CN100549142C - The method of producing lubricating oil base oil by hydrogenating tail oil - Google Patents
The method of producing lubricating oil base oil by hydrogenating tail oil Download PDFInfo
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- CN100549142C CN100549142C CNB2006100478610A CN200610047861A CN100549142C CN 100549142 C CN100549142 C CN 100549142C CN B2006100478610 A CNB2006100478610 A CN B2006100478610A CN 200610047861 A CN200610047861 A CN 200610047861A CN 100549142 C CN100549142 C CN 100549142C
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- 239000003921 oil Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000002199 base oil Substances 0.000 title claims abstract description 21
- 239000010687 lubricating oil Substances 0.000 title abstract description 7
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 69
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000011148 porous material Substances 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 14
- 238000005292 vacuum distillation Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000003863 ammonium salts Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of method of producing lubricating oil base oil by hydrogenating tail oil.With the hydrocracking tail oil is raw material, directly carries out underpressure distillation, under suitable condition, can obtain the lube base oil production.This hydrocracking tail oil is to be raw material with vacuum distillate, solvent treatment deasphalted oil and Fischer-Tropsch synthesis oil, employing comprises the hydrocracking catalyst that contains modified beta molecular sieve, wherein beta-molecular sieve is selected little crystal grain, low acidity, high silica alumina ratio, high-crystallinity for use, is had the modified beta molecular sieve of certain secondary pore, and the pour point that obtains by hydrocracking or hydrocracking process is less than-10 ℃ tail oil.The present invention without pour point depression and treating process, can produce the lube base oil production of excellent property by selecting this hydrogenation tail oil that is obtained by the processing of suitable hydrogenation cracking catalyst.
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 hydrocracking catalyst and handle the hydrogenation tail oil that heavy feed stock obtains, the method for direct production lubricant base with strong isomery function.
Background technology
Traditional lubricant base production is to adopt solvent treatment technology, and its main two steps are to adopt solvent treatment to 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 process or hydrotreatment-isomerization dewaxing-hydrofining process integration to produce lubricant base, and its advantage is that feed flexibility is big, base oil yield is high, by-product value is high.
CN1175620A 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 method for non-hydro-dewaxing process lubricant base.It is raw material with the hydrogenation tail oil that CN 1091150A has introduced a kind of, adopts the method for Hydrodewaxing process 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, with the hydrocracking tail oil is that the raw material production lubricant base generally need solve two problems, the one, the pour point of hydrocracking tail oil is higher, does not reach the requirement of lubricant base, and the method that prior art adopts is pour point depression technologies such as solvent dewaxing, catalytic dewaxing, isomerization dewaxing; In addition, the colour index of hydrocracking tail oil does not reach the requirement of lubricant base, and the solution that prior art adopts is clay-filtered or medium-pressure hydrocracking is made with extra care.The production process of above-mentioned existing method is complicated, and cost is higher.
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 that hydrocracking tail oil of the present invention is produced lubricant base 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, employing contains the hydrocracking catalyst of modified beta molecular sieve under hydrocracking condition, carry out hydrocracking, isocrackate carries out fractionation by distillation, obtains pour point less than-10 ℃ hydrocracking tail oil.The initial boiling point of hydrocracking tail oil is generally 320 ℃～390 ℃.Hydrocracking tail oil carries out underpressure distillation, and the tail oil of 1wt%～30wt%, preferred 3wt%～5wt% is separated, and rest part is the lube base oil production that indexs such as pour point, color all satisfy standard-required.Described hydrocracking 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%～40wt% in the catalyzer, be preferably 1wt%～10wt%, 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 inventive method can adopt the single hop technical process, i.e. single-stage hydrocracking technology; Also can series process flow, i.e. serial hydrocracking technology.Single-stage hydrocracking technology 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 hydrocracking technology, raw material is at first by conventional Hydrobon catalyst bed, then by containing the hydrocracking catalyst bed of beta-molecular sieve.Single-stage hydrocracking technology is used the hydrocracking catalyst that contains beta-molecular sieve.The reaction conditions of raw material when containing the hydrocracking catalyst bed of 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.Being preferably 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 serial hydrocracking technology, raw material can be identical with the condition by the beta-molecular sieve hydrocracking 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, temperature 230～430, hydrogen to oil volume ratio 200～2000, volume space velocity 0.5～10.0h
-1, preferably in by the operational condition scope that contains beta-molecular sieve hydrocracking catalyst bed.
The hydrocracking catalyst that contains 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: modified beta molecular sieve generally is 1wt%～40wt%, better is 1wt%～10wt%; The group vib metal is generally 15wt%～30wt% in oxide compound, is preferably 18wt%～26wt%; The group VIII metal is generally 1wt%～9wt% in oxide compound, is preferably 5wt%～7wt%; Amorphous aluminum silicide generally is 10wt%～60wt%, better is 20wt%～50wt%.The porous refractory 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.Porous refractory oxide content is generally 0wt%～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 0wt%～23wt%, is preferably 16wt%～22wt%.The specific surface area of catalyzer is 160～230m
2/ g, pore volume are 0.32～0.45ml/g.Each composition weight content sum of hydrocracking catalyst is 100%.
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, crystal grain (crystal grain) mean sizes 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.
Because the pour point of hydrogenation tail oil has satisfied the index request of lubricant base, again by underpressure distillation with 1wt%-30wt%, the darker tail oil of color of preferred 3wt%-5wt% is separated, thereby obtains the lube base oil production that indexs such as pour point, color all satisfy the different viscosity grade of standard-required at the vacuum distillation tower side line.The underpressure distillation that the present invention adopts is to well known to a person skilled in the art technology.Condition as underpressure distillation is generally: the vacuum distillation tower feeding temperature is 350 ℃～410 ℃, and suitable feeding temperature is 375 ℃～400 ℃; The vacuum distillation tower tower top pressure is 4KPa～10KPa, and suitable tower top pressure is 5KPa～8KPa; The vacuum distillation tower tower top temperature is 110～180 ℃, can obtain some light-end products.According to the requirement of lube base oil production, vacuum distillation tower generally can be opened 1～5 side line, obtains the lube base oil production of required character.When for example adopting 5 side lines, the temperature of each side line is followed successively by from low to high: 300 ℃～320 ℃, and 340 ℃～350 ℃, 355 ℃～365 ℃, 365 ℃～375 ℃, 380 ℃～395 ℃.According to feedstock property,, obtain the base oil product of needed different viscosity grade by regulating the temperature of each side line.The VACUUM TOWER BOTTOM tail oil loops back hydrocracking process, or adopts alternate manner further to handle.
The present invention has technical process and simply reaches investment advantage such as low, by selecting suitable hydrogenation cracking catalyst and technological process, 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.The hydrocracking tail oil that the hydrocracking catalyst reaction of selecting through the present invention that contains modified beta zeolite obtains, when seeing in appearance directly as lubricant base, the requirement that can not touch the mark of its color value, according to this area general knowledge and prior art, need to adopt clay-filtered or methods such as hydrofining are further processed, make the requirement that touches the mark of product colour value.The present invention is by analysing in depth and learn containing hydrocracking tail oil that β zeolite hydrocracking catalyst obtains, the essential substance that influences this hydrocracking tail oil colour index is the condensed-nuclei aromatics that produces in a small amount of reaction process, the boiling point of these condensed-nuclei aromaticss is higher, therefore do not adopt clay-filtered or unifining process, only separate the darker heavy constituent of color in this type of hydrocracking tail oil by vacuum distillation process again, can obtain to meet the lube base oil production of lube base oil standard.
The hydrocracking 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 hydrocracking purpose product intermediate oil yield, obtain the hydrogenation tail oil that pour point reduces significantly, only can produce the lube base oil production, simplify technical process significantly by underpressure distillation.
Embodiment
Hydrocracking 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 hydrocracking 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.
Hydrocracking catalyst adopts conventional pickling process production, with beta-molecular sieve, porous refractory 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.
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 hydrocracking process of vacuum distillate, solvent treatment deasphalted oil and Fischer-Tropsch synthesis oil, and specific nature sees Table 2.
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 hydrocracking catalyst, 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), 40.5 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 hydrocracking 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 isocrackate, processing condition and result specifically see Table 4.From table 4 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 hydrocracking catalyst 3976 that development Fushun petrochemical industry branch office of Fushun Petrochemical Research Institute produces that this Comparative Examples adopts hydrocracking catalyst, and character sees Table 3.Processing condition and result that this catalyst treatment subtracts three-way distillate specifically also see Table 4.
Embodiment 5
3 kinds of hydrogenation tail oils that embodiment 4 is obtained carry out the condition of underpressure distillation production lubricant base and the results are shown in Table 5.From table 5 data as can be seen, the lubricant base of the various viscosity grades that obtain all 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 | 46 |
| Modified beta molecular sieve, wt% | 6 | 3 | 13 |
| Macroporous aluminium oxide, wt% | 16 | 10 | 19 |
| Tackiness agent, wt% | 25 | 28 | 22 |
| Pore volume/mlg -1 | 0.596 | 0.573 | 0.620 |
| Specific surface area/m 2·g -1 | 300 | 280 | 349 |
| 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 | 0.381 |
| Specific surface area/m 2·g -1 | 201 | 182 | 210 |
Table 2 test feedstock property
| Raw material | Subtract three-way distillate | Frivolous oil | The Fischer-Tropsch synthetic wax |
| Density (20 ℃), kg/m 3 | 878.3 | 901.9 | |
| Boiling range, ℃ (D1160) | |||
| IBP | 315 | 361 | |
| 10％ | 341 | 519 | |
| 30％ | 377 | 543 | |
| Sulphur, wt% | 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, wt% | 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) |
The main composition and the character of table 3.3976 catalyzer
| Catalyzer | 3976 |
| Carrier | Al 2O 3/ Y zeolite |
| Reactive metal is formed, wt% | |
| WO 3 | 25.7 |
| MoO 3 | |
| NiO | 5.8 |
| P 2O 5，wt％ | |
| SiO 2，wt％ | 26.9 |
| Pore volume/mlg -1 | 0.304 |
| Specific surface area/m 2·g -1 | 257 |
The processing condition of table 4. embodiment 4 and Comparative Examples 1 and result
The processing condition of table 5 embodiment 5 and result
| Hydrocracking tail oil | 1 | 2 | 3 |
| The underpressure distillation condition | |||
| The decompression tower top pressure, KPa | 5.66 | 7.58 | 6.39 |
| The vacuum distillation tower feeding temperature/℃ | 375 | 396 | 382 |
| Isolate the last running tail oil and account for hydrocracking tail oil ratio, wt% | 5 | 15 | 3 |
| Isolate last running tail oil boiling range, ℃ | ＞495 | ＞488 | ＞491 |
| Isolate the color (D1500) of tail oil, number | 8.0 | 8.0 | 6.0 |
| The color (D1500) of separating the tail oil rear section, number | 1.5 | 1.5 | 1.0 |
The various base oil main character (isolating 5% last running) that table 6 obtains from hydrocracking tail oil 1
| Hydrocracking tail oil | 1 | HVI standard (Q/SHR001-95) |
| The underpressure distillation condition | ||
| The decompression tower top pressure, KPa | 5.66 | |
| The vacuum distillation tower feeding temperature/℃ | 375 | |
| Tower top temperature/℃ | 165 | |
| The vacuum 1st side cut recovered temperature/℃ | 301 | |
| The second line of distillation recovered temperature/℃ | 340 | |
| Subtract three-way recovered temperature/℃ | 357 | |
| Subtract four line recovered temperatures/℃ | 366 | |
| Subtract five line recovered temperatures/℃ | 382 | |
| The vacuum 1st side cut product property | HVI100 or HVI 150 | |
| Color (D1500)/number | 0.5 | Be not more than 1.0 or 1.5 |
| Pour point/℃ | -18 | Be not higher than-9 |
| Viscosity (40 ℃), mm/s 2 | 21.50 | 20-32 |
| Flash-point/℃ | 190 | Be not less than 185 or 200 |
| Viscosity index | 108 | Be not less than 100 |
| Rotary oxygen bomb (T501 0.8%)/min | 240 | Be not less than 180 |
| The second line of distillation product property | HVI150 or HVI 200 | |
| Color (D1500)/number | 1.0 | Be not more than 1.5 or 2.0 |
| Pour point/℃ | -12 | Be not higher than-9 |
| Viscosity (40 ℃), mm/s 2 | 28.50 | 28-42 |
| Flash-point/℃ | 208 | Be not less than 200 or 210 |
| Viscosity index | 112 | Be not less than 100 or 98 |
| Rotary oxygen bomb (T501 0.8%)/min | 265 | Be not less than 180 |
| Subtract three-way product property | HVI200 or HVI350 | |
| Color (D1500)/number | 1.5 | Be not more than 2.0 or 3.0 |
| Pour point/℃ | -9 | Be not higher than-5 |
| Viscosity (40 ℃), mm/s 2 | 41.50 | 38-72 |
| Flash-point/℃ | 214 | Be not less than 210 or 220 |
| Viscosity index | 114 | Be not less than 95 |
| Rotary oxygen bomb (T501 0.8%)/min | ＞300 | Be not less than 180 |
| Subtract four line products character | HVI350 or HVI 400 | |
| Color (D1500)/number | 2.5 | Be not more than 3.0 or 3.5 |
| Pour point/℃ | -9 | Be not higher than-5 |
| Viscosity (40 ℃), mm/s 2 | 67.59 | 65-82 |
| Flash-point/℃ | 226 | Be not less than 220 or 225 |
| Viscosity index | 113 | Be not less than 95 |
| Rotary oxygen bomb (T501 0.8%)/min | ＞300 | Be not less than 180 |
| Subtract five line products character | HVI500 or HVI650 | |
| Color (D1500)/number | 3.0 | Be not more than 4.0 or 5.0 |
| Pour point/℃ | -6 | Be not higher than-5 |
| Viscosity (40 ℃), mm/s 2 | 97.65 | 95-135 |
| Flash-point/℃ | 244 | Be not less than 235 or 255 |
| Viscosity index | 117 | Be not less than 95 |
| Rotary oxygen bomb (T501 0.8%)/min | ＞300 | Be not less than 180 |
Claims (10)
1, a kind of hydrocracking tail oil is produced the method for lubricant base, comprise 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, employing contains the hydrocracking catalyst of modified beta molecular sieve under hydrocracking condition, carry out hydrocracking, isocrackate carries out fractionation by distillation, obtain pour point less than-10 ℃ hydrocracking tail oil, the initial boiling point of hydrocracking tail oil is 320 ℃～390 ℃; Hydrocracking tail oil carries out underpressure distillation, and the tail oil of 1wt%～30wt% is separated, and rest part is the lube base oil production that pour point, colour index all satisfy standard-required; Contain modified beta molecular sieve 1wt%～40wt% in the described hydrocracking catalyst that contains modified beta molecular sieve, the silicon-dioxide of modified beta molecular sieve/aluminium sesquioxide weight ratio is 50～90, and average grain size is 0.1～0.5 micron.
2, in accordance with the method for claim 1, it is characterized in that described hydrocracking tail oil underpressure distillation separates 3wt%～5wt% tail oil.
3, in accordance with the method for claim 1, it is characterized in that containing in the described hydrocracking catalyst modified beta molecular sieve 1wt%～10wt%, the infrared acidity 0.1～0.4mmol/g of modified beta molecular sieve.
4, in accordance with the method for claim 1, the character that it is characterized in that described modified beta molecular sieve is: its silicon-dioxide/aluminium sesquioxide weight ratio is 60～80,0.1～0.3 micron of average grain size, the secondary pore pore volume of 2～10nm accounts for 30～60% of total pore volume.
5, in accordance with the method for claim 1, it is characterized in that described hydrocracking catalyst comprises the group vib metal, counts 15wt%～30wt% with oxide compound; The group VIII metal is counted 1wt%～9wt% with oxide compound; Amorphous aluminum silicide, content are 10wt%～60wt%.
6, in accordance with the method for claim 5, 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.
7, in accordance with the method for claim 1, it is characterized in that in the described series process flow that raw material is at first by conventional Hydrobon catalyst bed, then by containing the hydrocracking catalyst bed of modified beta molecular sieve; The hydrocracking catalyst that contains modified beta molecular sieve is used in described single hop technical process; The reaction conditions of raw material when containing the hydrocracking 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.
8, in accordance with the method for claim 7, it is characterized in that the reaction conditions of described raw material when containing the hydrocracking 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.
9, in accordance with the method for claim 1, it is characterized in that the condition of described underpressure distillation is: the vacuum distillation tower feeding temperature is 350 ℃～410 ℃, and the vacuum distillation tower tower top pressure is 4KPa～10KPa, and the vacuum distillation tower tower top temperature is 110～180 ℃.
10, according to claim 1 or 9 described methods, it is characterized in that described vacuum still opens 1～5 side line, obtain the lubricant base of required character.
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| CN102465024B (en) * | 2010-11-05 | 2014-09-17 | 中国石油化工股份有限公司 | Hydrocracking method for producing lube base oil |
| CN102559253A (en) * | 2010-12-17 | 2012-07-11 | 中国石油天然气股份有限公司 | Method for producing API II/III base oil from hydrocracking tail oil |
| CN103627430B (en) * | 2012-08-23 | 2015-08-26 | 中国石油化工股份有限公司 | The method of hydrotreating of the low Solidification Point Lube Base Oils of a kind of direct production |
| CN103627428B (en) * | 2012-08-23 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of method of hydrotreating producing low Solidification Point Lube Base Oils |
| CN103627432B (en) * | 2012-08-23 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method of hydrotreating producing low freezing point diesel fuel and lubricant base |
| CN104611018B (en) * | 2013-11-05 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of inferior raw material produces the process of lube 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 |
| CN106753718B (en) * | 2016-12-19 | 2019-10-01 | 大大科技(宁国)有限公司 | A kind of jack oil that ultralow temperature uses |
| CN107937025A (en) * | 2017-11-23 | 2018-04-20 | 海南汉地阳光石油化工有限公司 | A kind of oil hydrocracking tail oil prepares low-temperature lubrication oil base oil and preparation method thereof |
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