CN107345160B - A kind of production method of lube base oil - Google Patents

Abstract

The invention discloses a kind of production methods of lube base oil.This method is using being hydrocracked and post-refining process, process is as follows: in the presence of hydrocracking catalyst, hydrocracking raw material carries out hydrocracking reaction, resulting isocrackate is separated, obtain hydrocracking tail oil, hydrocracking tail oil obtains lube base oil through post-refining；For hydrocracking catalyst used in it using Modified Zeolite Y, amorphous silica-alumina and aluminium oxide as carrier, Modified Zeolite Y therein is a kind of Y type molecular sieve concentrated rich in mesoporous, effective pore sife distribution.Hydrogenation tail oil prepared by this method has the characteristics that pour point is lower and yield is high, and it is lower directly to refine production pour point, the better lube base oil of stability.

Description

A kind of production method of lube base oil

Technical field

The present invention relates to a kind of production lube base oil methods, are hydrocracked and hydrofinishing work more particularly to one kind The method that skill combines production lube base oil.

Background technique

Being hydrocracked is one of most important processing of heavy oil means in current petroleum refining industry.Raw material is raw after being hydrocracked The primary product of production has the products such as gas, gasoline, diesel oil, jet fuel and high-quality hydrogenation tail oil, and hydrocracking tail oil is rich in chain Alkane and cycloalkane have the advantages that arene content is few and sulphur, nitrogen impurity content are low etc..

Due to worldwide crude oil in poor quality, so that being suitable for conventionally produced base oil of high viscosity index lubricant Paraffinic base crude oil quantity gradually decrease, therefore, hydrogenation method produce Lubricating Oil Technique development it is very rapid.Hydrogenation method technique refers to Lube base is produced using hydrotreating or hydrocracking process-hydrodewaxing or isomerization dewaxing-hydrofinishing process integration The process of oil, which is feed flexibility is big, base oil yield is high, by-product value is high etc..Lubricating oil isomerization dewaxing It is the new technology of the production high quality API II/III class lubricating oil base oil of last century the nineties exploitation.Isomerization dewaxing be by The higher linear paraffin of condensation point generates isoparaffin by isomerization reaction in oil product, and reaching reduces product pour point and keep higher The technology of lube base oil yield.Compared with solvent dewaxing and catalytic dewaxing, isomerization dewaxing base oil yield is high, pour point is low, Viscosity index (VI) is high, is the excellent blend component of modern high performance I. C. engine oil.

The key of lubricating oil Isodewaxing Technology is isomerization catalyst.According to the reaction mechanism of alkane isomerization, All isomerization dewaxing catalysts are made of the molecular sieve of the noble metal component of high hydrogenation activity and acid active component Bifunctional catalyst.This composition determines that catalyst is very sensitive to sulphur, the nitrogen impurity in isomerization dewaxing raw material, and raw material must Hydrotreating of the palpus Jing Guo depth, or such as using the seldom raw material of sulphur, nitrogen impurity content: hydrocracking tail oil and F- T synthesis Wax etc., the raw material into isomerization reactor will control sulfur content less than 10 μ g/g, and nitrogen content is less than 5 μ g/g.

It is that feedstock oil hydro-upgrading production high viscosity refers to that CN201210408445.4, which discloses one kind by APII class base oil, The method of number lube base oil.AP II class base oil initially enters hydro-upgrading reaction zone after mixing with hydrogen in this method, With the catalyst for hydro-upgrading haptoreaction containing Y type molecular sieve, polycyclic ring alkane ring-opening reaction occurs；Reaction effluent is through dividing The lube base oil product that viscosity index (VI) meets AP IIII class base oil requirement is obtained after evaporating.This method keeps APII class basic Ring-opening reaction occurs for the bicyclic above polycyclic ring alkane and polycyclic aromatic hydrocarbon in oily raw material, and it is polycyclic to reduce low-viscosity index component in product The content of cycloalkane and polycyclic aromatic hydrocarbon greatly improves the viscosity index (VI) of product, obtains the AP IIII class that viscosity index (VI) is greater than 120 Base oil product.

CN97196410.6 discloses a kind of side of hydrotreating-isomerization dewaxing-hydrofinishing production lube base oil Method, this method require the viscosity index (VI) of raw material to be greater than 75, II class and Group III base oil of the production viscosity index (VI) greater than 110.

CN102145307A discloses a kind of method of lube base oil for producing high viscosity index (HVI), mainly uses one Cracking Component of the kind aluminium silicon composite material as Cracking catalyst is that raw material produces viscosity with vacuum distillate or deasphalted oil etc. The lube base oil that index is 86 or so, since using aluminium silicon composite material, as Cracking Component, the activity of catalyst is lower, The lube base oil viscosity index (VI) of production is relatively low.

CN1944588A discloses a kind of method of producing lubricating oil base oil by hydrogenating tail oil, and wherein hydrogenation tail oil is to use Hydrotreating catalyst containing beta-molecular sieve, obtained after hydrotreating pour point less than -10 DEG C hydrogenation tail oil through it is clay-filtered or in Hydrofinishing process is pressed, lube base oil product is obtained；Wherein the property of b molecular sieve is as follows: silica/tri- oxidations Two aluminium weight ratios are 50 ~ 90, and average grain size is 0.1 ~ 0.5 micron, and infrared 0.1 ~ 0.4mmol/g of acidity, this method is given birth to The hydrogenation tail oil pour point of production is higher, usually -15 ~ -10 DEG C, directly affects the low temperature flow of prepared lube base oil.

The production method of above-mentioned existing base oil of high viscosity index lubricant is with petroleum distillate, mainly reduced pressure distillate Oil is raw material, using the technical process of hydrotreating-isomery (catalysis) dewaxing-hydrofinishing, produces viscosity index (VI) and is greater than 120 Lube base oil.The prior art can not produce viscosity index (VI) by raw material of the AP II class base oil that conventional solvent technique produces AP Group III lube base oil greater than 120.

Summary of the invention

Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of production methods of lube base oil. Hydrogenation tail oil prepared by this method has the characteristics that pour point is lower and yield is high, and it is lower directly to refine production pour point, stablizes The better lube base oil of property.

The production method of lube base oil of the present invention, using being hydrocracked and post-refining process, process are as follows: adding In the presence of hydrogen Cracking catalyst, hydrocracking raw material carries out hydrocracking reaction, and resulting isocrackate is separated, obtained To hydrocracking tail oil, hydrocracking tail oil obtains lube base oil through post-refining；Wherein hydrocracking catalyst is such as Under: it include carrier and hydrogenation active metal component, carrier includes Modified Zeolite Y, amorphous silica-alumina and aluminium oxide, wherein institute The Modified Zeolite Y stated, property are as follows: relative crystallinity is 110% ~ 150%, SiO₂/Al₂O₃Molar ratio is 55 ~ 100, brilliant Born of the same parents' parameter is 2.425 ~ 2.435nm, and total pore volume is 0.55 ~ 1.0mL/g, preferably 0.6 ~ 1.0mL/g, and mesoporous pore volume Zhan is total 70% or more of pore volume, preferably 80% ~ 95%.

The grain size of the Modified Zeolite Y is 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm.

In the Modified Zeolite Y, mesoporous bore dia is 2 ~ 10nm.

The specific surface area of the Modified Zeolite Y is 650 ~ 1000m²/ g, preferably 750 ~ 1000m²/g。

The infrared total acid content of the Modified Zeolite Y is 0.1 ~ 0.5mmol/g.

In the Modified Zeolite Y, Na₂The weight content of O is 0.15wt% or less.

In the hydrocracking catalyst, the carrier, on the basis of the weight of carrier, Modified Zeolite Y Content is 10% ~ 50%, preferably 15% ~ 45%, and the content of amorphous silica-alumina is 5% ~ 30%, preferably 10% ~ 25%, and aluminium oxide contains Amount is 20% ~ 85%, preferably 30% ~ 75%.

The hydrogenation active metals generally use the metal of group VIB and group VIII, and vib metals are preferably molybdenum And/or tungsten, group VIII metal are preferably cobalt and/or nickel.In hydrocracking catalyst catalyst of the present invention, with the weight of catalyst On the basis of amount, the content of vib metals (in terms of oxide) is 10.0% ~ 30.0%, group VIII metal (in terms of oxide) Content be 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.

The property of hydrocracking catalyst of the present invention is as follows: specific surface area is 250 ~ 450m²/ g, pore volume be 0.30 ~ 0.50mL/g。

The preparation method of hydrocracking catalyst of the present invention, preparation and load hydrogenation active metal component including carrier, Wherein the preparation process of carrier is as follows: Modified Zeolite Y, amorphous silica-alumina, aluminium oxide are mixed, molding, it is then dry and Roasting, is made catalyst carrier, wherein the preparation method of Modified Zeolite Y, includes the following steps:

(1) NaY type molecular sieve and (NH₄)₂SiF₆Aqueous solution contact is reacted, and is filtered and is dried after reaction；

(2) hydro-thermal process is carried out to Y type molecular sieve obtained by step (1)；Hydrothermal conditions: gauge pressure be 0.20 ~ 0.40MPa, temperature are 600 ~ 800 DEG C, and the processing time is 0.5 ~ 5.0 hour；

(3) hydrothermal crystallizing processing is carried out under the conditions of by Y type molecular sieve obtained by step (2) existing for the organic formwork agent, so By filtering and drying；

(4) step (3) resulting Y type molecular sieve is roasted under low temperature oxygen-enriched atmosphere, modification Y type point of the invention is made Son sieve.

In the method for the present invention step (1), the property of NaY type molecular sieve is as follows:

SiO₂/Al₂O₃Molar ratio be 3 ~ 6, preferably 4.5 ~ 5.5, grain size be 1.0 ~ 2.5 μm, preferably 1.2 ~ 1.8 μm, Relative crystallinity is 80% ~ 110%, and cell parameter is 2.465 ~ 2.470nm, Na₂The weight content of O is 6.0wt% ~ 8.0wt%, than Surface area is 600 ~ 900m²/ g, total pore volume are 0.3 ~ 0.4 mL/g, and micropore pore volume accounts for 75% of total pore volume or more.

In the method for the present invention step (1), (NH₄)₂SiF₆Additional amount be NaY type molecular sieve dry weight 5wt% ~ 20wt%。

In the method for the present invention step (1), (NH₄)₂SiF₆The mass concentration of aqueous solution is 50 ~ 100g/L.NaY type molecular sieve With (NH₄)₂SiF₆Aqueous solution contacts the reaction condition that is reacted: temperature is 80 ~ 150 DEG C, preferably 90 ~ 120 DEG C, when reaction Between be 0.1 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.

In the method for the present invention step (1), NaY type molecular sieve and (NH₄)₂SiF₆After aqueous solution contact is reacted, separation point Son sieve and by-product, can wash, refilter, dry, it is preferably dry after resulting Y type molecular sieve butt be 60wt% ~ 80wt%.Dry condition is usually 0.5 ~ 5.0 hour dry at 50 ~ 95 DEG C.

In the method for the present invention step (2), hydro-thermal process is the molecular sieve obtained in saturated steam processing step (1), Treatment conditions: 0.20 ~ 0.40MPa of gauge pressure, preferably 0.25 ~ 0.40MPa, 600 ~ 800 DEG C of temperature, preferably 610 ~ 750 DEG C, place The reason time 0.5 ~ 5.0 hour, preferably 1.0 ~ 3.0 hours.

In the method for the present invention step (3), organic formwork agent is tetraethyl ammonium hydroxide, tetramethylammonium hydroxide, tetrapropyl The one or more of ammonium hydroxide.Wherein, after evenly mixing by Y type molecular sieve obtained in step (2) and organic formwork agent, into Row hydrothermal crystallizing, process are as follows: Y type molecular sieve obtained in step (2) being beaten in organic formwork agent aqueous solution, liquid weighs admittedly Amount is than being 3:1 ~ 8:1, and temperature is 70 ~ 90 DEG C, and the time is 0.5 ~ 5.0 hour, the mass concentration of organic formwork agent aqueous solution is 3% ~ 10%, mixed material is then placed in crystallization in crystallizing kettle, crystallization temperature is 80 ~ 120 DEG C, and crystallization time is 4 ~ 10h, and gauge pressure is 0.1~0.2MPa.After crystallization, being filtered and being dried can be carried out using conventional method, and generally dry condition is as follows: 50 ~ Dry 1 ~ 10h at 110 DEG C.

In the method for the present invention, step (4) is roast under low temperature oxygen-enriched atmosphere by the Y type molecular sieve that step (3) obtains, Wherein oxygen-enriched atmosphere refers to that oxygen content is greater than 50v%, and maturing temperature is 300 ~ 450 DEG C, and calcining time is 5 ~ 10h.Roasting is general Using the method roasted under temperature programming again constant temperature, heating rate is preferably 1 ~ 2 DEG C/min.

Hydrocracking raw material of the present invention can be vacuum distillate, wax tailings, solvent refining deasphalted oil And one or more of Fischer-Tropsch synthesis oil.

The present invention, which is hydrocracked, can also use series process flow using single stage process process.Tandem process stream Cheng Zhong, raw material pass through conventional hydro catalyst for refining bed first, then pass through hydrocracking catalyst bed.Single stage process makes Use hydrocracking catalyst.Raw material pass through hydrocracking catalyst bed when reaction condition generally react stagnation pressure be 12.0 ~ 20.0MPa, volume space velocity is 0.5 ~ 5.0h when liquid^-1, hydrogen to oil volume ratio is 1000:1 ~ 2000:1, and reaction temperature is 350 ~ 435 ℃.Using series process flow, raw material by the condition of conventional hydro catalyst for refining bed reaction zone can with by adding hydrogen The condition of Cracking catalyst is identical, can also be different, the reaction condition of general hydrofinishing be reaction pressure be 12.0 ~ 20.0MPa, temperature are 350 ~ 435 DEG C, and hydrogen to oil volume ratio is 1000:1 ~ 2000:1, and volume space velocity is 0.5 ~ 5.0h when liquid^-1；One As the reaction condition that is hydrocracked be reaction pressure be 12.0 ~ 20.0MPa, temperature is 350 ~ 435 DEG C, and hydrogen to oil volume ratio is 1000:1 ~ 2000:1, volume space velocity is 0.5 ~ 5.0h when liquid^-1。

The method that the hydrocracking tail oil post-refining process used in the present invention generallys use hydrofining.It is described Hydrofinishing be that alumina-based supports are used, generally with group VIB and group VIII using conventional Hydrobon catalyst Metal is hydrogenation active metal component, and vib metals are preferably molybdenum and/or tungsten, the metal of group VIII be preferably cobalt and/or Nickel.On the basis of the weight of catalyst, the content of vib metals (in terms of oxide) is 15.0% ~ 30.0%, group VIII gold The content for belonging to (in terms of oxide) is 4.0% ~ 8.0%.Operating condition used by post-refining is generally as follows: temperature be 220 ~ 350 DEG C, preferably 230 ~ 320 DEG C, hydrogen partial pressure are 2.5 ~ 8.0MPa, preferably 3.0 ~ 7.0MPa, and volume space velocity is 0.5 ~ 2.0h when liquid^-1, hydrogen to oil volume ratio is 300:1 ~ 1000:1.

Hydrocracking catalyst used by the method for the present invention, wherein Y type molecular sieve is using (NH₄)₂SiF₆To NaY points Son sieve is modified processing, while realizing modulation molecular sieve silica alumina ratio, can take off together the sodium ion in NaY molecular sieve Out, hydrothermal crystallizing then is carried out to the molecular sieve after hydro-thermal process in the presence of organic formwork agent, part silicon atom can be made in this way Enter framework of molecular sieve structure under organic formwork agent effect with aluminium atom, in the further bone stablized and improve modified molecular screen While frame structure, the non-skeleton structure generated in zeolite-water heat treatment process, unimpeded cellular structure, the organic mould in part are eliminated Plate agent is also able to enter in the duct of molecular sieve, cooperates subsequent oxygen-enriched low-temperature treatment, can be by the organic formwork in molecular sieve Agent controllably orderly removes, to generate a large amount of ordered mesopore structures, and pore size distribution is more concentrated.

Y type molecular sieve acidity is suitable in hydrogen Cracking catalyst used by the method for the present invention, crystallinity is high, mesoporous institute's accounting Example is high, pore-size distribution is more concentrated.Since the Y type molecular sieve has bigger pore volume and mesopore volume, more in acidity The heart is exposed, and is conducive to raw material heavy oil macromolecular and is cracked, but also has more preferably pore size distribution range, can be effective Ground controls the cracking degree of reactant, and is conducive to product and is diffused in duct, in this way in cracking reaction, opposite can increase Add activated centre, and heavy oil macromolecular can be made to carry out the cracking reaction of suitable degree, both improves the open loop and chain rupture of heavy oil Can, catalyst can show good cracking activity and product selectivity.

Hydrogenation tail oil prepared by the method for the present invention has the characteristics that pour point is lower and yield is high, can directly refine production and incline Lower, the better lube base oil of stability of point.

Detailed description of the invention

Fig. 1 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of embodiment；

Fig. 2 is the SEM electromicroscopic photograph of 1 gained Modified Zeolite Y of comparative example；

Fig. 3 is the XRD diffraction pattern of 1 gained Modified Zeolite Y of embodiment.

Specific embodiment

Aluminium oxide can be using oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention Change aluminium, such as macroporous aluminium oxide and small porous aluminum oxide, the mass ratio of general macroporous aluminium oxide and small porous aluminum oxide is 1:8 ~ 8:1.Institute The property for the macroporous aluminium oxide stated is as follows: pore volume is 0.6 ~ 1.3mL/g, and specific surface area is 300 ~ 450m²/g。

Adhesive therefor of the present invention is made of small porous aluminum oxide and inorganic acid and/or organic acid.Aperture oxidation used Aluminium pore volume is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m²/g。

Amorphous silica-alumina used in catalyst carrier of the present invention can be prepared by coprecipitation or grafting copolymerization process, by document Middle conventional method preparation.In amorphous silica-alumina obtained, SiO₂Weight content be 10% ~ 60%, preferably 20% ~ 55%, The pore volume of amorphous silica-alumina is 0.6 ~ 1.1mL/g, and preferably 0.8 ~ 1.0mL/g, specific surface area is 300 ~ 500m²/ g, preferably For 350 ~ 500m²/g。

Detailed process is as follows for catalyst carrier for hydrgenating preparation of the present invention: by Modified Zeolite Y, amorphous silica-alumina, oxygen Change aluminium mixing, molding, then dry and roasting is prepared into carrier；It is small that drying can dry 3 ~ 6 at a temperature of 80 DEG C ~ 150 DEG C When, roasting is roasted 2.5 ~ 6.0 hours at 500 DEG C ~ 600 DEG C.

Carrier of hydrocracking catalyst of the present invention loads hydrogenation active metal component (group VIB and by conventional methods Group VIII metal component such as Co, Ni, Mo, W etc.), it is prepared into hydrocracking catalyst.Using load side conventional in the prior art Method, preferably infusion process can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst for containing required active component Agent carrier, carrier after dipping 100 DEG C ~ 150 DEG C drying 1 ~ 12 hour, it is then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 When, final catalyst is made.

The following examples are for being described in more detail technical solution of the present invention, but the scope of the present invention is not limited solely to this The range of a little embodiments.In the present invention, wt% is mass fraction.

Analysis method of the present invention: specific surface area, pore volume, mesoporous pore volume use low temperature liquid nitrogen determination of adsorption method, relatively Crystallinity and cell parameter use x-ray diffraction method, and silica alumina ratio is measured using XRF method (x ray fluorescence spectrometry), molecular sieve Grain size using SEM(scanning electron microscope) by the way of measure.Meleic acid amount uses Pyridine adsorption IR spectra method, sodium Content uses plasma emission spectrometry.

NaY molecular sieve original powder employed in the embodiment of the present invention and comparative example be it is industrially prepared, property is as follows: SiO₂/ Al₂O₃Molar ratio is 5.1, and grain size is ~ 1.7 μm, relative crystallinity 95%, cell parameter 2.468nm, Na₂The weight content of O For 6.5wt%, specific surface area 856m²/ g, total pore volume 0.32mL/g, micropore pore volume account for the 81.3% of total pore volume, butt 72.0wt%。

Embodiment 1

It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 95 DEG C, start that (NH is added dropwise into molecular sieve pulp₄)₂SiF₆Aqueous solution dropped evenly the (NH that 307mL solution concentration is 72g/L at 60 minutes₄)₂SiF₆Solution, constant temperature after completion of dropwise addition Stirring 2 hours, is filtered and is dried after constant temperature, and the butt of molecular sieve is 65.3wt% after drying；After above-mentioned drying Molecular sieve is added in hydrothermal treatment device, to molecule under the conditions of gauge pressure 0.25MPa, 610 DEG C of temperature, processing the time 1.0 hours Sieve carries out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into the tetraethyl hydrogen-oxygen that 520mL mass concentration is 5.3% Change in aqueous ammonium, constant temperature stirs 4 hours under the conditions of 80 DEG C, and then mixed material is transferred in crystallizing kettle and carries out hydro-thermal crystalline substance Change, 90 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and is dried after crystallization；By hydro-thermal The drying sample that crystallization obtains roasts under oxygen-enriched state, in calcination atmosphere oxygen content be 70v%, heating rate be 1 DEG C/ Min, constant temperature calcining temperature are 420 DEG C, and the constant temperature calcining time is 6 hours, obtain molecular sieve of the present invention.Sample number into spectrum LAY-1, point Son sieve property is listed in table 1.

Embodiment 2

It takes NaY original powder 278g to be put into 800mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp (NH₄)₂SiF₆Aqueous solution dropped evenly the (NH that 182mL solution concentration is 55g/L at 60 minutes₄)₂SiF₆Solution, completion of dropwise addition Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 68.0wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature, processing 2.0 hours time condition Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 910mL mass concentration is 7.5% In propyl ammonium hydroxide aqueous solution, under the conditions of 90 DEG C constant temperature stir 4 hours, then by mixed material be transferred in crystallizing kettle into Row hydrothermal crystallizing, 110 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 10 hours, is filtered and dries place after crystallization Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 65v%, heating rate in calcination atmosphere For 1 DEG C/min, constant temperature calcining temperature is 360 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-2, molecular sieve property are listed in table 1.

Embodiment 3

It takes NaY original powder 278g to be put into 1000mL water purification, is warming up to 100 DEG C, start to be added dropwise into molecular sieve pulp (NH₄)₂SiF₆Aqueous solution dropped evenly the (NH that 417mL solution concentration is 85g/L at 60 minutes₄)₂SiF₆Solution, completion of dropwise addition Constant temperature stirs 3 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 67.2wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, under the conditions of gauge pressure 0.35MPa, 700 DEG C of temperature, processing the time 3.0 hours Hydro-thermal process is carried out to molecular sieve；Molecular sieve after taking 130g hydro-thermal process is put into the tetrem that 1040mL mass concentration is 3.5% In base ammonium hydroxide aqueous solution, constant temperature is stirred 3 hours under the conditions of 85 DEG C, and then mixed material is transferred in crystallizing kettle and is carried out Hydrothermal crystallizing, 80 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 5 hours, is filtered and is dried after crystallization； The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 75v%, heating rate 1 in calcination atmosphere DEG C/min, constant temperature calcining temperature is 320 DEG C, and the constant temperature calcining time is 8 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY- 3, molecular sieve property is listed in table 1.

Embodiment 4

It takes NaY original powder 278g to be put into 1400mL water purification, is warming up to 95 DEG C, start to be added dropwise into molecular sieve pulp (NH₄)₂SiF₆Aqueous solution dropped evenly the (NH that 200mL solution concentration is 60g/L at 60 minutes₄)₂SiF₆Solution, completion of dropwise addition Constant temperature stirs 2 hours afterwards, is filtered and dries after constant temperature, and the butt of molecular sieve is 68.1wt% after drying；It will be above-mentioned dry Molecular sieve after dry is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 750 DEG C of temperature, processing 2.0 hours time condition Under to molecular sieve carry out hydro-thermal process；Molecular sieve after taking 130g hydro-thermal process is put into four that 520mL mass concentration is 6.8% In propyl ammonium hydroxide aqueous solution, under the conditions of 90 DEG C constant temperature stir 3 hours, then by mixed material be transferred in crystallizing kettle into Row hydrothermal crystallizing, 95 DEG C of crystallization temperature, gauge pressure 0.1MPa crystallization time 8 hours, is filtered and dries place after crystallization Reason；The drying sample that hydrothermal crystallizing obtains is roasted under oxygen-enriched state, oxygen content is 70v%, heating rate in calcination atmosphere For 1 DEG C/min, constant temperature calcining temperature is 380 DEG C, and the constant temperature calcining time is 10 hours, obtains molecular sieve of the present invention.Sample number into spectrum LAY-4, molecular sieve property are listed in table 1.

Comparative example 1

It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature Stirring 2 hours, is filtered after constant temperature, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Temperature programming Molecular sieve is roasted 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Second of ammonium of 100g is taken to hand over Molecular sieve after changing is put into the tetraethyl ammonium hydroxide aqueous solution that 650mL mass concentration is 7.5%, permanent under the conditions of 80 DEG C Mixed material, is then transferred in crystallizing kettle and carries out crystallization by temperature stirring 2 hours, and 100 DEG C of crystallization temperature, gauge pressure 0.1MPa, It crystallization time 8 hours, is filtered and is dried after crystallization；The drying sample that crystallization obtains is roasted under oxygen-enriched state It burns, oxygen content is 60v% in calcination atmosphere, and heating rate is 1 DEG C/min, and constant temperature calcining temperature is 360 DEG C, when constant temperature calcining Between be 8 hours, obtain molecular sieve.Sample number into spectrum LDAY-1, molecular sieve property are listed in table 1.

Comparative example 2

It takes NaY original powder 278g to be put into the solution that 1000mL ammonium nitrate concn is 1.5mol/L, is warming up to 95 DEG C, constant temperature Stirring 2 hours divides after constant temperature and is filtered, washs and dries, and the butt of molecular sieve is 63.8wt% after drying；Program liter Temperature roasts molecular sieve 3 hours at 600 DEG C；Then repeat an ammonium exchange, and filtering and drying；Take second of ammonium of 100g Molecular sieve after exchange is put into the dust technology that 800mL concentration is 0.3mol/L, and constant temperature stirs 2 hours under the conditions of 80 DEG C, It is filtered and is dried after constant temperature；Molecular sieve after above-mentioned drying is added in hydrothermal treatment device, in gauge pressure 0.30MPa, 670 DEG C of temperature obtain molecular sieve to molecular sieve progress hydro-thermal process under the conditions of the 2.0 hours time of processing；Sample is compiled Number LDAY-2, molecular sieve property are listed in table 1.

Comparative example 3

Molecular sieve, sample number into spectrum LDAY-3, molecular sieve are prepared using the method for embodiment 1 in CN201510147788.3 Matter is listed in table 1.

The property of 1 Y type molecular sieve of table

Product number	LAY-1	LAY-2	LAY-3	LAY-4
					Specific surface area, m2/g	912	887	941	923
Pore volume, cm3/g	0.74	0.69	0.88	0.72
					Lattice constant, nm	2.433	2.431	2.428	2.426
Relative crystallinity, %	131	119	140	132
					Average crystallite size, μm	1.7	1.7	1.7	1.7
SiO2/Al2O3Molar ratio	73.6.3	62.3	81.9	65.8
					Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts for total pore volume ratio, %	86	83	91	87
Infrared total acid content, mmol/g	0.45	0.33	0.30	0.21
					Na2O, wt%	0.05	0.06	0.03	0.07

Continued 1

Product number	LDAY-1	LDAY-2	LDAY-3
				Specific surface area, m2/g	633	703	603
Pore volume, cm3/g	0.44	0.37	0.38
				Lattice constant, nm	2.439	2.433	2.449
Relative crystallinity, %	98	103	86
				Average crystallite size, μm	1.7	1.7	1.7
SiO2/Al2O3Molar ratio	7.5	33.5	8.6
				Mesoporous pore volume (bore dia 2nm ~ 10nm) accounts for total pore volume ratio, %	47	31	37
Infrared total acid content, mmol/g	0.77	0.35	0.71
				Na2O, wt%	0.21	0.19	0.45

Embodiment 5

By 100 grams of LAY-1 molecular sieves (butt 90wt%), 64.3 grams of amorphous silica-alumina (SiO₂Content 25wt%, pore volume 0.85mL/g, specific surface area 370m²/ g, butt 70wt%), 150 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface areas 400m²/ g, butt 70wt%), (molar ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4) to be put into stone roller for 200 grams of adhesives Mixed grind in press, adds water, is rolled into paste, and extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, Obtain carrier ZS-1.

Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4 Hour, catalyst HC-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Embodiment 6

By 50 grams of LAY-1 molecular sieves (butt 90wt%), 50 grams of amorphous silica-alumina (SiO₂Content 25wt%, pore volume 0.85mL/g, specific surface area 370m²/ g, butt 70wt%), 214.3 grams of macroporous aluminium oxides (pore volume 1.0mL/g, specific surface areas 400m²/ g, butt 70wt%), (molar ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4) to be put into stone roller for 200 grams of adhesives Mixed grind in press, adds water, is rolled into paste, and extrusion, extrusion item is 4 hours dry at 110 DEG C, then roasts 4 hours at 550 DEG C, Obtain carrier ZS-2.

Maceration extract room temperature immersion 2 hours of carrier tungstenic and nickel, 120 DEG C drying 4 hours, 500 DEG C of temperature programming roasting 4 Hour, catalyst HC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.

Embodiment 7 ~ 8

As described in Example 5, it changes LAY-1 into LAY-2, LAY-3 respectively, carrier ZS-3, ZS-4 and catalysis is made Agent HC-3 and HC-4, carrier and catalyst composition are shown in Table 2.

Comparative example 4 ~ 6

As described in Example 5, change LAY-1 into LDAY-1, LDAY-2, LDAY-2 respectively, be made carrier DZS-1, DZS-2, DZS-3 and catalyst DHC-1, DHC-2 and DHC-3, carrier and catalyst composition are shown in Table 3.

The composition and physico-chemical property of 2 catalyst carrier of table and catalyst

Carrier composition and property
					Number	ZS-1	ZS-2	ZS-3	ZS-4
Composition
					Modified Zeolite Y, wt%	30.0	15.0	30.0	30.0
Amorphous silica-alumina, wt%	15.0	15.0	15.0	15.0
					Macroporous aluminium oxide, wt%	35.0	50.0	35.0	35.0
Adhesive, wt%	Surplus	Surplus	Surplus	Surplus
					Property
Pore volume, mL/g	0.65	0.70	0.67	0.69
					Specific surface area, m2/g	529	445	538	521
Catalyst composition and property
					Number	HC-1	HC-2	HC-3	HC-4
WO3, wt%	22.52	23.52	21.94	23.15
					NiO, wt%	5.71	5.98	5.84	5.83
Pore volume, mL/g	0.42	0.45	0.41	0.44
					Specific surface area, m2/g	429	386	425	433

Continued 2

Carrier composition and property
				Number	DZS-1	DZS-2	DZS-3
Composition
				Modified Zeolite Y, wt%	30.0	30.0	30.0
Amorphous silica-alumina, wt%	15.0	15.0	15.0
				Macroporous aluminium oxide, wt%	35.0	35.0	35.0
Adhesive, wt%	Surplus	Surplus	Surplus
				Property
Pore volume, mL/g	0.51	0.50	0.54
				Specific surface area, m2/g	422	433	428
Catalyst composition and property
				Number	DHC-1	DHC-2	DHC-3
WO3, wt%	22.49	22.50	22.56
				NiO, wt%	5.81	5.78	5.89
Pore volume, mL/g	0.30	0.30	0.27
				Specific surface area, m2/g	322	335	305

This embodiment describes the evaluation results of the method for the present invention.It is evaluated, is commented on fixed bed hydrogenation experimental rig Valence condition are as follows: the reaction condition of hydrofinishing is that reaction pressure is 16.0MPa, and catalyst is 3936 catalyst for refining, and temperature is 380 DEG C, hydrogen to oil volume ratio 1200:1, volume space velocity is 1.0h when liquid^-1；Cracking zone reaction condition: pressure 16.0MPa, hydrogen oil Volume ratio 1500, volume space velocity 0.9h when liquid^-1, use vacuum distillate (VGO) as feedstock oil, raw material oil nature is listed in table 3. Catalyst HC-1, HC-2, HC-3, HC-4, DHC-1, DHC-2 and DHC-3 are evaluated under identical process conditions, what is obtained comments Valence result is listed in table 4.

Table 6 lists hydrogenation tail oil post-refining process process and result.Wherein, supplement Hydrobon catalyst is to use FHDA-1 catalyst for refining, table 5 list FHDA-1 catalyst property.

3 raw material oil nature of table

Density (20 DEG C), g/cm3	0.9254
		Boiling range/DEG C
IBP/10%	313/372
		30%/50%	402/425
70%/90%	455/495
		95%/EBP	520/554
Condensation point/DEG C	35
		Sulphur/wt%	2.08
Nitrogen, μ g/g	1180
		Carbon/wt%	85.28
Hydrogen/wt%	12.52
		BMCI value	44.06

4 performance evaluation condition of table and result

Catalyst	HC-1	HC-2	HC-3	HC-4
					Feedstock oil	Vacuum distillate	Vacuum distillate	Vacuum distillate	Vacuum distillate
Hydrocracking operation condition
					Volume space velocity when liquid, h-1	0.9	0.9	0.9	0.9
React stagnation pressure, MPa	16.0	16.0	16.0	16.0
					Hydrogen to oil volume ratio	1500:1	1500:1	1500:1	1500:1
Reaction temperature, DEG C	378	382	375	379
					Hydrocracking tail oil		Tail oil 1
Yield, wt%	43.50	46.20	40.2	39.3
					Boiling range, DEG C	380~510	380~510	380~510	380~510
Pour point, DEG C	-16	-15	-17	-16
					Aromatic hydrocarbons, w%	1.0	0.5	0.8	0.6
Viscosity index (VI)	138	141	140	135

Continued 4

Catalyst	HDC-1	HDC-2	HDC-3
				Feedstock oil	Vacuum distillate	Vacuum distillate	Vacuum distillate
Hydrocracking operation condition	Tail oil 2
				Volume space velocity when liquid, h-1	0.9	0.9	0.9
React stagnation pressure, MPa	16.0	16.0	16.0
				Hydrogen to oil volume ratio	1500:1	1500:1	1500:1
Reaction temperature, DEG C	395	398	403
				Hydrocracking tail oil
Yield, wt%	32.16	30.22	29.8
				Boiling range, DEG C	380~510	380~510	380~510
Pour point, DEG C	-6	-4	-4
				Aromatic hydrocarbons, w%	1.3	2.8	3.1
Viscosity index (VI)	121	115	112

5 FHDA-1 catalyst physicochemical property of table

Catalyst	FHDA-1
		Kong Rong, mL/g	0.45
Specific surface area, m2/g	190
		Shape	Bar shaped

6 hydrogenation tail oil post-refining process condition of table and result

Feedstock oil	Tail oil 1	Tail oil 2
			Operating condition
Volume space velocity when liquid, h-1	1.5	1.5
			React stagnation pressure, MPa	6.0	6.0
Hydrogen to oil volume ratio	600:1	600:1
			Reaction temperature, DEG C	280	300
Basic oil nature
			Appearance	It is water-white transparent	It is transparent
Color (D1500)/number
			Pour point, DEG C	-15	-6
Viscosity index (VI)	313	105
			Yield, wt%	99.8	97.9

The lube base oil pour point that it can be seen from evaluation result prepared by the method for the present invention is lower, and yield is higher, viscosity The features such as index is high.

Claims (22)

1. a kind of production method of lube base oil, using being hydrocracked and post-refining process, process are as follows: hydrogen being added to split In the presence of changing catalyst, hydrocracking raw material carries out hydrocracking reaction, and resulting isocrackate is separated, added Hydrogen cracking tail oil, hydrocracking tail oil obtain lube base oil through post-refining；Wherein hydrocracking catalyst is as follows: packet Containing carrier and hydrogenation active metal component, carrier includes Modified Zeolite Y, amorphous silica-alumina and aluminium oxide, wherein described Modified Zeolite Y, property are as follows: relative crystallinity is 110% ~ 150%, SiO₂/Al₂O₃Molar ratio is 55 ~ 100, structure cell ginseng Number is 2.425nm ~ 2.435nm, and total pore volume is 0.55mL/g ~ 1.0mL/g, and mesoporous pore volume accounts for 70% of total pore volume or more.

2. according to the method for claim 1, it is characterised in that: the property of the Modified Zeolite Y is as follows: total pore volume For 0.6mL/g ~ 1.0mL/g, mesoporous pore volume accounts for the 80% ~ 95% of total pore volume.

3. according to the method for claim 1, it is characterised in that: the grain size of the Modified Zeolite Y is 1.0 μm ~ 2.5 μm。

4. according to the method for claim 1, it is characterised in that: the grain size of the Modified Zeolite Y is 1.2 μm ~ 1.8 μm。

5. according to the method for claim 1, it is characterised in that: the mesoporous bore dia of the Modified Zeolite Y is 2nm ~10nm。

6. according to the method for claim 1, it is characterised in that: the specific surface area of the Modified Zeolite Y is 650m²/g~ 1000m²/g。

7. according to the method for claim 1, it is characterised in that: the specific surface area of the Modified Zeolite Y is 750m²/g~ 1000m²/g。

8. according to the method for claim 1, it is characterised in that: the infrared total acid content of the Modified Zeolite Y is 0.1mmol/g~0.5mmol/g。

9. according to the method for claim 1, it is characterised in that: in the Modified Zeolite Y, Na₂The weight content of O is 0.15wt% or less.

10. according to the method for claim 1, it is characterised in that: the property of the hydrocracking catalyst is as follows: specific surface Product is 250m²/g~450m²/ g, pore volume are 0.30mL/g ~ 0.50mL/g.

11. according to the method for claim 1, it is characterised in that: the hydrogenation active metals are group VIB and Section VIII The metal of race, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Using the weight of catalyst as base Standard, content of the vib metals in terms of oxide are 10.0% ~ 30.0%, and content of the group VIII metal in terms of oxide is 4.0% ~ 8.0%, the content of carrier is 62.0% ~ 86.0%.

12. according to method described in claim 1 or 11, it is characterised in that: the carrier of hydrocracking catalyst, to carry On the basis of the weight of body, the content of Modified Zeolite Y is 10% ~ 50%, and the content of amorphous silica-alumina is 5% ~ 30%, aluminium oxide Content is 20% ~ 85%.

13. according to method described in claim 1 or 11, it is characterised in that: the carrier of hydrocracking catalyst, to carry On the basis of the weight of body, the content of Modified Zeolite Y is 15% ~ 45%, and the content of amorphous silica-alumina is 10% ~ 25%, aluminium oxide Content be 30% ~ 75%.

14. according to the method for claim 1, it is characterised in that: in the amorphous silica-alumina, SiO₂Weight content be 10% ~ 60%, the property of amorphous silica-alumina is as follows: pore volume is 0.6mL/g ~ 1.1mL/g, specific surface area 300m²/g~500m²/ g。

15. according to the method for claim 1, it is characterised in that: in the amorphous silica-alumina, SiO₂Weight content be 20% ~ 55%, the property of amorphous silica-alumina is as follows: pore volume is 0.8mL/g ~ 1.0mL/g, specific surface area 350m²/g~500m²/ g。

16. according to the method for claim 1, it is characterised in that: used hydrocracking raw material is vacuum distillate, coke Change one or more of wax oil, solvent refining deasphalted oil and Fischer-Tropsch synthesis oil.

17. according to the method for claim 1, it is characterised in that: described to be hydrocracked using single stage process process.

18. according to the method for claim 1, it is characterised in that: it is described to be hydrocracked using series process flow, that is, adding Hydrobon catalyst is loaded before hydrogen Cracking catalyst, which is using alumina-based supports, with Section VI B Race and group VIII metal are hydrogenation active metal component, and vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt And/or nickel, on the basis of the weight of catalyst, content of the vib metals in terms of oxide is 15.0% ~ 30.0%, Section VIII Content of race's metal in terms of oxide is 4.0% ~ 8.0%.

19. according to the method for claim 18, it is characterised in that: the reaction condition of hydrofinishing is that reaction pressure is 12.0MPa ~ 20.0MPa, temperature are 350 ~ 435 DEG C, and hydrogen to oil volume ratio is 1000:1 ~ 2000:1, and volume space velocity is 0.5h when liquid^-1 ~5.0h^-1。

20. according to method described in claim 1,17 or 18, it is characterised in that: when raw material passes through hydrocracking catalyst bed Reaction condition be reaction stagnation pressure be 12.0MPa ~ 20.0MPa, volume space velocity is 0.5h when liquid^-1~5.0h^-1, hydrogen to oil volume ratio is 1000:1 ~ 2000:1, reaction temperature are 350 ~ 435 DEG C.

21. according to the method for claim 1, it is characterised in that: the Hydrobon catalyst that post-refining uses, using oxygen Change alumina-based support, using group VIB and group VIII metal as hydrogenation active metal component, vib metals be molybdenum and/or tungsten, The metal of group VIII is cobalt and/or nickel；On the basis of the weight of catalyst, content of the vib metals in terms of oxide is 15.0% ~ 30.0%, content of the group VIII metal in terms of oxide is 4.0% ~ 8.0%.

22. according to method described in claims 1 or 21, it is characterised in that: operating condition used by post-refining is as follows: anti- Answering temperature is 220 DEG C ~ 350 DEG C, and hydrogen partial pressure is 2.5MPa ~ 8.0MPa, and volume space velocity is 0.5h when liquid^-1~2.0h^-1, hydrogen oil volume Than for 300:1 ~ 1000:1.