CN1718689A - Pretreatment method of lubricating oil hydrogenation isomeric dewax raw material - Google Patents
Pretreatment method of lubricating oil hydrogenation isomeric dewax raw material Download PDFInfo
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- CN1718689A CN1718689A CN 200410020930 CN200410020930A CN1718689A CN 1718689 A CN1718689 A CN 1718689A CN 200410020930 CN200410020930 CN 200410020930 CN 200410020930 A CN200410020930 A CN 200410020930A CN 1718689 A CN1718689 A CN 1718689A
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 21
- 239000002994 raw material Substances 0.000 title claims description 46
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 24
- 238000002203 pretreatment Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 51
- 230000008569 process Effects 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 239000003921 oil Substances 0.000 claims description 37
- 238000006317 isomerization reaction Methods 0.000 claims description 34
- 238000007670 refining Methods 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 239000005864 Sulphur Substances 0.000 claims description 23
- 239000003463 adsorbent Substances 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000002594 sorbent Substances 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- -1 granular carclazyte Chemical compound 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 1
- 230000000274 adsorptive effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000003351 photoxidation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 239000003974 emollient agent Substances 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A process for pretreating raw lubricating oil by hydrogenating, isomerizing and dowaxing features the combination of adsorptive prerefining with hydrorefining to obtain high-quality lubricating oil.
Description
Technical field
The present invention relates to a kind of pretreatment process of lube oil hydrogenation isomerization dewaxing raw material, is raw material with straight run vacuum distillate and deasphalted oil particularly, adopts the hydroisomerization dewax method to produce the preprocessing method of raw materials of lubricating oil or lubricant base.
Background technology
The low-temperature fluidity of lubricating oil is one of critical nature of storage and service requirements, and the technology of improving the oil product low-temperature fluidity mainly contains solvent dewaxing, catalytic dewaxing and isomerization dewaxing.The method of solvent dewaxing employing physics removes the requirement of satisfying the lubricating oil low-temperature fluidity with the straight-chain paraffin of high condensation point in the oil product, and the mode of catalytic dewaxing by shape slective cracking is converted into gas and light-end products with straight-chain paraffin, thereby reaches the purpose that reduces the lubricating oil pour point.The subject matter that solvent dewaxing and catalytic dewaxing exist is that the yield and the viscosity index of purpose product lubricant base are lower.
The lubricating oil isomerization dewaxing is the new technology of the production high quality API II/III class lubricating oil base oil of the nineties exploitation in last century.Isomerization dewaxing is that the straight-chain paraffin that condensation point in the oil product is higher generates isoparaffin by isomerization reaction, reaches the technology that reduces the product pour point and keep higher lubricant base yield.Compare with catalytic dewaxing with solvent dewaxing, isomerization dewaxing base oil yield height, pour point is low, viscosity index is high, is the good blend component of modern high performance I. C. engine oil.
The key of lubricating oil isomerization dewaxing technology is an isomerization catalyst.According to the reaction mechanism of alkane isomerization, all isomerization dewaxing catalysts all are the dual-function catalysts that molecular sieve constituted by the noble metal component and the acid active ingredient of high hydrogenation activity.This composition has determined catalyzer very responsive to the sulphur in the isomerization dewaxing raw material, nitrogen impurity, raw material must be through the hydrotreatment of the degree of depth, or adopt sulphur, nitrogen impurity content raw material seldom as: hydrocracking tail oil and take-hold in the palm synthetic wax etc., the raw material that enters isomerization reactor in a word will be controlled sulphur content less than 10 μ g/g, and nitrogen content is less than 5 μ g/g.
Lubricating oil isomerization dewaxing raw material generally adopts the deep hydrogenation pre-treatment, can reach the feed impurities content of heterogeneous catalyst requirement.US 6,676, and 827 disclose the low method of coagulating lubricant base of a kind of isomerization dewaxing production.Adopt hydrotreatment-isomerization dewaxing two-stage hydrogenation operational path, its hydroprocessing condition is: 340 ℃～380 ℃ of temperature of reaction, reaction pressure 3.5MPa～21MPa, volume space velocity 1.0h
-1～2.0h
-1US 6,231, the technological process that base oil of high viscosity index lubricant is produced in 749 isomerization that disclose a kind of high waxy feeds.The isomerization raw material carries out mild hydrocracking earlier at first section, and its condition is reaction pressure 7MPa～21MPa, and temperature of reaction is pressed transformation efficiency less than 20%～30% control, and then carries out isomerization reaction.This technology adopts hydrocracking to carry out the yield that raw materials pretreatment influences lubricant base.Adopt above-mentioned deep hydrogenation method can meet the demands, but under aerobic and light-struck condition to the impurity such as sulphur nitrogen that the isomery raw material carries out the lubricant base that pre-treatment obtains, the darkening of oil product, and then produce vaporific throw out, generate precipitation at last.This not only is related to the outward appearance of oil product, and its use properties is also seriously influenced.
Adopt anti-sulphur, heterogeneous catalyst that the nitrogen ability is strong, can improve the foreign matter content of charging to a certain extent, and then reduce the pretreated degree of depth.As US 6,264,826 disclose a kind of method that adopts the mild hydrogenation treating processes to prepare the isomerization dewaxing raw material.This technology is used a kind of platinum-palladium catalyst of anti-sulphur, 260 ℃～427 ℃ of temperature of reaction, under the hydroprocessing condition of reaction pressure 11MPa, obtains the isomerization dewaxing charging less than 20ppm of sulphur, nitrogen content.The hydrotreatment pressure of this technology is still higher.And under so high sulphur, nitrogen content feed conditions, isomerization catalyst is difficult to carry out long-term operation, and the selection of heterogeneous catalyst is restricted.
Refining with adsorbents is one of lubricant base purified common method, mainly removes alkali nitrogen material in the lubricant base by acid sorbent material, improves the oxidation stability of base oil.As the lubricant base supplementing refining method of CN1253165A, the foreign matter content of the base oil after the refining with adsorbents is still higher, can not be as the raw material of isomerization dewaxing.US 6,248, and 230 grades use sorbent material to remove part alkali nitrogen in hydrogenating desulfurization, hydrogenation aromatics-removing, mild hydrocracking and the hydrocracking process of petroleum naphtha, intermediate oil, to improve desulfurization degree.The main purpose of this method is to remove the polarity nitrogenous substances, improves the desulphurizing activated of catalyzer such as hydrogenating desulfurization.Aforesaid method can not be used for the isomerization dewaxing process, because the charging requirement that foreign matter contents such as its sulphur, nitrogen still do not reach isomerization dewaxing.CN 1362486A discloses a kind of zinc oxide desulfurizer that increases before the white oil noble metal hydrogenation catalyst, main effect is to remove hydrogen sulfide, and the protection noble metal catalyst does not have removal effect to nitrogenous impurity.This method can only be used for the white oil hydrogenation dearomatization and produce the food-level white oil process, because the sulphur nitrogen impurity content in the white oil is very low, sweetening agent can play a role in long running period, and in the lube oil hydrogenation isomery, still have certain sulphur, nitrogen, sweetening agent can very fast inactivation and is ineffective, be contained in the anti-device of noble metal catalyst, be not easy to take out and regenerate.
Lubricating oil oil base plinth behind the hydroisomerizing carries out post-refining again can solve the photoxidation stability problem, and as US 5,393, the 408 hydrofinishing processes that disclose a kind of high reactivity, high stability are used for improving the stability of hydrotreatment oil.Reaction conditions is 6MPa～20MPa.Volume space velocity 0.3h
-1～0.7h
-1, 230 ℃～340 ℃ of temperature of reaction.Hydrofinishing need operated than under the exacting terms, its equipment cost and process cost are higher, for nonfood grade and the pharmaceutical grade lube product that aromaticity content does not require, only carry out harsh hydrofinishing for the photoxidation stability that improves product, cost is too high.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of raw materials pretreatment technology of lube oil hydrogenation isomerization dewaxing, reduce the severity of existing hydrogenation preconditioning technique, improve the stability in storage of isomerization dewaxing product simultaneously.
Lube oil hydrogenation isomerization dewaxing preprocessing method of raw materials of the present invention comprises: be raw material with the vacuum distillate, carry out hydrofining, before hydrofining, or/and carry out refining with adsorbents afterwards, make sulphur content, the hygrogenating isomerization reaction charging that nitrogen content requires less than 5 μ g/g less than 10 μ g/g.Vacuum distillate is that raw material can carry out the solvent treatment processing earlier before above-mentioned pre-treatment.
Wherein the suitable hydrogenation catalyst for refining is adopted in hydrofining, and operational condition is 230 ℃～360 ℃ of temperature, best 260 ℃～310 ℃; Hydrogen dividing potential drop 3.0MPa～9.0MPa, preferred 4.0MPa～8.0MPa; Volume space velocity 0.4h
-1～2.0h
-1, best 1.0h
-1～1.5h
-1Hydrogen to oil volume ratio 300: 1～1000: 1, preferred 400: 1～800: 1.
Wherein the sorbent material of refining with adsorbents employing is gac, silica gel, granular carclazyte, molecular sieve, activated alumina, ion exchange resin etc. or its mixture.Wherein the specification of granular carclazyte is: density 0.7g/cm
3-0.85g/cm
3, granularity 20-90 order, specific surface area 300m
2/ g-800m
2/ g.The index of gac is: density 1.8g/cm
3-2.8g/cm
3, specific surface area 500m
2/ g-1300m
2/ g, mean pore size are 2nm-20nm.The density of silica gel is 2.0g/cm
3-2.5g/cm
3, specific surface area 300m
2/ g-900m
2/ g, mean pore size are 1nm-15nm.Sorbent material need carry out activation treatment before use, so that it has higher adsorptive power.Granular carclazyte adopts the sulfuric acid of 10-15% to activate 2-5 hour; Silica gel heated 1-5 hour down at 120-180 ℃; Gac should heat 2-4 hour down at 200-500 ℃.
Refining with adsorbents can be adopted fixed bed operate continuously mode, also can adopt andnon-continuous operation manner.Be preferably the operate continuously mode: by above-mentioned bed through the activation treatment sorbent material is housed, the refining with adsorbents condition is with the hydroisomerization dewax raw material: working pressure be normal pressure to 1MPa, be preferably normal pressure, adsorption temp 100-250 ℃, be preferably 120-180 ℃; Volume space velocity 0.1-5.0h
-1, be preferably 1.0-2.0h
-1
Product after the inventive method is handled can adopt hydroisomerization dewax to produce high-quality lubricant base.Described hydroisomerization catalyst is various suitable lube oil hydrogenation heterogeneous catalysts, carrier is the NU-10 molecular sieve of aluminum oxide and TON structure or ZSM-22 molecular sieve and SAPO-11 molecular sieve, β zeolite etc., the content of molecular sieve in catalyzer is 30wt%～80wt%, be preferably 40wt%～70wt%, also can add partial oxidation silicon, amorphous silicon aluminium etc. in the carrier; Active metal component be among Pt, Pd, Ru, Rh and the Ni one or more, the content in catalyzer is 0.1wt%～30.0wt%.Selectable adjuvant component is one or more in boron, fluorine, chlorine and the phosphorus, and the content in catalyzer is 0.1wt%～5.0wt%; The specific surface of this catalyzer is 150～500m
2/ g, pore volume are 0.15～0.60ml/g.Before using catalyzer is reduced, hydrogenation active metals is in reaction process goes back ortho states.The reaction conditions of described hydroisomerizing is: temperature is 220 ℃～380 ℃, and preferred 280 ℃～350 ℃, the hydrogen dividing potential drop is 4.0MPa～12.0MPa, and preferred 6.0～10.0MPa, volume space velocity are 0.6h
-1～1.8h
-1, preferred 0.8h
-1～1.5h
-1, hydrogen to oil volume ratio 300: 1～1200: 1, preferred 500: 1～800: 1.
The present invention adopt the absorption pre-refining can with some sulfur-nitrogen compounds of under hydroprocessing condition, being difficult to be removed in the raw material as: thionaphthene, dibenzothiophene and heterocyclic nitrogen compound etc. are adsorbing and removing with comparalive ease, thereby greatly reduced the severity of hydrotreatment reaction, obtain sulphur content less than 10 μ g/g under than demulcent hydrofining condition, nitrogen content is less than the hydroisomerization dewax raw material of 5 μ g/g.If refining with adsorbents is arranged on after the hydrofining, the partial impurities that hydrofining is difficult for removing adopts the method for absorption to remove, realize the mutual supplement with each other's advantages of two kinds of schemes, and because hydrofining is with most of impurity removal, so sorbent material can obtain relatively long running period, reduce regeneration times.The present invention combines refining with adsorbents and hydrofining, not only can under than the demulcent condition, obtain qualified hydroisomerizing charging, the more important thing is that the lubricant base that can obtain than the same charging that other method obtains has higher photoxidation stability.Hydrofining and refining with adsorbents are the methods of the lube base oil production post-refining used always, hydrofining and refining with adsorbents all are to be used for further improving the color and the stability of product, so in general, both can not combined, certainly more not can for the object of the invention with both combinations, can not expect the beneficial effect that brings after the present invention organically combines both yet.
Embodiment
The manageable raw material of the inventive method comprises various vacuum distillates, as the second line of distillation distillate, subtract three-way distillate, subtract four line distillates, frivolous pitch wet goods, or the solvent-refined oil of above-mentioned raw materials, solvent treatment can adopt ordinary method to carry out.
If adopt refining with adsorbents-unifining process, enter that sulphur content should be controlled at 100～500 μ g/g in the hydrofining raw material, preferred 250～400 μ g/g, nitrogen content should be controlled at 10～80 μ g/g, preferred 20～50 μ g/g.If adopt hydrofining-refining with adsorbents process, enter that sulphur content should be controlled at 80～300 μ g/g in the raw material of refining with adsorbents, preferred 100～150 μ g/g, nitrogen content should be controlled at 10～60 μ g/g, preferred 20～40 μ g/g.
The used Hydrobon catalyst of unifining 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.
Below each embodiment raw materials used for the Middle East subtracts three-way distillate, subtracts four line solvent-refined oils and frivolous oil, specific nature sees Table 1; Used sorbent material character is as shown in table 2.The Hydrobon catalyst that adopts is Mo-Ni/Al
2O
3Catalyzer is a benchmark with the weight of catalyzer, MoO
3Content be 29.34%, the content of NiO is 4.45%, P
2O
5Content be 2.25%; Its specific surface is 249m
2/ g, pore volume are 0.413ml/g.The isomerization dewaxing catalyst that uses among the embodiment is difunctional noble metal catalyst, is benchmark with the weight of catalyzer, ZSM-22 molecular sieve content 50%, and for the content of Pt is 0.15%, the aluminum oxide equal amount.The specific surface of catalyzer is 210m
2/ g, pore volume are 0.31ml/g.
Embodiment 1
Test the silochrom that used sorbent material is produced for the chemical plant, Qingdao, before using it is activated 4 hours down at 160 ℃.Adopt the absorption pre-refining-hydrofining technology condition in the table 3, stock oil is handled, the product property that obtains sees Table 4.
Embodiment 2
The gac that test employing Liyang gac company limited produces down activates 3 hour at 200 ℃ as sorbent material before using.Adopt the absorption pre-refining-hydrofining technology condition in the table 3, stock oil is handled, the product property that obtains sees Table 4.
Embodiment 3
The granular carclazyte that test employing Fushun chemical plastic factory produces is as sorbent material, and the sulfuric acid with 15w% before using activates 3 hours.Adopt the absorption pre-refining-hydrofining technology condition in the table 3, stock oil is handled, the product property that obtains sees Table 4.
Comparative Examples 1
Still to subtract four line solvent-refined oils with the Middle East be raw material in test, adopts Deep Hydrotreating technology to prepare the raw material of hydroisomerization dewax, and processing condition and product property see Table 3 and table 4 respectively.
Table 1 experiment stock oil character
| Raw material | Raw material 1 | Raw material 2 | Raw material 3 |
| The source | Subtract three-way distillate | It is refining to subtract the shallow degree of four lines | Frivolous oil |
| Density (20 ℃), kg/m 3 | 878.3 | 891 | 901.9 |
| Boiling range, ℃ (D1160) | |||
| IBP | 315 | 330 | 361 |
| 10％ | 341 | 384 | 519 |
| 30％ | 377 | 409 | 543 |
| Sulphur, m% | 0.89 | 1.15 | 1.21 |
| Nitrogen, μ g/g | 63.5 | 80.2 | 193.1 |
| Condensation point, ℃ | 35 | 41 | 51 |
| Viscosity, mm/s 2 100℃ | 3.68 | 4.26 | 19.25 |
| Carbon residue, % | 0 | ＜0.01 | 0.64 |
| Flash-point (opening), ℃ | 203 | 232 | 320 |
| Acid number, mgKOH/g | 0.01 | 0.02 | 0.02 |
| Wax content, m% | 15.21 | 16.65 | 20.17 |
| Hydrocarbon composition, m% | |||
| Paraffinic hydrocarbons | 25.77 | 21.3 | 20.0 |
| Naphthenic hydrocarbon | 40.01 | 35.5 | 30.3 |
| Aromatic hydrocarbons | 34.22 | 43.2 | 49.7 |
| Colloid | 0 | 0 | 0 |
Table 2 sorbent material character
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Sorbent material | Silica gel | Gac | Granular carclazyte |
| Density, g/cm 3 | 2.25 | 2.35 | 0.80 |
| Specific surface area, m 2/g | 490 | 1050 | 600 |
| Mean pore size, nm | 8 | 8.5 | 60 orders (granularity) |
The processing condition of table 3 embodiment and Comparative Examples
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| Raw material | ||||
| Absorption pre-refining condition | ||||
| Adsorption temp, ℃ | 120 | 160 | 180 | |
| Air speed, h -1 | 1.5 | 1.0 | 2.0 | |
| Absorption back sulphur content, μ g/g | 240～350 | 200～300 | 210～370 | |
| Absorption back nitrogen content, μ g/g | 22～45 | 20～40 | 31～48 | |
| The hydrofining condition | Hydrotreatment | |||
| Temperature, ℃ | 310 | 280 | 260 | 380 |
| The hydrogen dividing potential drop, MPa | 6.0 | 4.0 | 8.0 | 14.5 |
| Volume space velocity, h -1 | 1.2 | 1.5 | 1.0 | 0.6 |
| Hydrogen to oil volume ratio | 400 | 700 | 600 | 800 |
| Character after the raw materials pretreatment | ||||
| Density (20 ℃), kg/m 3 | 873.5 | 878.3 | 879.2 | 859.9 |
| Sulphur, μ g/g | 4.4 | 5.6 | 4.0 | 5.0 |
| Nitrogen, μ g/g | 1.0 | 1.0 | 1.0 | ＜1.0 |
| Viscosity, mm/s 2 100℃ | 6.124 | 6.185 | 6.157 | 6.019 |
Each embodiment of table 4 and Comparative Examples character
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| The isomerization dewaxing operational condition | ||||
| Temperature, ℃ | 320 | |||
| The hydrogen dividing potential drop, MPa | 9.0 | |||
| Volume space velocity, h -1 | 1.0 | |||
| Hydrogen to oil volume ratio | 800 | |||
| The isomerization dewaxing oil property | ||||
| Pour point, ℃ | -18 | -15 | -21 | -18 |
| Viscosity, mm/s 2 40℃ | 67.15 | 65.79 | 68.37 | 67.04 |
| 100℃ | 8.81 | 8.56 | 8.913 | 8.75 |
| Solar radiation is the oil product outward appearance after 72 hours | Transparent | Transparent | Transparent | There are a large amount of precipitations to produce |
Embodiment 4
Adsorption refining method after elder generation's hydrofining.
| Embodiment | Embodiment 4 |
| Raw material | Subtract three-way distillate |
| The hydrofining condition | |
| Temperature, ℃ | 310 |
| The hydrogen dividing potential drop, MPa | 6.0 |
| Volume space velocity, h -1 | 1.2 |
| Hydrogen to oil volume ratio | 400 |
| Sulphur content behind the hydrogenation, μ g/g | 136 |
| Nitrogen content behind the hydrogenation, μ g/g | 28 |
| Absorption pre-refining condition | |
| Sorbent material | Gac |
| Adsorption temp, ℃ | 120 |
| Air speed, h -1 | 1.5 |
| Character after the raw materials pretreatment | |
| Density (20 ℃), kg/m 3 | 875.5 |
| Sulphur, μ g/g | 3.1～7.3 |
| Nitrogen, μ g/g | 1.0～2.5 |
| Viscosity, mm/s 2 100℃ | 4.88 |
| Press character behind the embodiment 1 described hydroisomerizing | |
| Pour point, ℃ | -18 |
| Viscosity, mm/s 2 40℃ | 29.15 |
| 100℃ | 5.32 |
| Solar radiation is the oil product outward appearance after 72 hours | Transparent |
Claims (10)
1, a kind of pretreatment process of lube oil hydrogenation isomerization dewaxing raw material, comprise unifining process, it is characterized in that before unifining process or/and carry out refining with adsorbents afterwards, wherein hydrofining condition is 230 ℃～360 ℃ of temperature, hydrogen dividing potential drop 3.0MPa～9.0MPa, volume space velocity 0.4h
-1～2.0h
-1, hydrogen to oil volume ratio 300: 1～1000: 1; Wherein refining with adsorbents condition be the working pressure normal pressure to 1MPa, temperature 100-250 ℃, volume space velocity 0.1-5.0h
-1
2, in accordance with the method for claim 1, it is characterized in that the raw materials pretreatment of described lube oil hydrogenation isomerization dewaxing after sulphur content less than 10 μ g/g, nitrogen content is less than 5 μ g/g.
3, in accordance with the method for claim 1, it is characterized in that described hydrofining condition is 260 ℃～310 ℃ of temperature, hydrogen dividing potential drop 4.0MPa～8.0MPa, volume space velocity 1.0h
-1～1.5h
-1, hydrogen to oil volume ratio 400: 1～800: 1; Described refining with adsorbents condition is that working pressure is a normal pressure, adsorption temp 120-180 ℃, and volume space velocity 1.0-2.0h
-1
4, in accordance with the method for claim 1, it is characterized in that the sorbent material that described refining with adsorbents is used is gac, silica gel, granular carclazyte, molecular sieve, activated alumina, ion exchange resin or said mixture.
5, in accordance with the method for claim 4, the specification that it is characterized in that described granular carclazyte is: density 0.7g/cm
3-0.85g/cm
3, granularity 20-90 order, specific surface area 300m
2/ g-800m
2/ g; The index of described gac is: density 1.8g/cm
3-2.8g/cm
3, specific surface area 500m
2/ g-1300m
2/ g, mean pore size are 2nm-20nm; The density of described silica gel is 2.0g/cm
3-2.5g/cm
3, specific surface area 300m
2/ g-900m
2/ g, mean pore size are 1nm-15nm.
6, in accordance with the method for claim 5, it is characterized in that described sorbent material carries out activation treatment before use, the sulfuric acid activation of granular carclazyte employing 10-15% 2-5 hour, silica gel heated 1-5 hour down at 120-180 ℃, and gac should heat 2-4 hour down at 200-500 ℃.
7, in accordance with the method for claim 2, it is characterized in that described raw material sources in subtract four line distillates, subtract three-way distillate, second line of distillation distillate, frivolous asphalt oil, or the solvent-refined oil of above-mentioned raw materials.
8, in accordance with the method for claim 1, when it is characterized in that adopting refining with adsorbents-unifining process, enter that sulphur content is controlled at 100～500 μ g/g in the hydrofining raw material, nitrogen content should be controlled at 10～80 μ g/g; When adopting hydrofining-refining with adsorbents process, enter that sulphur content is controlled at 80～300 μ g/g in the raw material of refining with adsorbents, nitrogen content should be controlled at 10～60 μ g/g.
9, in accordance with the method for claim 8, when it is characterized in that adopting refining with adsorbents-unifining process, enter that sulphur content is controlled at 250～400 μ g/g in the hydrofining raw material, nitrogen content should be controlled at 20～50 μ g/g; When adopting hydrofining-refining with adsorbents process, enter that sulphur content is controlled at 100～150 μ g/g in the raw material of refining with adsorbents, nitrogen content should be controlled at 20～40 μ g/g.
10, a kind of lube oil hydrogenation isomery treatment process is a raw material with the vacuum distillate, and process comprises pre-treatment and hydroisomerizing processing; Wherein pre-treatment comprises hydrofining, and before hydrofining or/and carry out refining with adsorbents afterwards; The hydrofining condition is 230 ℃～360 ℃ of temperature, hydrogen dividing potential drop 3.0MPa～9.0MPa, volume space velocity 0.4h
-1～2.0h
-1, hydrogen to oil volume ratio 300: 1～1000: 1; The refining with adsorbents condition be the working pressure normal pressure to 1MPa, temperature 100-250 ℃, volume space velocity 0.1-5.0h
-1The hydroisomerizing treatment condition are that temperature is 220 ℃～380 ℃, and the hydrogen dividing potential drop is 4.0MPa～12.0MPa, and volume space velocity is 0.6h
-1～1.8h
-1, hydrogen to oil volume ratio 300: 1～1200: 1.
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Cited By (7)
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| CN101921608A (en) * | 2009-06-09 | 2010-12-22 | 武汉保华石化新材料开发有限公司 | Method for removing colloid asphalt from catalytic slurry oil by using solid-phase adsorbent |
| CN102755874A (en) * | 2011-04-26 | 2012-10-31 | 武汉润尔华科技有限公司 | Adsorption refining agent for lubricant base oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3839189A (en) * | 1969-08-18 | 1974-10-01 | Sun Oil Co | Hydrorefined lube oil and process of manufacture |
| US4719007A (en) * | 1986-10-30 | 1988-01-12 | Uop Inc. | Process for hydrotreating a hydrocarbonaceous charge stock |
| US4747937A (en) * | 1986-11-24 | 1988-05-31 | Uop Inc. | Process for the removal of hydrogenatable hydrocarbonaceous compounds from a hydrocarbonaceous stream and hydrogenating these compounds |
| US5454933A (en) * | 1991-12-16 | 1995-10-03 | Exxon Research And Engineering Company | Deep desulfurization of distillate fuels |
| CN1055953C (en) * | 1997-11-24 | 2000-08-30 | 中国石油化工总公司 | Method for treating fundamental oil of lubricant oil by solvent refinement-hydrogenation |
| US6248230B1 (en) * | 1998-06-25 | 2001-06-19 | Sk Corporation | Method for manufacturing cleaner fuels |
| EP1057879A3 (en) * | 1999-06-02 | 2001-07-04 | Haldor Topsoe A/S | A combined process for improved hydrotreating of diesel fuels |
| US6228254B1 (en) * | 1999-06-11 | 2001-05-08 | Chevron U.S.A., Inc. | Mild hydrotreating/extraction process for low sulfur gasoline |
| CN1118541C (en) * | 1999-11-04 | 2003-08-20 | 中国石化集团武汉石油化工厂 | Improvement of electric refining method for lubricant base-oil denitrification process |
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