CN1926220A - Process to continuously prepare two or more base oil grades and middle distillates - Google Patents
Process to continuously prepare two or more base oil grades and middle distillates Download PDFInfo
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- CN1926220A CN1926220A CNA2005800066544A CN200580006654A CN1926220A CN 1926220 A CN1926220 A CN 1926220A CN A2005800066544 A CNA2005800066544 A CN A2005800066544A CN 200580006654 A CN200580006654 A CN 200580006654A CN 1926220 A CN1926220 A CN 1926220A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
Abstract
Process to prepare simultaneously two or more base oil grades and middle distillates from a de-asphalted oil or a vacuum distillate feed or their mixtures by performing the following steps: (a) hydrocracking the feed, thereby obtaining an effluent; (b) distillation of the effluent as obtained in step (a) into one or more middle distillates and a residue boiling substantially above 340 < DEG >C; (c) separating, by means of a further distillation step said residue into a light base oil precursor fraction and a heavy base oil precursor fraction; (d) reducing the pour point of each separate base oil precursor-fraction iri''two simultaneously and parallel operated catalytic dewaxing reactors obtaining a first and second dewaxed oil; (e) hydrotreating the first dewaxed oil as obtained when dewaxing the heavy base oil precursor fraction in step (d); (f) isolating from the second dewaxed oil from the light base oil precursor fraction from step (d) and the hydrotreated oil from step (e) two or more base oil grades.
Description
Technical field
The present invention relates to prepare continuously the method for two or more base oil fractions and middle runnings.
Background technology
WO-A-0250213 has described a kind of method that wherein prepares different base oil fractions with so-called " modularization " pattern.Bottom fraction with the fuel method for hydrogen cracking is separated into various base oil precursor fractions in the method, and this method also obtains middle runnings as product thus.Use platinum-ZSM-5 catalyst based subsequently with the catalytic dewaxing in succession of these fractions.
WO-A-9718278 discloses a kind of wherein by the initial preparation of bottom fraction of the fuels hydrocracker method of 4 kinds of base oil fractions such as 60N, 100N and 150N at the most.In the method, the bottom fraction is fractionated into 5 kinds of fractions by vacuum distilling, and wherein 4 kinds of heavier fractions of fraction further are processed into different base oil fractions by at first carrying out catalytic dewaxing hydrofining step subsequently.
WO-A-02/50213 discloses so-called " modularization " method that a kind of bottom fraction by the fuel method for hydrogen cracking prepares different base oil fractions.
A shortcoming of above method is that process is discontinuous.In other words, the base oil fraction is not to make simultaneously but in turn make.When hydrocracker bottom fraction by fractionation and when waiting for by catalytic dewaxing, resulting intermediates need basin.Another shortcoming is the corrosion that device heating and the conversion of device refrigerative pattern can cause device.This pattern conversion also can cause at every turn, and the timesharing of the new level of processing produces middle substandard product.These slop oils need be reprocessed or be disposed, and this is disadvantageous.
EP-A-649896 discloses a kind of by comprising that method that the counterweight petroleum carries out hydrotreating step and hydrocracking step prepares the method for the residual oil that comprises base oil.This hydrotreating step can obtain a kind of product, and can obtain middle runnings and bottom fraction (residual oil) by this product.The base oil fraction that subsequently will this bottom fraction solvent dewaxing becomes single-stage to divide.
EP-A-0272729 discloses a kind of method of producing lubricating base oil, wherein will send into hydroeracking unit by the flash distillation thing that the residual oil method for transformation makes.To send into catalytic dewaxing unit from the effluent of hydroeracking unit, and after this choose wantonly whole dewaxing liquid stream is carried out hydrotreatment.
WO-A-9723584 discloses a kind of method of the bottom fraction of fuels hydrocracker being carried out catalytic dewaxing step.Pressed oil partly is recycled to hydrocracking step and part obtains as lubricating base oil.
The shortcoming that is described in the aforesaid method among the WO-A-9723584 is if isolate more than one base oil fraction from pressed oil, wide pour point then occurred and has distributed.In other words, gained will have low pour point than low viscosity base oil fraction.This pour point has been sacrificed desirable value or different with desirable value, indicates that described more low viscous base oil fraction productive rate loses.
An object of the present invention is to provide a kind of method, this method can prepare two or more base oil fractions simultaneously and their pour points separately more approach desired value.
Another object of the present invention provides a kind of interchangeable method.
Summary of the invention
Following method has realized one or more above purposes or other purpose.
Prepare the method for two or more base oil fractions and middle runnings by carrying out following steps simultaneously by deasphalted oil or the charging of vacuum cut or their mixture:
(a), obtain effluent thus with the charging hydrocracking;
(b) effluent that obtains in the step (a) is distilled into one or more middle runningss and boiling point apparently higher than 340 ℃ residual oil;
(c) by further distilation steps described residual oil is separated into lighter body precursor fraction and heavy base oil precursor fraction;
(d) pour point of each isolating base oil precursor fraction of reduction in the catalytic dewaxing reactor of two whiles and parallel running obtains first and second pressed oils;
(e) the first pressed oil hydrotreatment that will obtain in the time of will in step (d), making the dewaxing of heavy base oil precursor fraction;
(f) from going out two or more base oil fractions from second pressed oil of the lighter body precursor fraction of step (d) with from the hydrotreatment of step (e) is separating of oil.
The applicant finds, can prepare two or more base oil fractions continuously man-hour when adding by the present invention, and reduce the hydrotreatment capacity simultaneously, and this is because only will need the heavier fraction of further hydrotreatment to carry out described step (e).In addition, can avoid the pour point sacrifice of any product,, make the pour point low and high viscosity base oil fraction of gained approach desired value because can operate the dewaxing reactor of two parallel runnings.Any pour point sacrifice indicates that all the productive rate that is lower than the fraction of wishing pour point loses.
Embodiment
The charging of step (a) can be the crude oil derived charging of any typical mineral substance of sending into hydrocracker.This class charging can be the vacuum gas oil that the long residuum distillation of crude mineral oil charging obtained under near the condition of vacuum or heavier cut.The deasphalted oil that obtains during the residual oil diasphaltene that obtains in described vacuum distilling also can be used as charging.Cut that the heat-lightening that obtains in the lightweight that obtains in fluidized catalytic cracking method (FCC) and heavy cycle oil, the solvent extraction procedure of processing in traditional base oil process can also be steamed and the extract that is rich in aromatic substances are as charging.Above-mentioned charging also is suitable as charging with the mixture in other hydrocarbon source of choosing wantonly.Except above-mentioned charging, the optional hydrocarbon source of another kind that can be preferably exists with the amount of the 2-30wt% of the charging of step (a) is the paraffin that obtains in Fischer-Tropsch process.Preferably, the charging of step (a) is by the crude oil derived feed composition of mineral substance.
Step (a) can be carried out under the transformation efficiency of 15-90wt%.Transformation efficiency is represented with the weight percent that the boiling point that is converted to boiling point in the charging and is lower than 370 ℃ product is higher than 370 ℃ fraction.It is petroleum naphtha, kerosene and gas oil that boiling point is lower than 370 ℃ main products.The example that is suitable for carrying out the possible method for hydrogen cracking of step (a) is described in EP-A-699225, EP-A-649896, WO-A-9718278, EP-A-705321, EP-A-994173 and US-A-4851109.
The operational condition of the method for hydrogen cracking of single step preferably includes: 350-450 ℃ temperature; The hydrogen pressure of 9-200MPa more preferably is higher than 11MPa; 0.1-10kg the weight hourly space velocity of (kg/l/hr) (WHSV) of oil/every liter of catalyzer/per hour, preferred 0.2-5kg/l/hr, more preferably 0.5-3kg/l/hr; And 100-2, the hydrogen of 000 liter of hydrogen/every liter of oil and oily ratio.
Preferably, operate hydrocracker with two steps, these two steps are made up of pre-hydrotreating step and hydrocracking step.In hydrotreating step, nitrogen and sulphur are removed in a large number, aromatic substances is saturated to naphthenic hydrocarbon in a large number, and part naphthenic hydrocarbon is changed into paraffin by ring-opening reaction.In order to improve the productive rate of more tacky base oil fraction, more preferably operate fuels hydrocracker in the following manner: at first (i) under feedstock conversion with hydrocarbon charging hydrotreatment, wherein as defined above transformation efficiency less than 30wt%, be preferably 15-25wt%, (ii) in the presence of hydrocracking catalyst with the hydrogenation of net product cracking of step (i), make that step (i) and total conversion rate (ii) are 15-90wt%, preferred 40-85wt%.
The operational condition of hydrotreating step is preferably: 350-450 ℃ temperature; The hydrogen pressure of 9-200MPa more preferably is higher than 11MPa; 0.1-10kg the weight hourly space velocity of (kg/l/hr) (WHSV) of oil/every liter of catalyzer/per hour, preferred 0.2-5kg/l/hr, more preferably 0.5-3kg/l/hr; And 100-2, the hydrogen of 000 liter of hydrogen/every liter of oil and oily ratio.
The operational condition that makes up the hydrocracking step that carries out with hydrotreating step is preferably: 300-450 ℃ temperature; The hydrogen pressure of 9-200MPa more preferably is higher than 11MPa; 0.1-10kg the weight hourly space velocity of (kg/l/hr) (WHSV) of oil/every liter of catalyzer/per hour, preferred 0.2-5kg/l/hr, more preferably 0.5-3kg/l/hr; And 100-2, the hydrogen of 000 liter of hydrogen/every liter of oil and oily ratio.
The residual oil that makes by aforesaid method contains low-down sulphur content (be usually less than 250 or even be lower than 150ppmw) and low-down nitrogen content (being usually less than 30ppmw).This residual oil is full range residual oil preferably.
Have been found that hydrotreatment and hydrocracking step by making up have as mentioned above obtained residual oil, this residual oil obtains a large amount of more tacky base oil fractions (also being known as medium machine oil fraction) and has acceptable viscosity index quality.In addition, petroleum naphtha, kerosene and the gas oil of q.s have been obtained by this method.Realized the fuels hydrocracker method thus, wherein obtained product and the residual oil of petroleum naphtha to gas oil simultaneously, this residual oil can obtain medium machine oil base oil fraction.The viscosity index of gained base oil fraction is suitably 95-120, and this base oil for the viscosity index that obtains having API Group II specification is acceptable.
The viscosity index that has been found that the base oil fraction of residual oil and gained in hydrotreating step (i) raises along with the transformation efficiency in the described hydrotreating step.By surpassing this hydrotreating step of operation under the high conversion of 30wt%, can realize that the base oil of gained obviously surpasses 120 viscosity index value.But the shortcoming of such high conversion is that the productive rate of medium machine oil fraction can undesirably reduce in step (i).Under above-mentioned transform level, carry out step (i), can obtain medium other base oil of machine oil level of API GroupII with desirable amount.To be that the viscosity index of 95-120 is come the minimum transformation efficiency in the determining step (i) by the desired value of gained base oil fraction, and the minimum acceptable yield by medium machine oil fraction come the maximum conversion rate in the determining step (i).
Usually adopt catalyzer and condition in the above-mentioned publication relevant to carry out pre-hydrotreating step with hydrocracking.Suitable hydrotreating catalyst is generally comprised within for example metal hydrogenation component on silica-alumina or the aluminum oxide of porous support, is suitably IVB or VIII family metal for example cobalt-molybdenum, nickel-molybdenum etc.Hydrotreating catalyst does not contain zeolitic material aptly or its content is the low levels less than 1wt%.The example of suitable hydrotreating catalyst is: commercialization ICR 106, the ICR120 of ChevronResearch and Technology Co.; CriterionCatalyst Co. 244,411, DN-120, DN-180, DN-190 and DN-200; The TK-555 of HaldorTopsoe A/S and TK-565; The HC-k of UOP, HC-P, HC-R and HC-T; KF-742, KF-752, KF-846, KF-848STARS and the KF-849 of AKZO Nobel/Nippon Ketjen; HR-438/448 with Procatalyse SA.
Hydrocracking step preferably comprises in porous carrier materials and carries out under the acid large aperture zeolite effect, and described catalyzer has additional metal hydrogenation/dehydrogenation.Metal with hydrogenation/dehydrogenation effect is the combination of VIII family/group vib metal, for example nickel-molybdenum and nickel-tungsten preferably.Carrier is porous support preferably, for example silica-alumina and aluminum oxide.Realize the high yield of medium machine oil fraction when having been found that for operation hydrocracker under aforesaid preferred transformation efficiency in full range residual oil, it is favourable containing minimum zeolite in catalyzer.Preferably, the zeolite above 1wt% is present in the catalyzer.The example of suitable zeolite is X zeolite, Y, ZSM-3, ZSM-18, ZSM-20 and zeolite beta, wherein zeolite Y most preferably.The example of suitable hydrocracking catalyst is commercialization ICR 220 and the ICR142 of Chevron Research and Technology Co.; The Z-763 of Zeolist International, Z-863, Z-753, Z-703, Z-803, Z-733, Z-723, Z-673, Z-603 and Z-623; The TK-931 of Haldor TopsoeA/S; The DHC-32 of UOP, DHC-41, HC-24, HC-26, HC-34 and HC-43; KC2600/1, KC2602, KC2610, KC2702 and the KC2710 of AKZO Nobel/Nippon Ketjen; And the HYC642 of Procatalyse SA and HYC652.
The effluent of hydrocracker is separated into one or more above-mentioned fuel fractions and residual oil.Wherein residual oil is mainly in boiling more than 340 ℃, used as the charging of step (c).Mainly be meant especially that in boiling more than 340 ℃ the material that surpasses 80wt% is being higher than 340 ℃ of boilings down, the material that preferably surpasses 90wt% is being higher than 340 ℃ of boilings down.Because most residual oil can seethe with excitement, therefore after dewaxing, can reclaim quite a large amount of gas oil with good cold flow performance in the gas oil boiling range.Preferably, the pressed oil that obtains in this process of 10-40wt% seethes with excitement in 350-400 ℃ heavy gas oil boiling range.Certainly it should be understood that in step (c) and also obtained more lower boiling gas oil fraction.
The full boiling point of residual oil is incited somebody to action the full boiling point decision of part by the charging of step (a), and can be far longer than 700 ℃, till can not measuring by standard method of test.
The part residual oil that obtains in the step described in EP-A-0994173 (b) can randomly be recycled to step (a), and this publication is quoted as a reference at this.Described in EP-B-0699225, residual oil randomly can only be recycled to the hydrocracking step of step (a), and this publication is quoted as a reference at this.The residual oil that preferably will be less than 15wt% is recycled to step (a), does not more preferably have residual oil to be recycled to step (a).Have been found that and under the condition that needn't carry out this class recirculation, can make API Group II base oil with excellent quality.
In step (c), charging is separated into lighter body precursor fraction and heavy base oil precursor fraction and optional vacuum gas oil fraction by distillation.Preferably, from lighter body precursor fraction, do not separate any vacuum gas oil but maintenance and described fraction combination, thus dewaxing in step (d) equally.Under reduced pressure implement distillation under the condition aptly, more preferably under the pressure of 0.01-0.3 crust, carry out vacuum distilling.Preferably, the recovery point of the heavy base oil precursor fraction that obtains in step (c) of 10wt% is 420-550 ℃, more preferably 440-520 ℃.
The charging of step (d) will be included in the base oil precursor fraction that obtains in the step (c).Randomly, the part isomerized paraffin of some boiling points in heavy or lighter body precursor fraction boiling range can mix with described lighter body precursor fraction with form of mixtures and exists.Also be known as the wax Residual oil as this paraffin wax product that in fischer-tropsch or solution-air method, obtains.This class wax Residual oil can be by the preparation of the method described in the WO-02070630, and this publication is quoted as a reference at this.
Randomly, precious metal is protected a upstream that can just be arranged at the dewaxing catalyst bed in dewaxing reactor in step (d), to reduce the content of sulphur and especially nitrogen compound.This class protection bed may be particularly advantageous in the dewaxing reactor of processing heavy base oil precursor fraction.The example of these class methods is described among the WO-A-9802503, and this reference is herein incorporated by reference.
Can be by the catalytic dewaxing step of operating in the reactor that carries out in step (d), carrying out in any method that reduces base oil fraction pour point in the presence of catalyzer and the hydrogen at parallel running.Aptly, at least 10 ℃ of depressions of pour point, and preferably reduce at least 20 ℃.Suitable dewaxing catalyst is to comprise for example heterogeneous catalyst of the combination of VIII family metal of molecular sieve and optional and the metal with hydrogenation.Molecular sieve shows under catalytic dewaxing condition reducing the good catalytic capability of pour point of base oil fraction for the zeolite of intermediate pore size preferablyly.Preferably, the zeolite of intermediate pore size has the aperture of 0.35-0.8nm.The zeolite of suitable intermediate pore size is ZSM-5, ZSM-12, ZSM-22, ZSM-23, SSZ-32, ZSM-35 and ZSM-48.Another preferred molecule screen banks is silicon-aluminate or phosphate (SAPO) material that is described among the US-A-4859311, wherein SAPO-11 most preferably.Under the condition that exists without any VIII family metal, the optional form with its HZSM-5 of ZSM-5 can be used.Other molecular sieve preferably uses with the VIII family metallic combination that adds.Suitable VIII family metal is nickel, cobalt, platinum and palladium.The example of possible combination is Ni/ZSM-5, Pt/ZSM-23, Pd/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11.Other details and the example of suitable molecular sieve and dewaxing condition for example are described among WO-A-9718278, US-A-5053373, US-A-5252527 and the US-A-4574043.
Method of the present invention can use dewaxing catalyst to prepare base oil continuously, and described dewaxing catalyst shows wide relatively pour point and distributes under the situation of processing full range residual oil described in WO-A-9723584.By utilizing the present invention, although used the dewaxing catalyst of this class performance relative mistake also can avoid this wide pour point to distribute.The example that shows this class catalyzer of wide relatively pour point distribution is that ZSM-5 is catalyst based.Therefore can be advantageously be used for the present invention with ZSM-5 is catalyst based.Present method can also be used different dewaxing catalysts in the reactor of parallel running, these catalyzer can be more suitable in they corresponding chargings.
Aptly, dewaxing catalyst also comprises tackiness agent.Tackiness agent can be synthetic or natural formation (inorganic) material, for example clay, silicon-dioxide and/or metal oxide.The clay of natural formation for example is polynite and kaolin series.Tackiness agent is preferably for example refractory oxide of porous adhesive material, and its example is: aluminum oxide, silica-alumina, silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silicon-dioxide-titanium oxide and ternary composition be silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-magnesium oxide and silica-magnesia-zirconium white for example.More preferably use the low acid refractory oxide adhesive material of basic oxygen-free aluminium.The example of these adhesive materials is these two or more mixtures that silicon-dioxide, zirconium white, titanium dioxide, germanium dioxide, boron oxide and its example are listed in the above.Most preferred tackiness agent is a silicon-dioxide.
A preferred class dewaxing catalyst comprises the low acid refractory oxide adhesive material of aforesaid medium zeolite crystal and aforesaid basic oxygen-free aluminium, wherein by aluminosilicate zeolite crystallites is carried out surperficial dealumination treatment with the surface modification of aluminosilicate zeolite crystallites.Preferred dealumination treatment is for example to be described in passing through among the US-A-5157191 extrudate of tackiness agent and zeolite is contacted with the aqueous solution of silicofluoride.Described in WO-A-200029511 and EP-B-832171, the example of above-mentioned suitable dewaxing catalyst is that silicon-dioxide is bonding and Pt/ZSM-5, silicon-dioxide dealuminzation are bonding and Pt/ZSM-23, silicon-dioxide dealuminzation are bonding and the Pt/ZSM-12 of dealuminzation and silicon-dioxide is bonding and the Pt/ZSM-22 of dealuminzation.
Catalytic dewaxing condition is well known in the art, and generally includes: 200-500 ℃ service temperature is suitably 250-400 ℃; The hydrogen pressure of 10-200 crust; 0.1-10kg the weight hourly space velocity of (kg/l/hr) (WHSV) of oil/every liter of catalyzer/per hour is suitably 0.2-5kg/l/hr, is 0.5-4kg/l/hr preferablyly; And 100-2, the hydrogen of 000 liter of hydrogen/every liter of oil and oily ratio.Process weight hourly space velocity (WHSV) in the catalytic dewaxing step of lighter body precursor fraction therein and preferably be higher than WHSV in the dewaxing step of heavy base oil precursor fraction.More preferably, in the dewaxing step of lighter body precursor fraction, WHSV is 1-5kg/l/hr.
If the step that will dewax and the cascade of hydrofining step are carried out, then the stress level in these two steps is suitably the same order of magnitude.Because pressure preferred higher in the hydrofining step is to obtain the having base oil of wishing performance, the step that then dewaxes is carried out under this higher pressure equally suitably, although can realize having more optionally dewaxing under lower pressure.If do not need the hydrofining step,, then can advantageously use lower catalytic dewaxing pressure as for obtaining pressed oil by lighter body precursor fraction for the situation of preparation spindle oil base oil fraction.Suitable pressure is the 15-100 crust, is 1.5-6.5MPa preferablyly.
It is the hydrofining step that improves the quality of dewaxing fraction that hydrotreating step (e) is also called.In this step, the alkene of lube range is by saturated, and heteroatoms and coloring matter are removed, and if the sufficiently high words of pressure, remaining aromatic substances is also by saturated.Preferably selection condition to obtain to comprise the base oil fraction above the 95wt% saturates, more preferably obtains to comprise the base oil above the 98wt% saturates.Aptly the dewaxing step cascade of hydrofining step and heavy base oil precursor fraction is carried out.
The hydrofining step suits 230-380 ℃ temperature; Carry out under the stagnation pressure of 1-25MPa (preferably being higher than 10MPa, more preferably 12-25MPa).WHSV (weight hourly space velocity) is 0.3-10kg oil/every liter of catalyzer/per hour (kg/l.h).
Hydrofining or hydrogenation catalyst are suitably the supported catalyst that comprises dispersive VIII family metal.Possible VIII family metal is cobalt, nickel, palladium and platinum.The catalyzer that contains cobalt and nickel can also comprise IVB family metal, is suitably molybdenum and tungsten.
Suitable carriers or support materials are low tart amorphous refractory oxides.The example of suitable amorphous refractory oxides comprises inorganic oxide, for example the mixture of two or more of aluminum oxide, silicon-dioxide, titanium oxide, zirconium white, boron oxide, silica-alumina, fluorizated aluminum oxide, fluorizated silica-alumina and these.
Suitable hydrogenation catalyst comprises: the quantity with respect to total catalyst weight that comprises in element is 1-25 weight percent (wt%), one or more of the nickel (Ni) of preferred 2-15wt% and cobalt (Co), with the quantity in element with respect to total catalyst weight be 5-30wt%, those catalyzer of one or more group vib metal components of preferred 10-25wt%.The example of suitable nickeliferous-molybdenum catalyst is KF-847 and KF-8010 (AKZO Nobel), M-8-24 and M-8-25 (BASF), and C-424, DN-190, HDS-3 and HDS-4 (Criterion).The example of suitable nickeliferous-tungsten catalyst is NI-4342 and NI-4352 (Engelhard), C-454 (Criterion).The suitable example that contains the cobalt-molybdenum catalyzer is KF-330 (AKZO-Nobel), HDS-22 (Criterion) and HPC-601 (Engelhard).
In the present invention, with preferred platiniferous and more preferably the catalyzer of platiniferous and palladium be used for containing the hydrocracking charging of a small amount of sulphur.The total amount that is present in these VIII family noble metal component in the catalyzer is suitably 0.1-10wt%, preferred 0.2-5wt%, and this weight percent is represented with respect to the amount of the metal of total catalyst weight (in element).
Being used for these preferred vectors that contain the catalyzer of palladium and/or platinum is soft silica-aluminum oxide, and wherein more preferably this silica-alumina comprises the aluminum oxide of 2-75wt%.The example of suitable silica-alumina carriers is disclosed among the WO-A-9410263.Preferred catalyzer comprises preferred negative and is loaded in the palladium on soft silica-alumina supporter and the alloy of platinum, and the example of this catalyzer is commercially available Criterion Catalyst Company (Houston, TX) catalyzer C-624 and C-654.
In step (f), from from isolating two or more base oil fractions and the optional fraction that comprises gas oil the lighter body precursor fraction of step (d) and the hydrotreatment oil from step (e).Base oil preferably separates from the mixture of these logistics with the optional fraction that comprises gas oil.This is favourable, because be present in the base oil yield that any compound in the heavy base oil precursor fraction that is converted to lighter body fraction boiling range in step (d) will help described lighter body fraction.
Because the gas oil product of above-mentioned gained has been carried out catalytic dewaxing step, so the fuel product that has obtained having low-down aromatic substances and sulphur content, and described fuel product has made up good low-temperature performance.Especially can in step (d), obtain to have the very low sulfur content that is lower than 10ppm, the low aromatic content that is lower than 0.1mmol/100g, good cold flow performance be such as being lower than-30 ℃ pour point and being lower than the gas oil of-30 ℃ cold filter clogging temperature.This gas oil also has excellent lubricating properties.This makes this class gas oil become good especially refining blend components and is blended in the doctor negative gas oil.This gas oil can also be used as the drilling mud component, electrical oil, machining oil, aluminium rolling oil or as the fruit spray oil.
Can carry out step (f) by extracting product out by well known to a person skilled in the art under near the condition of vacuum from rectifying tower.The so-called side strippers of advantageous applications is isolated base oil product.In order to satisfy the volatility requirement of required base oil fraction, fraction in the middle of can also extracting out.Aptly at the distilation steps that can under about atmospheric condition, carry out elevated pressures before the above-mentioned low-pressure distillation step, so that any petroleum naphtha, kerosene and gas oil fraction are separated from pressed oil separately or as mixture.These middle runningss can use like this or be recycled to step (b) with obtained to dewax with hydrocracking the mixture of midbarrel fuel.Therefore in step (f), in the last distillation of step (f), obtained gaseous state top fraction, comprised the liquid top fraction and the various base oil fraction of above-mentioned middle runnings, for example spindle oil, lightweight machine oil and medium base oil etc.
In the context of the present invention, term " spindle oil ", " lightweight machine oil " and " medium machine oil " are meant the base oil fraction that has the kinematic viscosity that increases progressively under 100 ℃, and wherein spindle oil has maximum volatility specification in addition.For arbitrary group of base oil with these different viscosity requirements and volatility specification, the advantage of present method has obtained realization.Preferably, spindle oil is to be lower than 5.5cSt and preferably to be higher than the lighter body product of 3.5cSt 100 ℃ of following kinematic viscosity.Spindle oil can have by what CEC L-40-T87 method was measured and preferably is lower than 20% and more preferably less than 18% Noack volatility, perhaps as by what ASTM D93 measured is higher than 180 ℃ flash-point.Preferably, the kinematic viscosity of lightweight machine oil under 100 ℃ is lower than 9cSt and preferably is higher than 6.5cSt, more preferably 8-9cSt.Preferably, the kinematic viscosity of medium machine oil under 100 ℃ is lower than 14cSt and preferably is higher than 10cSt, more preferably 11-13cSt.Corresponding base oil fraction can have the viscosity index of 95-120.The boiling point of the gas oil that obtains in the method for the present invention is generally 150-370 ℃ and have 340-400 ℃ T90wt%.
Further set forth method of the present invention by Fig. 1.Fig. 1 shows the hydrocarbon feeding line (1) of hydrocracker (2).In distillation tower (4), hydrocracking thing (3) is separated into petroleum naphtha (5), kerosene (6), gas oil (7), bottom fraction (8).In distillation tower (9), bottom fraction or full range residual oil (4) are divided into lighter body precursor fraction (10) and heavy base oil precursor fraction (11).In dewaxing reactor (12),, obtain pressed oil (16 with lighter body precursor fraction (10) dewaxing; " second pressed oil ").In dewaxing reactor (13), heavy base oil precursor fraction (11) is dewaxed.In hydrofining reactor (14) with this pressed oil (15; " first pressed oil ") hydrotreatment, obtain dewaxing and hydrotreatment after oil (17).Oil (16) and (17) are merged.In separator (18), hydrogen (19) separated and be recycled to dewaxing device (12) and (13) afterwards mending fresh hydrogen (20).In distillation tower (22), oil (21) is separated into lower boiling fraction (26), spindle oil fraction (23), lightweight machine oil fraction (24) and medium machine oil fraction (25) subsequently.The processing sections that fraction (26) is recycled to hydrocracker (2) is to isolate valuable fuel fractions.
Claims (10)
1. prepare the method for two or more base oil fractions and middle runnings by carrying out following steps simultaneously by deasphalted oil or the charging of vacuum cut or their mixture:
(a), obtain effluent thus with the charging hydrocracking;
(b) effluent that obtains in the step (a) is distilled into one or more middle runningss and boiling point apparently higher than 340 ℃ residual oil;
(c) by further distilation steps described residual oil is separated into lighter body precursor fraction and heavy base oil precursor fraction;
(d) pour point of each isolating base oil precursor fraction of reduction in the catalytic dewaxing reactor of two whiles and parallel running obtains first and second pressed oils;
(e) the first pressed oil hydrotreatment that will obtain in the time of will in step (d), making the dewaxing of heavy base oil precursor fraction;
(f) from going out two or more base oil fractions from second pressed oil of the lighter body precursor fraction of step (d) with from the hydrotreatment of step (e) is separating of oil.
2. the method for claim 1, wherein the residual oil that obtains in step (b) is higher than 340 ℃ above the boiling point of 80wt%, and the first and second pressed oil meter 10-40wt% boiling points that wherein made in step (d) based on combination are lower than 400 ℃ heavy gas oil boiling range fraction.
3. each method of claim 1-2, wherein the heavy base oil precursor fraction that obtains in step (c) with 20-40wt% is recycled to step (a).
4. each method of claim 1-3, wherein the recovery point of the heavy base oil precursor fraction that obtains in step (c) of 10wt% is 420-550 ℃.
5. the method for claim 4, wherein the recovery point of the heavy base oil precursor fraction that obtains in step (c) of 10wt% is 440-520 ℃.
6. each method of claim 1-5, wherein the charging of step (d) also be included in obtain in the Fischer-Tropsch process and boiling point be in the isomerized paraffin of part in heavy and/or the lighter body precursor fraction boiling range.
7. each method of claim 1-6 wherein is higher than in dewaxing step (d) WHSV when the timesharing of processing heavy base oil precursor level when the weight hourly space velocity of processing lighter body precursor level timesharing in catalytic dewaxing step (d).
8. the method for claim 7, wherein the WHSV when the timesharing of processing lighter body precursor level is 1-5kg/l/hr.
9. each method of claim 1-8 is the 15-65 crust with the pressure of lighter body precursor fraction dewaxing in step (d) wherein, is the 100-250 crust with the pressure of heavy base oil precursor fraction dewaxing.
10. each method of claim 1-9, wherein the mixture implementation step (f) of first pressed oil of second pressed oil that timesharing obtains to processing lighter body precursor level and processing heavy base oil precursor level timesharing hydrotreatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04290569.5 | 2004-03-02 | ||
| EP04290569 | 2004-03-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1926220A true CN1926220A (en) | 2007-03-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800066544A Pending CN1926220A (en) | 2004-03-02 | 2005-03-01 | Process to continuously prepare two or more base oil grades and middle distillates |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20070175794A1 (en) |
| EP (1) | EP1733008A1 (en) |
| JP (1) | JP2007526380A (en) |
| KR (1) | KR20060130675A (en) |
| CN (1) | CN1926220A (en) |
| WO (1) | WO2005085393A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216430A (en) * | 2008-10-01 | 2011-10-12 | 雪佛龙美国公司 | A process to manufacture a base stock and a base oil manufacturing plant |
| CN107532093A (en) * | 2015-04-15 | 2018-01-02 | 耐思特公司 | Method for producing oil-base components |
| CN108473881A (en) * | 2015-09-09 | 2018-08-31 | 雪佛龙美国公司 | The improvement of heavy API class ii base oils produces |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009001314A1 (en) | 2007-06-25 | 2008-12-31 | Bruno Weber | Fuel oil substitution product |
| KR101779605B1 (en) * | 2010-06-04 | 2017-09-19 | 에스케이이노베이션 주식회사 | Method for producing base oil using deasphalt oil from reduced pressure distillation |
| US9487723B2 (en) | 2010-06-29 | 2016-11-08 | Exxonmobil Research And Engineering Company | High viscosity high quality group II lube base stocks |
| US8992764B2 (en) | 2010-06-29 | 2015-03-31 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
| WO2015038693A1 (en) * | 2013-09-12 | 2015-03-19 | Chevron U.S.A. Inc. | A two-stage hydrocracking process for making heavy lubricating base oil from a heavy coker gas oil blended feedstock |
| EP3194534B1 (en) | 2014-09-17 | 2021-01-20 | Ergon, Inc. | Process for producing naphthenic bright stocks |
| CN106715659B (en) * | 2014-09-17 | 2019-08-13 | 埃尔根公司 | The method for producing cycloalkanes base oil |
| CN110121545A (en) * | 2016-12-29 | 2019-08-13 | 埃克森美孚研究工程公司 | Oil base stock and lubricant oil composite containing the oil base stock |
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| US3876522A (en) * | 1972-06-15 | 1975-04-08 | Ian D Campbell | Process for the preparation of lubricating oils |
| DE3587895T2 (en) * | 1984-05-03 | 1994-12-01 | Mobil Oil Corp | Catalytic dewaxing of light and heavy oils in two parallel reactors. |
| US4574043A (en) * | 1984-11-19 | 1986-03-04 | Mobil Oil Corporation | Catalytic process for manufacture of low pour lubricating oils |
| US4859311A (en) * | 1985-06-28 | 1989-08-22 | Chevron Research Company | Catalytic dewaxing process using a silicoaluminophosphate molecular sieve |
| GB8629476D0 (en) * | 1986-12-10 | 1987-01-21 | Shell Int Research | Manufacture of lubricating base oils |
| US4764266A (en) * | 1987-02-26 | 1988-08-16 | Mobil Oil Corporation | Integrated hydroprocessing scheme for production of premium quality distillates and lubricants |
| US4851109A (en) * | 1987-02-26 | 1989-07-25 | Mobil Oil Corporation | Integrated hydroprocessing scheme for production of premium quality distillates and lubricants |
| US5053373A (en) * | 1988-03-23 | 1991-10-01 | Chevron Research Company | Zeolite SSZ-32 |
| US5252527A (en) * | 1988-03-23 | 1993-10-12 | Chevron Research And Technology Company | Zeolite SSZ-32 |
| AU715730B2 (en) * | 1995-11-14 | 2000-02-10 | Mobil Oil Corporation | Integrated lubricant upgrading process |
| US6569313B1 (en) * | 1995-12-22 | 2003-05-27 | Exxonmobil Research And Engineering Company | Integrated lubricant upgrading process |
| HUP0104314A3 (en) * | 1998-11-16 | 2003-05-28 | Shell Int Research | Catalytic dewaxing process |
| JP4208233B2 (en) * | 2000-12-19 | 2009-01-14 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing spindle oil, light machine oil and medium machine oil base oil grade from bottom fraction in fuel hydrocracking process |
-
2005
- 2005-03-01 KR KR1020067019612A patent/KR20060130675A/en not_active Application Discontinuation
- 2005-03-01 US US10/591,115 patent/US20070175794A1/en not_active Abandoned
- 2005-03-01 EP EP05708063A patent/EP1733008A1/en not_active Withdrawn
- 2005-03-01 JP JP2007501274A patent/JP2007526380A/en active Pending
- 2005-03-01 WO PCT/EP2005/050857 patent/WO2005085393A1/en active Application Filing
- 2005-03-01 CN CNA2005800066544A patent/CN1926220A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216430A (en) * | 2008-10-01 | 2011-10-12 | 雪佛龙美国公司 | A process to manufacture a base stock and a base oil manufacturing plant |
| CN102216430B (en) * | 2008-10-01 | 2014-07-09 | 雪佛龙美国公司 | A process to manufacture a base stock and a base oil manufacturing plant |
| CN107532093A (en) * | 2015-04-15 | 2018-01-02 | 耐思特公司 | Method for producing oil-base components |
| CN108473881A (en) * | 2015-09-09 | 2018-08-31 | 雪佛龙美国公司 | The improvement of heavy API class ii base oils produces |
| TWI742001B (en) * | 2015-09-09 | 2021-10-11 | 美商雪維隆美國有限公司 | Improved production of heavy api group ii base oil |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005085393A1 (en) | 2005-09-15 |
| US20070175794A1 (en) | 2007-08-02 |
| JP2007526380A (en) | 2007-09-13 |
| EP1733008A1 (en) | 2006-12-20 |
| KR20060130675A (en) | 2006-12-19 |
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