CN111378499A - Combined method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil - Google Patents
Combined method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil Download PDFInfo
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- CN111378499A CN111378499A CN201811652326.7A CN201811652326A CN111378499A CN 111378499 A CN111378499 A CN 111378499A CN 201811652326 A CN201811652326 A CN 201811652326A CN 111378499 A CN111378499 A CN 111378499A
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- 239000002199 base oil Substances 0.000 title claims abstract description 42
- 239000010692 aromatic oil Substances 0.000 title claims abstract description 35
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000003921 oil Substances 0.000 claims abstract description 86
- 239000002904 solvent Substances 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000000605 extraction Methods 0.000 claims abstract description 46
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000007670 refining Methods 0.000 claims description 19
- 239000011959 amorphous silica alumina Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012296 anti-solvent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910017318 Mo—Ni Inorganic materials 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 229910017313 Mo—Co Inorganic materials 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 24
- 229920001971 elastomer Polymers 0.000 abstract description 23
- 239000005060 rubber Substances 0.000 abstract description 23
- 238000011049 filling Methods 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- 238000000638 solvent extraction Methods 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 238000000513 principal component analysis Methods 0.000 description 10
- 239000008186 active pharmaceutical agent Substances 0.000 description 6
- -1 bicyclic aromatic hydrocarbons Chemical class 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a combined method for producing lubricating oil base oil and environment-friendly aromatic oil. API I lubricating oil base oil with low content of polycyclic aromatic hydrocarbon produced by 'three sets of old' processes is extracted by a solvent, and the extraction depth is controlled, so that the aromatic hydrocarbon in raffinate oil is further reduced; then, the color and the stability are improved and the viscosity index is increased through hydrofining and hydro-upgrading, so that the indexes of the base oil of the API III lubricating oil are reached; meanwhile, aromatic hydrocarbon is enriched in the extract oil, so that the content of polycyclic aromatic hydrocarbon in the extract oil is less than 3.0 percent, and the content of aromatic hydrocarbon is more than 20 percent, and excellent rubber filling oil for the tire industry is obtained. The method can simultaneously obtain two products with high added values by modifying the I-type base oil, and has the advantages of high yield of target products, low operation cost and no waste treatment in the processing process.
Description
Technical Field
The invention relates to a combination method for simultaneously obtaining environment-friendly aromatic oil and III-class lubricating oil base oil, in particular to a method for producing III-class lubricating oil base oil by adopting a solvent secondary extraction process to obtain the environment-friendly aromatic oil and a hydrorefining/hydroupgrading process.
Background
The rubber extender oil plays an important role as an auxiliary agent in the rubber industry, can improve the plasticity of rubber materials, reduce the viscosity of the rubber materials and the temperature during mixing, can promote the dispersion and mixing of other compounding agents, plays a role in lubricating the extrusion of calendering, can reduce the hardness of vulcanized rubber and improve the performance of the vulcanized rubber. The rubber filling oil can also increase the rubber yield, reduce the cost, improve the processability and the service performance of the rubber and has important position in the rubber processing industry.
As a rubber filling oil with the largest dosage and wide application, aromatic oil (DAE) has good compatibility with rubber, can endow the tire with excellent performance such as good wet skid resistance and the like, is cheap and has good adaptability, and can be widely used in rubber such as Styrene Butadiene Rubber (SBR), Butadiene Rubber (BR), nitrile butadiene rubber (NBR/I R, CR) and products thereof, and the SBR, the NBR and the BR filled with the rubber filling oil have good processing performance and high tensile strength and tear strength. In the manufacture of rubber articles, particularly tires, conventional aromatic oils (DAE) are used which contain a significant amount of condensed ring aromatic hydrocarbons (PCA), with tires and rubber articles containing more or less PCA due to entrainment of aromatic oils. Along with the deep research on the toxicity of developed countries, the aromatic oil contains carcinogenic polycyclic aromatic hydrocarbon, and the problem that the aromatic oil causes harm to human bodies and the environment is accepted by the public. The European Union directive 2005/69/EC for the ban on rubber filling oils such as toxic aromatic oils in tire production was released at the end of 2005, and the PCA content (dimethyl sulfoxide extraction IP 346) must be used in tire production from 1/1 of 2010<3 percent of environment-friendly aromatic oil. The directive explicitly limits the total content of eight carcinogenic fused ring aromatics in DAE to no more than 10 mg/kg, with benzopyrene content no more than 1 mg/kg. Meanwhile, the aromatic oil used as rubber oil follows the principle of similar compatibility, needs to keep good intermiscibility with rubber, and has no adverse effect on the performance of rubber products, so that the environment-friendly aromatic oil ensures the content of PCA<3 percent, and simultaneously, the higher aromatic hydrocarbon content (the aromatic hydrocarbon content is that the carbon atoms on the aromatic ring account for the whole molecule in carbon type analysis)Percent of total number of carbon atoms CAValue expression, generally requiring CA>20%）。
The current production technology of the environment-friendly aromatic oil mainly comprises two schemes of solvent extraction and hydrogenation of the aromatic oil.
EP-A-417980 discloses ｃA process for the solvent extraction treatment of aromatic oils. The solvent extract oil of the refining process of the lubricating oil solvent is taken as the raw material, the polar solvent such as furfural, phenol and NMP is selected to carry out countercurrent extraction with the raw material to produce PCA<3%，CA>50 percent of environment-friendly aromatic oil. The technological process is simple, but a liquid-liquid extraction tower needs to be newly built on the basis of the existing solvent refining device so as to avoid the pollution of the environment-friendly aromatic oil product by the polycyclic aromatic hydrocarbon.
WO9844075 discloses a process for the reextraction treatment of aromatic oils with selective solvents. The solvent extract oil in the refining process of the lubricating oil solvent is used as a raw material, and dimethyl sulfoxide (DMSO) is used as a solvent to extract and produce the environment-friendly aromatic oil.
CN101591453A discloses a production method of environment-friendly rubber filling oil. Solvent such as furfural, dimethyl sulfoxide, NMP and the like is adopted for extraction to produce the environment-friendly rubber filling oil.
EP1260569-A2 discloses a process for the production of aromatic oils by hydrotreating. Mixing vacuum distillate oil and solvent extraction oil in a lubricating oil solvent refining process to serve as a raw material, and adopting a nickel-molybdenum or nickel-cobalt type hydrofining catalyst at the reaction pressure of 6.0-8.0 MPa, the reaction temperature of 265-320 ℃ and the airspeed of 0.5h-1Under the condition of (1), producing the environment-friendly aromatic oil. Adopts a nickel-molybdenum or nickel-cobalt type hydrofining catalyst, and the content of the solvent extract oil is not more than 50 percent. In addition, under the condition of hydrofining, in order to reduce the polycyclic aromatic hydrocarbon to meet the environmental protection quality index, the loss of the aromatic hydrocarbon value is more, the two indexes cannot be considered simultaneously, the hydrogen consumption is higher, and the operation cost is increased.
CN1351114A discloses a processing method of heavy aromatic oil. And in the second scheme, a combined solvent refining-hydrotreating process is adopted, heavy aromatic oil is firstly subjected to solvent refining, and then the extract oil is subjected to hydrotreating. The method has the disadvantages that the contents of polycyclic aromatic hydrocarbon, asphaltene and colloid in the extract oil after solvent extraction are greatly improved, the difficulty of hydrotreating is increased, and the service life of the catalyst is influenced.
CN103773443A discloses a method for producing high-viscosity-index lubricating oil base oil by using API I base oil as raw oil through hydro-upgrading. The API I base oil and hydrogen are mixed and then enter a hydro-upgrading reaction zone to be in contact reaction with an amorphous silicon-aluminum hydro-upgrading catalyst to generate a polycyclic cycloparaffin ring-opening reaction, and the reaction effluent is fractionated to obtain a lubricating oil base oil product with the viscosity index meeting the requirements of the API III base oil. The technology has the following disadvantages: after the I-type base oil is subjected to hydro-upgrading, irrational components (polycyclic naphthenic hydrocarbon and a small amount of polycyclic aromatic hydrocarbon) of some lubricating oil are converted into ideal components, but inevitable cracking reaction simultaneously reduces the yield of a target product, and the poorer the raw material is, the lower the yield is, and meanwhile, the environment-friendly aromatic oil cannot be produced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a combined method for producing environment-friendly aromatic oil by a solvent secondary extraction process with mild process conditions and obtaining II-type lubricating oil base oil by a hydrofining/hydro-upgrading process.
The invention relates to a combination method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil, which comprises the following steps:
(1) the raw material of the I-type base oil firstly enters an extraction tower and fully contacts with a solvent in the extraction tower for extraction to obtain raffinate oil with further reduced aromatic hydrocarbon content and extract oil rich in polycyclic aromatic hydrocarbon;
(2) recovering the solvent from the raffinate oil obtained in the step (1) to obtain the lubricating oil base oil with reduced aromatic hydrocarbon content; after the obtained extract oil is subjected to solvent recovery, environment-friendly aromatic oil with the content of condensed ring aromatic hydrocarbons PCA <3% and the content of aromatic carbon CA >20% is obtained;
(3) mixing the lubricating oil base oil obtained in the step (2) with hydrogen, and allowing the mixture to enter a hydrofining reaction zone for a refining reaction to remove sulfur and nitrogen and simultaneously saturate part of aromatic hydrocarbon;
(4) and (4) allowing the hydrofining effluent obtained in the step (3) to enter a hydro-upgrading reaction zone for hydro-upgrading, and performing gas-liquid separation and fractionation on the hydro-upgrading product to obtain III-type lubricating oil base oil with increased viscosity index.
In the invention, the hydrofining reaction zone in the step (3) sequentially comprises Mo-Ni type and Mo-Co type hydrofining catalysts according to the material flow sequence.
The method comprises the steps of performing countercurrent full contact in an extraction tower by utilizing the specific gravity difference of raw oil and a solvent to perform extraction, dissolving polycyclic aromatic hydrocarbons in the raw oil into the solvent, automatically settling the polycyclic aromatic hydrocarbons in the bottom area of the tower, automatically lifting the extracted raw oil to the top of the tower, and respectively allowing raffinate oil and extract oil to flow out from the top and the bottom of the extraction tower, wherein the solvent comprises a main solvent and an anti-solvent, the solubility of the main solvent to the aromatic hydrocarbons is greater than that to the alkanes, and the anti-solvent can improve the selectivity of the solvent to the polycyclic aromatic hydrocarbons.
The raw oil of the method of the invention is I-type base oil which is subjected to traditional solvent dewaxing, solvent refining and clay refining. The solvent used for extraction contains a main solvent and an anti-solvent, wherein the main solvent can be one or more of furfural, sulfolane, dimethyl sulfone, dimethyl sulfoxide and N-methylpyrrolidone (NMP); the anti-solvent used for extraction is one or more of methanol, ethanol, benzyl alcohol, ethylene glycol, formic acid, acetic acid and morpholine. The solubility of the main solvent to the aromatic hydrocarbon is larger than that to the alkane, and the anti-solvent can improve the selectivity of the solvent to the polycyclic aromatic hydrocarbon. Wherein the content of the anti-solvent is 1-10% of the weight of the solvent, and the content of the main solvent is 90-99% of the weight of the solvent.
The extraction process conditions of the extraction tower in the step (1) are as follows: the volume ratio of solvent oil (raw oil) to solvent oil (raw oil) is 0.5: 3-3: 0.5, preferably 1: 1-2: 1; the temperature of the tower bottom is 10-50 ℃, the temperature of the tower top is 10-50 ℃ higher than that of the tower bottom, the temperature of the tower bottom is preferably 15-40 ℃, and the temperature of the tower top is 20-40 ℃ higher than that of the tower bottom; the extraction pressure is 0.1-0.4 MPa, preferably 0.1-0.3 MPa.
In the hydrofining reaction zone, the volume ratio of the molybdenum-nickel hydrofining catalyst to the molybdenum-cobalt hydrofining catalyst is 0.5: 1-2.0: 1, preferably 1.0: 1-1.5: 1. the volume ratio of the hydrofining reaction zone to the hydro-upgrading reaction zone is 0.5: 1-2.0: 1, preferably in a volume ratio of 1.0: 1-1.5: 1, using a hydro-upgrading catalyst containing amorphous silica-alumina in the hydro-upgrading reaction zone.
The hydrofining reaction zone uses a conventional hydrofining catalyst, the active metal components of the hydrofining catalyst are VIB group and VIII group metals, and the catalyst is vulcanized before being used, so that the hydrofining active metal is in a vulcanized state in the reaction process. The VIB group metal is selected from Mo and/or W, and the content of the metal is preferably 10 to 35 weight percent in terms of oxide; the group VIII metal is selected from Co and/or Ni, preferably in an amount of 3 to 7 wt.% calculated as oxide. Wherein the atomic ratio VIB/(VIB + VIII) is 0.30-0.70, preferably 0.45-0.50.
The carrier of the hydrogenation modification catalyst containing amorphous silica-alumina used in the method contains amorphous silica-alumina. The amorphous silica-alumina can be amorphous silica-alumina commonly used in the field of hydro-upgrading. The carrier of the hydro-upgrading catalyst contains 20wt% -80 wt% (wt% weight percentage) of amorphous silica-alumina, and the specific surface area of the carrier is 200-500 m2The pore volume is 0.15-0.90 mL/g, and the infrared acidity is generally 0.30-0.50 mmol/g; preferably 40 to 70 weight percent of amorphous silica-alumina, and the specific surface area of the amorphous silica-alumina is 300 to 400 m2The pore volume is 0.40-0.70 mL/g. The pore distribution characteristics of the catalyst carrier are as follows: the pore volume of the pores with the diameters of 4-16 nm accounts for 50-90% of the total pore volume, and the pore volume of the pores with the diameters larger than 20nm does not exceed 10% of the total pore volume. The invention relates to amorphous silica-alumina, which has the physicochemical properties that: the silica content is generally from 5% to 70% by weight, preferably from 15% to 45% by weight; the pore volume is generally 0.6-1.6 mL/g, preferably 1.0-1.4 mL/g; the specific surface is generally 400-550 m2A ratio of 450 to 500 m/g is preferred2(ii)/g; the infrared acidity is usually 0.25 to 0.55mmol/g, preferably 0.35 to 0.45 mmol/g. The hydro-upgrading catalyst contains 10-30 wt% of group VIB metal (calculated by oxide) and 4-10 wt% of group VIII metal (calculated by oxide). The specific surface area of the hydro-upgrading catalyst is 220-300 m2The pore volume is 0.3-0.6 mL/g, and the pore volume with the pore diameter of 3-10 nm accounts for 75-95% of the total pore volume, preferably 85-95%.
The operating conditions of the hydrofining reaction zone are as follows: the reaction pressure is 0.5-18.0 MPa, preferably 6.0-15.0 MPa; the reaction temperature is 230-430 ℃, and preferably 280-380 ℃; the volume ratio of hydrogen to oil is 200-1500, preferably 600: 1-800: 1; the volume airspeed is 0.5-10.0 h-1Preferably 1.0 to 3.0 hours-1。
The operation conditions of the hydro-upgrading reaction zone are as follows: the reaction pressure is 0.5-18.0 MPa, preferably 6.0-15.0 MPa; the reaction temperature is 230-430 ℃, and preferably 350-410 ℃; the volume ratio of hydrogen to oil is 200-1500, preferably 600: 1-1000: 1; the volume airspeed is 0.5-10.0 h-1Preferably 0.8 h-1～1.5h-1。
The environment-friendly aromatic oil is produced by adopting a solvent extraction technology taking traditional vacuum distillate oil and deasphalted oil as raw materials, although a large amount of polycyclic aromatic hydrocarbon can be extracted to reach the European Union standard, the product yield is low, or eight polycyclic aromatic hydrocarbons are difficult to be qualified. Further according to the general knowledge in the art and the prior art, the solvent refined extract oil is subjected to deep hydrogenation saturation to meet the content of condensed ring aromatics PCA using a hydrofining catalyst<The requirement of 3 percent is required to be carried out under a harsher condition, the extract oil belongs to heavy distillate oil and contains higher metal, colloid, asphaltene and other substances, so that the hydrogen consumption in the whole hydrogenation process is increased, the activity of the catalyst is damaged, more importantly, when the polycyclic aromatic hydrocarbon is hydrogenated and saturated, a large amount of monocyclic and bicyclic aromatic hydrocarbons are also hydrogenated and saturated, and the aromatic hydrocarbon content of the aromatic hydrocarbon oil product is lower (C)A<10%) and has greatly reduced compatibility with rubber and is not suitable for use in tire production.
The method of the invention takes I-type lubricating oil base oil as a raw material, has mild process conditions, can obtain two target products by killing two birds with one stone, and has the advantages of good product quality and the like. In the method, the raw oil is I-type lubricating oil base oil which is subjected to solvent dewaxing, solvent refining and clay refining, the contents of polycyclic aromatic hydrocarbon, colloid, asphaltene and heavy metal in the raw oil are greatly reduced, eight polycyclic aromatic hydrocarbon problems do not exist, secondary solvent extraction can be carried out under a mild condition, aromatic hydrocarbon is redistributed in two target products, a small amount of aromatic hydrocarbon in the raw material is enriched in the extracted oil, and the solvent is recovered to obtain the environment-friendly aromatic oil for tires, which meets European Union standards, and has the contents of the polycyclic aromatic hydrocarbon (PCA) of less than 3% and the aromatic Carbon (CA) of more than 20%.
Meanwhile, the raffinate oil raw material with reduced aromatic hydrocarbon content is mixed with hydrogen, firstly contacts with a hydrofining catalyst loaded in a hydrofining reaction zone, and preferentially hydrogenates and saturates the polycyclic aromatic hydrocarbon part with more than three rings under mild conditions. The product of the hydrorefining reaction zone enters a hydroupgrading reaction zone to contact with a hydroupgrading catalyst, and further the residual polycyclic aromatic hydrocarbons with more than three rings undergo a ring-opening reaction to generate long side chain monocyclic and bicyclic aromatic hydrocarbons with high viscosity indexes and remain in the generated oil. The hydrofining reaction zone comprises a Mo-Ni type catalyst and a Mo-Co type catalyst, and although the Mo-Ni type hydrofining catalyst has better denitrification performance and saturation performance and also has better effect on removing simple sulfides, the effect on removing thiophene aromatic compounds in raw materials is not ideal due to the existence of steric hindrance. In the invention, after passing through the Mo-Ni type hydrofining catalyst, the catalyst passes through the Mo-Co type catalyst bed layer to carry out transalkylation reaction at a higher temperature, so that the steric hindrance effect of sulfur can be eliminated, and thiophene compounds are converted into biphenyl structures; then through the hydrogenation modification catalyst bed, the C-C bond in the biphenyl compound is broken to generate monocyclic or bicyclic aromatic hydrocarbon, then the modification is carried out to continue the ring opening, and finally the long side chain monocyclic naphthenic hydrocarbon or aromatic hydrocarbon with higher viscosity index is generated. Therefore, by adopting the combination of the hydrofining catalyst gradation and the hydro-upgrading catalyst, the yield and the viscosity index of a target product can be effectively improved, the color and the stability are improved, and the indexes of the base oil of the III-class lubricating oil are reached. The hydrogenation byproduct has low sulfur and nitrogen content and can be used as a raw material of low aromatic solvent oil. The method can obtain two useful products at one stroke, has high yield of the target product, simultaneously has low operation cost, and has no waste treatment problem in the processing process.
Detailed Description
The solvent extraction-hydrotreatment combined process for producing the environment-friendly tire aromatic oil comprises the following contents: the raw oil enters from the lower part of a solvent extraction tower, and the extraction solvent enters from the upper part of the solvent extraction tower (a packed tower, the number of theoretical extraction stages is generally 5 stages). The method comprises the steps of utilizing the density difference of raw oil and a solvent to perform extraction through countercurrent contact in an extraction tower, dissolving more than three rings of components such as fused ring aromatic hydrocarbon, asphalt and the like into the solvent in the process, settling at the bottom of the extraction tower to obtain extract oil, extracting raffinate oil from the top of the extraction tower, separating by a raffinate oil solvent recovery device to obtain a recovered solvent and lubricating oil base oil, extracting the extract oil from the lower part of the extraction tower, separating by a extract oil solvent recovery device to obtain the recovered solvent and environment-friendly tire rubber filling oil meeting European Union standards, and returning the recovered solvents of the extract oil and the raffinate oil to the solvent extraction device for recycling. The lubricating oil base oil after solvent recovery and hydrogen are mixed and enter a hydrofining reaction zone to remove sulfur and nitrogen and simultaneously saturate part of aromatic hydrocarbon, and then enter a hydro-upgrading reaction zone to open the aromatic ring of the remaining polycyclic aromatic hydrocarbon to generate monocyclic or bicyclic cycloalkane with long side chains with higher viscosity index, so that the III-class lubricating oil base oil with better color and stability and higher viscosity index is obtained.
The hydro-upgrading catalyst of the present invention may be a commercial catalyst according to its properties or may be prepared according to the knowledge in the art.
The catalyst containing amorphous silica-alumina can be prepared according to the prior patent technologies such as CN97122134.0 and the like, for example, as described in CN97122134.0, a catalyst carrier contains amorphous silica-alumina and a small-pore alumina binder, the content of the amorphous silica-alumina is 40wt% -80 wt%, the content of the amorphous silica-alumina contains 15wt% -50 wt%, and the surface area of the carrier is 300-450 m2The pore volume is 0.45-0.80 mL/g, and the infrared acidity is 0.30-0.50 mmol/g. Contains 10-30 wt% of group VIB metal (calculated by oxide) and 4-10 wt% of group VIII metal (calculated by oxide).
The hydrofining catalyst of the invention can select commercial catalysts according to properties, such as hydrogenation catalysts of 3936, FF-36, FHUDS-5 and the like developed and produced by the smooth petrochemical research institute. It can also be prepared according to the prior patent technologies such as CN98114346.6, CN01114183.2, CN03134003.2 and the like.
The following examples are provided to illustrate the details and effects of the method of the present invention.
The following examples further illustrate the process provided by the present invention, but do not limit the scope of the invention. The properties of the raw materials treated by the method are shown in table 1, and the physical properties of the hydro-upgrading catalyst are shown in table 2.
Table 1 properties of the raw materials used for the tests.
Table 2 hydro-upgrading catalyst properties.
Example 1
The I-type 250SN base oil which is obtained by subjecting Daqing three-line distillate oil to solvent dewaxing, solvent refining and clay refining is taken as a raw material, and the properties of the base oil are shown in Table 1. The temperature of the top of the extraction tower is 75 ℃, the temperature of the bottom of the extraction tower is 35 ℃, the extraction pressure is 0.1MPa, the extraction solvent is a mixed solvent of furfural and ethanol, wherein the ethanol content is 5% of the total solvent weight, the mass ratio of the solvent to the raw oil is 1:1, the raffinate oil and the extract oil are recovered by adopting nitrogen stripping, the residual pressure is 500mmHg, the gas injection amount is 0.5L/KG, and the temperature is 130 ℃. The pressure of hydrofining/hydro-upgrading of raffinate oil after solvent recovery is 15.0MPa, and the volume space velocity of hydrofining/hydro-upgrading (2.0 h)-1/2.0h-1) The volume ratio of hydrogen to oil is 1000:1, the specific results obtained are shown in tables 3-4.
Example 2
The hydrofining catalyst selects FF-36 (molybdenum-nickel type) and FHUDS-5 (molybdenum-cobalt type), and the volume ratio of the catalyst is 1: the hydro-upgrading catalyst properties are shown in table 2.
The properties of the feed oil are shown in Table 1. The temperature at the top of the extraction tower is 75 ℃, the temperature at the bottom of the extraction tower is 35 ℃, the extraction pressure is 0.1MPa, the extraction solvent is a mixed solvent of furfural and ethanol, wherein the ethanol content is 5 percent of the total solvent weight, and the mass of the solvent and the raw oil isThe ratio is 1:1, the raffinate oil and the extract oil solvent are recovered by nitrogen stripping, the residual pressure is 500mmHg, the gas injection amount is 0.5L/KG, and the temperature is 130 ℃. The pressure of hydrofining/hydro-upgrading of raffinate oil after solvent recovery is 15.0MPa, and the volume space velocity of hydrofining/hydro-upgrading (2.0 h)-1/2.0h-1) The volume ratio of hydrogen to oil is 1000:1, the specific results obtained are shown in tables 3-4.
Example 3
The hydrofining catalyst selects FF-36 (molybdenum-nickel type) and FHUDS-5 (molybdenum-cobalt type), and the volume ratio of the catalyst is 1: the hydro-upgrading catalyst properties are shown in table 2.
The raw material oil is I-type 400SN base oil which is obtained by performing solvent dewaxing, solvent refining and clay refining on mixed distillate oil of Miocene, namely three-line and four-line, and the properties of the raw material oil are shown in Table 1. The temperature of the top of the extraction tower is 75 ℃, the temperature of the bottom of the extraction tower is 35 ℃, the extraction pressure is 0.1MPa, the extraction solvent is a mixed solvent of furfural and ethanol, wherein the ethanol content is 5% of the total solvent weight, the mass ratio of the solvent to the raw oil is 1:1, the raffinate oil and the extract oil are recovered by adopting nitrogen stripping, the residual pressure is 500mmHg, the gas injection amount is 0.5L/KG, and the temperature is 130 ℃. The pressure of hydrofining/hydro-upgrading of raffinate oil after solvent recovery is 15.0MPa, and the volume space velocity of hydrofining/hydro-upgrading (2.0 h)-1/2.0h-1) The volume ratio of hydrogen to oil is 1000:1, the specific results obtained are shown in tables 3-4.
Comparative example 1
The same feed, same solvent to feed ratio and same temperature profile in the extraction column as in example 1 were used, except that no hydrofinishing/hydro-upgrading process was used. Specific results obtained are shown in tables 3-4.
Comparative example 2
The same feedstock as in example 1 was used, except that the group I base oil was directly hydro-upgraded without solvent extraction. Specific results obtained are shown in tables 3-4.
Table 3 process conditions of comparative examples and examples.
Table 4 results of comparative example and example.
It can be seen from the properties of the products of examples 1-3 and comparative example 1 that API group I base oil with very low content of polycyclic aromatic hydrocarbon produced by the traditional solvent dewaxing, solvent refining and clay refining processes is used as a raw material, and a solvent secondary extraction process is adopted, so that lubricating oil base oil with higher viscosity index and better color and stability and environment-friendly aromatic oil for tires meeting European Union standards can be simultaneously produced.
Wherein, the embodiment 1-3 adopts the combined process of solvent secondary extraction and hydrofining/hydro-upgrading, not only can obtain aromatic carbon CAMore than 20 percent, less than 3 percent of PCA (principal component analysis), and the eight polycyclic aromatic hydrocarbons are qualified and meet the quality requirement of European Union instructions 2005/69/EC on environment-friendly aromatic rubber oil; meanwhile, the API I lubricating oil base oil raw material with the viscosity index of 60-90 undergoes secondary extraction, and under the condition that aromatic hydrocarbon is greatly reduced, under the action of an amorphous silicon-aluminum containing hydrogenation modified catalyst, a hydrogenation ring-opening reaction of cycloparaffin and aromatic hydrocarbon occurs, and the polycyclic cycloparaffin and the polycyclic aromatic hydrocarbon are converted into monocyclic cycloparaffin and paraffin hydrocarbon, so that the viscosity index of the raw material is greatly improved, and the API III lubricating oil base oil with the low sulfur and nitrogen content, the higher viscosity index, the better color and stability and the viscosity index greater than 120 can be obtained.
The scheme of hydrofining catalyst grading can remove sulfur and nitrogen as much as possible under very mild conditions, reduces hydrogenolysis reaction brought by sulfur and nitrogen removal of a hydroupgrading catalyst during ring opening of naphthenes and aromatics by hydrogenation, and has higher liquid yield and target product yield. Wherein the scheme of hydrofining catalyst grading is superior to the single-agent scheme.
Claims (14)
1. A combined method for producing high-quality lubricating oil base oil and environment-friendly aromatic oil comprises the following steps:
(1) the method comprises the following steps of (1) enabling a type I base oil raw material to enter an extraction tower firstly, and enabling the type I base oil raw material to be in full contact with a solvent in the extraction tower for extraction to obtain raffinate oil and extract oil;
(2) recovering the solvent from the raffinate oil obtained in the step (1) to obtain the lubricating oil base oil with reduced aromatic hydrocarbon content; after the obtained extract oil is subjected to solvent recovery, environment-friendly aromatic oil with the content of condensed ring aromatic hydrocarbons PCA <3% and the content of aromatic carbon CA >20% is obtained;
(3) mixing the lubricating oil base oil obtained in the step (2) with hydrogen, and allowing the mixture to enter a hydrofining reaction zone for a refining reaction to remove sulfur and nitrogen and simultaneously saturate part of aromatic hydrocarbon;
(4) the hydrofining effluent obtained in the step (3) enters a hydro-upgrading reaction zone for hydro-upgrading, and the hydro-upgrading product is subjected to gas-liquid separation and fractionation to obtain III-class lubricating oil base oil with increased viscosity index;
wherein, the hydro-upgrading reaction zone uses a hydro-upgrading catalyst containing amorphous silica-alumina.
2. The process of claim 1 wherein the hydrofinishing reaction zone contains a hydrofinishing catalyst having an active metal component selected from the group consisting of group VIB and group VIII metals, the group VIB metal being selected from Mo and/or W in an amount of from 10wt% to 25wt% on an oxide basis; the group VIII metal is selected from Co and/or Ni, and the content of the group VIII metal is 3-7 wt% calculated by oxide; the atomic ratio VIB/(VIB + VIII) is 0.30-0.70, preferably 0.45-0.50.
3. The process of claim 1, wherein the hydrofinishing reaction zone of step (3) comprises, in order of mass flow, a hydrofinishing catalyst of the Mo-Ni type and a hydrofinishing catalyst of the Mo-Co type.
4. The process according to claim 2, characterized in that the volume ratio of the Mo-Ni type hydrofinishing catalyst to the Mo-Co type hydrofinishing catalyst is 0.5: 1-2.0: 1, preferably 1.0: 1-1.5: 1.
5. the process of claim 1 wherein the volume ratio of the hydrofinishing reaction zone to the hydro-upgrading reaction zone is from 0.5: 1-2.0: 1, preferably 1.0: 1-1.5: 1.
6. the process according to claim 1, wherein the feedstock is a group I base oil obtained by solvent dewaxing, solvent refining, and clay refining.
7. The process of claim 1 wherein the solvent comprises a primary solvent and an anti-solvent; the main solvent is one or more selected from furfural, sulfolane, dimethyl sulfone, dimethyl sulfoxide and N-methyl pyrrolidone; the antisolvent is selected from one or more of methanol, ethanol, benzyl alcohol, ethylene glycol, formic acid, acetic acid, and morpholine.
8. The method of claim 1, wherein the primary solvent is present in an amount of 90 to 99% by weight of the solvent and the anti-solvent is present in an amount of 1 to 10% by weight of the solvent.
9. The method according to claim 1, wherein the extraction process conditions of the extraction column in the step (1) are as follows: the volume ratio of the solvent to the oil is 0.5: 3-3: 0.5, preferably 1: 1-2: 1; the temperature of the tower bottom is 10-50 ℃, and the temperature of the tower top is 10-50 ℃ higher than that of the tower bottom; preferably, the temperature of the tower bottom is 15-40 ℃, and the temperature of the tower top is 20-40 ℃ higher than that of the tower bottom; the extraction pressure is 0.1-0.4 MPa, preferably 0.1-0.3 MPa.
10. The method according to claim 1, wherein the carrier of the hydro-upgrading catalyst contains 20-80 wt% of amorphous silica-alumina, and the specific surface area of the carrier is 200-500 m2The pore volume is 0.15-0.90 mL/g, and the infrared acidity is 0.30-0.50 mmol/g; the pore distribution characteristics of the catalyst carrier are as follows: the pore volume of the pores with the diameters of 4-16 nm accounts for 50-90% of the total pore volume, and the pore volume of the pores with the diameters larger than 20nm does not exceed 10% of the total pore volume.
11. The method of claim 10, wherein the physical and chemical properties of the amorphous silica-alumina are: silicon oxide content5 to 70wt%, a pore volume of 0.6 to 1.6mL/g, and a specific surface area of 400 to 550m2The infrared acidity is 0.25-0.55 mmol/g.
12. The process of claim 10 wherein the hydro-upgrading catalyst comprises from 10wt% to 30wt% of a group vib metal oxide and from 4wt% to 10wt% of a group viii metal oxide; the specific surface area of the hydro-upgrading catalyst is 220-300 m2The pore volume is 0.3-0.6 mL/g, and the pore volume with the pore diameter of 3-10 nm accounts for 75-95% of the total pore volume.
13. The process of claim 1 wherein the hydrofinishing reaction zone is operated under the following conditions: the reaction pressure is 0.5-18.0 MPa, preferably 6.0-15.0 MPa; the reaction temperature is 230-430 ℃, and preferably 280-380 ℃; the volume ratio of hydrogen to oil is 200-1500, preferably 600: 1-800: 1; the volume airspeed is 0.5-10.0 h-1Preferably 1.0 to 3.0 hours-1。
14. The process of claim 1 wherein the hydro-upgrading reaction zone is operated under the following conditions: the reaction pressure is 0.5-18.0 MPa, preferably 6.0-15.0 MPa; the reaction temperature is 230-430 ℃, and preferably 350-410 ℃; the volume ratio of hydrogen to oil is 200-1500, preferably 600: 1-1000: 1; the volume airspeed is 0.5-10.0 h-1Preferably 0.8 h-1～1.5h-1。
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| CN103773493A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Production method of environmentally friendly aromatic hydrocarbon oil |
| CN103773442A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for production of high-viscosity-index lubricant base oil by hydrogenation |
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| CN103773493A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Production method of environmentally friendly aromatic hydrocarbon oil |
| CN103773442A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for production of high-viscosity-index lubricant base oil by hydrogenation |
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| CN114437816A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Combined production method and device of lubricant base oil and aromatic base mineral oil |
| CN114437816B (en) * | 2020-10-30 | 2023-10-10 | 中国石油化工股份有限公司 | Method and apparatus for combined production of lubricating base oil and aromatic mineral oil |
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Effective date of registration: 20231007 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |