CN105378035A

CN105378035A - Process to prepare two or more base oils

Info

Publication number: CN105378035A
Application number: CN201480039751.2A
Authority: CN
Inventors: D·J·维德洛克
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2013-07-15
Filing date: 2014-07-15
Publication date: 2016-03-02
Anticipated expiration: 2034-07-15
Also published as: CN105378035B; WO2015007692A1; US20160168490A1

Abstract

The present invention provides a process to prepare two or more base oils, which process at least comprises the following steps: (a) providing a paraffinic hydrocarbon feedstock stream; (b) subjecting a paraffinic hydrocarbon feedstock stream provided in step (a) to a hydrocracking/ hydroisomerization step to obtain an at least partially isomerised product stream; (c) separating the product stream of step (b), thereby obtaining a lower boiling fraction and a higher boiling fraction; (d) dewaxing the lower boiling fraction of step (c) to obtain a light base oil; and (e) dewaxing the higher boiling fraction of step (c) to obtain a heavy base oil.

Description

Prepare the method for two or more base oils

The present invention relates to the method for two or more base oils of preparation.

Known at one and carry out to the alkane base oil precursor component of wide region carbon number the base oil that catalytic dewaxing prepares two or more in the same equipment.Such as, in WO02/070631, describe the method preparing two or more base oil grades from wax-like paraffin Fischer-Tropsch (Fischer-Tropsch) product.In WO02/070631, first prepared Fischer-tropsch derived overhead product base oil precursor fraction, it has the viscosity corresponding to the base oil product expected.This overhead product base oil precursor stands catalytic dewaxing step subsequently, then last vacuum distilling, with one of base oil obtaining expectation.

The problem of method disclosed in WO02/070631 is the base oil expected for each, and base oil precursor needs to be stored in tank, and needs to repeat all method stepss.In addition, it is poor that the base oil prepared by method disclosed in WO02/070631 can have large cloud point/pour point.

An object of the present invention is to provide the more effective method for the preparation of two or more with the base oil of different viscosity.

Another object of the present invention is to provide the alternative method of the base oil for the preparation of two or more with different viscosity.

One of above-mentioned purpose or other object can realize by providing the method for two or more base oils of preparation according to the present invention, and the method at least comprises the following steps:

A () provides paraffinic feed stream;

B () makes the paraffinic feed stream provided in step (a) stand hydrocracking/hydroisomerisation step to obtain at least part of isomerized product stream;

Product stream in (c) separating step (b), thus obtain low boiler cut and high boiling fraction;

D () dewaxes to the low boiler cut in step (c), to obtain lighter body; And

E () dewaxes to the high boiling fraction in step (c), to obtain heavy basestock.

Find surprisingly now, according to the present invention, can with simple surprisingly and the mode of gentleness prepares the base oil that two or more have different viscosity continuously.

It is poor that important advantage of the present invention is that two or more base oils obtained have low cloud point/pour point.

At one and in the same equipment, prepare two or more base oils by carrying out catalytic dewaxing to the alkane base oil precursor component with the carbon number covering some viscosity, the base oil with high cloud point/pour point difference can be produced.These high cloud points/pour point difference shows the isomerization of the difference of pyroparaffine in the base oil obtained.

The base oil according to the present invention with different viscosity can therefore to have the effective means preparation of low cloud point/pour point difference.

Further advantage of the present invention be by individually but simultaneously catalytic dewaxing is low and high boiling fraction to obtain lightweight and heavy basestock, catalytic dewaxing respectively low with high boiling fraction before do not need tundish (intermediatetankage) to store these cuts individually.

In the step (a) of method according to the present invention, provide paraffinic feed stream.

Suitably, paraffinic feed stream is wax oil (hydrowax) charging, Fischer-Tropsch product or its mixture.Preferably, paraffinic feed stream is Fischer-Tropsch product.

The known various methods that wax oil is provided in the prior art.Term " wax oil " refers to mineral feed product, and described product is derived from crude oil.Suitably, wax oil by comprising the method that the hydrocarbonaceous feed being derived from wax-like crude oil and hydroisomerisation catalysts contacted under hydroisomerization condition derived from wax-like crude oil, and its be optimize for gasoline fuels hydrocracker ~ 370 DEG C+end cut.The method is such as described in EP-A-0400742.

Suitably, wax oil at 70 DEG C according to the density of ASTMD-4052 at 800-850kg/m ³between, preferably at 810-820kg/m ³between, more preferably at 819-820kg/m ³between.

The initial boiling point that wax oil preferably has between 200-430 DEG C, more preferably between 228-421 DEG C, most preferably between 322-421 DEG C, and full boiling point between 400-540 DEG C, preferably between 420-485 DEG C, more preferably between 425-483 DEG C, 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.In fischer-tropsch process, synthetic gas is converted to synthetic product.Synthetic gas or synthesis gas are the mixtures of hydrogen and carbon monoxide, and it obtains by transforming hydrocarbonaceous feed.Suitable charging comprises Sweet natural gas, crude oil, heavy oil fraction, coal, biomass and brown coal.Fischer-Tropsch product also can be called GTL (cyclostrophic liquid) product.

The preparation of Fischer-Tropsch product is described in such as WO2003/070857.

The Fischer-Tropsch product of fischer-tropsch process is separated into current, gaseous stream usually by distilling, it comprises unconverted synthetic gas, carbonic acid gas, rare gas element and C1 to C2 and C3+ product stream.The obtainable equipment of business can be used.Distillation can under atmospheric pressure be carried out, but also can use decompression.Fischer-Tropsch product in the present invention refers to C3+ product stream.

In step (b), the paraffinic feed stream provided in step (a) stands hydrocracking/hydroisomerisation step to obtain at least part of isomerized product stream.

Find that the amount of isomerization product depends on hydrocracking/hydroisomerization condition.

Hydrocracking/hydroisomerization process is that prior art is known, and does not therefore discuss in detail at this.

Hydrocracking/hydroisomerization and hydrocracking/hydroisomerization condition are such as described in " HydrocrackingScienceandTechnology " the impact of the amount of isomerization product, JuliusScherzer; A.J.Cruia, MarcelDekker, Inc, NewYork, the 6th chapter of 1996, ISBN0-8247-9760-4.

The preparation of the isomerization charging Fischer-tropsch derived at least partly in step (b) has been described in such as WO2009/080681.The preparation of the isomerization charging of at least part of mineral origin in step (b) has been described in such as EP-A-0400742.

In step (c), the product stream of separating step (b) is to obtain low boiler cut and high boiling fraction.

Preferably, the low boiler cut of step (c) seethes with excitement in the temperature range of 350-500 DEG C, and the high boiling fraction of step (c) seethes with excitement in the temperature range of 425-600 DEG C.

Boiling point under atmospheric condition refers to atmospheric boiling point, and this boiling point can measure by using method such as ASTMD2887 or ASTMD7169.

Be separated and carry out preferably by molecular distillation.

Low boiler cut in step (c) preferably comprises C20 to C30 cut, more preferably comprises C20 to C23 cut.

High boiling fraction in step (c) preferably comprises C30 to C40 cut, more preferably comprises C23 to C40 cut.

In step (d), the low boiler cut in step (c) is dewaxed to obtain lighter body.

In another aspect of this invention, provide by the obtainable lighter body of method according to the present invention.

The feature of lighter body can be one or more feature described below, does not have other restrictive art-recognized meanings owing to this mark " lightweight ".

Common process for dewaxing is catalytic dewaxing and solvent dewaxing.Catalysis and solvent dewaxing are known in the prior art, and therefore do not describe in detail at this.Common catalysis and solvent-dewaxing method are such as described in " Lubricantbaseoilandwaxprocessing ", AvilinoSequeira, Jr., MarcelDekker, Inc, NewYork, the 7th and the 8th chapter of 1994, ISBN0-8247-9256-4.

The dewaxing of the low boiler cut in step (d) is carried out preferably by catalytic dewaxing process.

Common catalytic dewaxing process is such as described in WO2009/080681 and WO2012055755.

Suitably, catalytic dewaxing is carried out under the catalyzer comprising molecular sieve and group VIII metal exists.

Suitable dewaxing catalyst is heterogeneous catalyst, and it comprises molecular sieve, more suitably intermediate pore size zeolites, and optionally combination has the metal such as group VIII metal of hydride functional.Preferably, the aperture of intermediate pore size zeolites is between 0.35-0.8nm.

Preferably, catalytic dewaxing is carried out under the catalyzer comprising molecular sieve and group VIII metal exists, and wherein molecular screening is from MTW, MTT, TON type molecular sieve, ZSM-12, ZSM-48 and EU-2.

In the present invention, mention that ZSM-48 and EU-2 is used to refer to that spendable all zeolites belong to the ZSM-48 race of random structure, also referred to as * MRE race, and be described in the name of StructureCommissionoftheInternationalZeoliteAssocation in the theCatalogofDisorderinZeoliteFrameworks of publication in 2000.Even if EU-2 can be considered to be different from ZSM-48, but ZSM-48 and EU-2 all can be used in the present invention.Zeolite ZBM-30 and EU-11 is similar to ZSM-48 very much, and is also considered to the member that its structure belongs to the zeolite of ZSM-48 race.In this application, ZBM-30 and EU-11 zeolite is also referred to any mentioning of ZSM-48 zeolite.

Except ZSM-48 and/or EU-2 zeolite, in catalyst composition, also can there is other zeolite, if especially expect its catalytic property of modification.Find that to there is zeolite ZSM-12 can be favourable, described zeolite defined with the name of theStructureCommissionoftheInternationalZeoliteAssocatio n in the DatabaseofZeoliteStructures to publish for 2007/2008 year.

Suitable group VIII metal is nickel, cobalt, platinum and palladium.Preferably, group VIII metal is platinum or palladium.

Dewaxing catalyst also compatibly comprises tackiness agent.Tackiness agent can be non-acid.The example of suitable tackiness agent is clay, silicon-dioxide, titanium dioxide, zirconium white, aluminum oxide, above-mentioned mixture and combination and other tackiness agent well known by persons skilled in the art.

Preferably, catalyzer comprises silicon-dioxide or titanium dioxide tie agent.

The lighter body of the catalytic dewaxing in step (d) preferably have according to the cloud point of ASTMD-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 lower than-40 DEG C.

The lighter body of the catalytic dewaxing in step (d) be preferably 2.5-6.0mm according to ASTMD-445 the kinematic viscosity of 100 DEG C ²/ s, more preferably 3.0-5.0mm ²/ s, more preferably 3.5-4.5mm ²/ s most preferably 3.8-4.2mm ²/ s.

The pour point according to ASTMD5950 of lighter body preferably lower than 0 DEG C, more preferably less than-5 DEG C, more preferably less than-15 DEG C, more preferably less than-20 DEG C and most preferably lower than-25 DEG C and preferably, at most 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 describes as above.

Preferably, the catalytic dewaxing of the low boiler cut of step (c) with the catalytic dewaxing obtaining the high boiling fraction of lighter body and step (c) simultaneously but occur individually.Therefore, suitably, step (d) of the present invention and (e) occur simultaneously.

Another aspect provides by the obtainable heavy basestock of method according to the present invention.The feature of heavy basestock can be one or more feature described below, does not have other restrictive art-recognized meanings owing to this mark " heavy ".

Catalytic dewaxing heavy basestock in step (e) preferably have according to the cloud point of ASTMD-2500 lower than-10 DEG C, preferably lower than-15 DEG C, more preferably less than-18 DEG C and most preferably lower than-20 DEG C.

Catalytic dewaxing heavy basestock in step (e) be preferably 5.0-12.0mm according to ASTMD-445 the kinematic viscosity of 100 DEG C ²/ s, more preferably 6.0-10.0mm ²/ s, more preferably 7.0-9.0mm ²/ s most preferably 7.5-8.5mm ²/ s.

The pour point according to ASTMD5950 of catalytic dewaxing heavy basestock preferably lower than-5 DEG C, more preferably less than-10 DEG C, more preferably less than-15 DEG C, more preferably less than-20 DEG C, and most preferably preferably maximum higher than-48 DEG C lower than-25 DEG C.

Suitably, be the Fischer-tropsch derived base oil of II group mineral base oil, III group mineral base oil and III group according to lightweight of the present invention and heavy basestock, its according to AmericanPetroleumInstitute (API) to the definition of II and III class.These API class declarations at APIPublication1509, the 15th edition, annex E, in April, 2002.

On the other hand, method according to the present invention comprises further step (f), and the lighter body wherein in step (d) and the heavy basestock in step (e) are separated to remove lighting end each via vacuum distilling and obtain the first lighter body and the first heavy basestock and lighting end.Usually, lighting end is compound such as methane, ethane and propane, and the lighting end wherein in the present invention is obtained by cracking in catalytic dewaxing step (d) and (e).

Difference between the cloud point of the catalytic dewaxing lighter body in step (d) and the heavy basestock in step (e) and pour point be less than 6 DEG C, be preferably less than 3 DEG C, be more preferably less than 2 DEG C.

Fig. 1 show schematically show the method flow diagram of the preferred implementation according to method of the present invention.

For the object of this specification sheets, single reference numerals will be assigned to the stream carried in circuit and this circuit.

Method flow diagram is quoted by reference numerals 1 usually.

Paraffin product stream 10a is obtained in paraffinic hydrocarbons method reactor 2a.This product is fed to hydrocracking/hydroisomerization reactor 3a, and wherein paraffin product stream 10a is converted at least part of isomerized product stream 20a.This isomerized product stream 20a distills to reclaim low boiler cut 30a and high boiling fraction 30b in distillation tower 4a.

The low boiler cut 30a of distillation tower 4a is fed to catalytic dewaxing reactor 5a to obtain lighter body 40a.The effluent 40a of reactor 5a distills to reclaim further base oil 50a in distillation tower 6a, and it has 2.5-6.0mm at 100 DEG C ²/ s, preferably 3.0-5.0mm ²/ s, more preferably 3.5-4.5mm ²/ s most preferably 3.8-4.2mm ²the different motion viscosity of/s.

While preparing lighter body 40a as mentioned above, prepare heavy basestock 40b.

The high boiling fraction 30b of distillation tower 4a is fed to catalytic dewaxing reactor 5b to obtain heavy basestock 40b.The effluent 40b of reactor 6b distills to reclaim further base oil 50b in distillation tower 6b, and it has 5.0-12.0mm at 100 DEG C ²/ s, preferably 6.0-10.0mm/s, more preferably 7.0-9.0mm ²/ s most preferably 7.5-8.5mm ²the different motion viscosity of/s.

The present invention is described below with reference to the following examples, and described embodiment is not intended to limit the scope of the invention by any way.

Embodiment 1

The preparation of the APIGPII base oil of catalytic dewaxing

GPII base oil derives from wax oil charging (also referred to as fuels hydrocracker bottoms).This wax oil charging is available from ShellPernis refinery (Pernis, Holland)

The character of wax oil charging is recited in table 1.

Table 1

Wax oil charging by continuous feed to hydrocracking step.In hydrocracking step, cut contacts with the hydrocracking catalyst of the embodiment 1 in EP-A-532118.Condition in hydrocracking step (a) is: fresh feed weight hourly space velocity (WHSV) is 0.6kg/l.h, and recycle feed WHSV is 0.17kg/l.h, hydrogen gas rate=750Nl/kg, total pressure=77 bar, and temperature of reactor is 334 DEG C.

The effluent (isomerization product) of hydrocracking step under vacuo continuous still battery to produce 4 kinds of cuts (see table 2: experiment A, B, C and D).

In hydrodewaxing step, the dealuminzation silica bound ZSM-5 catalyst exposure described in the embodiment of above-mentioned 4 kinds of cuts and WO-A-0029511, described catalyzer comprises the Pt of the 0.7 % by weight and ZSM-5 of 30 % by weight.Dewaxing conditions is the hydrogen of 40 bar, WHSV=lkg/l/h and temperature is 355 DEG C.The character of the catalytic dewaxed base oils obtained is enumerated in table 3.

Table 2

Table 3

Comparative Example A An

Repeat the program of embodiment 1, condition be isomerization product before being distilled into several base oil at one and catalyzed dewaxing in identical device.

Isomerization product as above carries out catalytic dewaxing to obtain the mineral source base oils of catalytic dewaxing described in embodiment 1.

The base oil of the mineral origin of the catalytic dewaxing obtained is distilled into 4 kinds of base oil fractions.

These 4 kinds of basic oil propertiess are enumerated in table 4.

Table 4

Fig. 2 show the cloud point with the GPII base oil of several viscosity/pour point difference (embodiment 1) of obtaining according to the present invention with when before isomerization product being separated into the cut with different boiling ranges by this isomerization product at one and simply the comparing of the cloud point with the base oil of several viscosity/pour point difference (Comparative Example A An) obtained during catalytic dewaxing in same apparatus.

Discuss

The result (embodiment 1) of table 4 shows that method according to the present invention creates several clarification and bright GPII base oil, and it is poor that it has low cloud point/pour point.This shows that crystallite particles can be easy to be separated from the base oil obtained, or in other words, compared with the isomerization of the difference of pyroparaffine in the base oil of acquisition.When comparing with Comparative Example A An (see Fig. 2), the wherein catalyzed dewaxing of charging but charging is not separated in advance the cut with different boiling ranges, then catalytic dewaxing is separated into GPII base oil that several GPII base oil produces, and to have high cloud point/pour point poor.

Claims

1. prepare the method for two or more base oils, described method at least comprises the following steps:

A () provides paraffinic feed stream;

D () dewaxes to the low boiler cut in step (c), to obtain lighter body; And

2. method according to claim 1, wherein said paraffinic feed stream is wax oil charging, Fischer-Tropsch product or its mixture.

3. method according to claim 1 and 2, described low boiler cut wherein in step (c) seethes with excitement in the temperature range of 350-500 DEG C, and the described high boiling fraction in step (c) seethes with excitement in the temperature range of 425-600 DEG C.

4. the method according to any one of claim 1-3, is wherein dewaxed and to be carried out under the existence of catalyzer comprising molecular sieve and group VIII metal by catalytic dewaxing process.

5. method according to claim 4, wherein said molecular screening is from MTW, MTT, TON type molecular sieve, ZSM-12, ZSM-48 and EU-2.

6., according to the method for claim 4 or 5, wherein said group VIII metal is platinum or palladium.

7. the method according to any one of claim 4-6, wherein said catalyzer comprises silicon-dioxide or titanium dioxide tie agent.

8. the method according to any one of claim 1-7, the cloud point of the lighter body of the described catalytic dewaxing wherein in step (d) lower than-15 DEG C, preferably lower than-20 DEG C, more preferably less than-28 DEG C, more preferably less than-32 DEG C and most preferably lower than-40 DEG C.

9. the method according to any one of claim 1-8, the lighter body of the described catalytic dewaxing wherein in step (d) is 2.5-6.0mm the kinematic viscosity of 100 DEG C ²/ s, preferably 3.0-5.0mm ²/ s, more preferably 3.5-4.5mm ²/ s most preferably 3.8-4.2mm ²/ s.

10. the method according to any one of claim 1-9, the pour point of the lighter body of the described catalytic dewaxing wherein in step (d) lower than 0 DEG C, preferably lower than-5 DEG C, more preferably less than-15 DEG C, more preferably less than-20 DEG C and most preferably preferably maximum higher than-48 DEG C lower than-25 DEG C.

11. methods according to any one of claim 1-10, wherein step (d) and (e) occur simultaneously.

12. methods according to any one of claim 1-11, the cloud point of the heavy basestock of the described catalytic dewaxing wherein in step (e) lower than-10 DEG C, preferably lower than-15 DEG C, more preferably less than-18 DEG C and most preferably lower than-20 DEG C.

13. methods according to any one of claim 1-12, the heavy basestock of the described catalytic dewaxing wherein in step (e) is 5.0-12.0mm the kinematic viscosity of 100 DEG C ²/ s, preferably 6.0-10.0mm ²/ s, more preferably 7.0-9.0mm ²/ s most preferably 7.5-8.5mm ²/ s.

14. methods according to any one of claim 1-13, the pour point of the heavy basestock of the described catalytic dewaxing wherein in step (e) lower than-5 DEG C, preferably lower than-10 DEG C, more preferably less than-15 DEG C, more preferably less than-20 DEG C, and most preferably preferably maximum higher than-48 DEG C lower than-25 DEG C.

15. methods according to any one of claim 1-14, wherein said lightweight and heavy basestock are the Fischer-tropsch derived base oil of II group mineral base oil, III group mineral base oil and III group, its definition to II and III class defined in API publication 1509 according to AmericanPetroleumInstitute (API).

16. methods according to any one of claim 1-15, the difference between the cloud point of the described heavy basestock in the lighter body of the described catalytic dewaxing wherein in step (d) and step (e) and pour point is less than 6 DEG C, is preferably less than 3 DEG C and is more preferably less than 2 DEG C.