CN105209580B - The method for preparing weight base oil - Google Patents

The method for preparing weight base oil Download PDF

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Publication number
CN105209580B
CN105209580B CN201480024800.5A CN201480024800A CN105209580B CN 105209580 B CN105209580 B CN 105209580B CN 201480024800 A CN201480024800 A CN 201480024800A CN 105209580 B CN105209580 B CN 105209580B
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hydrotreating
product
hydrocarbon
catalyst
base oil
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CN105209580A (en
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L·G·胡弗
J·J·巴瑞克
N·博门德耶尔
J·W·杜伊尼克
G·J·阿特斯
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Abstract

The present invention provides a kind of method for preparing weight base oil, includes the following steps：(a) hydrocarbon-containing feedstock is provided, the hydrocarbon-containing feedstock includes hydrocarbon, the nitrogen of 800 2500ppmw and the sulphur of 1.5 4.0wt% that at least boiling point of 50wt% is higher than 460 DEG C；(b) under hydroprocessing conditions in the presence of hydrogen-containing gas with hydrocarbon-containing feedstock described in hydrotreating catalyst hydrotreating, the product after obtaining nitrogen content as 30 80ppmw and hydrotreating that sulfur content is 200 450ppmw；(c) after the hydrotreating that is obtained in step (b) of removing present in product at least 50% NH3And H2S；(d) make with dewaxing catalyst product catalytic dewaxing after at least part hydrotreating that step (c) obtains in the presence of hydrogen-containing gas under catalytic dewaxing conditions, to obtain dewaxed product, the dewaxing catalyst includes group VIII metal hydrogenation component, the aluminosilicate zeolite crystallites of dealuminzation and the low in acidity refractory oxide binder material for being substantially free of aluminium oxide；(e) make at least part dewaxed product hydrofinishing of step (d) acquisition with Hydrobon catalyst in the presence of hydrogen-containing gas under Hydrofinishing conditions, to obtain weight base oil；(f) the heavy base oil is recycled.

Description

The method for preparing weight base oil
Technical field
The present invention relates to the methods for preparing weight base oil.
Background technology
Being mainly applicable in lubricating oil such as automobile oil of base oil protects the internal combustion engine in motor vehicles.Lubrication Oil is usually made of to obtain ideal characterisitics main base oil and various additives.
Light lubricating base oil is mainly used for automobile application, and weight lubricating base oil is then applied for heavy duty and started as peculiar to vessel Machine and industrial process.
It is prepared on a large scale by following process for the base oil in lubricating oil：Make vacuum gas oily distillate first And/or deasphalted oil hydrotreating and then make 370 DEG C of fluid product after the fluid product after hydrotreating or hydrotreating The catalytic dewaxing of+fraction and hydrofinishing.Noble metal dewaxing catalyst is applied usually in catalytic dewaxing step.It is well known that organic Nitrogen and organosulfur compound can make noble metal dewaxing catalyst be poisoned, therefore in order to fully reduce the 370 of hydrotreater DEG C+production Organic nitrogen and sulfur concentration in product, it is necessary to the harsh hydrotreating step of application.
Higher processing depth would generally be improved at 370 DEG C as base oil device raw material+plus hydrogen in hydrotreater The quality of product after reason.But higher hydrotreating depth means that the yield of product after 370 DEG C+hydrotreating is lower and all Product lightens (since boiling point transfer occurs for Deep Hydrotreating) after hydrotreating, and as consequence, this significantly reduces lubricate again Ratio between base oil and light lubricating base oil.
When weight base oil demand is high, the yield reduction of weight lubricating base oil is undesirable.
It is therefore an object of the present invention to the method for upgrading of hydrocarbon-containing feedstock is provided, wherein the height that weight lubricating base oil will be obtained Yield.
Invention content
When hydrocarbon-containing feedstock is subjected to the grading process for the processing step for including particular sequence, above-mentioned purpose is realized.
Therefore, the present invention relates to a kind of method for preparing weight base oil, include the following steps：
(a) hydrocarbon-containing feedstock is provided, the hydrocarbon-containing feedstock includes at least hydrocarbon of the boiling point of 50wt% higher than 460 DEG C, 800- The nitrogen of 2500ppmw and the sulphur of 1.2-4.0wt%；
(b) hydrotreating catalyst or hydrotreating catalyst packet are used in the presence of hydrogen-containing gas under hydroprocessing conditions Hydrocarbon-containing feedstock described in hydrotreating, using obtain nitrogen content be 30-80ppmw and sulfur content as the hydrotreating of 200-450ppmw after Product；
(c) after the hydrotreating that is obtained in step (b) of removing present in product at least 50% NH3And H2S；
(d) make at least portion of step (c) acquisition with dewaxing catalyst in the presence of hydrogen-containing gas under catalytic dewaxing conditions Product catalytic dewaxing after point hydrotreating, to obtain dewaxed product, the dewaxing catalyst includes group VIII metal hydrogenation group Point, the aluminosilicate zeolite crystallites of dealuminzation and the low in acidity refractory oxide binder material for being substantially free of aluminium oxide；
(e) step (d) is made to obtain extremely with Hydrobon catalyst in the presence of hydrogen-containing gas under Hydrofinishing conditions Small part dewaxed product hydrofinishing, to obtain weight base oil；With
(f) the heavy base oil is recycled.
According to the present invention, weight lubricating base oil can be obtained in high yield.The heavy lubricating base oil obtained includes having High heavy lubricating base oil and light lubricating base oil than Section II kind and Section III kind lubricating base oil.This heavy lubricating base oil With high viscosity so that they are very attractive for heavy duty application.
Specific embodiment
The hydrocarbon-containing feedstock that step (a) provides is preferably comprised more than 65wt% but at least boiling point of 50wt% is higher than 460 DEG C Hydrocarbon.Suitably, the hydrocarbon-containing feedstock that step (a) provides contains the viscosity at 100 DEG C and is higher than the 370 of 12cSt, preferably at least 14cSt DEG C+fraction.
The nitrogen content of hydrocarbon-containing feedstock is 800-2500ppmw, and preferably 1000-1500ppmw and sulfur content are 1.2- 4.0wt%, preferably 1.5-3.0wt%.
In the hydrocarbon-containing feedstock provided in step (a), hydrocarbon-fraction and boiling point that boiling point is 370-460 DEG C are 460-800 DEG C Ratio between hydrocarbon-fraction is preferably smaller than 10.
Example for the hydrocarbon-containing feedstock of the present invention has straight run gas oil, hydrocracking gas oil, thermal cracking gas oil, coke Change gas oil, vacuum gas oil (VGO), light or heavy-cycle oil, deasphalted oil (DAO) or the combination of two or more in them.Hydrocarbon is former Material can also be the waxy raffinate after solvent extraction.The hydrocarbon-containing feedstock that step (a) provides at least partly can be suitably to pass through The blend for making at least one distillate fraction (preferably depressurizing distillate fraction) and deasphalted oil (DAO) blending and obtaining. Adaptable DAO is obtained suitably by (preferably decompression residuum) depitching of residual oil hydrocarbon ils is made.The depitching step It can implement in any conventional manner.Known and suitable de-asphalting method be solvent deasphalting, including with Extraction solvent adverse current Handle residual oil hydrocarbon oil crude material.This Extraction solvent is usually comprising paraffin compound such as propane, fourth with 3-8 carbon atom Alkane, iso-butane, pentane, isopentane, hexane and two or more in them mixture lighter hydrocarbons solvent.Preferred alkane For those with 3-5 carbon atom, wherein propane, butane, pentane and their mixture are most preferred.Solvent takes off drip Blueness processing is easily implemented in rotary-disk contactor or plate column, and residual oil hydrocarbon oil crude material enters top area and Extraction solvent enters Bottom section.It is dissolved in Extraction solvent compared with lighter hydrocarbons present in residual oil hydrocarbon ils, and the top extraction of slave device.It is extracted in recycling DAO is obtained by the overhead fraction after solvent.The bottom extraction of asphalitine slave device insoluble in Extraction solvent.Implement deasphalting Condition is well known in the art.Suitably, in total Extraction solvent and the ratio of residual oil hydrocarbon ils is 1.5-8wt/wt, pressure is 1-50bar and temperature are to implement depitching at 50-230 DEG C.
It is obtained by residue oil fraction (preferably vacuum residue fraction) depitching for alloing the hydrocarbon comprising at least 460 DEG C of boiling point Deasphalted oil.
In step (b), under hydroprocessing conditions in the presence of hydrogen-containing gas with suitable hydrotreating catalyst or Hydrocarbon-containing feedstock described in hydrotreating catalyst packet hydrotreating, to obtain, nitrogen content is 30-80ppmw and sulfur content is 200- Product after the hydrotreating of 450ppmw.
The hydrotreating catalyst or catalyst packet applied in the first reaction zone in step (a) can be suitably de- Sulfur catalyst or desulphurization catalyst combination (are included in possible catalyst for demetalation or catalyst for demetalation group before desulfurized step It closes).The desulphurization catalyst can be known in the art any Hydrobon catalyst or hydrotreating catalyst combination, it The hydrotreating with expected nitrogen and sulphur concentration will be exported and flow out object.In general, these catalyst are included in porous catalyst carrier On (be usually aluminium oxide or amorphous silica-alumina) as the periodic table of elements group VIII metal of hydrogenation component with The compound of vib metals.It is plus hydrogenated close object appropriate combination known example include cobalt-molybdenum, nickel-molybdenum, nickel-tungsten and nickel- Cobalt-molybdenum.It is preferred that compound comprising nickel and/or cobalt and molybdenum, which makees the plus hydrogenated Hydrobon catalyst for closing object,.Step (b) obtains Product includes the nitrogen of 30-80ppmw and the sulphur of 200-450ppmw after the hydrotreating obtained, this shows the hydrotreating of step (b) It is not Deep Hydrotreating process.Therefore, suitably application is not that the too strong hydrotreating catalyst of activity or hydrotreating are urged Agent combines.It is therefore preferable that using alumina base hydrotreating catalyst.Catalyst is preferably substantially free of Cracking Component.Comprising The nickel and/or cobalt and molybdenum that carry on alumina but catalyst without zeolite as cracking compound or catalyst combination are especially excellent Choosing.
Two of which or more can also be applied to plant the stacked bed construction that hydrotreating catalyst stacks in step (b).
The temperature of hydrotreating step is suitably 250-480 DEG C, preferably 280-450 DEG C and more preferably 350-420 ℃。
Suitable hydroprocessing pressure is 30-250bara.Hydroprocessing pressure is preferably 110-180bara, more preferably 120-170bara。
Weight (hourly) space velocity (WHSV) is suitably 0.2-10hr-1, preferably 0.2-2.0hr-1More preferably 0.2-1.0hr-1。
It will be understood that accurate hydroprocessing condition particularly depends on applied catalyst and hydrocarbon in step (a) The sulfur content and nitrogen content of raw material.
Nitrogen content and the ratio (N/S) of sulfur content are suitably 0.1-0.3 in product after the hydrotreating that step (b) obtains, Preferably 0.12-0.28.
In step (c), by present in product after the hydrotreating of step (b) acquisition at least 50% NH3And H2S takes off It removes.Suitably, after the hydrotreating obtained step (b) by steam stripping by stripping, preferably present in product at least Part NH3And H2S is removed.Stripping is suitably in 100-350 DEG C, preferably 130-240 DEG C of temperature and 1-50bar, preferably 1.5- Implement under the pressure of 10bar.In step (c), after the hydrotreating for preferably obtaining step (b) present in product at least 80%th, more preferably at least 90% and most preferably at least 95% NH3And H2S is removed after hydrotreating in product.Preferably, exist The hydrocarbon that boiling point is less than 370 DEG C is also isolated in step (c) from product after the hydrotreating that step (b) obtains.
It is preferred that make step (b) obtain whole hydrotreatings after product be subjected to step (c).
In step (d), obtain step (c) with dewaxing catalyst in the presence of hydrogen-containing gas under catalytic dewaxing conditions At least part hydrotreating after product catalytic dewaxing, to obtain dewaxed product, the dewaxing catalyst includes group VIII gold Belong to hydrogenation component, the aluminosilicate zeolite crystallites of dealuminzation and low in acidity refractory oxide binding agent.
It is preferred that make step (c) obtain whole hydrotreatings after product be subjected to step (d).
Catalytic dewaxing refers herein to not assign height by being selectively converted into the oily raw material components for assigning high pour point and incline The product of point and the method that reduces lubrication base oil product pour point.The product for assigning high pour point is with dystectic compound. These compounds are referred to as wax.Wax compound includes normal paraffin hydrocarbons, iso- alkane and the list-cycle compound of such as high temperature melting. It is preferred that pour point is reduced at least 40 DEG C and more preferably at least 60 DEG C of reduction.Therefore, hydrocarbon-containing feedstock contains tax in the methods of the invention Give the waxy molecules of undesired high pour point.These a small amount of compounds can significantly affect pour point.Raw material suitably includes These wax compounds less than 2% and at most 80%.
In the catalytic dewaxing step of the present invention, make under catalytic dewaxing conditions after hydrotreating raw material with comprising Section VIII The carbon monoxide-olefin polymeric of race's metal hydrogenation component, the aluminosilicate zeolite crystallites of dealuminzation and low in acidity refractory oxide binding agent Contact.
It has been found that this kind of dewaxing catalyst is very stable even if when in oily raw material there are when high sulphur and nitrogen content.It is this The example of catalyst is described in WO-A-9641849.
Aluminosilicate zeolite crystallites preferably have the hole of a diameter of 0.35-0.80nm.The diameter refers to maximum diameter of hole.As logical It is often recognized, the hole in molecular sieve is the polygonal shaped channels with minimum and maximum aperture.For the purpose of the present invention, most Large aperture is key parameter because it is determined that can access aperture waxy molecules size.
Be suitble to the example of aluminosilicate zeolites applied in the present invention have ferrierite, ZSM-5, ZSM-11, ZSM-12, ZSM-22、ZSM-23、ZSM-35、ZSM-38、ZSM-48、ZSM-57、SSZ-23、SSZ-24、SSZ-25、SSZ-26、SSZ-32、 The mixture of SSZ-33 and MCM-22 and two or more in these.Zeolite component be preferably ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 or ZSM-48.
On the basis of the total weight of dewaxing catalyst, the zeolite component in dewaxing catalyst is preferably with the amount of 10-50wt% In the presence of.
Preferred aluminosilicate zeolites are MFI- topological structures such as ZSM-5.
To obtain optimal catalytic activity, preferably using small crystals.It is preferred that application is 1 micron less than 10 microns and more preferably less than Crystal.Actual lower limit is suitably 0.1 micron.
Dewaxing catalyst is also comprising the low in acidity refractory oxide binder material for being substantially free of aluminium oxide.Example has low Acidic refractory oxide such as silica, zirconium oxide, titanium dioxide, germanium dioxide, boron oxide and these in two kinds or more A variety of mixtures.Most preferred binding agent is silica.The weight ratio of modified molecular screen and binding agent is suitably 05/95 To 95/05.
The dealuminzation of aluminosilicate zeolites can cause present in zeolite alumina part quantity to reduce, and thus cause oxygen Change aluminium molar percentage to reduce.The term " alumina part " applied herein refers to Al2O3Unit, it is aluminosilicate zeolites skeleton A part, i.e., it with aluminosilicate zeolites skeleton in other oxide portions such as silica (SiO2) pass through covalently bonded It closes.The mole percent of aluminium oxide present in aluminosilicate zeolites is defined as relative to composition aluminosilicate zeolites (dealuminzation Before) or modified molecular screen (after dealuminzation) oxide total mole number Al2O3Mole percent.
Preferably, make the surface selectivity dealuminzation of zeolite crystal.The surface dealuminzation of selectivity can cause the table of zeolite crystal Face acidic site points are reduced, but not influence the internal structure of zeolite crystal.
Can dealuminzation be realized by method as known in the art.Particularly useful method selectively occurs for wherein dealuminzation Or howsoever selectivity is happened at those on molecular sieve crystal surface.The example of dealumination process is in aforementioned WO-A-9641849 In be described.
Preferably, dealuminzation is implemented by the method that wherein zeolite is contacted with the aqueous solution of fluosilicate, wherein the fluorine silicon Hydrochlorate is represented by the following general formula：(A)2/bSiF6, wherein ' Α ' it is metal or non-H with chemical valence ' b'+It is nonmetallic sun from Son.This processing is also referred to as AHS processing.The example of cation ' b' has alkylammonium, NH4 +、Mg++、Li+、Na+、K+、Ba++、Cd++、Cu+、Ca++、Cs+、Fe++、Co++、Pb++、Mn++、Rb+、Ag+、Sr++、Tl+And Zn++.' Α ' it is preferably ammonium cation.Zeolite material Material can suitably be contacted with pH for the fluosilicate of 3-7.This dealumination process is for example described in US-A-5157191.It is described Dealumination treatment is also referred to as AHS- processing.
Dewaxing catalyst for the present invention is preferably prepared by following process：Aluminosilicate zeolites and bonding are squeezed out first Then agent makes the extrudate be subjected to dealumination treatment, preferably be subjected to above-mentioned AHS processing.It has been found that when according to this step When prepared by sequence, the increased catalyst extrudates of mechanical strength can be obtained.
By known technology such as ion exchange technique to the catalyst extrudates of the aluminosilicate zeolite crystallites comprising dealuminzation In suitably add in the group VIII metal of periodic table.The selected zeolite of typical ion exchange technique requirement is with wanting what is replaced The salt contact of cation.Although a variety of salt may be used, particularly preferred chloride, nitrate and sulfate.It is representative from Sub- switching technology is described in multiple patents including US-A-3140249, US-A-3140251 and US-A-3140253.
In step (d), the dewaxing catalyst for including group VIII metal hydrogenation component is applied.Group VIII metal group Divide and include based on noble metal and those non-noble metal components.Therefore specially suitable group VIII metal component for sulfide, The palladium of oxide and/or element form, platinum, nickel and/or cobalt.Based on the total amount of carrier by elements, periodic table Section VIII The total amount of race's metal is suitably no more than 10wt% and preferably 0.1-5.0wt%, more preferably 0.2-3.0wt%.If platinum All exist with palladium, the weight ratio of platinum and palladium can change in a wide range, but be suitably 0.05-10, be more suitably 0.1- 5.As the catalyst of hydrogenation component it is preferred comprising palladium, platinum and nickel.Group VIII metal hydrogenation component is preferably platinum or palladium, More preferably platinum.
The method of the present invention the step of in (d), catalytic dewaxing condition is typical catalytic dewaxing condition.Therefore, temperature is closed It is 300-400 DEG C, preferably 320-390 DEG C and more preferably 330-380 DEG C suitablely.Suitable dewaxing pressure is 80- 240bara.The pressure that dewaxes is preferably 100-180bara, more preferably 120-170bara.The weight (hourly) space velocity (WHSV) of step (d) is suitably For 0.4-7hr-1, preferably 0.5-2.5hr-1More preferably 0.65-2.25hr-1。
Step (d) is implemented in the presence of hydrogen.Hydrogen is suitably supplied to the second reaction with the rate of 350-1500Nl/kg raw materials Area.
The dewaxed product that step (d) obtains has the viscosity index (VI) (VI) that can produce high VI lubricating base oils.Step (d) The sulfur content of the dewaxed product of acquisition is suitably less than 350ppmw, and preferably smaller than 300ppmw and nitrogen content are less than 80ppmw, excellent Choosing is less than 60ppmw.Dewaxed product viscosity at 100 DEG C is suitably 10-17cSt, preferably 10-15cSt.
In step (e), make step (d) with Hydrobon catalyst in the presence of hydrogen-containing gas under Hydrofinishing conditions At least part dewaxed product hydrofinishing of acquisition, to obtain weight base oil.
It is preferred that whole dewaxed products that step (d) obtains is made to be subjected to step (e).
Hydrofinishing is well known in the art and the example of suitable hydrofinishing step is for example in US-A- 5139647th, it is disclosed in WO-A-9201657 and WO-A-9201769.In general, hydrofinishing be included in it is relatively mild Under the conditions of hydrocarbon raw material (raw material to include dewaxing lubricating base oil in this case) is made to contact with hydrogenation catalyst, so as to make In dewaxed base oil there are still at least part aromatic hydrocarbons saturation.Suitable catalyst is commonly used in the noble metal of this purpose for those Base catalyst, the catalyst for including Pt and/or Pd such as carried on an amorphous silica-alumina carrier.In the present invention An alternate embodiment in, in the hydrotreating step of step (b), using non-noble metal hydrogenation catalyst for refining, i.e., So-called underlying metal Hydrobon catalyst such as nickel-molybdenum on the alumina support.
By the present invention, Hydrofinishing conditions include：At most 390 DEG C and preferably 300-380 DEG C of operation temperature, more preferably It is 330-370 DEG C；Operating pressure is 80-200bara, preferably 100-170bara；It is 0.3-2.5hr with weight (hourly) space velocity (WHSV)-1, it is excellent It is selected as 0.5-1.5hr-1。
When compared with being hydrocracked the known method for preparing base oil with catalytic dewaxing step with application, in step (e) The yield higher of weight base oil.This heavy base oil that can be expressed as obtaining in the step (e) in high yield of weight base oil and The ratio of light base oil.Such as the 500N base oils and 150N that can be expressed as obtaining in step (e) in high yield of heavy base oil The ratio of base oil.500N base oils are the heavy class ii base oil that viscosity is usually 10.0-12.9cSt at 100 DEG C, and 150N Base oil is the light class ii base oil that viscosity is usually 4.8-6.8cSt at 100 DEG C.Suitably, it is obtained in step (e) The ratio of 500N base oils and 150N base oils is at least 1.0, preferably at least 1.5, more preferably at least 2.5 and is most preferably At least 3.0.
Weight this of base oil is established in high yield in the particular order of processing step (a)-(e) and using special catalyst And/or in catalyst combination and the main improvement to the known method for preparing base oil is formed, it particularly stands in counterweight base today From the perspective of the demand of plinth oil is growing.
The recycling weight base oil in step (f).Such as by conventional method as atmospheric distillation or rectification under vacuum can be by steps Suddenly other components of heavy base oil and unifining process effluent that (e) is obtained separate (including light base oil).Work as at these In, rectifying under reduced pressure is most suitable application (including vacuum flashing and rectification under vacuum).The cut-point of distillate fraction is selected, Each product distillate so as to be recycled is respectively provided with preferably weighs base oil characteristic for its desired use.
The sulfur content of the heavy base oil of step (f) recycling is suitably less than 300ppmw, and preferably smaller than 200ppmw and nitrogen contain Amount is less than 80ppmw, preferably smaller than 50ppmw.Viscosity of the weight base oil at 100 DEG C is suitably 10-15cSt, preferably 10- 13cSt。
Embodiment
The present invention is described below by following nonlimiting examples
Basra (Basrah) lightweight wax in step (a) is provided and distillates raw material.
Table 1：The key property of raw material
Laboratory solvent dewaxing temperature ℃ -20
Wax content Wt% 9.2
Cross oil strain
Kinematic viscosity
40℃ cSt 272.22
100℃ cSt 17.16
Viscosity index (VI) 53.6
Sulfur content Wt% 2.93
Basic n content ppmw 414
Aromatic hydrocarbons (UV methods)
It is monocyclic mmol/100g 47.8
It is bicyclic mmol/100g 9.3
It is polycyclic mmol/100g 47.1
In step (b), hydrotreating is carried out to raw material.
Embodiment 1 (present invention)
(the present embodiment is used with the NiMo hydrotreating catalysts on conventional aluminium oxide from Criterion The C-424 of catalyst portfolio) hydrotreating is carried out to the raw material described in table 1, target is to generate the nitrogen containing about 50ppm Effluent (370 DEG C+fraction) after the hydrotreating of about 300ppm sulphur.
The operating condition and main result of hydrotreating step are given in Table 2 below.
Table 2：The effluent after production hydrotreating in step (b) of the present invention
Embodiment 2 (comparative example)
Hydrotreating is carried out to identical raw material (such as table 1) in a usual manner, to be substantially reduced nitrogen and sulfur content respectively extremely< 5ppmw and<50ppmw, so as to meet the typical case of two level noble metal isomerization-dewaxing and Hydrobon catalyst in practice at present It is required that.For this, the NiMo/Al of high activity is needed2O3- II classes hydrotreating catalyst (such as from Criterion The DN-3100 of catalyst portfolio).The operating condition and main result of hydrotreating step are given in Table 3.
Table 3：Effluent after production hydrotreating in a usual manner
Step (b) conclusive table
Step (b) Effluent-embodiment 1 Effluent-embodiment 2
Catalyst Conventional NiMo/Al2O3 High activity NiMo/Al2O3
Nitrogen, ppmw 50 2
Sulphur, ppmw 275 55
370 DEG C+yield, wt% 85.8 70.7
460 DEG C+, % 71 63
Vk100, cSt 10.41 8.30
Viscosity index (VI) 101 115
Pour point, DEG C +48 +44
In step (c), H is stripped off in the effluent obtained by Examples 1 and 22S and NH3Impurity and light-end products.With Afterwards, in step (d), the product that step (c) obtains is made to be subjected to the hydrodewaxing step of the present invention and conventional hydrodewaxing step.
Embodiment 3 (present invention)
Catalytic dewaxing is carried out to 370 DEG C+fraction of embodiment 1 using the dewaxing catalyst SLD-800 commercially available from Shell, The catalyst is specifically developed underlying metal (Ni) catalyst to dewax for serious pollution raw material.
The operating condition and main result of catalytic dewaxing step are given in Table 4.
Table 4：Catalytic dewaxing product is produced by the present invention
Embodiment 4 (comparative example)
Catalytic dewaxing is carried out to 370 DEG C+fraction of embodiment 2 using the dewaxing catalyst SLD-821 commercially available from Shell, The catalyst is Deep Hydrotreating raw material to be made to dewax and specifically developed noble metal in order to produce base oil II and III and be directed to (Pt) catalyst.
The operating condition and main result of catalytic dewaxing step are given in Table 5.
Table 5：Catalytic dewaxing product is produced in a usual manner
Step (d) conclusive table
Step (d) Embodiment 3 Embodiment 4
Catalyst SLD-800 SLD-821
370 DEG C+yield, wt% (steps 2) 83.3 87.0
370 DEG C+yield, wt% (step 1+2) 71.5 61.5
Vk100, cSt 10.30 8.81
Viscosity index (VI) 91 106
Pour point, DEG C -12 -12
In step (e), make the dewaxed product hydrofinishing obtained by step (d) of the present invention.
Embodiment 5 (present invention)
370 DEG C+the fraction that the embodiment 3 of all gas is stripped off is made to be subjected to hydrofinishing step, the step application foundation Metal hydrogenation catalyst for refining (the NiMo/Al of high activity2O3Class catalyst) such as embodiment 5a or application noble metal hydrogenation essence Catalyst (such as Criterion LN-5) such as embodiment 5b processed, it is known that latter catalyst has high hydrogenation capability and to sulphur and nitrogen It is poisoned high tolerance.
The operating condition and main result of hydrofinishing step (e) are given in Table 6.
Table 6：Hydrofinishing product is produced by the step (e) of the present invention
Embodiment 6 (comparative example)
Make to be stripped off the comparative example of all gas using the noble metal hydrogenation catalyst for refining (LN-5) obtained from Criterion 4 370 DEG C+fraction is subjected to hydrofinishing step (e).
The operating condition and main result of hydrofinishing step (e) are given in Table 7.
Table 7：Hydrofinishing product is produced in a usual manner
From above said content it can be clearly seen that the method for the present invention improves the conventional method for preparing weight base oil.

Claims (15)

1. a kind of method for preparing weight base oil, includes the following steps：
(a) hydrocarbon-containing feedstock is provided, the hydrocarbon-containing feedstock includes at least hydrocarbon of the boiling point of 50wt% higher than 460 DEG C, 800- The nitrogen of 2500ppmw and the sulphur of 1.5-4.0wt%；
(b) hydrocarbon-containing feedstock described in hydrotreating catalyst hydrotreating is used in the presence of hydrogen-containing gas under hydroprocessing conditions, Using obtain nitrogen content be 30-80ppmw and sulfur content as the hydrotreating of 200-450ppmw after product；
(c) after the hydrotreating that is obtained in step (b) of removing present in product at least 50% NH3And H2S；
(d) at least part for obtaining step (c) with dewaxing catalyst in the presence of hydrogen-containing gas under catalytic dewaxing conditions adds Product catalytic dewaxing after hydrogen processing, to obtain dewaxed product, the dewaxing catalyst includes group VIII metal hydrogenation component, takes off The aluminosilicate zeolite crystallites of aluminium and not salic low in acidity refractory oxide binder material；
(e) make at least portion of step (d) acquisition with Hydrobon catalyst in the presence of hydrogen-containing gas under Hydrofinishing conditions Divide dewaxed product hydrofinishing, to obtain weight base oil；With
(f) the heavy base oil is recycled.
2. the method for claim 1 wherein the boiling point that the hydrocarbon-containing feedstock provided in step (a) is included more than 65wt% is higher than 460 DEG C hydrocarbon.
It is glued at least the 100 of 50wt% DEG C 3. the hydrocarbon-containing feedstock provided in the method for claims 1 or 2, wherein step (a) includes Hydrocarbon of the degree more than 14cSt.
4. nitrogen content and the weight of sulfur content in product after the hydrotreating that the method for claims 1 or 2, wherein step (b) obtain Amount is than being 0.1-0.3.
5. the method for claims 1 or 2, wherein by stripping from product after the hydrotreating that step (b) obtains in step (c) Middle removing NH3And H2S。
6. the method for claims 1 or 2, wherein existing in product after the hydrotreating that removing step (b) obtains in step (c) At least 90% NH3And H2S。
7. the method for claims 1 or 2, wherein with the total weight of dewaxing catalyst, the boiling in the dewaxing catalyst of step (d) Stone component exists with the amount of 10-50wt%.
8. the method for claim 7, wherein the zeolite component is ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 or ZSM-48.
9. the hydroprocessing condition in the method for claims 1 or 2, wherein step (b) includes 250-480 DEG C of temperature, 30- The pressure and 0.2-10hr of 250bar-1Weight (hourly) space velocity (WHSV)；Dewaxing conditions in step (d) include 350-460 DEG C of temperature, 80- The pressure and 0.4-7hr of 240bar-1Weight (hourly) space velocity (WHSV)；Include 300-390 DEG C of temperature with the Hydrofinishing conditions in step (e) Degree, the pressure of 80-200bar and 0.5-2.5hr-1Weight (hourly) space velocity (WHSV).
10. the Hydrobon catalyst in the method for claims 1 or 2, wherein step (e) is catalyzed for the hydrofinishing of noble metal base Agent.
11. the Hydrobon catalyst in the method for claims 1 or 2, wherein step (e) is basic metal hydrogenation refining catalytic Agent.
12. the method for claims 1 or 2, wherein also dividing from product after the hydrotreating that step (b) obtains in step (c) Separate out the hydrocarbon that boiling point is less than 370 DEG C.
13. the method for claims 1 or 2, wherein product is subjected to step (c) after making the whole hydrotreatings obtained in step (b).
14. the method for claims 1 or 2, wherein product is subjected to step (d) after making the whole hydrotreatings obtained in step (c).
15. the method for claims 1 or 2, wherein the whole dewaxed products obtained in step (d) is made to be subjected to step (e).
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