CN102051233A - Preparation method of high-viscosity index lubricant base oil - Google Patents
Preparation method of high-viscosity index lubricant base oil Download PDFInfo
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- CN102051233A CN102051233A CN2009102361234A CN200910236123A CN102051233A CN 102051233 A CN102051233 A CN 102051233A CN 2009102361234 A CN2009102361234 A CN 2009102361234A CN 200910236123 A CN200910236123 A CN 200910236123A CN 102051233 A CN102051233 A CN 102051233A
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- 239000002199 base oil Substances 0.000 title claims abstract description 55
- 239000000314 lubricant Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003921 oil Substances 0.000 claims abstract description 101
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 239000001257 hydrogen Substances 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000009833 condensation Methods 0.000 claims description 31
- 230000005494 condensation Effects 0.000 claims description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
- 239000010937 tungsten Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 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 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 8
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 239000001993 wax Substances 0.000 description 21
- 238000006317 isomerization reaction Methods 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000000470 constituent Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000012169 petroleum derived wax Substances 0.000 description 3
- 235000019381 petroleum wax Nutrition 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- -1 polycyclic naphthene hydrocarbon Chemical class 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of high-viscosity index lubricant base oil, which comprises the following steps: (1) contacting a raw material with a dewaxing solvent to obtain dewaxed oil and oil-bearing wax, wherein the raw material is vacuum gas oil and/or light deasphalted oil; (2) contacting the dewaxed oil with a hydrotreating catalyst in the presence of hydrogen to obtain a hydrotreating product; (3) mixing the hydrotreating product with the oil-bearing wax, and contacting the mixture with a first hydrofining catalyst in the presence of hydrogen to obtain a first hydrofining product; (4) sequentially contacting the first hydrofining product with a hydroisomerizing catalyst and a second hydrofining catalyst in the presence of hydrogen to obtain a second hydrofining product; and (5) cutting the second hydrofining product to obtain the high-viscosity index lubricant base oil product. The preparation method provided by the invention can be used for producing lubricant base oil of which the viscosity index is higher than 120, from the low-wax-content intermediate base raw material at a high yield of 60-70%.
Description
Technical field
The invention relates to a kind of preparation method of base oil of high viscosity index lubricant.
Background technology
Because the upgrading of engine oil is more and more harsher to viscosity index, vaporization losses and the temperature pumping performance demands of lubricant base.Top-grade lubricating oil requires its base oil to have better viscosity temperature characteristic, lower vaporization losses, more excellent oxidation stability and low-temperature fluidity.
Viscosity index is the index that the viscosity with temperature of lubricant base changes, it is the numerical value that calculates through standard method by the kinematic viscosity under 40 ℃ and 100 ℃ of the base oils, be used for representing that the viscosity with temperature of base oil changes and the performance of variation, i.e. viscosity temperature characteristic.Between 0-150, the viscosity index value is big more usually for the viscosity index of the lubricant base of producing with mineral oil, and the viscosity temperature characteristic of expression base oil is good more, and is good more to the lubricity of engine under high and low temperature of working under wide temperature range.The base oil that viscosity temperature characteristic is good, viscosity index is higher, and when the temperature variation certain numerical value, basic oil viscosity rangeability is smaller.The base oil of viscosity temperature characteristic difference, viscosity index is lower, and when the temperature variation certain numerical value, basic oil viscosity rangeability is bigger.The viscosity index of base oil is relevant with its composition, the higher base oil viscosity index of paraffinic components content is higher, the higher base oil viscosity index of naphthene content is lower, so the base oil viscosity index of paraffinic crude production is higher than the base oil that intermediate base crude oil is produced, the viscosity index of the base oil of intermediate base crude oil production is higher than the base oil that naphthenic base crude is produced.
Condensation point is the index that characterizes the base oil low-temperature fluidity, when the base oil condensation point is higher, in use is subjected to the influence of variation of ambient temperature, and when envrionment temperature was reduced to its condensation point temperature, base oil lost flow capacity, influences the lubricated of mechanical moving element.The naphthenic hydrocarbon of the condensation point of base oil and its positive structure hydrocarbon, belt length side chain or the content of aromatic hydrocarbon are relevant, usually the component that adopts low temperature crystallization, filtering separation will influence low-temperature fluidity in the production process removes, and the component that removes mainly is to form solid wax molecule at a lower temperature easily.
The isomerization dewaxing technology is a new developing technology in the lubricating oil processing process over nearly 10 years, be different from the physical separation method of conventional procedure, the isomerization dewaxing process is incorporated into hydrogenation reaction and produces in the benzolketon dewaxing process, realized the corresponding fully base unit that replaces conventional lubrication oil base plinth oil production process of hydrogen addition technology, specifically, utilize the hydrotreatment process to replace the solvent dewaxing process, pass through hydrocracking with separating the undesirable components of removing in the solvent treatment process, make it to become the ideal composition of lubricating oil; Utilize known isomerization dewaxing technology generation for the solvent dewaxing process, the petroleum wax of having to separate for the low-temperature fluidity that reduces base oil in the conventional procedure is converted into the component of base oil by isomerization reaction, reduce the condensation point of product, make base oil satisfy the requirement of low temperature use properties; Utilize the hydrofinishing technology generation for the carclazyte refining with adsorbents process in the conventional procedure, improve the color and the stability of base oil product.
The characteristics that the isomerization dewaxing technology is different from general hydrogenation process are to have adopted in the reaction process to align the catalyzer that the structure hydrocarbon has isomerization reaction activity, this catalyzer can will have the normal alkane isomerization of high condensation point in the raw material, thereby be converted into low condensation point component, thereby improve the low-temperature fluidity of product.But such catalyzer requires very high to foreign matter contents such as the sulfide in the raw material, nitride, in case contain more above-mentioned impurity in the raw material, then cause the poisoning of catalyst inactivation, make raw material in the paraffin isomerization reaction can't carry out, therefore, require under the reaction conditions of harshness, to operate with the hydrotreatment unit of pour point depression process coupling.But under the hydroprocessing condition of harshness, during the process residues feed of base oil, then cause overcracking easily, cause the kinematic viscosity of processed products significantly to reduce, can't be met the product of lube base oil viscosity requirement.
CN1533424A discloses a kind of method that is prepared base oil by waxy oil, this method comprises: (a) in the presence of hydrogen raw material is contacted with the vulcanized Hydrobon catalyst that contains nickel and tungsten/acid amorphous silicon oxide-alumina supporter, and (b) effluent of step (a) is reduced condensation point, so that make base oil.The viscosity index of the base oil that obtains is 120-150, and yield is 45-47 weight %.
CN1703488A discloses and has a kind ofly prepared fuel and comprise the method for the lube basestocks of heavy lubricant base stock from the fischer-tropsch wax that is included in ebullient hydrocarbon-fraction in fuel and the lubricating oil boiling range, this method comprises that (i) comprises described wax Hydrodewaxing the isomerate of the lubricating oil distillate of Hydrodewaxing fuel and partial hydrogenation dewaxing with preparation, (ii) separate this two kinds of cuts, (iii) the lubricating oil distillate of described partial hydrogenation dewaxing is separated into last running and than low boiler cut, (iv) distinguish further Hydrodewaxing than low boiler cut and last running, comprise the lube basestocks of heavy lubricant base stock with preparation described.
CN101074393A discloses a kind of method of producing petroleum wax and base oil of high viscosity index lubricant simultaneously, this method comprises stock oil is contacted with solvent, dewaxing agent, under comparatively high temps, carry out the dewaxing of 2-3 section, obtain the sweat oil of petroleum wax, first section dewaxing and the sweat oil of second to the 3rd section dewaxing; With described pressed oil with after sweat oil mixes successively through hydrotreatment, flash distillation and isomerization dewaxing, produce the base oil of high viscosity index (HVI).
US5882505 discloses the method that a kind of F-T synthetic wax prepares base oil, and this method comprises carries out hydroisomerization and catalytic dewaxing successively with raw material, obtains the base oil of low condensation point.
Above-mentioned existing method is a purpose with the lubricant base of production viscosity index＞120 mainly, and the raw material of employing is gatch or the contour wax stock of Fischer-Tropsch synthetic wax, to improve the product viscosity index.For the low intermediate base stock oil of the content of wax, viscosity index＞120 above lubricant bases are very difficult to adopt aforesaid method production, need the realization that is converted of the degree of depth of raw material, but often bring the problem of big (viscosity index is generally 50-80%) of yield of lubricating oil low (having only 10-20% usually) or product viscosity loss.
Therefore, be necessary to develop a kind of method that can use the low intermediate base stock oil of the content of wax to come high produced in yields base oil of high viscosity index lubricant.
Summary of the invention
The objective of the invention is for provide a kind of can be with the method for the low intermediate base raw material innage produced in yields base oil of high viscosity index lubricant of the content of wax.
The invention provides a kind of preparation method of base oil of high viscosity index lubricant, wherein, this method may further comprise the steps:
(1) raw material is contacted with dewaxing solvent, remove the wax in the waxy oil, obtain pressed oil and gatch, the condition of contact makes the condensation point of gained pressed oil be-30 ℃ to 5 ℃, and described raw material is vacuum distillate and/or frivolous asphalt oil;
(2) above-mentioned pressed oil is contacted with hydrotreating catalyst in the presence of hydrogen, obtain sulphur content be reduced to be not higher than 60ppm, nitrogen content is reduced to the hydrotreatment products that is not higher than 5ppm;
(3) above-mentioned hydrotreatment products is mixed with step (1) gained gatch, in the presence of hydrogen, contact, obtain sulphur content and be reduced to first hydrotreated product that is not higher than 10ppm with first Hydrobon catalyst;
(4) above-mentioned first hydrotreated product is contacted with second Hydrobon catalyst with hydroisomerization catalyst in the presence of hydrogen successively, obtain condensation point and be not higher than-18 ℃, colourity and be not more than No. 0.5 second hydrotreated product;
(5) above-mentioned second hydrotreated product is cut, obtain the lube base oil production.
The preparation method of the lubricant base that present method provides can adopt the low intermediate base raw material of the content of wax with high produced in yields base oil of high viscosity index lubricant, viscosity index up to the yield of the lubricant base more than 120 up to 60-70%.This shows, method provided by the invention can reduce the specification of quality to the raw material of producing lubricant base under the situation that guarantees yield and viscosity index, the reply raw material changes and produces lubricant base from vacuum residuum, can adopt intermediate base or the mixed base stock oil that can only produce low-viscosity index lube base oil production by traditional method, high yield produce that kinematic viscosity meets the requirements, the lube base oil production of high viscosity index (HVI) and low condensation point.
Description of drawings
Fig. 1 is the preparation method's of a lubricant base provided by the invention schema.
Embodiment
As shown in Figure 1, the preparation method of lubricant base provided by the invention may further comprise the steps:
(1) raw material is contacted with dewaxing solvent, remove the wax in the waxy oil, obtain pressed oil and gatch, the condition of contact makes the condensation point of gained pressed oil be-30 ℃ to 5 ℃, and described raw material is vacuum distillate and/or frivolous asphalt oil;
(2) above-mentioned pressed oil is contacted with hydrotreating catalyst in the presence of hydrogen, obtain sulphur content be reduced to be not higher than 60ppm, nitrogen content is reduced to the hydrotreatment products that is not higher than 5ppm;
(3) above-mentioned hydrotreatment products and step (1) gained gatch are mixed the back and in the presence of hydrogen, contact, obtain sulphur content and be reduced to first hydrotreated product that is not higher than 10ppm with first Hydrobon catalyst;
(4) above-mentioned first hydrotreated product is contacted with second Hydrobon catalyst with hydroisomerization catalyst in the presence of hydrogen successively, obtain condensation point and be not higher than-18 ℃, colourity and be not more than No. 0.5 second hydrotreated product;
(5) above-mentioned second hydrotreated product is cut, obtain the lube base oil production.
According to preparation method provided by the invention, described raw material can be frivolous asphalt oil and/or vacuum distillate.Particularly described raw material can derive from relatively low intermediate base stock oil of wax content or mixed base stock oil.Particularly, the wax content of described intermediate base stock oil or mixed base stock oil can be low to moderate below the 10 weight %, and the wax content of common paraffin-base oil material is more than the 15 weight %.
Described vacuum distillate for example can be the various vacuum distillates of refinery, as in the line oil that reduces pressure, decompression two wires oil, decompression third fractional oil and the four line oil that reduce pressure one or more.
According to preparation method provided by the invention, in the step (1), raw material contacts the condition optimization that carries out solvent dewaxing with dewaxing solvent makes the condensation point by step (1) gained pressed oil be-30 ℃ to 5 ℃, and the condensation point of raw material itself is usually above 40 ℃.
Described dewaxing solvent can be the mixture of various ketone and aromatic hydrocarbons, mixture as methylethylketone and/or acetone and toluene and/or benzene, be preferably the mixture of methylethylketone and toluene, the weight ratio of ketone and aromatic hydrocarbons is 60: 40-70: 30, more preferably 65: 35-70: 30.Described dewaxing condition comprises that the volume ratio of dewaxing solvent and raw material can be 4-6: 1, be preferably 4.5-5.5: and 1, the temperature of dewaxing is preferably-5 ℃ to 25 ℃.The condensation point of pressed oil preferably is controlled at 5 ℃ to-30 ℃, further preferably is controlled at 0 ℃ to-20 ℃.The cold spot material temperature can be 34-36 ℃, and the cold spot solvent temperature is 28-32 ℃, and final cooling temperature and filtration temperature all can be-5 ℃ to 25 ℃.By above-mentioned solvent dewaxing, can obtain low condensation point pressed oil and high condensation point gatch, the content of the two is respectively 70-80 weight % and 20-30 weight % usually.
In the step (2), pressed oil is mixed with hydrogen in the presence of catalyzer, carry out hydrotreatment, obtain the first hydrogenation full distillate oil that sulphur, nitrogen, total aromatic hydrocarbons and naphthene content reduce, and sulphur content reduces to below the 60ppm, nitrogen content is reduced to below the 5ppm.Among the present invention, unless stated otherwise, described total aromaticity content refers to the total content of various aromatic hydrocarbons.
The condition of described hydrotreatment reaction can for: hydrogen partial pressure is 3-25MPa, and temperature of reaction is 250-410 ℃, and volume space velocity is 0.3-4h
-1, hydrogen to oil volume ratio is 100-3000: 1; Optimum condition is: hydrogen partial pressure 8-20MPa, and temperature of reaction is 280-390 ℃, volume space velocity is 0.5-3h
-1, hydrogen to oil volume ratio is 200-1500: 1; Further preferred condition is: hydrogen partial pressure 9-11MPa, temperature of reaction 300-390 ℃, volume space velocity is 0.8-1.2h
-1, hydrogen to oil volume ratio is 350-800: 1.
Described hydrotreating catalyst can be preferably the sulphided state hydrotreating catalyst, more preferably base metal sulphided state hydrotreating catalyst for the various hydrotreating catalysts that adopted in the hydrotreatment reaction.Under the preferable case, described hydrotreating catalyst is made up of active ingredient, fluorine auxiliary agent and carrier, described active ingredient is selected from least a in cobalt, nickel, molybdenum and the tungsten, and described carrier is aluminum oxide, aluminium oxide-silicon oxide or molecular sieve, and is benchmark with the total amount of described hydrotreating catalyst, in oxide compound, the content of nickel is 1-5 weight %, and the content of tungsten is 12-35 weight %, in element, the content of fluorine is 1-9 weight %, and surplus is described carrier.Further under the preferable case, described carrier is served as reasons one or more little porous aluminum oxides and one or more macroporous aluminium oxides according to 75: 25-50: 50 weight ratio is composited, to be bore dia account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in bore dia 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%.In the present embodiment employed hydrotreating catalyst for according to disclosed method among the CN 1169336A prepared be auxiliary agent with the fluorine, nickel-tungsten is the catalyzer of active constituent loading on alumina supporter, wherein the total amount with catalyzer is a benchmark, in the content of the nickel of oxide compound is that the content of 2.3 weight % and tungsten is 22 weight %, content in the fluorine of element is 4 weight %, and all the other are aluminum oxide.
Contact with hydrotreating catalyst by the mixture of this step pressed oil and hydrogen, remove partial vulcanization thing, nitride in the pressed oil, and with aromatic hydrocarbons and the open loop of polycyclic naphthene hydrocarbon hydrogenation, the aromatic hydrocarbons in the reduction pressed oil and the content of naphthenic hydrocarbon, improve hydrotreatment and generate the oil viscosity index, obtain the hydrotreatment products that a kind of viscosity index improves.
In order to remove the H in the hydrotreatment products
2S and C
5Following light component, method provided by the invention is mixed with gatch after preferably the hydrotreatment products gas that obtains being carried again, enters the mild hydrogenation refining system, contacts with first Hydrobon catalyst, and the mild hydrogenation that carries out step (3) is refining.The refining preferred sulphided state hydrotreating catalyst that adopts of mild hydrogenation, mild hydrogenation purified reaction conditions can for: hydrogen partial pressure is 3.0-25MPa, and temperature of reaction is 250-390 ℃, and volume space velocity is 0.3-5.0h
-1, hydrogen to oil volume ratio is 100-3000: 1.Mild hydrogenation purified reaction conditions is preferably hydrogen partial pressure 8.0-20MPa, and temperature of reaction 280-360 ℃, volume space velocity 0.5-4.0h
-1, hydrogen to oil volume ratio 200-1500: 1.
According to method provided by the invention, first Hydrobon catalyst that is adopted can be various Hydrobon catalysts well known by persons skilled in the art, is preferably comparatively demulcent Hydrobon catalyst, for example base metal sulphided state Hydrobon catalyst.For example, employing with at least a base metal in cobalt, nickel, molybdenum and the tungsten as active constituent loading at supported catalyst, be that described first Hydrobon catalyst is made up of active ingredient and carrier, described active ingredient is selected from least a in cobalt, nickel, molybdenum and the tungsten, described carrier is aluminum oxide or aluminium oxide-silicon oxide, and the total amount with described Hydrobon catalyst is a benchmark, in oxide compound, the content of nickel is 1-5 weight %, the content of tungsten is 12-35 weight %, and surplus is described carrier.The total amount that consists of with described first Hydrobon catalyst of used first Hydrobon catalyst is a benchmark in the embodiment of the invention, and in oxide compound, the content of nickel is 2.9 weight %, and the content of tungsten is 27 weight %, and all the other are aluminum oxide.
According to method provided by the invention, by gatch is separated, and only pressed oil is carried out hydrotreatment from raw material, sulphur, nitrogen and aromatic hydrocarbons on the one hand can effective elimination pressed oil, naphthenic hydrocarbon open loop cracking improves viscosity index.Can also effectively prevent wax molecule in the gatch on the other hand by the unnecessary small molecules that is cracked into, thereby guarantee that the lube product viscosity index that finally obtains is higher, yield is higher.Experimental results show that, if directly pressed oil in the distillate and gatch are carried out hydrotreatment together, under the identical situation of other condition, the viscosity index of products obtained therefrom is generally 100-110, be difficult to obtain viscosity index and be higher than 120 lube base oil production, and yield to hang down about 10%.
In addition, directly gatch is mixed with pressed oil after the hydrotreatment and first hydrofining if gatch is not carried out first hydrofining, the sulphur nitrogen impurity of mixing oil is difficult to satisfy hydroisomerization dewax charging requirement, can cause the inactivation of isomerization dewaxing catalyst.
After mild hydrogenation is refining, in the step (4), first hydrotreated product is fed isomerization dewaxing, back refining reaction system, contact with second Hydrobon catalyst with hydroisomerization catalyst successively, carry out isomerization dewaxing and back refining (it is saturated mainly to play hydrogenation).Described hydroisomerization catalyst is preferably the precious metal molecular sieve type catalyst, and second Hydrobon catalyst is preferably also ortho states catalyzer of precious metal.The condition that contacts with hydroisomerization catalyst can for: hydrogen partial pressure is 1-20MPa, and temperature of reaction is 250-400 ℃, and volume space velocity is 0.3-3.0h
-1, hydrogen to oil volume ratio is 100-3000: 1.The condition optimization that contacts with hydroisomerization catalyst is that hydrogen partial pressure is 4.0-18MPa, and temperature of reaction is 310-380 ℃, volume space velocity 0.5-1.5h
-1, hydrogen to oil volume ratio 200-1000: 1.The condition that contacts with second Hydrobon catalyst can be hydrogen partial pressure 1-20MPa, and temperature of reaction is 150-380 ℃, and volume space velocity is 0.3-3.0h
-1, hydrogen to oil volume ratio is 100-3000: 1.The condition optimization that contacts with second Hydrobon catalyst is: hydrogen partial pressure 4.0-18MPa, temperature of reaction 180-350 ℃, volume space velocity 0.5-1.5h
-1, hydrogen to oil volume ratio 200-1000: 1.The condition that contacts with hydroisomerization catalyst can be identical or different with the condition that contacts with second Hydrobon catalyst.
According to method provided by the invention, described hydroisomerizing reaction is a purpose with the straight waxes molecule of hydrogenation catalyst conversion solvent dewaxing remnants and the alkane that the collateralization degree is lower, condensation point is higher.Wherein catalyst system therefor can be selected from the catalytic dewaxing known in this area, isomerization dewaxing with in the catalyzer one or more, is generally and aligns the molecular sieve catalyst that the structure hydrocarbon molecule has selectivity shape slective cracking performance.Consisting of of described hydroisomerization catalyst is conventionally known to one of skill in the art, for example is the disclosed catalyzer that contains aluminium silicophosphate molecular sieve of CN 1382526A.Particularly, described hydroisomerization catalyst contains metal active composition and mesoporous molecular sieve, described metal active composition is to be selected from least a in nickel, platinum and the palladium, described metal active composition exists with at least a form in simple substance, oxide compound and the sulfide, in simple substance, and be benchmark with the total catalyst weight, the content of described group VIII metal component is 0.01-10 weight %, more preferably 0.1-5 weight %.Metal component loads on the mesoporous molecular sieve.Described mesoporous molecular sieve is well known in the art, for example, can be to be selected among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, SAPO-11 and the SAPO-41 one or more.In metal and with the catalyzer is benchmark, and the content of described group VIII metal is preferably 0.1-10 weight %, more preferably 0.1-5 weight %.
According to method provided by the invention, by the hydrogenation catalyst isomery, positive structure wherein can be become the higher isoparaffin of side chain degree with the lower paraffinic hydrocarbons isomery of side chain degree, further improve the viscosity index of lubricant base.
According to method provided by the invention, second Hydrobon catalyst that is adopted in the hydrofining reaction that carries out after described hydroisomerizing reaction can be various Hydrobon catalysts well known by persons skilled in the art, preferably adopt the noble metal hydrogenation catalyst for refining in the present invention, promptly load has the catalyzer of palladium and/or platinum on the carrier.Described second Hydrobon catalyst contains carrier and the hydrogenation activity composition that loads on the carrier, total amount with described second Hydrobon catalyst is a benchmark, the content of described hydrogenation activity composition is 0.01-15 weight %, the content of described carrier is 85-99.99 weight %, described hydrogenation activity composition is selected from precious metal or precious metal and Mo, Co, Ni, W, among V and the Zn one or more, described carrier is poriness silicon oxide-aluminum oxide, and in poriness silicon oxide-aluminum oxide, the content of silicon oxide is 1-40 weight %, alkali-metal content is less than 1 weight %, the BET specific surface area is the 150-350 meters squared per gram, pore volume is 0.15-1.5 cubic meter/gram, the k value is 1-15, k=B/M
SiO2, wherein, k is the B acid amount that corresponding silica-alumina is measured in unit mole silicon oxide introducing, B is the B acid amount of silica-alumina, M
SiO2Be silicon oxide molar fraction in the silica-alumina.Second Hydrobon catalyst is according to the prepared catalyzer of disclosed method among the CN 1510112A in the embodiment of the invention, this catalyzer is the catalyzer of load platinum and metallic palladium on the carrier silica, be benchmark wherein with the catalyzer total amount, the content of palladium is that the content of 0.2 weight %, platinum is 0.3 weight %, all the other are carrier, total amount with carrier is a benchmark, and the content of silicon oxide is 30 weight %.
By the distillation cutting, can obtain the lubricant base of high viscosity index (HVI) at last.Cut point can be determined according to the lubricant base of required acquisition, specifically has been conventionally known to one of skill in the art.
Can obtain viscosity index by aforesaid method is not less than 120 ℃, condensation point and is not higher than-20 ℃ and all satisfactory lube base oil production of other index, and because oil in the stock oil and wax all participate in the preparation lubricant base, lubricant base can be up to more than 60% with respect to the yield of raw material, even up to 70%.
The present invention is applicable to the occasion of refinery with frivolous asphalt oil or vacuum distillate production lubricant base.Existing " old three cover " device all is based on oil property paraffinic crude design preferably, can not adapt to the variation significantly of raw material, causes lubricant base to produce difficulty, even can not produce lubricant base.And the isomerization dewaxing technology because the hydrotreatment or the hydrocracking degree of depth that its catalyzer to the restriction harshness of the sulphur content in the raw material, causes cooperating with it increase, causes too high viscosity loss and yield losses.Method provided by the invention has solved above-mentioned shortcoming, can produce the high-quality lubricant base, and has higher yield.
The present invention is described further for mode that below will be by embodiment.Among the present invention, unless stated otherwise, described colourity is meant the colourimetric number that adopts GB/T 6540 to record, and described kinematic viscosity adopts the GB/T265 method to record, and described viscosity index adopts the GB/T1995 method to record, and condensation point adopts GB/T 3535 methods to record.
Embodiment 1
This embodiment is used to illustrate the preparation method of lubricant base provided by the invention.
According to the described flow preparation lubricant base of Fig. 1.
(1) is raw material (character of vacuum distillate 1 is as shown in table 1 below) with refinery's vacuum distillate 1, above-mentioned raw materials is contacted with dewaxing solvent, remove the wax in the waxy oil, obtain yield and be respectively the pressed oil of 70 weight % and the gatch of 30 weight %.Employed dewaxing solvent is the mixture of methylethylketone and toluene, its volume ratio is 65/35, and the dewaxing condition is the weight ratio 4.4: 1 of dewaxing solvent and stock oil, and the cold spot material temperature is 36 ℃, 32 ℃ of cold spot solvent temperatures, final cooling temperature and filtration temperature are 10 ℃.Gained dewaxing oil properties is as shown in table 2 below.
(2) step (1) gained pressed oil is carried out hydrotreatment under condition shown in the following table 3, wherein hydrotreating catalyst for according to disclosed method among the CN 1169336A prepared be auxiliary agent with the fluorine, nickel-tungsten is the catalyzer of active constituent loading on alumina supporter, be benchmark wherein with the catalyzer total amount, in the content of the nickel of oxide compound is that the content of 2.3 weight % and tungsten is 22 weight %, content in the fluorine of element is 4 weight %, and all the other are aluminum oxide.Pressed oil after the acquisition hydrotreatment is hydrotreatment products, and the sulphur content of gained hydrotreatment products is that 30ppm, nitrogen content are that 3ppm, total aromaticity content are that 5 weight %, colourity are No. 0.5.The character of hydrotreatment products is as shown in table 4.
(3) pressed oil after step (2) the gained hydrotreatment and step (1) gained gatch being mixed the back contacts with first Hydrobon catalyst (Hydrobon catalyst of the CH-21 trade mark that catalyzer branch office of China Petrochemical Industry produces) in the presence of hydrogen, the condition of contact is as shown in table 6 below, wherein step
(2) character of gained mixture was as shown in table 5 below after the pressed oil after the gained hydrotreatment mixed with step (1) gained gatch, obtained first hydrotreated product, and the character of the hydrotreated product of winning is as shown in table 7 below.
(4) with step (3) the hydrotreated product of winning (according to disclosed method preparation among the CN 1382526A is the catalyzer of active constituent loading on SAPO-11 molecular sieve-alumina supporter with platinum with hydroisomerization catalyst successively in the presence of hydrogen, be benchmark wherein with the catalyzer total amount, the content of platinum is 0.3 weight %, all the other are carrier, with the carrier is benchmark, the content of SAPO-11 molecular sieve is 75 weight % in this carrier, and all the other are aluminum oxide.) and second Hydrobon catalyst (according to the prepared catalyzer of disclosed method among the CN 1510112A, this catalyzer is the catalyzer of load platinum and metallic palladium on the carrier silica, be benchmark wherein with the catalyzer total amount, the content of palladium is that the content of 0.2 weight %, platinum is 0.3 weight %, all the other are carrier, total amount with carrier is a benchmark, the content of silicon oxide is 30 weight %) contact, the condition of contact is as shown in table 8 below, obtain second hydrotreated product, the character of second hydrotreated product is as shown in table 9.
(5) step (4) gained second hydrotreated product is distilled, isolate corresponding lube base oil production, character is as shown in table 10 below.Described lube base oil production is 70 weight % with respect to the yield of vacuum distillate 1.The yield of described lubricant base is meant that the weight of lubricant base accounts for the weight percent of vacuum distillate 1 raw material inlet amount.
Embodiment 2-3
This embodiment is used to illustrate the preparation method of lubricant base provided by the invention.
Method according to embodiment 1 prepares lubricant base, different is, the raw material oil properties, the dewaxing oil properties, the condition of hydrotreatment, the character of hydrotreatment products, the character of pressed oil and gatch mixture, the first hydrorefined condition, the character of first hydrotreated product, the hydrorefined condition of hydrogenation catalyst isomery/second, the character of second hydrotreated product is respectively shown in following table 1-9, the character of gained lube product is as shown in table 10 below, and described lube base oil production is respectively 68 weight % and 65 weight % with respect to the raw materials used yield of step (1).
Comparative Examples 1
Method according to embodiment 1 prepares lubricant base, different is, stock oil is without the solvent dewaxing of step (1) and directly carry out hydrotreatment, first hydrofining, hydrogenation catalyst isomery/second hydrofining and the distillation of step (2)-(5), the character of gained lube product is as shown in table 10 below, and the described lube base oil production yield raw materials used with respect to step (1) is 58 weight %.
Table 1 raw material oil properties
| The embodiment numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The stock oil title | Vacuum distillate 1 | Vacuum distillate 2 | Lightweight deasphalted oil |
| Density (20 ℃, g/cm 3) | ?0.8900 | 0.9138 | 0.9334 |
| Kinematic viscosity | |||
| 100℃(mm 2/s) | ?8.30 | 13.50 | 32.65 |
| Condensation point (℃) | ?45 | 47 | 52 |
| Color (number) | ?5 | 5 | 8 |
| Sulphur (weight %) | ?0.407 | 0.75 | 0.77 |
| Wax content (weight %) | ?10 | 8 | 9 |
| Aromaticity content (weight %) | ?24 | 28 | 33 |
Table 2 solvent dewaxing oil properties
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Kinematic viscosity/(mm 2·s -1) | |||
| 100℃ | 10.50 | 16.40 | 35.80 |
| Condensation point (℃) | -12 | -5 | -5 |
| Aromaticity content (weight %) | 26 | 32 | 37 |
| Sulphur content (μ gg -1) | 0.65 | 0.85 | 0.89 |
The condition of the hydrotreatment of table 3 pressed oil
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Hydrogen partial pressure/MPa | 15.0 | 15.0 | 15.0 |
| Temperature of reaction/℃ | 375 | 385 | 380 |
| Volume space velocity/h -1 | 0.5 | 0.4 | 0.6 |
| Hydrogen to oil volume ratio | 500 | 700 | 900 |
| Hydrogenated products yield/% | ～100 | ～100 | ～100 |
The character of table 4 hydrotreatment products
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 ℃, g/cm 3) | 0.8825 | 0.8990 | 0.9075 |
| Kinematic viscosity/(mm 2·s -1) |
| 100℃ | 7.200 | 12.25 | 29.50 |
| Color/number | 0.5 | 0.5 | 1.0 |
| Condensation point/℃ | -5 | 0 | 0 |
| Sulphur content/μ gg -1 | 30 | 45 | 55 |
| Nitrogen content/μ gg -1 | 3 | 5 | 5 |
| Aromaticity content/weight % | ＜5 | ＜5 | ＜5 |
The oil properties of mixing of table 5 hydrotreatment products and gatch
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 ℃, g/cm 3) | 0.8750 | 0.8970 | 0.9025 |
| Kinematic viscosity/(mm 2·s -1) | |||
| 100℃ | 6.800 | 11.45 | 28.90 |
| Color/number | 1.0 | 1.0 | 2.0 |
| Condensation point/℃ | 35 | 41 | 44 |
| Sulphur content/μ gg -1 | 500 | 560 | 650 |
| Nitrogen content/μ gg -1 | 20 | 30 | 45 |
The table 6 first hydrorefined condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Hydrogen partial pressure/MPa | 10.0 | 10.0 | 12.0 |
| Temperature of reaction/℃ | 350 | 350 | 360 |
| Volume space velocity/h -1 | 1.0 | 0.8 | 0.8 |
| Hydrogen to oil volume ratio | 500 | 600 | 800 |
| Yield/% | ～100 | ～100 | ～100 |
The character of table 7 first hydrotreated product
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 ℃, g/cm 3) | 0.8732 | 0.8840 | 08900 |
| Kinematic viscosity/(mm 2·s -1) | |||
| 100℃ | 6.750 | 10.22 | 27.65 |
| Color/number | 0.5 | 0.5 | 0.5 |
| Condensation point/℃ | 35 | 37 | 42 |
| Sulphur content/μ gg -1 | ＜10 | ＜10 | ＜10 |
| Nitrogen content/μ gg -1 | ＜2 | ＜2 | ＜2 |
The table 8 hydrogenation catalyst isomery/second hydrorefined condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Hydrogen partial pressure/MPa | 12.0 | 10.0 | 6.4 |
| Temperature of reaction (isomery/hydrofining)/℃ | 360/210 | 365/210 | 360/210 |
| Volume space velocity (isomery/hydrofining)/h -1 | 0.7/1.0 | 0.5/0.8 | 0.7/1.0 |
| Hydrogen-oil ratio/volume ratio | 500 | 600 | 800 |
| Hydrogenated products yield/% | ～95 | ～95 | ～95 |
The character of table 9 second hydrotreated product
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 ℃, g/cm 3) | 0.8433 | 0.8478 | 0.8545 |
| Condensation point/℃ | -32 | -35 | -28 |
| Color/number | 0.5 | 0.5 | 0.5 |
| Outward appearance | As clear as crystal | As clear as crystal | As clear as crystal |
Table 10 purpose product property
| Project | Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Embodiment 3 |
| Purpose product yield/% | 70 | 58 | 68 | 65 |
| Kinematic viscosity/(mm 2·s -1) | ||||
| 100℃ | 6.325 | 6.215 | 10.21 | 26.78 |
| 40℃ | 36.05 | 38.25 | 73.55 | 291 |
| Condensation point/℃ | -21 | -21 | -24 | -18 |
| Viscosity index | 126 | 109 | 122 | 121 |
| Outward appearance | As clear as crystal | As clear as crystal | As clear as crystal | As clear as crystal |
From the result of table 10 as can be seen, adopt method of the present invention, can be with the lube base oil production of the acquisition high viscosity index (HVI) of the second-rate high yield of raw material.And the method for Comparative Examples 1 has been owing to carried out hydrotreatment with wax, thereby the viscosity index of gained lube base oil production reduces greatly, and yield has also reduced by 12 percentage points.
Claims (19)
1. the preparation method of a base oil of high viscosity index lubricant is characterized in that, this method may further comprise the steps:
(1) raw material is contacted with dewaxing solvent, remove the wax in the waxy oil, obtain pressed oil and gatch, the condition of contact makes the condensation point of gained pressed oil be-30 ℃ to 5 ℃, and described raw material is vacuum distillate and/or frivolous asphalt oil;
(2) above-mentioned pressed oil is contacted with hydrotreating catalyst in the presence of hydrogen, obtain sulphur content be reduced to be not higher than 60ppm, nitrogen content is reduced to the hydrotreatment products that is not higher than 5ppm;
(3) above-mentioned hydrotreatment products and step (1) gained gatch are mixed the back and in the presence of hydrogen, contact, obtain sulphur content and be reduced to first hydrotreated product that is not higher than 10ppm with first Hydrobon catalyst;
(4) above-mentioned first hydrotreated product is contacted with second Hydrobon catalyst with hydroisomerization catalyst in the presence of hydrogen successively, obtain condensation point and be not higher than-18 ℃, colourity and be not more than No. 0.5 second hydrotreated product;
(5) above-mentioned second hydrotreated product is cut, obtain the lube base oil production.
2. preparation method according to claim 1, wherein, in the step (1), described dewaxing condition comprises that the volume ratio of dewaxing solvent and content of wax treated oil is 4-6: 1, dewaxing temperature is-5 ℃ to 25 ℃.
3. preparation method according to claim 1 and 2, wherein, described dewaxing solvent is the mixture of ketone and aromatic hydrocarbons, and the weight ratio of ketone and aromatic hydrocarbons is 60: 40-70: 30.
4. preparation method according to claim 1, wherein, in the step (2), the condition that contacts with hydrotreating catalyst comprises that hydrogen partial pressure is 3-25MPa, and temperature of reaction is 250-410 ℃, and volume space velocity is 0.3-4h
-1, hydrogen to oil volume ratio is 100-3000: 1.
5. preparation method according to claim 4, wherein, in the step (2), the condition that contacts with hydrotreating catalyst comprises that hydrogen partial pressure is 8-20MPa, and temperature of reaction is 280-390 ℃, and volume space velocity is 0.5-3h
-1, hydrogen to oil volume ratio is 200-1500: 1.
6. according to claim 4 or 5 described preparation methods, wherein, described hydrotreating catalyst is made up of active ingredient, fluorine auxiliary agent and carrier, and described active ingredient is selected from least a in cobalt, nickel, molybdenum and the tungsten, described carrier is aluminum oxide, aluminium oxide-silicon oxide or molecular sieve, and the total amount with described hydrotreating catalyst is a benchmark, and in oxide compound, the content of nickel is 1-5 weight %, the content of tungsten is 12-35 weight %, in element, the content of fluorine is 1-9 weight %, and surplus is a carrier.
7. preparation method according to claim 6, wherein, described carrier is served as reasons one or more little porous aluminum oxides and one or more macroporous aluminium oxides according to 75: 25-50: 50 weight ratio is composited, to be bore dia account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to wherein little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in bore dia 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%.
8. preparation method according to claim 1, wherein, in the step (3), the condition that contacts with first Hydrobon catalyst comprises: hydrogen partial pressure is 3-25MPa, temperature of reaction is 250-390 ℃, volume space velocity 0.3-5.0h
-1, hydrogen to oil volume ratio is 100-3000: 1.
9. preparation method according to claim 8, wherein, in the step (3), the condition that contacts with first Hydrobon catalyst comprises that hydrogen partial pressure is 8-20MPa, temperature of reaction 280-360 ℃, volume space velocity 0.5-4.0h
-1, hydrogen to oil volume ratio 200-1500: 1.
10. according to Claim 8 or 9 described preparation methods, wherein, described first Hydrobon catalyst is made up of active ingredient and carrier, described active ingredient is selected from least a in cobalt, nickel, molybdenum and the tungsten, and described carrier is aluminum oxide or aluminium oxide-silicon oxide, and is benchmark with the total amount of described Hydrobon catalyst, in oxide compound, the content of nickel is 1-5 weight %, and the content of tungsten is 12-35 weight %, and surplus is a carrier.
11. preparation method according to claim 1, wherein, in the step (4), the condition that contacts with described hydroisomerization catalyst comprises that hydrogen partial pressure is 1-20MPa, and temperature of reaction is 250-400 ℃, and volume space velocity is 0.3-3.0h
-1, hydrogen to oil volume ratio is 100-3000.
12. preparation method according to claim 11, wherein, in the step (4), hydrogen partial pressure 4-18MPa, temperature of reaction 310-380 ℃, volume space velocity 0.5-1.5h
-1, hydrogen to oil volume ratio 200-1000.
13. according to claim 11 or 12 described preparation methods, wherein, described hydroisomerization catalyst contains metal active composition and aluminium silicophosphate molecular sieve, described metal active composition is to be selected from least a in nickel, platinum and the palladium, described metal active composition exists with at least a form in simple substance, oxide compound and the sulfide, in simple substance, and be benchmark with the total catalyst weight, the content of described group VIII metal component is 0.01-10 weight %.
14. preparation method according to claim 1, wherein, in the step (4), the condition that contacts with second Hydrobon catalyst comprises that hydrogen partial pressure is 1-20MPa, and temperature of reaction is 150-380 ℃, and volume space velocity is 0.3-3.0h
-1, hydrogen to oil volume ratio is 100-3000.
15. preparation method according to claim 14, wherein, in the step (4), the condition that contacts with second Hydrobon catalyst comprises hydrogen partial pressure 4-18MPa, temperature of reaction 180-350 ℃, and volume space velocity 0.5-1.5h
-1, hydrogen to oil volume ratio 200-1000.
16. according to claim 14 or 15 described preparation methods, wherein, described second Hydrobon catalyst contains carrier and the hydrogenation activity composition that loads on the carrier, total amount with described second Hydrobon catalyst is a benchmark, the content of described hydrogenation activity composition is 0.01-15 weight %, the content of described carrier is 85-99.99 weight %, described hydrogenation activity composition is selected from precious metal or precious metal and Mo, Co, Ni, W, among V and the Zn one or more, described carrier is poriness silicon oxide-aluminum oxide, and in poriness silicon oxide-aluminum oxide, the content of silicon oxide is 1-40 weight %, alkali-metal content is less than 1 weight %, and the BET specific surface area is the 150-350 meters squared per gram, and pore volume is 0.15-1.5 cubic meter/gram, the k value is 1-15, k=B/M
SiO2, wherein, k is the B acid amount that corresponding silica-alumina is measured in unit mole silicon oxide introducing, B is the B acid amount of silica-alumina, M
SiO2Be silicon oxide molar fraction in the silica-alumina.
17. preparation method according to claim 16, wherein, described hydrogenation activity composition is Pd and Pt, and Pd/ (Pd+Pt) weight ratio is 0.3-1.
18. preparation method according to claim 17, wherein, total amount with described second Hydrobon catalyst is a benchmark, the content of described Pd is 0.1-0.5 weight %, the content of described Pt is 0.1-0.5 weight %, the content of silicon oxide is 25-35 weight %, and the content of aluminum oxide is 64-74.8 weight %.
19. preparation method according to claim 1, wherein, described raw material comes from intermediate base stock oil.
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| CN102952571B (en) * | 2011-08-25 | 2014-12-03 | 中国石油化工股份有限公司 | Solvent dewaxing method of low-wax content heavy hydrocarbon oil |
| CN103361117A (en) * | 2012-03-31 | 2013-10-23 | 中国石油化工股份有限公司 | Preparation method of high-viscosity index lubricating oil base oil |
| CN103361117B (en) * | 2012-03-31 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of preparation method of base oil of high viscosity index lubricant |
| CN112996595A (en) * | 2018-11-02 | 2021-06-18 | Sk新技术株式会社 | Hydrofinishing catalyst and method for preparing base oil by using same |
| CN112996595B (en) * | 2018-11-02 | 2023-10-13 | Sk 新技术株式会社 | Hydrofinishing catalyst and method for preparing base oil by using same |
| CN118594531A (en) * | 2024-05-30 | 2024-09-06 | 重庆工商大学 | Waste wind power lubricating oil hydrogenation catalyst, preparation method and application |
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