CN100413944C - Method for producing lubricating oil base oil by hydrogenating tail oil - Google Patents
Method for producing lubricating oil base oil by hydrogenating tail oil Download PDFInfo
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- CN100413944C CN100413944C CNB2005100473735A CN200510047373A CN100413944C CN 100413944 C CN100413944 C CN 100413944C CN B2005100473735 A CNB2005100473735 A CN B2005100473735A CN 200510047373 A CN200510047373 A CN 200510047373A CN 100413944 C CN100413944 C CN 100413944C
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Abstract
The present invention provides method of producing base oil for lubricant oil with hydrogenated tail oil. Hydrogenated tail oil as material is treated through one white clay refining process or one medium pressure hydrogenating and refining process under proper condition to obtain the lubricant oil base oil product. The hydrogenated tail oil is produced with vacuum gas oil, refined solvent oil or Fischer-Tropsch synthesized oil as material and through hydrocracking or hydrotreating process under the action of hydrogenating catalyst, and has pour point lower than -10 deg.c. The lubricant oil base oil product has excellent performance.
Description
Technical field
The present invention relates to a kind of method of producing lubricating oil base oil by hydrogenating tail oil, select for use by hydrogenation catalyst and handle the hydrogenation tail oil obtain, directly clay-filtered or method that the medium-pressure hydrocracking post-refining is produced lubricant base with strong isomery function.
Background technology
Traditional lubricant base production all is to adopt solvent treatment technology, with the technology of this solvent treatment explained hereafter base oil history in an existing nearly century, its main two steps are still solvent treatment and remove undesirable components such as aromatic hydrocarbons and solvent dewaxing to guarantee the low temperature flowability of base oil.In addition, generally also to carry out carclazyte or hydrofinishing.
Day by day the performance that develops rapidly lubricant base of Yan Ge environmental legislation and mechanical industry has proposed more and more higher requirement.Simultaneously, because worldwide crude oil poor qualityization, the feasible crude oil quantity that is suitable for producing lubricating oil reduces gradually.Therefore, the technical development of hydrogenation method production lubricating oil is very rapid.Hydrogenation method technology is meant the process that adopts hydrocracking or hydrotreatment-isomerization dewaxing-hydrofining production basis oil, and its advantage is that feed flexibility is big, base oil yield is high, by-product value is high.
CN 1175620A has introduced a kind of method that is adopted solvent dewaxing-clay treatment production food-grade paraffin wax and lubricant base by hydrogenation tail oil.It is raw material with the hydrogenation tail oil that CN 1218094A has introduced a kind of, adopts the non-hydro-dewaxing process to produce the method for lubricant base.It is raw material with the hydrogenation tail oil that CN 1091150A has introduced a kind of, adopts the Hydrodewaxing process to produce the method for lubricant base.US5,358,628 disclose a kind of hydrogenation tail oil is produced base oil of high viscosity index lubricant by hydroisomerization dewax-solvent dewaxing process process method.US 4851109 discloses the method that a kind of hydrocracking-hydroisomerization dewax is produced lubricant base.
In sum, be that the prior art of raw material production lubricant base all needs the technological process that hydrogenation tail oil carries out solvent dewaxing or catalytic dewaxing or isomerization dewaxing reached and reduces pour point ground purpose with the hydrogenation tail oil, production process is complexity.
Summary of the invention
At the deficiencies in the prior art, the invention provides the method that a kind of technical process is simplified by producing lubricating oil base oil by hydrogenating tail oil.
The method of producing lubricating oil base oil by hydrogenating tail oil of the present invention specifically comprises following content: with in vacuum distillate, solvent treatment deasphalted oil and the Fischer-Tropsch synthesis oil one or more is raw material, adopt single hop or series process flow, with a kind of hydrotreating catalyst of modified beta molecular sieve that contains under hydroprocessing condition, hydrotreatment products is carried out fractionation by distillation, obtains pour point less than-10 ℃ hydrogenation tail oil.The initial boiling point of hydrogenation tail oil is generally 320 ℃～390 ℃.Described hydrotreating catalyst comprises beta-molecular sieve, refractory porous oxide, group vib and the VIII family metal oxide of amorphous aluminum silicide, modification, weight percent with catalyzer is a benchmark, contain modified beta molecular sieve 1wt%～9wt% in the catalyzer, the silicon-dioxide of modified beta molecular sieve/aluminium sesquioxide weight ratio is 50～90, average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.Because the pour point of hydrogenation tail oil has satisfied the index request of lubricant base, therefore directly adopt clay-filtered or medium-pressure hydrocracking post-refining process process, under suitable operational condition, can obtain the lube base oil production.
The inventive method can adopt the single hop hydroprocessing technique, also can adopt the serial hydrogenation treatment process.The single hop hydroprocessing technique refers to use a kind of type catalyst (protective material etc. can be arranged).Series process flow refers to that dissimilar catalyzer have formed the two or several different reaction zone of order, can in a reactor, load dissimilar catalyzer, form the cascade reaction district, also can use and use dissimilar catalyzer in two or more tandem reactors, form the cascade reaction district.In the serial hydrogenation treatment process, raw material is at first by conventional Hydrobon catalyst bed, then by containing the hydrotreating catalyst bed of modified beta molecular sieve.The single hop hydroprocessing technique uses the hydrotreating catalyst that contains modified beta molecular sieve.The reaction conditions of raw material when containing the hydrotreating catalyst bed of modified beta molecular sieve is generally reaction pressure 4.0～18.0MPa, hydrogen to oil volume ratio 300～2500, volume space velocity 0.4～10.0h
-1, 290～430 ℃ of temperature of reaction.Preferred reaction conditions is reaction pressure 5.0～18.0MPa, hydrogen to oil volume ratio 500～1500, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.If adopt the serial hydrogenation treatment process, raw material can be identical with the condition by the modified beta molecular sieve hydrotreating catalyst by the condition of conventional Hydrobon catalyst bed reaction zone, also can be different.Can be conventional hydroprocessing condition, general reaction conditions be reaction pressure 0.5～18.0MPa, 230～430 ℃ of temperature, hydrogen to oil volume ratio 200～1500, volume space velocity 0.5～10.0h
-1, preferably in by the operational condition scope that contains modified beta molecular sieve hydrotreating catalyst bed.
The hydrotreating catalyst that contains modified beta molecular sieve comprises the beta-molecular sieve of amorphous aluminum silicide, modification, refractory porous oxide, group vib and VIII family metal oxide etc.Weight percent with catalyzer is a benchmark, and each components contents is in the catalyzer: amorphous aluminum silicide generally is 29wt%～52wt%, better is 32wt%～47wt%; Modified beta molecular sieve generally is 1wt%～9wt%, better is 2wt%～8wt%; The group vib metal is generally 15wt%～30wt% in oxide compound, is preferably 18wt%～26wt%; The group VIII metal is generally 3wt%～9wt% in oxide compound, is preferably 5wt%～7wt%.The refractory porous oxide, as in aluminum oxide, titanium oxide, zirconium white, boron oxide and the above-mentioned elements compounding oxide compound etc. one or more, preferred aluminum oxide.Refractory porous oxide content is generally 0～45wt%, is preferably 20wt%～35wt%.As containing macroporous aluminium oxide and aperture alumina adhesive, macroporous aluminium oxide is generally 0wt%～22wt%, is preferably 4wt%～14wt%; Little porous aluminum oxide is generally 0～23wt%, is preferably 16wt%～22wt%.The specific surface area of catalyzer is 160～230m
2/ g, pore volume are 0.32～0.45ml/g.
The character of described modified beta molecular sieve is: its silicon-dioxide/aluminium sesquioxide weight ratio is generally 50～90, be preferably 60～80, degree of crystallinity is generally 90～110, preferably 100～110, average grain size is generally 0.1～0.5 micron, preferably 0.1～0.3 micron, specific surface area 400～750m
2/ g, preferably 500～600m
2/ g, pore volume 0.25～0.50ml/g, 0.3～0.4ml/g preferably, Na
2O content is less than 0.10wt%, preferably less than 0.05wt%, and infrared acidity 0.1～0.4mmol/g, best 0.2～0.3mmol/g, the secondary pore pore volume of 2～10nm accounts for 30～60% of total pore volume.
SiO in the described amorphous aluminum silicide
2Content be 20wt%～75wt%, be preferably 35wt%～60wt%.The pore volume of amorphous aluminum silicide is 0.5～1.1ml/g, is preferably 0.6～0.8ml/g.Specific surface area is 200～500m
2/ g is preferably 280～500m
2/ g.
The macroporous aluminium oxide pore volume is 0.6～1.2ml/g, is preferably 0.8～1.2ml/g, and specific surface area is 200～550m
2/ g is preferably 300～500m
2/ g.Aperture aluminum oxide pore volume is 0.3～0.5ml/g, and specific surface area is 180～350m
2/ g.
The group vib metal is generally W and/or Mo, and the group VIII metal is generally Ni and/or Co.
The clay-filtered of the present invention's employing is quite sophisticated technology, both can be refining with adsorbents at the intermittence process that adopts the powder carclazyte, also can be the attached treating process of fixed bed continuous adsorption that adopts granular carclazyte.Clay-filtered condition is generally: under the normal pressure, extraction temperature is 100～200 ℃, and extraction temperature is 130 ℃ preferably; Intermittently the carclazyte consumption of refining with adsorbents process is 1%～7% (weight ratio) of material quantity, and suitable add-on is 3% (weight ratio); The refining time is 20～50 minutes, and the more suitable refining time is 30 minutes.The adsorption volume air speed 0.1-5.0h of continuous adsorption treating process
-1, be preferably 1.0-2.0h
-1
Medium-pressure hydrocracking post-refining process process of the present invention adopts the suitable hydrogenation catalyst for refining, and operational condition is 230 ℃～370 ℃ of temperature, preferred 260 ℃～330 ℃; Hydrogen dividing potential drop 3.0MPa～9.0MPa, preferred 4.0MPa～8.0MPa; Volume space velocity 0.4h
-1～2.5h
-1, best 1.0h
-1～2.0h
-1Hydrogen to oil volume ratio 300: 1～1500: 1, preferred 400: 1～1000: 1.
The present invention has technical process and simply reaches investment advantage such as low, handle catalyzer and technological process by selecting suitable hydrogenation, adopt optimized process conditions, obtaining pour point can be less than-10 ℃ hydrogenation tail oil, generally at-20 ℃～10 ℃, usually at-15 ℃～-10 ℃, so need not to reduce pour point through complicated solvent dewaxing process or hydrogenation (isomery) dewaxing process, directly pass through more clay-filtered or medium-pressure hydrocracking post-refining again, can obtain to meet the high-quality base oil of lube base oil standard.
The hydrotreating catalyst that the present invention selects is main acidic components with amorphous aluminum silicide, the beta-molecular sieve that adds a small amount of special modification is second acidic components, by compound and optimize this two kinds of catalytic materials, promptly given full play to its performance characteristics separately, produced concerted catalysis effect preferably again, make catalyzer of the present invention when activity improves, have good selective opening of cyclic paraffins, isomerization of paraffinic hydrocarbons, the hydrocracking of last running appropriateness again, aromatic hydrocarbons is saturated and heteroatoms removes performance.The modified beta molecular sieve silica alumina ratio that the present invention selects is higher, acidity a little less than, crystal grain is little, secondary pore is many, the long side chain alkyl of long chain alkane and aromatic hydrocarbons, naphthenic hydrocarbon there are suitable splitting action and good isomerization, can when keeping high hydrotreatment purpose product intermediate oil yield, obtain the hydrogenation tail oil that pour point reduces significantly, be the good raw material of producing lubricant base, and can simplify technical process significantly.
Embodiment
Hydrogenation tail oil of the present invention can adopt a segment process flow process, also can adopt series process flow to obtain.The modified beta molecular sieve hydrotreating catalyst that contains that uses in single hop technology and the tandem process can be that (character comprises modified beta molecular sieve content to the character homogeneous, modified beta molecular sieve character, the reactive metal kind, active metallic content, kind of carrier, in the carrier character etc. one or more) a kind of catalyzer, also several catalyzer of above-mentioned different in kind, as along the raw material flow direction, the catalyzer that uses several modified beta molecular sieve content to increase, or use the acid catalyzer that increases of several modified beta molecular sieve etc.This is more favourable to giving full play to catalyst performance.
The modified beta molecular sieve that contains in the modified beta molecular sieve catalyzer that technology of the present invention is used is to make by new synthesis modification method, and the key step of modification comprises:
(1) the beta-molecular sieve slurries after the crystallization directly carry out ammonium exchange, filtration, washing, drying and roasting;
(2) beta-molecular sieve that takes off behind the ammonium of roasting carries out acid treatment;
(3) the intact beta-molecular sieve of acid treatment carries out hydrothermal treatment consists again.
Beta-molecular sieve after the above-mentioned crystallization generally is to be template with organic ammonium (as tetraethyl ammonium hydroxide), uses the hydrothermal crystallization method synthetic.Its SiO
2/ Al
2O
3Weight ratio is generally 25～30, Na
2The content of O is 3.0wt%～4.0wt%.Beta-molecular sieve slurries after the crystallization directly carry out the ammonium salt exchange, and the concentration of ammonium salt in slurries is 0.5～5.0mol/l, and several is carried out in the ammonium exchange, make Na in the molecular sieve of exchange back
2The O weight content is not more than 0.5%, and general ammonium exchange 1～4 time can reach requirement.Beta-molecular sieve after the ammonium salt exchange filters, washes, drying and roasting, and wherein maturing temperature is controlled at 450 ℃～650 ℃, and the time is 5.0～15.0 hours.The beta-molecular sieve that roasting is taken off behind the ammonium carries out acid treatment, filters, and wherein acid treatment condition is for being that the mineral acid of 0.1～5.0mol/l is carrying out acid treatment with concentration under abundant agitation condition, 20 ℃～100 ℃ of treatment temps, and the treatment time is 0.5～5.0 hour.The intact beta-molecular sieve of acid treatment carries out pressurized thermal water to be handled, the hydrothermal treatment consists condition for 100% water vapor at 500 ℃～800 ℃, be preferably 550 ℃～700 ℃, system pressure is 0.05～1.0MPa, be preferably 0.1～0.5MPa, handled preferably 1～2 hour 0.5～5.0 hour.
Hydrotreating catalyst adopts conventional pickling process production, with beta-molecular sieve, refractory porous oxide, tackiness agent and the extrusion aid mixing of amorphous aluminum silicide, modification, and extruded moulding, drying, roasting, the impregnating metal component, dry, roasting prepares final catalyzer.
Clay-filtered used powder carclazyte or granular carclazyte need to carry out activation treatment before use, so that it has higher adsorptive power.Condition activates 2-5 hour for the sulfuric acid that adopts 10wt%-15wt%.
The used catalyzer of medium-pressure hydrocracking post-refining process is conventional Hydrobon catalyst, and its reactive metal is group vib and/or group VIII base metal, one or more among preferred W, Ni, Co, the Mo, and carrier is Al
2O
3Or Al
2O
3-SiO
2, can contain auxiliary agents such as P, Ti, B, Zr.Use procatalyst should carry out prevulcanized, guarantee that hydrogenation active metals is in sulphided state in reaction process.
Following implementation column will give further instruction to method provided by the invention, but scope not thereby limiting the invention.(wt% is weight percentage)
The hydrogenation tail oil that the present invention handles can be obtained by the hydrotreatment process of vacuum distillate, solvent treatment deasphalted oil and Fischer-Tropsch synthesis oil, and specific nature sees Table 2.
Powder that clay-filtered employing Fushun chemical plastic factory produces and granular carclazyte are as sorbent material, and the sulfuric acid with 15wt% before using activates 3 hours, and specific nature sees Table 3.
The used catalyzer of medium-pressure hydrocracking post-refining process is the commercial Hydrobon catalyst FH-98 that development Wenzhou Hua Hua group company of Fushun Petrochemical Research Institute produces, and specific nature sees Table 4.
Embodiment 1
With 227.1 gram amorphous aluminum silicide (SiO
2Content be 45wt%, pore volume is 0.75ml/g, specific surface area is 390m
2/ g), 18.8 the gram modifications beta-molecular sieves, 65.8 the gram macroporous aluminium oxides (pore volume is 1.0ml/g, and specific surface area is 460m
2/ g) put into rolling machine, mixed grind 30 minutes, (containing pore volume is that 0.4ml/g, specific surface area are 280m to add 288.5 gram tackiness agents then
2The aperture aluminum oxide 107.1g of/g, HNO
3With alumina molar ratio be 0.3), rolled 30 minutes, add 60 ml waters afterwards, continue to roll to can squeezing paste, extrusion is extruded bar 110 ℃ of dryings 6 hours.Dried strip temperature programming to 580 ℃ roasting 4 hours gets carrier.Carrier is with the steeping fluid room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 6 hours, and 480 ℃ of roastings of temperature programming 4 hours obtain hydrotreating catalyst A, and its physico-chemical property sees Table 1.
Wherein the beta-molecular sieve character of modification is: molecular sieve SiO
2/ Al
2O
3Weight ratio 70, relative crystallinity are 107, specific surface 570m
2/ g, infrared acidity 0.25mmol/g, the secondary pore pore volume of 2～10nm accounts for 45% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve of O 3.65wt% synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 85 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 550 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 1.2M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 85 ℃, and constant temperature stirred 2 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 600 ℃, control pressure 0.3MPa, and the treatment time is 2 hours.
Embodiment 2
With 252.8 gram amorphous aluminum silicide (SiO
2Content be 65wt%, pore volume is 0.58ml/g, specific surface area is 340m
2/ g), 9.4 the gram modifications beta-molecular sieves, 41.1 the gram macroporous aluminium oxides (pore volume is 0.75ml/g, and specific surface area is 360m
2/ g) put into the rolling machine mixed grind 20 minutes, (containing pore volume is that 0.45ml/g, specific surface area are 300m to add 323.1 gram tackiness agents then
2The aperture aluminum oxide 120.0g of/g, HPO
3With alumina molar ratio be 0.2), continued to roll 40 minutes, add 55 ml waters afterwards, roll to can squeezing paste, extrusion is extruded bar 140 ℃ of dryings 3 hours.Dried strip temperature programming to 530 ℃ roasting 5 hours gets carrier.Carrier is with the steeping fluid room temperature dipping of tungstenic, nickel 4 hours, 130 ℃ of dryings 3 hours, temperature programming to 460 ℃ roasting 5 hours, catalyst B.Physico-chemical property sees Table 1.
Wherein the beta-molecular sieve character of modification is: molecular sieve SiO
2/ Al
2O
3Weight ratio 60, specific surface 600m
2/ g, relative crystallinity are 105, infrared acidity 0.35mmol/g, and the secondary pore pore volume of 2～10nm accounts for 38% of total pore volume, average crystal grain diameter 0.3 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve of O 3.65wt% synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 3 hours, was cooled to 50 ℃ of filtrations, wet cake carries out second and third time exchange again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 500 ℃, constant temperature 12 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 0.8M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 4 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 570 ℃, control pressure 0.1MPa, and the treatment time is 3 hours.
Embodiment 3
With 201.4 gram amorphous aluminum silicide (SiO
2Content be 30wt%, pore volume is 0.89ml/g, specific surface area is 460m
2/ g), 31.3 the gram modifications beta-molecular sieves, 82.8 the gram macroporous aluminium oxides (with embodiment 1) put into the rolling machine mixed grind 40 minutes, add 265.4 gram tackiness agents (with embodiment 1) then, continued to roll 25 minutes, add 30 ml waters afterwards, roll to squeezing paste, extrusion is extruded bar 130 ℃ of dryings 4 hours.Dried strip temperature programming to 680 ℃ roasting 2.5 hours gets carrier.Carrier is with the steeping fluid room temperature dipping of tungstenic, nickel 8 hours, 130 ℃ of dryings 4 hours, 530 ℃ of roastings 3 hours, catalyzer C.Physico-chemical property sees Table 1.
Wherein the beta-molecular sieve character of modification is: molecular sieve SiO
2/ Al
2O
3Weight ratio 85, specific surface 530m
2/ g, relative crystallinity are 100, infrared acidity 0.15mmol/g, and the secondary pore pore volume of 2～10nm accounts for 52% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get industrial synthetic SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve slurries 2000ml of O 3.65wt%, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 3.5M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 600 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 2.5M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 3 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 650 ℃, control pressure 0.4MPa, and the treatment time is 4 hours.
Embodiment 4
Present embodiment has been introduced the hydrotreating catalyst that adopts the foregoing description preparation, handles different raw materials, the character of the various hydrogenation tail oils that obtain, and hydrogenation tail oil is a cut more than 350 ℃ in the hydrotreatment products, processing condition and result specifically see Table 5.From table 5 data as can be seen, the pour point of various hydrogenation tail oils is all less than-10 ℃.
Comparative Examples 1
It is the commercial hydrotreating catalyst 3976 that development Fushun petrochemical industry branch office of Fushun Petrochemical Research Institute produces that this Comparative Examples adopts hydrotreating catalyst, and character sees Table 4.Processing condition and result that this catalyst treatment subtracts three-way distillate specifically also see Table 5.
Embodiment 5
The hydrogenation tail oil that embodiment 4 is obtained carries out the condition of clay-filtered production lubricant base and the results are shown in Table 6.From table 6 data as can be seen, the lubricant base that obtains satisfies every index request of base oil standard.
Embodiment 6
The hydrogenation tail oil that embodiment 4 is obtained carries out the condition of medium-pressure hydrocracking post-refining production lubricant base and the results are shown in Table 7.From table 7 data as can be seen, the lubricant base that obtains satisfies every index request of base oil standard.
The physico-chemical property of table 1. catalyzer
| Catalyzer | A | B | C |
| Carrier is formed and character | |||
| Amorphous aluminum silicide, wt% | 53 | 59 | 47 |
| Modified beta molecular sieve, wt% | 6 | 3 | 10 |
| Macroporous aluminium oxide, wt% | 16 | 10 | 20 |
| Tackiness agent, wt% | 25 | 28 | 23 |
| Pore volume/mlg -1 | 0.596 | 0.573 | 0.618 |
| Specific surface area/m 2·g -1 | 300 | 280 | 336 |
| Catalyst chemical is formed and character | |||
| WO 3，wt％ | 20.3 | 22.1 | 25.2 |
| NiO，wt％ | 5.1 | 5.8 | 6.6 |
| SiO 2，wt％ | 22.2 | 27.6 | 16.3 |
| Al 2O 3，wt％ | Surplus | Surplus | Surplus |
| Pore volume/mlg -1 | 0.401 | 0.372 | 0.379 |
| Specific surface area/m 2·g -1 | 201 | 182 | 206 |
Table 2 test feedstock property
| Raw material | Subtract three-way distillate | Frivolous oil | Fischer-Tropsch synthesis oil |
| Density (20 ℃), kg/m 3 | 878.3 | 901.9 | |
| Boiling range, ℃ (D1160) | |||
| IBP | 315 | 361 | |
| 10％ | 341 | 519 | |
| 30％ | 377 | 543 | |
| Sulphur, w% | 0.89 | 1.21 | ＜1(μg/g) |
| Nitrogen, μ g/g | 63.5 | 193.1 | ＜1 |
| Condensation point, ℃ | 35 | 51 | 77 |
| Viscosity, mm/s 2100℃ | 3.68 | 19.25 | 8.0(135℃) |
| Carbon residue, % | 0 | 0.64 | 0 |
| Flash-point (opening), ℃ | 203 | 320 | 270 |
| Acid number, mgKOH/g | 0.01 | 0.02 | |
| Wax content, wt% | 15.21 | 20.17 | (0.1 oleaginousness) |
Table 3 carclazyte character
| Sorbent material | The powder carclazyte | Granular carclazyte |
| Density, g/cm 3 | 0.94 | 0.80 |
| Specific surface area, m 2/g | 1200 | 600 |
| Granularity | 〉=90% by 120 mesh sieves | 60 orders |
The main composition and the character of table 4.FH-98 and 3976 catalyzer
| Catalyzer | FH-98 | 3976 |
| Carrier | γ-Al 2O 3 | γ-Al 2O 3/ Y zeolite |
| Reactive metal is formed, wt% | ||
| WO 3 | 20.2 | 25.7 |
| MoO 3 | 9.3 | |
| NiO | 4.2 | 5.8 |
| P 2O 5，wt％ | 3.7 | |
| SiO 2，wt％ | / | 26.9 |
| Pore volume/mlg -1 | 0.30 | 0.304 |
| Specific surface area/m 2·g -1 | 140 | 257 |
The processing condition of table 5. embodiment 4 and Comparative Examples 1 and result
The processing condition of table 6 embodiment 5 and result
| Hydrogenation tail oil | 1 | 2 | 3 | HVI150 standard (Q/SHR001-95) |
| Carclazyte | Powder | Powder | Particle | |
| Clay-filtered mode | Intermittently | Intermittently | Continuously | |
| Adsorption temp, ℃ | 120 | 160 | 130 | |
| Air speed, h -1 | The 3wt% carclazyte * | The 5wt% carclazyte * | 1.0 | |
| The refining time, min | 30 | 30 | ||
| Clay-filtered oil nature | ||||
| Outward appearance | Transparent | Transparent | Transparent | Transparent |
| Color (D1500)/number | ＜1.0 | 1.0 | ＜1.0 | Be not more than 1.5 |
| Pour point/℃ | -14 | -12 | -12 | Be not higher than-9 |
| Flash-point/℃ | 252 | 287 | 270 | Be not less than 200 |
| Viscosity index | 118 | 122 | 131 | Be not less than 100 |
| Rotary oxygen bomb (adding T5010.8%)/min | 240 | 215 | 300 | Be not less than 180 |
*The carclazyte consumption accounts for the weight ratio of raw material.
The processing condition of table 7 embodiment 6 and result
Claims (11)
1. the method for a producing lubricating oil base oil by hydrogenating tail oil, specifically comprise: so that one or more are raw material in vacuum distillate, solvent treatment deasphalted oil and the Fischer-Tropsch synthesis oil, adopt single hop or series process flow, with a kind of hydrotreating catalyst of modified beta molecular sieve that contains under hydroprocessing condition, hydrotreatment products is carried out fractionation by distillation, obtain pour point less than-10 ℃ hydrogenation tail oil, hydrogenation tail oil adopts clay-filtered or medium-pressure hydrocracking post-refining process, obtains the lube base oil production; Wherein contain in the hydrotreating catalyst of modified beta molecular sieve and contain modified beta molecular sieve 1wt%～9wt%, the silicon-dioxide of modified beta molecular sieve/aluminium sesquioxide weight ratio is 50～90, average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g, the secondary pore pore volume of 2～10nm accounts for 30～60% of total pore volume; The reaction conditions of raw material when containing the hydrotreating catalyst bed of modified beta molecular sieve is: reaction pressure 4.0～18.0MPa, hydrogen to oil volume ratio 300～2500, volume space velocity 0.4～10.0h
-1, 290～430 ℃ of temperature of reaction.
2. in accordance with the method for claim 1, it is characterized in that described hydrotreating catalyst comprises beta-molecular sieve, refractory porous oxide, group vib and the VIII family metal oxide of amorphous aluminum silicide, modification.
3. in accordance with the method for claim 1, it is characterized in that in the described serial hydrogenation treatment process that raw material is at first by conventional Hydrobon catalyst bed, then by containing the hydrotreating catalyst bed of modified beta molecular sieve.
4. in accordance with the method for claim 1, it is characterized in that the reaction conditions of raw material when containing the hydrotreating catalyst bed of modified beta molecular sieve is: reaction pressure 5.0～18.0MPa, hydrogen to oil volume ratio 500～1500, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.
5. in accordance with the method for claim 2, it is characterized in that the described hydrotreating catalyst that contains modified beta molecular sieve is a benchmark with the weight percent of catalyzer, each components contents is in the catalyzer: amorphous aluminum silicide is 29wt%～52wt%, and modified beta molecular sieve is 2wt%～8wt%; The group vib metal is counted 15wt%～30wt% with oxide compound, and the group VIII metal is counted 3wt%～9wt% with oxide compound; The refractory porous oxide is 0～45wt%.
6. in accordance with the method for claim 2, it is characterized in that described group vib metal is W and/or Mo, the group VIII metal is Ni and/or Co, and the specific surface area of catalyzer is 160～230m
2/ g, pore volume are 0.32～0.45ml/g.
7. in accordance with the method for claim 1, it is characterized in that the silicon-dioxide/aluminium sesquioxide weight ratio of described modified beta molecular sieve is 60～80, degree of crystallinity is 90～110, and average grain size is 0.1～0.3 micron, Na
2O content is less than 0.10wt%, and infrared acidity is 0.2～0.3mmol/g.
8. according to claim 2 or 5 described methods, it is characterized in that SiO in the described amorphous aluminum silicide
2Content be 20wt%～75wt%, the pore volume of amorphous aluminum silicide is 0.5～1.1ml/g, specific surface area is 200～500m
2/ g.
9. in accordance with the method for claim 1, it is characterized in that described clay-filtered refining with adsorbents at intermittence process for employing powder carclazyte, or adopt the attached treating process of fixed bed continuous adsorption of granular carclazyte, extraction temperature is 100～200 ℃; Intermittently the carclazyte consumption of refining with adsorbents process is 1%～7% of a raw material weight, and the refining time is 20～50 minutes, the adsorption volume air speed 0.1-5.0h of continuous adsorption treating process
-1
10. in accordance with the method for claim 1, it is characterized in that described medium-pressure hydrocracking post-refining process process is, adopt Hydrobon catalyst, operational condition is 230 ℃～370 ℃ of temperature, hydrogen dividing potential drop 3.0MPa～9.0MPa, volume space velocity 0.4h
-1～2.5h
-1, hydrogen to oil volume ratio 300: 1～1500: 1.
11. in accordance with the method for claim 1, it is characterized in that described hydrogenation tail oil initial boiling point is 320 ℃～390 ℃, pour point is-20 ℃～-10 ℃.
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| CN100413944C true CN100413944C (en) | 2008-08-27 |
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| CN102660323B (en) * | 2012-05-18 | 2014-09-17 | 海南汉地阳光石油化工有限公司 | Device and method for producing high-viscosity oil |
| CN102703712B (en) * | 2012-06-29 | 2014-06-18 | 阳光凯迪新能源集团有限公司 | Combined filtration process for recovering noble metal catalyst from fischer-tropsch synthesis products |
| CN103627433B (en) * | 2012-08-23 | 2015-05-20 | 中国石油化工股份有限公司 | Hydrogenation method for producing lubricant basic oil with low pour point and high viscosity index |
| CN103289738B (en) * | 2013-06-25 | 2015-10-28 | 中石化南京工程有限公司 | A kind of hydrocracking tail oil hydrogenation produces the combined method of top-grade lubricating oil base oil |
| CN104673380B (en) * | 2013-11-26 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of production method of lube base oil |
| CN104673375B (en) * | 2013-11-26 | 2016-10-19 | 中国石油化工股份有限公司 | A kind of production lube base oil method |
| CN107345163B (en) * | 2016-05-05 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of production method of lube base oil |
| CN115851313B (en) * | 2022-11-14 | 2024-03-22 | 国家能源集团宁夏煤业有限责任公司 | Method for preparing lubricating oil base oil from Fischer-Tropsch hydrocracking tail oil |
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