CN105378035B - The method for preparing two or more base oils - Google Patents

The method for preparing two or more base oils Download PDF

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Publication number
CN105378035B
CN105378035B CN201480039751.2A CN201480039751A CN105378035B CN 105378035 B CN105378035 B CN 105378035B CN 201480039751 A CN201480039751 A CN 201480039751A CN 105378035 B CN105378035 B CN 105378035B
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boiling fraction
lighter body
point
heavy basestock
fraction
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CN105378035A (en
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D·J·维德洛克
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Shell Internationale Research Maatschappij BV
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • 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
    • 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
    • C10G45/60—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 characterised by the catalyst used
    • C10G45/62—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 characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G45/60—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 characterised by the catalyst used
    • C10G45/64—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 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • 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
    • 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
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
    • 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
    • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
    • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Abstract

The present invention provides the method for preparing two or more base oils, the method is at least included the following steps: (a) providing paraffinic feed stream；(b) make the paraffinic feed stream provided in step (a) be subjected to being hydrocracked/hydroisomerisation step to be to obtain the product stream of at least partly isomerization；(c) product stream in separating step (b), to obtain low-boiling fraction and high boiling fraction；(d) it dewaxes to the low-boiling fraction in step (c), to obtain lighter body；And (e) dewax to the high boiling fraction in step (c), to obtain heavy basestock.

Description

The method for preparing two or more base oils
The present invention relates to the methods for preparing two or more base oils.
It is known by being urged at one and in the same equipment to the alkane base oil precursor component of wide scope carbon number Change dewaxing to prepare the base oil of two or more.For example, describing in WO 02/070631 from wax-like paraffin Fischer-Tropsch (Fischer-Tropsch) method that product prepares two or more base oil grades.In WO 02/070631, make first For Fischer-tropsch derived distillate base oil precursor fraction, there is the viscosity corresponding to desired base oil product.This is distillated Object base oil precursor is then subjected to catalytic dewaxing step, then last vacuum distillation, to obtain one of desired base oil.
The problem of method disclosed in WO 02/070631, is that, for each desired base oil, base oil precursor needs It is stored in tank, and needs to repeat all method and steps.In addition, the base of the preparation of the method as disclosed in WO 02/070631 Plinth oil can have big cloud point/pour point poor.
It is an object of the present invention to provide be used to prepare more having for two or more base oils with different viscosities The method of effect.
It is a further object of the present invention to provide the substitutions for being used to prepare two or more base oils with different viscosities Method.
One of above-mentioned purpose or other purposes can prepare the side of two or more base oils by providing according to the present invention Method realizes that this method at least includes the following steps:
(a) paraffinic feed stream is provided；
(b) make the paraffinic feed stream provided in step (a) be subjected to being hydrocracked/hydroisomerisation step to be to obtain at least The product stream of moiety isomerization；
(c) product stream in separating step (b), to obtain low-boiling fraction and high boiling fraction；
(d) it dewaxes to the low-boiling fraction in step (c), to obtain lighter body；And
(e) it dewaxes to the high boiling fraction in step (c), to obtain heavy basestock.
It has now surprisingly been found that according to the present invention it is possible to continuously in surprisingly simple and mild mode Prepare two or more base oils with different viscosities.
Important advantage of the invention is that two or more base oils obtained have low cloud point/pour point poor.
At one and in the same equipment, by the alkane base oil precursor group with the carbon number for covering several viscosity Divide and carry out catalytic dewaxing to prepare two or more base oils, can produce with high cloud point/pour point difference base oil.These High cloud point/pour point difference shows the isomerization of the difference of heavy wax in the base oil of acquisition.
The base oil with different viscosities can be therefore with low cloud point/pour point difference effective means system according to the present invention It is standby.
It is a further advantage that by individually but catalytic dewaxing simultaneously is low and high boiling fraction is to obtain Lightweight and heavy basestock do not need pans (intermediate before catalytic dewaxing respectively is low and high boiling fraction Tankage) individually to store these fractions.
According to the method for the present invention the step of in (a), paraffinic feed stream is provided.
Suitably, paraffinic feed stream is or mixtures thereof wax oil (hydrowax) charging, Fischer-Tropsch product.Preferably, chain Alkane feeding flow is Fischer-Tropsch product.
It is well known in the art that the various methods of wax oil are provided.Term " wax oil " refers to mineral feed product, the production Object is derived from crude oil.Suitably, it includes that the hydrocarbonaceous feed from wax-like crude oil and hydroisomerisation catalysts exist that wax oil, which passes through, The method that is contacted under the conditions of hydroisomerization and derived from wax-like crude oil, and it is that fuel of the optimization for gasoline adds hydrogen to split Change device~370 DEG C+bottom fraction.This method for example describes in EP-A-0400742.
Suitably, wax oil at 70 DEG C according to the density of ASTM D-4052 in 800-850kg/m3Between, preferably exist 810-820kg/m3Between, more preferably in 819-820kg/m3Between.
The initial boiling point that wax oil preferably has exists between 200-430 DEG C, more preferably between 228-421 DEG C, most preferably Between 322-421 DEG C, and final boiling point between 400-540 DEG C, preferably between 420-485 DEG C, more preferably 425-483 DEG C it Between, most preferably between 458-483 DEG C.
Fischer-Tropsch product is known in the prior art.Term " Fischer-Tropsch product " refers to the synthetic product of fischer-tropsch process.Taking In support method, synthesis gas is converted to synthetic product.Synthesis gas or synthetic gas are the mixtures of hydrogen and carbon monoxide, are led to It crosses conversion hydrocarbonaceous feed and obtains.Suitable charging includes natural gas, crude oil, heavy oil fraction, coal, biomass and lignite.Take Support product is also referred to as GTL (gas turns liquid) product.
The preparation of Fischer-Tropsch product is described in such as WO2003/070857.
The Fischer-Tropsch product of fischer-tropsch process is usually separated into water flow, gaseous flow by distillation, and it includes unconverted synthesis Gas, carbon dioxide, inert gas and C1 are to C2 and C3+ product stream.Commercially available equipment can be used.Distillation can be in atmosphere Pressure carries out, but decompression can also be used.Fischer-Tropsch product in the present invention refers to C3+ product stream.
In step (b), the paraffinic feed stream provided in step (a) is subjected to being hydrocracked/hydroisomerisation step with Obtain the product stream of at least partly isomerization.
It has been found that the amount of isomerization product depends on being hydrocracked/hydroisomerization condition.
Be hydrocracked/hydroisomerization process is known in the art, and is not therefore discussed in detail herein.
Be hydrocracked/hydroisomerization and it is hydrocracked/influence example of the hydroisomerization condition to the amount of isomerization product As described in " Hydrocracking Science and Technology ", Julius Scherzer；A.J.Cruia, Marcel Dekker, Inc, New York, 1996, ISBN0-8247-9760-4 the 6th chapter.
The preparation of at least partly Fischer-tropsch derived isomerization charging in step (b) has been described in such as WO 2009/ In 080681.The preparation of the isomerization charging of at least partly mineral origin in step (b) has been described in such as EP-A- In 0400742.
In step (c), the product stream of separating step (b) is to obtain low-boiling fraction and high boiling fraction.
Preferably, the low-boiling fraction of step (c) is boiled within the temperature range of 350-500 DEG C, and step (c) is high boiling Point fraction boils within the temperature range of 425-600 DEG C.
Boiling point under atmospheric conditions refers to atmospheric boiling point, which can be used method such as ASTM D2887 or ASTM D7169 To measure.
Separation is preferably carried out by high vacuum distillation.
Low-boiling fraction in step (c) preferably comprises C20 to C30 fraction, more preferably comprising C20 to C23 fraction.
High boiling fraction in step (c) preferably comprises C30 to C40 fraction, more preferably comprising C23 to C40 fraction.
In step (d), the low-boiling fraction in step (c) is dewaxed to obtain lighter body.
In another aspect of this invention, the lighter body as obtained by according to the method for the present invention is provided.
The feature of lighter body can be one or more features described below, contain without other restrictive technologies Justice is attributed to the mark " lightweight ".
Common process for dewaxing is catalytic dewaxing and solvent dewaxing.Catalysis and solvent dewaxing are known in the prior art , and be therefore not described in herein.Common catalysis and solvent-dewaxing method for example describe " Lubricant base oil and wax processing",AvilinoSequeira,Jr.,Marcel Dekker,Inc,New York,1994, The the 7th and the 8th chapter of ISBN0-8247-9256-4.
The dewaxing of low-boiling fraction in step (d) is preferably carried out by catalytic dewaxing process.
Common catalytic dewaxing process for example describes in WO 2009/080681 and WO2012055755.
Suitably, catalytic dewaxing carries out in the presence of comprising the catalyst of molecular sieve and group VIII metal.
Suitable dewaxing catalyst is heterogeneous catalyst, and it includes molecular sieve, more suitably intermediate pore size zeolites, and optionally Ground combination has the metal such as group VIII metal of hydride functional.Preferably, the aperture of intermediate pore size zeolites is in 0.35-0.8nm Between.
Preferably, catalytic dewaxing carries out in the presence of comprising the catalyst of molecular sieve and group VIII metal, wherein molecular sieve Selected from MTW, MTT, TON type molecular sieve, ZSM-12, ZSM-48 and EU-2.
In the present invention, refer to that ZSM-48 and EU-2 be used to refer to that workable all zeolites belong to the ZSM- of disordered structure 48 races, also referred to as * MRE race, and describe with Structure Commission of the International Zeolite The the Catalog of Disorder in Zeolite Frameworks that the name of Assocation was published in 2000 In.Even if EU-2 can be considered different from ZSM-48, but ZSM-48 and EU-2 can be used in the present invention.Zeolite ZBM-30 and EU-11 is very similar to ZSM-48, and is also considered as the member that its structure belongs to the zeolite of ZSM-48 race.In this application, right Any refer to of ZSM-48 zeolite also refers to ZBM-30 and EU-11 zeolite.
Other than ZSM-48 and/or EU-2 zeolite, other zeolites also may be present in carbon monoxide-olefin polymeric, especially such as Fruiting period hopes its modified catalytic property.It was found that there are zeolite ZSM-12 to be advantageous, the zeolite is defined with the The name of Structure Commission of the International Zeolite Assocation is 2007/2008 In the Database of Zeolite Structures that year publishes.
Suitable group VIII metal is nickel, cobalt, platinum and palladium.Preferably, group VIII metal is platinum or palladium.
Dewaxing catalyst includes adhesive with being also suitable for.Adhesive can be non-acid.The example of suitable adhesive is Clay, silica, titanium dioxide, zirconium oxide, aluminium oxide, above-mentioned mixture and combination and well known by persons skilled in the art Other adhesives.
Preferably, catalyst includes silica or titanium dioxide tie agent.
The lighter body of catalytic dewaxing in step (d) preferably has according to the cloud point of ASTM D-2500 lower than -15 DEG C, more preferably less than -20 DEG C, more preferably less than -28 DEG C, more preferably less than -32 DEG C and most preferably less than -40 DEG C.
The lighter body of catalytic dewaxing in step (d) it is excellent in 100 DEG C of kinematic viscosity according to ASTM D-445 It is selected as 2.5-6.0mm2/ s, more preferable 3.0-5.0mm2/ s, more preferable 3.5-4.5mm2/ s and most preferably 3.8-4.2mm2/s。
The pour point according to ASTM D5950 of lighter body is preferably shorter than 0 DEG C, is more preferably less than -5 DEG C, is more preferably low In -15 DEG C, more preferably less than -20 DEG C and most preferably less than -25 DEG C and preferably, at most it is higher than -48 DEG C.
In step (e), the high boiling fraction in step (c) is dewaxed to obtain heavy basestock.
Preferred Dewaxing conditions step description is as above.
Preferably, the catalytic dewaxing of the low-boiling fraction of step (c) is to obtain the high boiling of lighter body and step (c) It puts the catalytic dewaxing of fraction simultaneously but individually occurs.Therefore, suitably, step (d) of the invention and (e) occur simultaneously.
Another aspect provides the heavy basestocks as obtained by according to the method for the present invention.Heavy base The feature of oil can be the one or more features being described herein below, and be attributed to the mark without other restrictive art-recognized meanings It infuses " heavy ".
Catalytic dewaxing heavy basestock in step (e) preferably have according to the cloud point of ASTM D-2500 lower than -10 DEG C, Preferably shorter than -15 DEG C, more preferably less than -18 DEG C and most preferably less than -20 DEG C.
Catalytic dewaxing heavy basestock in step (e) it is preferred in 100 DEG C of kinematic viscosity according to ASTM D-445 For 5.0-12.0mm2/ s, more preferable 6.0-10.0mm2/ s, more preferable 7.0-9.0mm2/ s and most preferably 7.5-8.5mm2/s。
Preferably shorter than -5 DEG C, more preferably less than -10 DEG C of the pour point according to ASTM D5950 of catalytic dewaxing heavy basestock, More preferably less than -15 DEG C, more preferably less than -20 DEG C, and be most preferably less than -25 DEG C and be preferably up to higher than -48 DEG C.
Suitably, lightweight according to the present invention and heavy basestock be II group mineral base oil, III group mineral base oil and The Fischer-tropsch derived base oil of III group determines II and Group III according to American Petroleum Institute (API) Justice.These API categories are defined on APIPublication 1509, and the 15th edition, annex E, in April, 2002.
It on the other hand, according to the method for the present invention include further step (f), the wherein lighter body in step (d) Heavy basestock in plinth oil and step (e) removes light fraction each by vacuum distillation separation and obtains the first lightweight basis Oil and the first heavy basestock and light fraction.In general, light fraction is compound such as methane, ethane and propane, wherein the present invention In light fraction pass through cracking acquisition in catalytic dewaxing step (d) and (e).
Between catalytic dewaxing lighter body in step (d) and the cloud point and pour point of the heavy basestock in step (e) Difference less than 6 DEG C, preferably smaller than 3 DEG C, more preferably less than 2 DEG C.
Fig. 1 schematically shows the method flow diagram of preferred embodiment according to the method for the present invention.
For the purpose this specification, single reference number will be assigned to the stream carried in route and the route.
Method flow diagram is usually quoted with reference number 1.
Paraffin product stream 10a is obtained in alkane method reactor 2a.The product be fed to be hydrocracked/add hydrogen Isomerization reactor 3a, wherein paraffin product stream 10a is converted into the product stream 20a of at least partly isomerization.The isomerization Product stream 20a distills in destilling tower 4a to recycle low-boiling fraction 30a and high boiling fraction 30b.
The low-boiling fraction 30a of destilling tower 4a is fed into catalytic dewaxing reactor 5a to obtain lighter body 40a.Reaction The effluent 40a of device 5a is distilled in destilling tower 6a to recycle further base oil 50a, has 2.5- at 100 DEG C 6.0mm2/ s, preferably 3.0-5.0mm2/ s, more preferable 3.5-4.5mm2/ s and most preferably 3.8-4.2mm2The different motion of/s is viscous Degree.
While with lighter body 40a is prepared as described above, it is prepared for heavy basestock 40b.
The high boiling fraction 30b of destilling tower 4a is fed to catalytic dewaxing reactor 5b to obtain heavy basestock 40b.Instead It answers the effluent 40b of device 6b to be distilled in destilling tower 6b to recycle further base oil 50b, there is 5.0- at 100 DEG C 12.0mm2/ s, preferably 6.0-10.0mm/s, more preferable 7.0-9.0mm2/ s and most preferably 7.5-8.5mm2The different motion of/s is viscous Degree.
The present invention is described as follows with reference to the following examples, and the embodiment is not intended to be limiting in any manner of the invention Range.
Embodiment 1
The preparation of the API GPII base oil of catalytic dewaxing
GPII base oil is from wax oil charging (also referred to as fuels hydrocracker bottoms).Wax oil charging is obtained from Shell Pernis oil plant (Pernis, Holland)
The property of wax oil charging is recited in table 1.
Table 1
Wax oil is fed by continuous feed to hydrocracking step.In hydrocracking step, in fraction and EP-A-532118 Embodiment 1 hydrocracking catalyst contact.Condition in hydrocracking step (a) are as follows: fresh feed weight (hourly) space velocity (WHSV) (WHSV) be 0.6kg/l.h, recycle feed WHSV be 0.17kg/l.h, hydrogen gas rate=750Nl/kg, gross pressure=77 bar, and Temperature of reactor is 334 DEG C.
The effluent (isomerization product) of hydrocracking step under vacuum continuous still to generate 4 kinds of fractions (referring to table 2: experiment A, B, C and D).
In hydrodewaxing step, dealuminzation silica knot described in the embodiment of above-mentioned 4 kinds of fractions and WO-A-0029511 The contact of ZSM-5 catalyst is closed, the catalyst includes the ZSM-5 of the Pt and 30 weight % of 0.7 weight %.Dewaxing conditions are 40 bars Hydrogen, WHSV=lkg/l/h and temperature are 355 DEG C.The property of the catalytic dewaxed base oils of acquisition is enumerated in table 3.
Table 2
Table 3
Comparing embodiment A
Repeat embodiment 1 program, condition be isomerization product before being distilled into several base oil in one and phase By catalytic dewaxing in same device.
Catalytic dewaxing is carried out described in isomerization product embodiment 1 as above to obtain the mineral source base of catalytic dewaxing Oil.
The base oil of the mineral origin of the catalytic dewaxing of acquisition is distilled into 4 kinds of base oil fractions.
The property of this 4 kinds of base oils is enumerated in table 4.
Table 4
Fig. 2 shows that cloud point/pour point of the GP II base oil with several viscosity obtained according to the present invention is poor (real Apply example 1) with when before being separated into isomerization product with the fraction of different boiling ranges by the isomerization product in one and phase With the letter of cloud point/pour point poor (comparing embodiment A) of the base oil with several viscosity obtained when catalytic dewaxing in device Digital ratio compared with.
It discusses
The result (embodiment 1) of table 4 shows to produce several clarification and bright GP II base according to the method for the present invention Plinth oil, it is poor with low cloud point/pour point.This shows that crystallite particles can be easy to from the base oil obtained separate, or in other words It says, the isomerization of the difference of heavier wax in the base oil of acquisition.When compared with comparing embodiment A (referring to fig. 2), wherein feeding Pre-separation by catalytic dewaxing but will not fed into the fraction with different boiling ranges, then catalytic dewaxing is separated into several GP The GP II base oil that II base oil generates has high cloud point/pour point poor.

Claims (17)

1. the method for preparing two or more base oils, the method at least include the following steps:
(a) paraffinic feed stream is provided, wherein the paraffinic feed stream is initial boiling point between 200-430 DEG C and final boiling point exists Wax oil charging between 400-540 DEG C；
(b) make the wax oil provided in step (a) charging be subjected to being hydrocracked/hydroisomerisation step to be to obtain at least partly isomery The product stream of change；
(c) product stream in separating step (b), to obtain low-boiling fraction and high boiling fraction；
(d) it dewaxes to the low-boiling fraction in step (c), to obtain lighter body；And
(e) it dewaxes to the high boiling fraction in step (c), to obtain heavy basestock,
Wherein between the cloud point and pour point of the heavy basestock in the lighter body in step (d) and step (e) Difference less than 6 DEG C.
2. according to the method described in claim 1, wherein the paraffinic feed stream is that initial boiling point is between 322-421 DEG C and whole Wax oil charging of the boiling point between 458-483 DEG C.
3. method according to claim 1 or 2, wherein temperature of the low-boiling fraction at 350-500 DEG C in step (c) Boiling in range is spent, and the high boiling fraction in step (c) boils within the temperature range of 425-600 DEG C.
4. method according to claim 1 or 2, wherein dewaxing is including molecular sieve and VIII group by catalytic dewaxing process It is carried out in the presence of the catalyst of metal.
5. according to the method described in claim 4, wherein the molecular sieve be selected from MTW, MTT, TON type molecular sieve, ZSM-12, ZSM-48 and EU-2.
6. method according to claim 4, wherein the group VIII metal is platinum or palladium.
7. according to the method described in claim 4, wherein the catalyst includes silica or titanium dioxide tie agent.
8. method according to claim 1 or 2, wherein the cloud point of the lighter body in step (d) is lower than -15 ℃。
9. method according to claim 1 or 2, wherein the lighter body in step (d) is viscous in 100 DEG C of movement Degree is 2.5-6.0mm2/s。
10. method according to claim 1 or 2, wherein the pour point of the lighter body in step (d) is lower than 0 DEG C.
11. method according to claim 1 or 2, wherein step (d) and (e) occur simultaneously.
12. method according to claim 1 or 2, wherein the cloud point of the heavy basestock in step (e) is lower than -10 ℃。
13. method according to claim 1 or 2, wherein movement of the heavy basestock at 100 DEG C in step (e) Viscosity is 5.0-12.0mm2/s。
14. method according to claim 1 or 2, wherein the pour point of the heavy basestock in step (e) is lower than -5 ℃。
15. method according to claim 1 or 2, wherein the lightweight and heavy basestock be II group mineral base oil, III group mineral base oil and the Fischer-tropsch derived base oil of III group, according to American Petroleum Institute (API) definition defined in the API publication 1509 to II and Group III.
16. method according to claim 1 or 2, wherein in the lighter body and step (e) in step (d) Difference between the cloud point and pour point of the heavy basestock is less than 3 DEG C.
17. method according to claim 1 or 2, wherein in the lighter body and step (e) in step (d) Difference between the cloud point and pour point of the heavy basestock is less than 2 DEG C.
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