reaction zone, thereby the thermal load of reduction the second hydroisomerizing reaction zone, only need one section of hydrogen recycle, simplified significantly technical process, and greatly reduce plant construction investment and process cost simultaneously.
Accompanying drawing explanation
Fig. 1 is hydrocracking-producing base oil of lubricating oil by isomerization dewaxing process flow diagram of the present invention.
Embodiment
In the embodiment of the present invention, hydrocracking reaction district adopts conventional one-stage serial hydrocracking process, and the gas obtaining after separating uses as the recycle hydrogen of hydrocracking.
The present invention produces the technical process of lubricant base and specifically sees Fig. 1: stock oil 1 enters hydrocracking pretreatment reaction district 3 after mixing with hydrogen, hydrogenation pre-treatment is flowed out thing 4 and is entered hydrocracking reaction district 5, under hydrogen and hydrocracking catalyst existence, carry out hydrocracking reaction, reaction product is after separation system 7 separates, gas phase 8 is returned to hydrocracking pretreatment reaction district 3 and hydrocracking reaction district 5 as recycle hydrogen through circulating hydrogen compressor, liquid product is after separation column 10 fractionation, obtain gasoline 11, diesel oil 12 and hydrocracking tail oil 13, wherein tail oil 13 is mixed into the first hydroisomerization dewax reaction zone 14 with new hydrogen 2, reaction effluent is after high-pressure separator 15 separates, gas 16 returns to hydrocracking pretreatment reaction district 3 and hydrocracking reaction district 5 as recycle hydrogen after circulating hydrogen compressor compression, liquid phase enters 17 and enters light pressure separator 18 and further separate, light pressure separator effluent 19 enters separation column 20, after separation column, obtain pour point qualified, the lighter body cut 21 that viscosity index is high and heavy grease base oil fractions, a part 22 for heavy grease base oil fractions is discharged as product, remainder heavy grease base oil fractions 23 is mixed and is continued to enter the second hydroisomerization dewax reaction zone 24 with new hydrogen 2, the second hydroisomerization dewax reaction zone reaction effluent 25 and the first hydroisomerization dewax reaction effluent are mixed and enter separation system.
The various catalyzer that relate in the embodiment of the present invention can be selected commercial catalyst by character, also can prepare by this area knowledge.Wherein, in one-stage serial hydrocracking process, the commercial catalysts that hydrocracking pretreatment reaction district can select as 3936,3996 of Fushun Petrochemical Research Institute (FRIPP) development and production, the pretreating catalyst by hydrocracking such as FF-16 and FF-26.The commercial catalysts that hydrocracking reaction district catalyzer can be selected as 3825,3974 of Fushun Petrochemical Research Institute (FRIPP) development and production, the commodity hydrotreating catalyst such as FC-14.Hydroisomerization dewax catalyzer is as the FIW-1 catalyzer of Fushun Petrochemical Research Institute (FRIPP) development and production.Also can be prepared above-mentioned catalyzer by prior art, as hydrocracking catalyst can be by the existing patented technology preparation such as CN97116403.7, CN00123130.8, CN00110021.1.Hydroisomerization dewax catalyzer can be by the existing patented technology preparation such as CN03133557.8, CN02133128.6.
As press as described in CN00123130.8, hydrocracking catalyst catalyzer comprises beta-molecular sieve, refractory porous oxide, group vib and the VIII family metal oxide of amorphous aluminum silicide, modification, take the weight percent of catalyzer as benchmark, in catalyzer, contain modified beta molecular sieve 1w%～9w%, silicon-dioxide/aluminium sesquioxide weight ratio of modified beta molecular sieve is 50～90, average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.
As press as described in CN02133128.6, hydroisomerization dewax support of the catalyst is NU-10 molecular sieve or the ZSM-22 molecular sieve of aluminum oxide and TON structure; The content of molecular sieve in catalyzer is 30wt%～80wt%; Active metal component be in Pt, Pd, Ru, Rh and Ni one or more, the content in catalyzer is 0.1wt%～30.0wt%; Its specific surface is 150～500m
2/ g, pore volume is 0.15～0.60ml/g.
The present invention has that technical process is simple, plant investment is low and the feature such as running cost is low.
Below by particular content and the effect of specific embodiment explanation the inventive method.
Implementation column below will be further described method provided by the invention, but scope not thereby limiting the invention.Raw material specific nature of the present invention is in table 1, and hydrocracking pretreatment reaction district is used 3936 catalyzer, and hydrocracking reaction district and hydroisomerization dewax reaction zone are that the physico-chemical property of catalyzer of use is in table 2.
Table 1 test feedstock property
| Raw material | Subtract three line distillates |
| Density (20 ℃), kg/m 3 | 878.3 |
| Boiling range, ℃ (D1160) | ? |
| IBP/10%/30% | 315/341/377 |
| Sulphur, wt% | 0.89 |
| Nitrogen, μ g/g | 63.5 |
| Condensation point, ℃ | 35 |
| Viscosity (100 ℃), mm/s 2 | 3.68 |
| Flash-point (opening), ℃ | 203 |
| Wax content, wt% | 15.21 |
The physico-chemical property of table 2 catalyzer
| Catalyzer | Hydrocracking catalyst | Hydroisomerization dewax catalyzer |
| Amorphous aluminum silicide, wt% | 59 | ? |
| Modified beta molecular sieve, wt% | 3 | ? |
| Macroporous aluminium oxide, wt% | 10 | ? |
| Molecular sieve NU-10, wt% | ? | 70 |
| Tackiness agent, wt% | 28 | ? |
| WO 3，wt% | 22.1 | ? |
| NiO，wt% | 5.8 | ? |
| Pt，wt% | ? | 0.15 |
| Pd，wt% | ? | 1.35 |
| P，wt% | ? | 3.35 |
| SiO 2，wt% | 27.6 | ? |
| Al 2O 3，wt% | Surplus | Surplus |
| Pore volume, mL/g | 0.372 | 0.55 |
| Specific surface area, m 2/g | 182 | 500 |
The present embodiment has been introduced hydrocracking unit and hydroisomerization dewax unit catalyzer in employing table 2 respectively, listed raw material in processing list 1.Hydroisomerization dewax unit hydrogen once passes through, and tail hydrogen is as the hydrogen make-up of hydrocracking, and the reaction conditions of hydrocracking reaction district and hydroisomerization dewax unit and reaction result are specifically in table 3.Vacuum fractionation tower behind the first hydroisomerization dewax reaction zone arranges two side lines, produces respectively No. 4 base oils and No. 6 base oils, and bottom product is produced No. 10 base oils.The cut-point control of light lubricating oil base oil and heavy grease base oil is 480 ℃.
Comparative example 1
Comparative example 1 adopts hydrocracking in the same manner as in Example 1 and hydroisomerization dewax catalyzer, and hydrocracking and hydroisomerization dewax process all adopt separately independently hydrogen cycle process, obtains result specifically in table 3.
Comparative example 2
Comparative example 2 adopts raw material in the same manner as in Example 1 and catalyzer, adopts the technological process of single hydroisomerization dewax reactor production basis oil, the results are shown in Table 3.
From table 3, the comparative data of embodiment and comparative example 2 is known, concerning raw material does not carry out the prior art scheme of prefractionation, can not obtain all qualified lubricant bases.The comparative data of embodiment and comparative example 1 is known, compared with prior art, under identical reaction conditions, the lubricant base product yield and the character that obtain are basic identical for process of the present invention, but owing to only adopting one section of hydrogen recycle, so plant investment and device process cost are reduced.
The processing condition of table 3 embodiment and comparative example and result
| Test number | Embodiment | Comparative example 1 | Comparative example 2 |
| Hydrocracking reaction district processing condition | ? | ? | ? |
| Temperature of reaction, ℃ | 375 | 375 | 375 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 |
| Hydrogen to oil volume ratio | 1000 | 1000 | 1000 |
| Volume space velocity, h -1 | 1.0 | 1.0 | 1.0 |
| The first hydroisomerization dewax district processing condition | ? | ? | ? |
| Temperature of reaction, ℃ | 305 | 305 | 315 |
| Reaction pressure, Mpa | 9.0 | 9.0 | 9.0 |
| Hydrogen to oil volume ratio | 600 | 600 | 600 |
| Volume space velocity, h -1 | 1.2 | 1.2 | 1.2 |
| The second hydroisomerization dewax district processing condition | ? | ? | ? |
| No. 10 base oil circulation mass ratioes | 2：1 | — | — |
| Temperature of reaction, ℃ | 320 | 320 | — |
| Reaction pressure, Mpa | 9.0 | 9.0 | — |
| Hydrogen to oil volume ratio | 600 | 600 | — |
| Volume space velocity, h -1 | 1.5 | 1.5 | — |
| No. 4 base oils | ? | ? | ? |
| Yield, % | 23.2 | 23.1 | 25.7 |
| Pour point, ℃ | -18 | -18 | -33 |
| Viscosity (40 ℃), mm/s 2 | 19.41 | 19.33 | 19.05 |
| Viscosity (100 ℃), mm/s 2 | 4.198 | 4.156 | 4.012 |
| Viscosity index | 121 | 118 | 108 |
| No. 6 base oils | ? | ? | ? |
| Yield, % | 19.6 | 19.2 | 18.6 |
| Pour point, ℃ | -18 | -18 | -24 |
| Viscosity (40 ℃), mm/s 2 | 34.54 | 34.33 | 34.68 |
| Viscosity (100 ℃), mm/s 2 | 6.127 | 6.101 | 5.965 |
| Viscosity index | 126 | 125 | 117 |
| No. 10 base oils | ? | ? | ? |
| Yield, % | 35.3 | 35.1 | 32.1 |
| Pour point, ℃ | -15 | -15 | -9 |
| Viscosity (40 ℃), mm/s 2 | 68.51 | 69.52 | 70.12 |
| Viscosity (100 ℃), mm/s 2 | 10.021 | 9.984 | 9.989 |
| Viscosity index | 130 | 124 | 125 |
Claims (13)
1. hydrocracking-isomerization dewaxing is produced a base oil of high viscosity index lubricant method, comprises the steps:
(1) stock oil and hydrogen are mixed into hydrocracking reaction district, contact with hydrocracking catalyst, carry out hydrocracking reaction;
(2) step (1) gained hydrocracking effluent enters separation system, and separating obtained gas returns to hydrocracking reaction district as recycle hydrogen, and liquid product enters fractionating system;
(3) hydrocracking tail oil obtaining after step (2) fractionation is mixed into the first hydroisomerization dewax reaction zone with new hydrogen, contacts and reacts with hydroisomerization dewax catalyzer;
(4) step (3) hydroisomerization dewax reaction effluent enters separation system, separating obtained gas as a supplement hydrogen returns to hydrocracking reaction district, and liquid product obtains that pour point meets the demands after separation system separates, the light lubricating oil base oil product of high viscosity index (HVI) and heavy grease base oil fractions;
(5) the heavy grease base oil fractions part that step (4) obtains is discharged as product, remainder is mixed into the second hydroisomerization dewax reaction zone with new hydrogen, the second hydroisomerization dewax reaction zone reaction effluent and the first hydroisomerization dewax reaction zone reaction effluent enter same separation system jointly, by controlling the isomerization reaction degree of depth of the second hydroisomerization dewax reaction zone, make separation system discharge meet index request as the pour point of the heavy grease base oil of product, and keep higher viscosity index.
2. it is characterized in that in accordance with the method for claim 1: stock oil is one or more in vacuum distillate, solvent treatment deasphalted oil and Fischer-Tropsch synthesis oil.
3. in accordance with the method for claim 1, it is characterized in that: the heavy grease base oil fractions that separation system obtains, circulation enters the amount of the second hydroisomerization dewax reaction zone and the ratio of amount that goes out device as product, and the mass ratio that circulates is 0.2:1～5:1.
4. it is characterized in that in accordance with the method for claim 3: circulation mass ratio is 0.5:1～2:1.
5. in accordance with the method for claim 1, it is characterized in that: hydrocracking reaction district arranges hydrogen gas circulating system, hydroisomerization dewax reaction zone hydrogen adopts one-pass mode.
6. in accordance with the method for claim 1, it is characterized in that: hydrocracking method adopts single-stage hydrocracking technique, or serial hydrocracking technique, it is main that single-stage hydrocracking technique refers to use a kind of type catalyst, serial hydrocracking technique refers to that dissimilar catalyzer has formed the two or several different reaction zone of order, in serial hydrocracking technique, raw material is first by conventional Hydrobon catalyst bed, then by hydrocracking catalyst bed.
7. in accordance with the method for claim 1, it is characterized in that: the operational condition in hydrocracking reaction district is reaction pressure 0.5～18.0MPa 230～430 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1500, volume space velocity 0.5～10.0h
-1.
8. in accordance with the method for claim 1, it is characterized in that: the viscosity index of light lubricating oil base oil fractions and heavy grease base oil fractions is all greater than 120, the pour point of light lubricating oil base oil fractions is-10～-30 ℃, and the pour point of heavy grease base oil fractions is-10～-25 ℃.
9. according to the method described in claim 1 or 3, it is characterized in that: the cut-point temperature of light lubricating oil base oil fractions and heavy grease base oil fractions is 450～520 ℃, boiling point is light lubricating oil base oil fractions lower than the lubricant base of cut-point, boiling point enters the second hydroisomerization dewax reaction zone higher than the heavy grease base oil fractions part of cut-point and further reacts, and remainder is discharged as product.
10. in accordance with the method for claim 1, it is characterized in that: the first hydroisomerization dewax reaction zone and the second hydroisomerization dewax reaction zone are used noble metal hydrogenation heterogeneous catalyst, hydroisomerization catalyst carrier is NU-10 molecular sieve or the ZSM-22 molecular sieve of aluminum oxide and TON structure, the content of molecular sieve in catalyzer is 30wt%～80wt%, active metal component be in Pt, Pd, Ru and Rh one or more, the content in catalyzer is 0.1wt%～5.0wt%.
11. in accordance with the method for claim 1, it is characterized in that: the reaction conditions of the first hydroisomerization dewax reaction zone is: temperature is 280 ℃～350 ℃, and hydrogen dividing potential drop is 2.0MPa～18.0MPa, and when raw material fluid, volume space velocity is 0.4 h
-1～6.0h
-1, hydrogen to oil volume ratio 400:1～1500:1; The reaction conditions of the second hydroisomerization dewax reaction zone is: temperature is 300 ℃～380 ℃, and hydrogen dividing potential drop is 2.0MPa～18.0MPa, and when raw material fluid, volume space velocity is 0.2h
-1～6.0h
-1, hydrogen to oil volume ratio 400:1～1500:1.
12. according to the method described in claim 1 or 11, it is characterized in that: the temperature of reaction in the second hydroisomerization dewax district is higher than 10～60 ℃, the first hydroisomerization dewax district.
13. in accordance with the method for claim 1, it is characterized in that: behind each hydroisomerization dewax reaction zone, increase hydrofinishing reaction zone, or a hydrofinishing reaction zone is only set behind the first hydroisomerization dewax reaction zone, to improve color and the stability of base oil product.
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| US10472581B2 (en) | 2016-06-30 | 2019-11-12 | Uop Llc | Process and apparatus for hydrocracking and hydroisomerizing a hydrocarbon stream |
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| US10472581B2 (en) | 2016-06-30 | 2019-11-12 | Uop Llc | Process and apparatus for hydrocracking and hydroisomerizing a hydrocarbon stream |
| CN114437774A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrocracking method for producing high-quality diesel oil and lubricating oil base oil |
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| CN114686261A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Production method of high-viscosity index lubricating oil base oil |
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| CN115584282A (en) * | 2022-11-08 | 2023-01-10 | 国家能源集团宁夏煤业有限责任公司 | Method for producing lubricating oil base oil by Fischer-Tropsch hydrogenated heavy oil and application |
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