CN115678611B - Method for producing bright stock from vacuum residuum - Google Patents
Method for producing bright stock from vacuum residuum Download PDFInfo
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- CN115678611B CN115678611B CN202110857205.1A CN202110857205A CN115678611B CN 115678611 B CN115678611 B CN 115678611B CN 202110857205 A CN202110857205 A CN 202110857205A CN 115678611 B CN115678611 B CN 115678611B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000002904 solvent Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000002199 base oil Substances 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 230000008569 process Effects 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 239000010687 lubricating oil Substances 0.000 claims abstract description 27
- 239000010771 distillate fuel oil Substances 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 120
- 238000005520 cutting process Methods 0.000 claims description 42
- 239000002808 molecular sieve Substances 0.000 claims description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 33
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 12
- 239000001294 propane Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000012188 paraffin wax Substances 0.000 claims description 11
- 238000004062 sedimentation Methods 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- -1 cobalt metal oxides Chemical class 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 239000010426 asphalt Substances 0.000 abstract description 4
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 2
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 44
- 238000007670 refining Methods 0.000 description 17
- 230000008901 benefit Effects 0.000 description 12
- 230000001050 lubricating effect Effects 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- 239000001993 wax Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 239000008186 active pharmaceutical agent Substances 0.000 description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- QEDCEMKTASAIQH-UHFFFAOYSA-O azanium;platinum;nitrate Chemical compound [NH4+].[Pt].[O-][N+]([O-])=O QEDCEMKTASAIQH-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method for producing bright stock and fuel oil by vacuum residuum, which comprises the following steps: (1) Solvent deasphalting the vacuum residuum raw material to obtain light deoiling, heavy deoiling and deoiling asphalt; (2) The hydrogen and the light deoiling are contacted with a catalyst a and a catalyst b in sequence to carry out hydrotreatment, so as to obtain refined light deoiling; (3) Contacting heavy deoiling with a catalytic cracking catalyst or a hydrocracking catalyst for reaction, and separating the obtained product into fuel oil fractions; (4) Contacting the refined light deoiling in the step (2) with a hydroisomerization catalyst to carry out hydroisomerization reaction, so as to obtain a hydroisomerization product; (5) And (3) carrying out contact reaction on the hydroisomerization product obtained in the step (4), hydrogen and a refined catalyst, and separating the obtained product into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock. The invention has simple process flow and can simultaneously produce high-quality bright stock, low-viscosity lubricating oil base oil and high-quality clean fuel oil.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a method for producing high-quality bright stock from vacuum residuum.
Background
With the stopping production of the three sets of devices of furfural refining-ketobenzene dewaxing-clay refining, the market of lubricating oil base oil and the market product supply of one type of oil are reduced. Meanwhile, with the improvement of the quality requirements of lubricating oil products, the demand of API II and API III type lubricating oil base oils is increased year by year, and particularly, the high-quality API III type lubricating oil base oils are obtained. The bright stock, namely the residue lubricating oil base oil, is high-viscosity heavy lubricating oil base oil, and is mainly applied to high-temperature or heavy-load conditions, such as ship engine oil, diesel locomotive engine oil, heavy-load gear oil, various lubricating grease and the like. Conventional processes for producing bright stock generally include: the vacuum residuum is subjected to solvent deasphalting to obtain deasphalted light deasphalted oil, the light deasphalted oil is subjected to solvent refining to obtain wax-containing refined oil, the wax-containing refined oil is subjected to solvent dewaxing to obtain dewaxed oil with a pour point reduced, and the dewaxed oil is subjected to clay adsorption refining to obtain bright oil products. The traditional method for producing the bright stock is to use a physical separation means for production, and the composition of the raw materials is not changed in the production process, so that the requirement on the quality of the raw materials is higher, the whole production process flow is longer, and the product yield is lower.
Zhang Weixing et al report a method for producing bright stock from deasphalted oil of Daqing crude oil as a raw material in "a process for producing bright stock by hydrotreatment" (journal of the smooth petroleum institute, vol.21, no.1,2001 (3) 27-30). The method is characterized in that light deasphalted oil produced by Daqing crude oil with higher viscosity index (viscosity index is 92) after solvent dewaxing is selected as a raw material, hydrotreated components are distilled and then subjected to solvent dewaxing to obtain dewaxed oil, and the dewaxed oil is subjected to clay adsorption refining to obtain a bright stock product. The pour point of the obtained bright stock product is-6 ℃, the viscosity index is 105, and the viscosity index is improved by 13 units compared with the product produced by the traditional method. The technical process can obtain partial deoiled wax, so that the product scheme cannot be used for producing fuel oil.
CN101768470a discloses a process for preparing bright stock with high viscosity index and low pour point, which comprises subjecting vacuum residuum to solvent deasphalting, removing part of macromolecular polycyclic aromatic hydrocarbon in the obtained light deasphalted oil to obtain wax-containing refined oil, contacting the mixture of the wax-containing refined oil and hydrogen with hydrotreating catalyst and hydrofining catalyst respectively to obtain hydrogenated whole distillate, removing light components with final distillation point less than 500 ℃ from the hydrogenated whole distillate to obtain wax-containing hydrotreated oil, subjecting the wax-containing hydrotreated oil to solvent dewaxing to obtain dewaxed oil, subjecting the dewaxed oil to catalytic dewaxing and hydrofining respectively, and then subjecting the obtained product to gas stripping to obtain the bright stock. The process comprises solvent deasphalting, residuum hydrogenation, solvent dewaxing, catalytic dewaxing and hydrofining. The technical process also obtains wax and bright stock products.
CN102732302B discloses a process for preparing bright stock, which comprises, under the first-stage residuum hydrotreating reaction condition of a residuum hydrotreating reaction unit, contacting hydrogen, residuum raw materials with residuum hydrotreating catalyst, separating the products to obtain a hydrogenated residuum with a flow of 470 ℃ or higher, under a solvent deasphalting unit and solvent deasphalting condition, subjecting the hydrogenated residuum with 470 ℃ or higher to solvent refining to obtain a solvent refined hydrogenated residuum, under a hydrotreating reaction unit and hydrotreating reaction condition, contacting hydrogen with the solvent refined hydrogenated residuum with hydrotreating catalyst, contacting hydrogen with the solvent refined residuum with hydrotreating catalyst, separating to obtain hydrogenated oil product with 470 ℃ or higher, and subjecting the hydrogenated product with 470 ℃ or higher to solvent dewaxing under a solvent dewaxing unit and solvent dewaxing condition to obtain bright stock product oil. The technical process also obtains wax and bright stock products.
CN102079994B discloses a process for preparing bright stock oil, which comprises contacting light deasphalted oil with solvent to obtain waxy refined oil, contacting waxy refined oil with dewaxing solvent to obtain dewaxed oil and microcrystalline wax paste, contacting dewaxed oil with hydrogen and hydrotreating catalyst to obtain first hydrogenated full distillate, contacting the first hydrogenated full distillate with hydrogen, hydroisomerization catalyst and hydrofining agent to obtain second hydrogenated full distillate, separating fraction with boiling point higher than 500 ℃ from the second hydrogenated full distillate as bright stock oil product.
CN104449841B discloses a process for preparing bright stock, which comprises using naphthenic light deasphalted oil (pour point not less than 0 deg.C, kinematic viscosity not less than 60mm at 100 deg.C) 2 And/s) as raw material, adopting hydrofining-isodewaxing-hydrofinishing reaction to convert high pour point paraffin molecule or naphthene with long side chain paraffin in the raw material oil into low pour point branched paraffin or naphthene with branched paraffin, retaining lubricating oil fraction in the raw material oil, and obtaining the invented product with high yield, low pour point (pour point is less than or equal to-18 deg.C), high viscosity (100 deg.C kinematic viscosity is more than or equal to 28 mm) 2 S) bright stock, and can produce both high-quality naphtha and middle distillate. The technical process can produce the bright stock and simultaneously produce part of light fuel oil, but the technology is mainly aimed at cycloalkyl light deoiling as the raw material, and has weak applicability to intermediate base and paraffin base raw materials with relatively high wax content.
CN108473889a and CN108473890a disclose a process for producing bright stock from residuum deasphalted oil, which comprises solvent deasphalting a raw material having a boiling point of T5 of 400 ℃ or higher, hydrotreating the deasphalted oil, having a sulfur content of less than 300ppm, a nitrogen content of less than 100ppm, separating the hydrogenated product into fuel oil and bottom oil, hydrocracking and catalytic dewaxing the bottom oil, and using a fraction of the catalytic dewaxed product of 510 ℃ or higher as a bright stock product, wherein the bright stock pour point of the technical disclosure is below-6 ℃ at 510 ℃.
Compared with the prior published patent technology, the traditional Laozhen process adopts a non-hydrogenation route, is easy to produce the API I type lubricating oil base oil, but cannot produce the high-quality API II/III type lubricating oil base oil. By adopting a light deoiling hydrotreating-hydrodewaxing-replenishing refining route, the condensation point of target bright stock and lubricating oil base oil can be effectively improved, but the yield of target products is lower due to the reaction process of converting linear alkane into micromolecules, and particularly, the treatment of high-wax-content raw materials is more obvious. Adopts a process route of solvent deasphalting, solvent refining, solvent dewaxing, hydrotreating, hydroisomerization, supplementary refining and fractionation, and the process route is relatively longer although the raw material has wide applicability. In the solvent deasphalting-light deoiling hydrotreatment-hydroisomerization-supplementary refining technology, the simple hydrotreatment is adopted, the structural composition of the product cannot be changed, the viscosity indexes of the bright stock and the lubricating oil base oil product are relatively poor, the process can only be compensated by a pressure reduction yield mode, and the technology has obvious effects on naphthenic base oil. In summary, the prior art route cannot meet the technical requirements of flexible and diverse production of high-yield and high-quality lubricating base oil and bright stock.
Disclosure of Invention
The invention aims to provide a method for producing bright stock from vacuum residuum, which solves the problem that the prior art route cannot give consideration to flexible and diversified production of high-yield and high-quality lubricating oil base oil and bright stock.
In order to achieve the above object, the present invention provides a method for producing bright stock from vacuum residuum, comprising the steps of:
(1) Solvent deasphalting a vacuum residuum feedstock to obtain a deasphalted oil;
(2) The hydrogen and the deasphalted oil are contacted with a catalyst a and a catalyst b in sequence to carry out hydrotreatment, so as to obtain refined deasphalted oil; the catalyst a comprises a carrier and a metal oxide, wherein the carrier is alumina and/or silica-alumina, and the metal oxide is one or more of nickel, molybdenum, tungsten and cobalt metal oxides; the catalyst b comprises a carrier, a molecular sieve and active metals, wherein the carrier is alumina and/or silica-alumina, the molecular sieve is a Y molecular sieve and/or a beta molecular sieve, and the active metals are one or more of nickel, molybdenum, tungsten and cobalt;
(3) Contacting the refined deasphalted oil in the step (2) with a hydroisomerization catalyst to carry out hydroisomerization reaction to obtain a hydroisomerization product;
(4) And (3) carrying out contact reaction on the hydroisomerization product obtained in the step (3), hydrogen and a refined catalyst, and separating the obtained product into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock.
In the solvent deasphalting process of the step (1), asphaltene, condensed ring compounds which are difficult to convert in the vacuum residue raw material and heavy metals, sulfur and nitrogen compounds which are harmful to the subsequent treatment process can be removed; in the hydrotreating process of the step (2), heteroatom compounds such as sulfur, nitrogen and the like in the deasphalted oil can be further removed, meanwhile, unremoved polycyclic aromatic hydrocarbon is moderately saturated, the viscosity-temperature performance of the oil is improved, the catalyst b has a moderate cracking function, and is matched with the catalyst a to generate moderate ring-opening cracking reaction, so that the property requirement of low pour point of the bright stock is further realized; in the hydroisomerization reaction process of the step (3), long-chain alkane in the raw material can be isomerized into a low-condensation-point base oil component, so that the yield of the base oil is improved, the viscosity loss is reduced, and the quality of lubricating oil is improved; in the supplementary refining process of the step (4), the residual aromatic hydrocarbon and olefin are subjected to further hydrogenation saturation reaction, and finally the reaction product is separated into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a catalyst a comprises 60-80 wt% of carrier, 15-30 wt% of metal oxide and 0-10 wt% of auxiliary agent, wherein the auxiliary agent is one or more of fluorine, boron and phosphorus, and preferably, the catalyst a comprises one or more of aluminum oxide, nickel, molybdenum, tungsten and cobalt metal oxide, and boron or phosphorus auxiliary agent.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a catalyst a comprises 65-78wt% of carrier, 18-28wt% of metal oxide and 0-7wt% of auxiliary agent; more preferably, the catalyst comprises 65 to 75 weight percent of carrier, 18 to 25 weight percent of metal oxide and 0 to 5 weight percent of auxiliary agent.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a catalyst b comprises 50-80 wt% of carrier, 5-30 wt% of molecular sieve and 15-30 wt% of active metal; preferably, the catalyst comprises 55 to 75 weight percent of carrier, 5 to 18 weight percent of molecular sieve and 18 to 25 weight percent of active metal.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the content of catalyst b is 1-60% by volume and based on catalyst a.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the vacuum residuum raw material is one or more of paraffin-based vacuum residuum, intermediate-based vacuum residuum and cycloalkyl vacuum residuum.
The method for producing the bright stock from the vacuum residuum, disclosed by the invention, has the advantages that the T5 boiling point of the vacuum residuum raw material is at least 500 ℃, the T70 boiling point is at least 700 ℃, and the kinematic viscosity at 100 ℃ is at least 118mm 2 /s。
The invention relates to a method for producing bright stock from vacuum residuum, wherein, in the step (4), products are separated into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock at 260-300 ℃ at a first cutting point and 500-570 ℃ at a second cutting point.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the first cutting point is 260-280 ℃, and the second cutting point is 510-550 ℃.
The light fuel oil in the step (4) can be one section below the first cutting point, or a plurality of sections from 65-135 ℃ and 135 ℃ to the first cutting point, or a plurality of sections from 65-180 ℃ and 180 ℃ to the first cutting point.
The method for producing the bright stock from the vacuum residuum comprises the step (4) that the low-viscosity lubricating base oil is a section from a first cutting point to a second cutting point.
According to the method for producing the bright stock from the vacuum residuum, the low-viscosity lubricating base oil in the step (4) can be divided into a combination of ultralow-viscosity lubricating base oil from the first cutting point to the third cutting point, medium-viscosity lubricating base oil from the third cutting point to the fourth cutting point and higher-viscosity lubricating base oil from the fourth cutting point to the second cutting point, wherein the third cutting point and the fourth cutting point are sequentially combined from the first cutting point to the second cutting point in sequence. In particular, low viscosity lubricant base oils may be divided into ultra low viscosity lubricant base oils from a first cut point to 360 ℃, medium viscosity lubricant base oils from 360-450 ℃ and higher viscosity lubricant base oils from 450 ℃ to a second cut point.
The invention relates to a method for producing bright stock from vacuum residuum, wherein solvent deasphalting in the step (1) is a two-stage extraction-sedimentation process.
The method for producing bright stock from vacuum residuum, disclosed by the invention, wherein the solvent deasphalting condition in the step (1) comprises the following steps: the mass ratio of the solvent to the vacuum residue is 3-9:1, the temperature of the top of the extraction tower is 50-100 ℃, the sedimentation temperature is 65-110 ℃, the extraction pressure is 3.0-7.0 MPa, and the solvent is propane or butane.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the hydrogenation treatment condition in the step (2) is that the reaction temperature is 355-400 ℃, the partial pressure of reaction hydrogen is 8-15 MPa, and the volume space velocity is 0.4-1.2 h -1 The volume ratio of the hydrogen oil is 500-1000: 1.
the invention relates to a method for producing bright stock from vacuum residuum, wherein, the hydrogenation isomerization reaction condition in the step (3) is that the reaction temperature is 340-390 ℃, the reaction hydrogen partial pressure is 10-15 MPa, and the volume space velocity is 0.3-1.0 h -1 The volume ratio of the hydrogen oil is 500-1000: 1.
the invention relates to a method for producing bright stock from vacuum residuum, wherein, the hydroisomerization catalyst in the step (3) comprises a carrier, a molecular sieve and active metals, wherein the carrier is alumina and/or silica-alumina, the molecular sieve is one or more of ZSM-5, ZSM-22 and ZSM-23, and the active metals are platinum and/or palladium.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a hydroisomerization catalyst comprises 10-50wt% of carrier, 50-80wt% of molecular sieve and 0.1-1wt% of active metal.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the refined catalyst in the step (5) consists of amorphous silica-alumina and at least one noble metal of group VIII, and the noble metal is Pt and/or Pd.
The method for producing the bright stock from the vacuum residue, disclosed by the invention, has the advantages that the yield of deasphalted oil is 30-70 wt%, preferably 40-70 wt%, the T5 boiling point is more than or equal to 420 ℃, preferably the T5 boiling point is more than or equal to 450 ℃, the pour point is less than or equal to 56 ℃, the viscosity index is less than or equal to 150, the asphaltene content is less than or equal to 0.2wt%, preferably, the asphaltene content is less than or equal to 0.1wt%, the sulfur content is less than or equal to 1500ppm, the nitrogen content is less than or equal to 1500ppm, the carbon residue content is less than or equal to 2wt%, preferably, the carbon residue content is less than or equal to 1.5wt%, the metal Ni+V content is less than or equal to 5ppm, preferably, and the metal Ni+V content is less than or equal to 3ppm relative to the mass of the vacuum residue raw material.
The method for producing bright stock from vacuum residuum, disclosed by the invention, has the advantages that the sulfur content in refined light deoiling is less than or equal to 2ppm, the nitrogen content is less than or equal to 2ppm, the boiling point of T5 is more than or equal to 300 ℃, the boiling point of T50 is more than or equal to 550 ℃, and the boiling point of T95 is more than or equal to 710 ℃.
The method for producing the bright stock from the vacuum residuum, disclosed by the invention, has the advantages that the yield of the high-viscosity bright stock is more than or equal to 58wt% relative to the light deoiling quality, the viscosity index is more than or equal to 120, and the pour point is less than or equal to-20 ℃.
The beneficial effects of the invention are as follows:
the method provided by the invention simplifies the process flow, adopts a combined technology of solvent deasphalting and full hydrogenation, and particularly adopts a combined catalyst technology in the hydrotreating process, when the processed raw materials belong to paraffin-based vacuum residuum with high paraffin content, the purpose of reducing sulfur and nitrogen can be realized by adopting a hydrotreating agent with high hydrodesulfurization denitrification arene saturation and a catalyst with low ring opening activity, the requirement of isomerism feeding is met, when the processed raw materials belong to intermediate base or cycloalkyl vacuum residuum with low paraffin content, the purpose of reducing sulfur and nitrogen and simultaneously improving the viscosity index of oil products can be realized by adopting a hydrotreating agent with high hydrodesulfurization denitrification arene saturation and a catalyst with high ring opening activity, and the purpose of ensuring the yield and quality of bright oil and low-viscosity lubricating oil base oil products under the condition of raw material diversity without increasing the process condition severity is further realized.
Drawings
FIG. 1 is a process flow diagram of the full hydrogenation process employed in the present invention to produce bright stock.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
As shown in fig. 1, a method for producing bright stock from vacuum residuum includes the following steps:
(1) Solvent deasphalting a vacuum residuum feedstock to obtain a deasphalted oil;
(2) The hydrogen and the deasphalted oil are contacted with a catalyst a and a catalyst b in sequence to carry out hydrotreatment, so as to obtain refined deasphalted oil; the catalyst a comprises a carrier and a metal oxide, wherein the carrier is alumina and/or silica-alumina, and the metal oxide is one or more of nickel, molybdenum, tungsten and cobalt metal oxides; the catalyst b comprises a carrier, a molecular sieve and active metals, wherein the carrier is alumina and/or silica-alumina, the molecular sieve is a Y molecular sieve and/or a beta molecular sieve, and the active metals are one or more of nickel, molybdenum, tungsten and cobalt;
(3) Contacting the refined deasphalted oil in the step (2) with a hydroisomerization catalyst to carry out hydroisomerization reaction to obtain a hydroisomerization product;
(4) And (3) carrying out contact reaction on the hydroisomerization product obtained in the step (3), hydrogen and a refined catalyst, and separating the obtained product into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock.
In the solvent deasphalting process of the step (1), asphaltene, condensed ring compounds which are difficult to convert in the vacuum residue raw material and heavy metals, sulfur and nitrogen compounds which are harmful to the subsequent treatment process can be removed; in the hydrotreating process of the step (2), heteroatom compounds such as sulfur, nitrogen and the like in the deasphalted oil can be further removed, meanwhile, unremoved polycyclic aromatic hydrocarbon is moderately saturated, the viscosity-temperature performance of the oil is improved, the catalyst b has a moderate cracking function, and is matched with the catalyst a to generate moderate ring-opening cracking reaction, so that the property requirement of low pour point of the bright stock is further realized; in the hydroisomerization reaction process of the step (3), long-chain alkane in the raw material can be isomerized into a low-condensation-point base oil component, so that the yield of the base oil is improved, the viscosity loss is reduced, and the quality of lubricating oil is improved; in the supplementary refining process of the step (4), the residual aromatic hydrocarbon and olefin are subjected to further hydrogenation saturation reaction, and finally the reaction product is separated into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a catalyst a comprises 60-80 wt% of carrier, 15-30 wt% of metal oxide and 0-10 wt% of auxiliary agent, wherein the auxiliary agent is one or more of fluorine, boron and phosphorus, and preferably, the catalyst a comprises one or more of aluminum oxide, nickel, molybdenum, tungsten and cobalt metal oxide, and boron or phosphorus auxiliary agent.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a catalyst a comprises 65-78wt% of carrier, 18-28wt% of metal oxide and 0-7wt% of auxiliary agent; more preferably, the catalyst comprises 65 to 75 weight percent of carrier, 18 to 25 weight percent of metal oxide and 0 to 5 weight percent of auxiliary agent.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a catalyst b comprises 50-80 wt% of carrier, 5-30 wt% of molecular sieve and 15-30 wt% of active metal; preferably, the catalyst comprises 55 to 75 weight percent of carrier, 5 to 18 weight percent of molecular sieve and 18 to 25 weight percent of active metal.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the content of catalyst b is 1-60% by volume and based on catalyst a.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the vacuum residuum raw material is one or more of paraffin-based vacuum residuum, intermediate-based vacuum residuum and cycloalkyl vacuum residuum.
The method for producing the bright stock from the vacuum residuum, disclosed by the invention, has the advantages that the T5 boiling point of the vacuum residuum raw material is at least 500 ℃, the T70 boiling point is at least 700 ℃, and the kinematic viscosity at 100 ℃ is at least 118mm 2 /s。
The invention relates to a method for producing bright stock from vacuum residuum, wherein, in the step (4), products are separated into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock at 260-300 ℃ at a first cutting point and 500-570 ℃ at a second cutting point.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the first cutting point is 260-280 ℃, and the second cutting point is 510-550 ℃.
The light fuel oil in the step (4) can be one section below the first cutting point, or a plurality of sections from 65-135 ℃ and 135 ℃ to the first cutting point, or a plurality of sections from 65-180 ℃ and 180 ℃ to the first cutting point.
The method for producing the bright stock from the vacuum residuum comprises the step (4) that the low-viscosity lubricating base oil is a section from a first cutting point to a second cutting point.
According to the method for producing the bright stock from the vacuum residuum, the low-viscosity lubricating base oil in the step (4) can be divided into a combination of ultralow-viscosity lubricating base oil from the first cutting point to the third cutting point, medium-viscosity lubricating base oil from the third cutting point to the fourth cutting point and higher-viscosity lubricating base oil from the fourth cutting point to the second cutting point, wherein the third cutting point and the fourth cutting point are sequentially combined from the first cutting point to the second cutting point in sequence. In particular, low viscosity lubricant base oils may be divided into ultra low viscosity lubricant base oils from a first cut point to 360 ℃, medium viscosity lubricant base oils from 360-450 ℃ and higher viscosity lubricant base oils from 450 ℃ to a second cut point.
The invention relates to a method for producing bright stock from vacuum residuum, wherein solvent deasphalting in the step (1) is a two-stage extraction-sedimentation process.
The method for producing bright stock from vacuum residuum, disclosed by the invention, wherein the solvent deasphalting condition in the step (1) comprises the following steps: the mass ratio of the solvent to the vacuum residue is 3-9:1, the temperature of the top of the extraction tower is 50-100 ℃, the sedimentation temperature is 65-110 ℃, the extraction pressure is 3.0-7.0 MPa, and the solvent is propane or butane.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the hydrogenation treatment condition in the step (2) is that the reaction temperature is 355-400 ℃, the partial pressure of reaction hydrogen is 8-15 MPa, and the volume space velocity is 0.4-1.2 h -1 The volume ratio of the hydrogen oil is 500-1000: 1.
the invention relates to a method for producing bright stock from vacuum residuum, wherein the hydroisomerization reaction condition in the step (3) is that the reaction temperature is 340-390 ℃,the partial pressure of the reaction hydrogen is 10-15 MPa, and the volume space velocity is 0.3-1.0 h -1 The volume ratio of the hydrogen oil is 500-1000: 1.
the invention relates to a method for producing bright stock from vacuum residuum, wherein, the hydroisomerization catalyst in the step (3) comprises a carrier, a molecular sieve and active metals, wherein the carrier is alumina and/or silica-alumina, the molecular sieve is one or more of ZSM-5, ZSM-22 and ZSM-23, and the active metals are platinum and/or palladium.
The invention relates to a method for producing bright stock from vacuum residuum, wherein a hydroisomerization catalyst comprises 10-50wt% of carrier, 50-80wt% of molecular sieve and 0.1-1wt% of active metal.
The invention relates to a method for producing bright stock from vacuum residuum, wherein the refined catalyst in the step (5) consists of amorphous silica-alumina and at least one noble metal of group VIII, and the noble metal is Pt and/or Pd.
The method for producing the bright stock from the vacuum residue, disclosed by the invention, has the advantages that the yield of deasphalted oil is 30-70 wt%, preferably 40-70 wt%, the T5 boiling point is more than or equal to 420 ℃, preferably the T5 boiling point is more than or equal to 450 ℃, the pour point is less than or equal to 56 ℃, the viscosity index is less than or equal to 150, the asphaltene content is less than or equal to 0.2wt%, preferably, the asphaltene content is less than or equal to 0.1wt%, the sulfur content is less than or equal to 1500ppm, the nitrogen content is less than or equal to 1500ppm, the carbon residue content is less than or equal to 2wt%, preferably, the carbon residue content is less than or equal to 1.5wt%, the metal Ni+V content is less than or equal to 5ppm, preferably, and the metal Ni+V content is less than or equal to 3ppm relative to the mass of the vacuum residue raw material.
The method for producing bright stock from vacuum residuum, disclosed by the invention, has the advantages that the sulfur content in refined light deoiling is less than or equal to 2ppm, the nitrogen content is less than or equal to 2ppm, the boiling point of T5 is more than or equal to 300 ℃, the boiling point of T50 is more than or equal to 550 ℃, and the boiling point of T95 is more than or equal to 710 ℃.
The method for producing the bright stock from the vacuum residuum, disclosed by the invention, has the advantages that the yield of the high-viscosity bright stock is more than or equal to 58wt% relative to the light deoiling quality, the viscosity index is more than or equal to 120, and the pour point is less than or equal to-20 ℃.
The invention is illustrated below by means of specific examples.
Example 1
The vacuum residuum feedstock properties are set forth in Table 1.
Taking vacuum residuum as raw material, carrying out propane deasphalting process in a propane deasphalting device comprising an extraction tower and a sedimentation tower to obtain deasphalted oil, wherein the operation conditions are as follows: feeding 1.3kg/h, extracting temperature 70-80 ℃, extracting pressure 4.5MPa, settling temperature 70-80 ℃ and agent-oil mass ratio 4:1, the yield of deasphalted oil is 55% and the yield of deasphalted asphalt is 45%. The deasphalted oil properties are listed in table 2.
The hydrotreating unit comprises a hydrotreating catalyst b and a with a content ratio of 0.3:1, wherein the catalyst a comprises (by mass) 74% of aluminum oxide, 5% of nickel oxide, 10% of molybdenum oxide, 10% of tungsten oxide and 1% of phosphorus pentoxide; the catalyst b consists of 20% of aluminum oxide, 55% of silicon oxide-aluminum oxide, 10% of Y molecular sieve, 4% of nickel oxide and 11% of tungsten oxide. The hydrotreating reaction conditions include: the reaction temperature is 380 ℃, the partial pressure of the reaction hydrogen is 13MPa, and the volume space velocity is 0.6h -1 The hydrogen oil volume ratio is 900:1. the properties of the refined deasphalted oil are shown in Table 3.
Hydroisomerization unit, hydroisomerization catalyst composition (by mass): 24.2% of aluminum oxide, 75% of ZSM-22 molecular sieve and 0.8% of palladium chloride. The hydroisomerization reaction conditions include: the reaction temperature is 373 ℃, the partial pressure of the reaction hydrogen is 12.5MPa, and the volume space velocity is 0.8h -1 The hydrogen oil volume ratio is 600:1.
a make-up refining unit, the reaction conditions including: the reaction temperature is 230 ℃, the partial pressure of the reaction hydrogen is 13MPa, and the volume space velocity is 1.5h -1 The hydrogen oil volume ratio is 500:1.
the product properties are shown in Table 4.
Example 2
The vacuum residuum feedstock properties are set forth in Table 1.
Taking vacuum residuum as raw material, carrying out propane deasphalting process in a propane deasphalting device comprising an extraction tower and a sedimentation tower to obtain deasphalted oil, wherein the operation conditions are as follows: feeding 1.5kg/h, extracting temperature 60-70 ℃, extracting pressure 5.0MPa, settling temperature 65-75 ℃ and agent-oil mass ratio 3:1, the yield of deasphalted oil is 60% and the yield of deasphalted asphalt is 40%. The deasphalted oil properties are listed in table 2.
Hydroprocessing unit, content ratio of hydroprocessing catalyst b to aThe catalyst a comprises (by mass) 70% of aluminum oxide, 6% of nickel oxide, 10% of molybdenum oxide, 12% of tungsten oxide and 2% of phosphorus pentoxide, wherein the ratio is 0.05:1. The catalyst b consists of 50% of aluminum oxide, 17% of silicon oxide-aluminum oxide, 5% of Y molecular sieve, 7% of nickel oxide and 21% of tungsten oxide. The hydrotreating reaction conditions include: the reaction temperature is 375 ℃, the partial pressure of the reaction hydrogen is 12.5MPa, and the volume space velocity is 0.8h -1 The hydrogen oil volume ratio is 800:1. the properties of the refined deasphalted oil are shown in Table 3.
Hydroisomerization unit, hydroisomerization catalyst composition (by mass): 35% of aluminum oxide, 20% of ZSM-22 molecular sieve, 44.5% of ZSM-23 molecular sieve and 0.5% of chloroplatinic acid. The hydroisomerization reaction conditions include: the reaction temperature is 373 ℃, the partial pressure of the reaction hydrogen is 12MPa, and the volume space velocity is 0.6h -1 The hydrogen oil volume ratio is 600:1.
a make-up refining unit, the reaction conditions including: the reaction temperature is 220 ℃, the partial pressure of the reaction hydrogen is 13MPa, and the volume space velocity is 1.7h -1 The hydrogen oil volume ratio is 500:1.
the product properties are shown in Table 4.
Example 3
The vacuum residuum feedstock properties are set forth in Table 1.
Taking vacuum residuum as raw material, carrying out propane deasphalting process in a propane deasphalting device comprising an extraction tower and a sedimentation tower to obtain deasphalted oil, wherein the operation conditions are as follows: 1.2kg/h of feed, 80-90 ℃ of extraction temperature, 7.0MPa of extraction pressure, 90-100 ℃ of sedimentation temperature and 5 of quality ratio of agent oil: 1, the yield of deasphalted oil is 70% and the yield of deasphalted asphalt is 30%. The deasphalted oil properties are listed in table 2.
The hydrotreating unit comprises a hydrotreating catalyst b and a with a content ratio of 0.5:1, wherein the catalyst a comprises (by mass) 70% of aluminum oxide, 6.5% of nickel oxide, 21.5% of molybdenum oxide and 2% of phosphorus pentoxide; the catalyst b comprises 20% of aluminum oxide, 52% of silicon oxide-aluminum oxide, 8% of Y molecular sieve, 5% of beta molecular sieve, 3.2% of nickel oxide and 11.8% of tungsten oxide. The hydrotreating reaction conditions include: the reaction temperature is 385 ℃, the partial pressure of the reaction hydrogen is 14MPa, and the volume space velocity is 0.5h -1 The hydrogen oil volume ratio is 1000:1. the properties of the refined deasphalted oil are shown in Table 3.
Hydroisomerization unit, hydroisomerization catalyst composition (by mass): 24% of aluminum oxide, 75.4% of ZSM-23 molecular sieve and 0.6% of ammonium platinum nitrate. The hydroisomerization reaction conditions include: reaction temperature 377 ℃, partial pressure of reaction hydrogen 12MPa and volume space velocity 0.5h -1 The hydrogen oil volume ratio is 800:1.
a make-up refining unit, the reaction conditions including: the reaction temperature is 230 ℃, the partial pressure of the reaction hydrogen is 14MPa, and the volume space velocity is 1.6h -1 The hydrogen oil volume ratio is 500:1.
the product properties are shown in Table 4.
Comparative example 1
This comparative example is used to illustrate the method of producing lube base stock in the existing laozhen process. The raw material was the same as in example 1, and the solvent deasphalting process was the same as in example 1, to obtain a deasphalted oil, and the deasphalted oil was subjected to solvent refining. The solvent refining process selects furfural with 97 percent (mass) purity and 8.0mgKOH/100ml acidity as solvent, and the raffinate oil is obtained as solvent refined oil under the conditions of extraction temperature of 80 ℃ and solvent-oil ratio of 4:1 and normal pressure. And then the solvent refined oil is subjected to solvent dewaxing, wherein the solvent is a mixture of methyl ethyl ketone and toluene, the volume ratio is 60/40, and the dewaxing conditions are as follows: the ratio of the agent to the oil is 4.5:1, the temperature of the raw materials is 65 ℃, the temperature of the solvent is 32 ℃, and the final cooling temperature and the filtering temperature are both-20 ℃, thus obtaining dewaxed oil. The dewaxed oil is adsorbed and refined by clay under the following operation conditions: the contact temperature of the dewaxed oil and the carclazyte is 86 ℃, the addition amount of the carclazyte accounts for 5% of the mass of the dewaxed oil, the top temperature of the evaporation tower is 130-140 ℃, the bottom temperature of the evaporation tower is 250 ℃, the contact time of the dewaxed oil and the carclazyte is 30min, the primary filtration temperature is 130-140 ℃, the secondary filtration temperature is 120-130 ℃, and the properties of the obtained lubricating oil are shown in Table 4.
Comparative example 2
This comparative example is intended to illustrate the manner in which other solvent deasphalting and solvent dewaxing and hydrogenation processes are combined to produce a lubricant base oil. The feedstock was identical to example 2 and the solvent deasphalting procedure was identical to the propane deasphalting procedure of example 2 to obtain a deasphalted oil, which was solvent dewaxed using a mixture of methyl ethyl ketone and toluene in a volume ratio of 60/40 under the following dewaxing conditions: the ratio of the agent to the oil is 4.5:1, the temperature of the raw materials is 65 ℃, the temperature of the solvent is 32 ℃, and the final cooling temperature and the filtering temperature are both-20 ℃, thus obtaining dewaxed oil. The dewaxed oil is sequentially subjected to a hydrogenation treatment unit in the embodiment 2, the reaction conditions are the same as those in the embodiment 2, hydrofined oil is obtained, distillate oil with the temperature of more than 280 ℃ is separated from the hydrofined oil through a fractionation unit, and the separated hydrofined oil with the temperature of more than 280 ℃ sequentially enters a hydroisomerization unit and a complementary refining unit in the embodiment 2, and the product properties are shown in the table 4.
Comparative example 3
This comparative example is used to illustrate the prior art method of producing lube base oils by combining solvent deasphalting with a hydrogenation process. The raw material is the same as that of example 3, the solvent deasphalting process is the same as that of example 3 propane deasphalting process, deasphalted oil is obtained, the deasphalted oil is subjected to a hydrotreating unit, the hydrotreating catalyst is catalyst a in example 3, namely a single hydrotreating catalyst, and the reaction temperature is 385 ℃, the hydrogen partial pressure is 14MPa, and the volume space velocity is 0.5h -1 The hydrogenation pretreatment is carried out under the condition of hydrogen-oil ratio of 1000:1 to obtain the hydrofining oil, then the distillate oil with the temperature higher than 280 ℃ is separated from the hydrofining oil through a fractionation unit, the separated hydrofining oil with the temperature higher than 280 ℃ enters a hydroisomerization unit, the process conditions are the same as those of the example 3, and finally the reaction product is subjected to the reaction at 230 ℃ and the hydrogen partial pressure of 14MPa and the volume space velocity of 1.7h -1 The product properties are shown in Table 4 after the finishing reaction is carried out at a hydrogen to oil ratio of 500:1.
TABLE 1 vacuum residuum Properties
Table 2 deasphalted oily matter
Table 3 properties of refined deasphalted oil
TABLE 4 lubricating oil product Properties
* The yield is the mass yield relative to the propane deasphalted oil entering the subsequent corresponding step.
As can be seen by combining example 1 and comparative example 1, the invention has significant product yield and quality advantages over the old three-set process; as can be seen from example 2 and comparative example 2, the present invention has the advantage of high product yield under the condition of equivalent product properties compared with the solvent refining-solvent dewaxing-hydrogenation combined process technology; as can be seen from example 3 and comparative example 3, the invention has the advantages of short process and good product properties while the yield is equivalent when processing the inferior raw materials. In general, the invention has flexible processing scheme for raw materials with different degrees of quality, and has obvious technical advantages in terms of technological process and product properties compared with the prior art.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (14)
1. A method for producing bright stock from vacuum residuum, comprising the steps of:
(1) Solvent deasphalting a vacuum residuum feedstock to obtain a deasphalted oil;
(2) The hydrogen and the deasphalted oil are contacted with a catalyst a and a catalyst b in sequence to carry out hydrotreatment, so as to obtain refined deasphalted oil; the catalyst a comprises 60-80 wt% of carrier, 15-30 wt% of metal oxide and 0-10 wt% of auxiliary agent, wherein the auxiliary agent is one or more of fluorine, boron and phosphorus; the carrier is alumina and/or silica-alumina, and the metal oxide is one or more of nickel, molybdenum, tungsten and cobalt metal oxides; the catalyst b comprises 50-80 wt% of carrier, 5-30 wt% of molecular sieve and 15-30 wt% of active metal, wherein the carrier is alumina and/or silica-alumina, the molecular sieve is Y molecular sieve and/or beta molecular sieve, and the active metal is one or more of nickel, molybdenum, tungsten and cobalt; the content of the catalyst b is 1-60% by volume and based on the catalyst a;
(3) Contacting the refined deasphalted oil in the step (2) with a hydroisomerization catalyst to carry out hydroisomerization reaction to obtain a hydroisomerization product;
(4) Carrying out contact reaction on the hydroisomerization product obtained in the step (3), hydrogen and a refined catalyst, and separating the obtained product into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock;
separating the product into light fuel oil, low-viscosity lubricating oil base oil and high-viscosity bright stock at 260-300 ℃ at a first cutting point and 500-570 ℃ at a second cutting point;
the yield of the high-viscosity bright stock is more than or equal to 58 weight percent, the viscosity index is more than or equal to 120, and the pour point is less than or equal to-20 ℃ relative to the mass of the deasphalted oil.
2. The method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the catalyst a comprises 65-78 wt% of carrier, 18-28 wt% of metal oxide and 0-7 wt% of auxiliary agent.
3. The method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the vacuum residuum raw material is one or more of paraffin-based vacuum residuum, intermediate-based vacuum residuum, and cycloalkyl vacuum residuum.
4. The process for producing bright stock from vacuum residuum as claimed in claim 1 wherein the vacuum residuum feedstock has a T5 boiling point of at least 500 ℃, a T70 boiling point of at least 700 ℃, and a 100 ℃ kinematic viscosity of at least 118mm 2 /s。
5. The method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the first cutting point is 260-280 ℃ and the second cutting point is 510-550 ℃.
6. The method for producing bright stock from vacuum residuum as claimed in claim 1 wherein the solvent deasphalting in step (1) is a two-stage extraction-settling process.
7. The process for producing bright stock from vacuum residuum as claimed in claim 1 wherein the solvent deasphalting conditions in step (1) comprise: the mass ratio of the solvent to the vacuum residue is 3-9:1, the temperature of the top of the extraction tower is 50-100 ℃, the sedimentation temperature is 65-110 ℃, the extraction pressure is 3.0-7.0 MPa, and the solvent is propane or butane.
8. The method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the hydrogenation treatment condition in the step (2) is that the reaction temperature is 355-400 ℃, the partial pressure of the reaction hydrogen is 8-15 MPa, and the volume space velocity is 0.4-1.2 h -1 The volume ratio of the hydrogen oil is 500-1000: 1.
9. the method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the hydroisomerization reaction condition in the step (3) is that the reaction temperature is 340-390 ℃, the partial pressure of the reaction hydrogen is 10-15 MPa, and the volume space velocity is 0.3-1.0 h -1 The volume ratio of the hydrogen oil is 500-1000: 1.
10. the method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the hydroisomerization catalyst in step (3) comprises a carrier, a molecular sieve and an active metal, the carrier is alumina and/or silica-alumina, the molecular sieve is one or more of ZSM-5, ZSM-22 and ZSM-23, and the active metal is platinum and/or palladium.
11. The method for producing bright stock oil from vacuum residuum as claimed in claim 10, wherein the hydroisomerization catalyst comprises 10wt% to 50wt% of the carrier, 50wt% to 80wt% of the molecular sieve, and 0.1wt% to 1wt% of the active metal.
12. The method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the yield of deasphalted oil is 30wt% to 70wt%, the pour point is less than or equal to 56 ℃, the viscosity index is less than or equal to 150, the asphaltene content is less than or equal to 0.2wt%, the sulfur content is less than or equal to 1500ppm, the nitrogen content is less than or equal to 1500ppm, the carbon residue content is less than or equal to 2wt%, and the metallic ni+v content is less than or equal to 5ppm relative to the mass of the vacuum residuum raw material.
13. The method for producing bright stock of claim 12, wherein the deasphalted oil has an asphaltene content of 0.1 wt.% or less.
14. The method for producing bright stock from vacuum residuum as claimed in claim 1, wherein the sulfur content in the refined deasphalted oil is less than or equal to 2ppm, the nitrogen content is less than or equal to 2ppm, the T5 boiling point is more than or equal to 300 ℃, the T50 boiling point is more than or equal to 550 ℃, and the T95 boiling point is more than or equal to 710 ℃.
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| CN101768470A (en) * | 2008-12-26 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing bright stock |
| CN102732301A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Method for producing bright stock |
| CN112126463A (en) * | 2020-07-20 | 2020-12-25 | 中国科学院大连化学物理研究所 | High-viscosity lubricating oil base oil and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768470A (en) * | 2008-12-26 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing bright stock |
| CN102732301A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Method for producing bright stock |
| CN112126463A (en) * | 2020-07-20 | 2020-12-25 | 中国科学院大连化学物理研究所 | High-viscosity lubricating oil base oil and preparation method thereof |
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