CN1775919A - Method for producing plastic plasticizer - Google Patents
Method for producing plastic plasticizer Download PDFInfo
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- CN1775919A CN1775919A CN 200510107236 CN200510107236A CN1775919A CN 1775919 A CN1775919 A CN 1775919A CN 200510107236 CN200510107236 CN 200510107236 CN 200510107236 A CN200510107236 A CN 200510107236A CN 1775919 A CN1775919 A CN 1775919A
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Abstract
The invention discloses a method to manufacture plastic plasticizer. The method is base oil and hydrogen taking hydrogenation prerefining contact with hydrogenation prerefining activator in the hydrogenation modificatioin device, taking hydrogenation modification with hydrogenation modification activator to gain hydrogenation making oil that would make plastic plasticizer after fractionating. The invention contains little impurity, has light color, good low temperature capability, no peculiar smell and no harm to environment.
Description
Technical field
The invention belongs to petrochemical industry, the coal tar fraction that relates to the generation of the coal course of processing is or/and the preparing ethylene by steam cracking tar in the petroleum refining process is produced the method for plastic plasticizer through hydro-upgrading.
Background technology
Along with fast growth of national economy, domestic demand to plastics is increasing.Igelite is wide because of the aspect purposes such as life industrial production and people, consumption is greatly extremely paid attention to.
In the production process of plastics such as polyvinyl chloride, must be used with suitable softening agent and could improve processing of plastic performance and use properties.Owing to the use properties of plastics is required different different with the performance of softening agent itself, present softening agent kind of selling on market is more, but based on the softening agent of organosilane ester.As dibutyl phthalate, dioctyl phthalate (DOP) Chang Zuowei primary plasticizer by extensively, use in large quantities.This class softening agent majority obtains by organic synthesis, and production cost is higher, and the required butanols of butyl ester class softening agent that particularly production usage quantity is bigger will consume a large amount of grain.China is populous, and annual grain that need be a large amount of comes mass production butyl ester class softening agent obviously unreasonable with grain.Therefore, the technician is constantly seeking new plasticizer production raw material and is developing new plasticizer production technology.
U.S. Pat 3511794 has been introduced and prepared direct production method as polyvinylhalide base polymer softening agent a kind of the separation from the last high boiling residue in oil routine processing back.This method carries out just obtaining after furfural extraction-separation solvent-hydrotreatment-processes such as distillation product as softening agent to raw material.The work flow of this method is long, production cost is higher.
Chinese patent CN88109747.0 discloses a kind of method of petroleum base softening agent and prepared petroleum base softening agent of preparing.This method is a raw material with the high boiling residue of naphthenic base oil after routine processing, and handling through simple underpressure distillation is the separable softening agent that obtains mainly being used as polyvinylhalide, particularly polyvinyl chloride.This method flow is shorter, and is simple to operate, and production cost is lower, but the softening agent of being produced by this method exists foreign matter content higher, and color is heavy, and deficiencies such as peculiar smell are arranged, and its use range is subjected to certain limitation.
It is the method for raw material production softening agent with the heavy aromatic oil that Chinese patent CN1351114A discloses a kind of.This method is carried out hydrotreatment and solvent treatment with heavy aromatic oil, sulphur, nitrogen, metal impurities in can the effective elimination heavy aromatic oil, macromole condensed-nuclei aromaticss such as colloid contained in the heavy aromatic oil, bituminous matter can be converted into micromolecular aromatic hydrocarbons again, increase the yield of desirable aromatic hydrocarbons in the heavy aromatic oil.The raw material of this technology can be the residual oil of technologies such as the extraction oil of catalytically cracked oil (clarified oil), lubricating oil solvent technology and viscosity breaking, thermally splitting, Pintsch process and coking recycle oil etc., and the softening agent that its product purification aromatic hydrocarbon oil can be used as plastics uses.This method has effectively utilized petroleum resources, and the quality of product is good, but work flow is longer, and production cost is higher.
Summary of the invention
The plastic plasticizer use properties that The present invention be directed to prior art production is relatively poor, and the more high deficiency of cost, mainly utilize the lower dead oil of price or/and the method that preparing ethylene by steam cracking tar is produced plastic plasticizer through hydro-upgrading and provide a kind of, the plastic plasticizer foreign matter content that uses this method to produce is low, of light color, low-temperature performance is good, cyclic hydrocarbon kind compound content height, free from extraneous odour, volatility is low, toxicity is low and environment is had no adverse effects.
Technical scheme of the present invention comprises the steps:
(1) stock oil contacts with hydrogenation pre-refining catalyzer earlier in hydro-upgrading unit with hydrogen, carry out the reaction of hydrogenation pre-refining, remove impurity such as sulphur, nitrogen, the reaction product of hydrogenation pre-refining contacts with catalyst for hydro-upgrading again reacts, and remove impurity such as sulphur, nitrogen, wherein the weight ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1～6: 4～9.The operational condition of hydrogenation pre-refining and hydro-upgrading is: the hydrogen dividing potential drop is 8.0Mpa～18.0Mpa, preferred 9.0Mpa～15.0Mpa; Volume space velocity is 0.1h during liquid
-1～2.5h
-1, preferred 0.2h
-1～1.0h
-1Temperature of reaction is 300 ℃～450 ℃, preferred 350 ℃～420 ℃; The volume ratio of hydrogen and stock oil is 500～4000, preferred 800～2000.
(2) hydrogenated oil that step (1) is obtained is delivered to the separation column that this technical field technician knows and is carried out air distillation and underpressure distillation, the overhead oil of atmospheric tower is a boiling point less than 320 ℃ distillate, can be used as the low oil fuel that coagulates of heavy aromatic solvent oil or low-sulfur, the overhead oil of vacuum distillation tower is a boiling range at 320～450 ℃ distillate, be plastic plasticizer product of the present invention, oil is got back to as rubber filling oil or as turning oil and is carried out hydrogenation reaction in the hydro-upgrading unit again at the bottom of the tower of vacuum distillation tower; Or the hydrogenated oil that obtains of step (1) carries out cutting and separating in a stage casing is provided with the separation column of one or several side line, cat head goes out boiling point less than 320 ℃ distillate, the distillate that the side line extraction is 320 ℃～450 ℃ is the plastic plasticizer product, and oil is got back to as rubber filling oil or as turning oil and carried out hydrogenation reaction in the hydro-upgrading unit again at the bottom of the tower.
Hydrogenation pre-refining catalyzer of the present invention and catalyst for hydro-upgrading mainly are made up of carrier and active ingredient, wherein carrier is the resistant to elevated temperatures inorganic oxide of porous (as silicon-dioxide, aluminum oxide and a silicon-aluminum mixture etc.), and active ingredient is the oxide compound (as the oxide compound of W, Mo, Ni or Co) of group vib and/or VIII family metal; In catalyzer, also optionally add some other auxiliary element (as F, B and P etc.).
Stock oil of the present invention is the mixing oil of dead oil, preparing ethylene by steam cracking tar or dead oil and other heavy arene distillate, when adopting the mixing oil of dead oil and other heavy arene distillate, the amount of mixing of other heavy arene distillate is 0～60 weight %, in the mixing oil gross weight.Described other heavy arene distillate is as furfural extract oil of catalytic cracking heavy oil etc.The distillate of coal tar is the mixing oil (as the mixing oil of cuts such as light oil, dephenolize oil, washing oil, carbolineum) of tar-bitumen with front-end volatiles, or the mixing oil of washing oil and carbolineum, or carbolineum; Preparing ethylene by steam cracking tar and other petroleum fractions that is rich in heavy arene are final boiling point less than 500 ℃ distillate.
Hydrogenation technique of the present invention can adopt single hop series connection, one way to pass through or partial hydrogenation heavy oil round-robin operating method, so the hydrogenation technique condition can require to select appropriate volume air speed and hydrogen dividing potential drop according to the transformation efficiency of the oil properties that processes raw material, requirement and to giving birth to olefiant refining depth.The hydro-upgrading technology adopts hydrogenation pre-refining well known to those skilled in the art of the present technique or hydro-upgrading technology, comprises fixed bed hydrogenation treatment technology, floating bed hydrogenation treatment technology, boiling bed hydrogenation treatment technology and expanded bed hydrotreatment technology etc.Using comparatively sophisticated on full scale plant at present is the fixed bed hydrogenation treatment technology.When adopting the fixed bed hydrogenation treatment technology, can adopt one-stage process or two-stage method hydrotreatment technology.
The present invention is that heavy aromatic oil carries out hydrotreatment and still-process combines with being rich in.Make the polycyclic aromatic hydrocarbons of heavy aromatic oil carry out fractional saturation by hydrotreatment, and remove impurity such as sulphur, nitrogen.Raw material sources of the present invention in addition are wide, especially by the carbolineum of coal tar processing because of its peculiar smell is big, the oil that acts as a fuel is difficult to sell, price is lower, after the art of this patent processing, can significantly improve value-added content of product.The plastic plasticizer foreign matter content of being produced by the inventive method is low, and cyclic hydrocarbon kind compound content height is not less than 92w%, and thermostability and chemical stability are good, and lower, the free from extraneous odour of toxicity has no adverse effects to environment.Compare with CN1351114A, with the distillate of the heavy aromatic oil after the inventive method processing softening agent as the PVC plastics, its viscosity is little, sulphur content and nitrogen content are low, of light color is light yellow, free from extraneous odour.The distillate of this heavy aromatic oil can be used for producing light plastics as the softening agent of PVC plastics, and the plastics free from extraneous odour.And the sulphur content and the nitrogen content of the heavy aromatic oil after the processing are lower, and sulphur content is 50 μ g/g～500 μ g/g, and nitrogen content is 150 μ g/g～800 μ g/g.
Embodiment
The present invention will be described in detail with specific embodiment below, but do not limit the scope of the invention.
Embodiment 1:
On medium-sized fixed bed hydrogenation testing apparatus, with Mo-Ni/Al
2O
3Type is hydrogenation pre-refining (R1) catalyzer (MoO wherein
3Account for 15.62% of total catalyst weight, NiO account for total catalyst weight 2.91%), with W-Mo-Ni/Al
2O
3Type is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1: 1 (weight), two reactors in series, the operating method that adopts one way to pass through has been carried out hydro-upgrading to the washing oil of coal tar fraction, the mixing oil of carbolineum (stock oil 1).Catalyzer adopts conventional pre-vulcanization process to carry out prevulcanized before use, treat that catalyst activity is stable after, carry out processing condition again and investigate test.
Stock oil 1 and hydrogen enter hydrogenator, elder generation and Mo-Ni/Al after mixing
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction product
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
The main character of the stock oil 1 of hydro-upgrading sees Table 1, has also listed the processing condition of hydro-upgrading in the table 1 and has given birth to olefiant main character.
On the true boiling point distillation device, the product liquid behind the above-mentioned hydro-upgrading is carried out fractionation by distillation, the main character of the plastic plasticizer that obtains sees Table 2.
The character of table 1 stock oil 1 and hydrogenated oil thereof
| The main character analytic density of stock oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, the processing condition hydrogen dividing potential drop of μ g/g smell hydro-upgrading, MPa temperature of reaction (R 1/R 2), ℃ volume space velocity (R 1/R 2)，h -1The main character analytic density of hydrogen to oil volume ratio hydrogenated oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, μ g/g smell | 1140.1 1.05 4.126 7,082 8955 pungent odours, 13.5 380/380 1.0/1.0,1,200 989.1 0.06 2.457 106 271 frees from extraneous odour |
The plastic plasticizer main character that table 2 is produced by stock oil 1 is analyzed
| Density, 20 ℃, kg/m 3Open flash point, ℃ pour point, ℃ viscosity, 40 ℃, mm 2/ s acid number, the mgKOH/g copper corrosion; (100 ℃, 3h) carbon residue, the m% aniline point, ℃ colourity moisture, v% smell outward appearance | 1035.8＞180＜-15 21.26 0.018 1b＜0.01＜10＜6 trace frees from extraneous odour are orange red transparent |
Embodiment 2:
On medium-sized fixed bed hydrogenation testing apparatus, with Mo-Ni/Al
2O
3Type is hydrogenation pre-refining (R1) catalyzer (MoO wherein
3Account for 15.62% of total catalyst weight, NiO account for total catalyst weight 2.91%), with W-Mo-Ni/Al
2O
3Type is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 2: 3 (weight), two reactors in series, and adopt operating method that one way passes through that coal tar fraction (stock oil 1) is mixed part preparing ethylene by steam cracking tar and carried out hydro-upgrading less than the mixing oil (test raw material oil 2) of 500 ℃ distillate (ratio is 4: 1).Catalyzer adopts conventional pre-vulcanization process to carry out prevulcanized before use, treat that catalyst activity is stable after, carry out processing condition again and investigate test.
Stock oil 2 and hydrogen enter hydrogenator, elder generation and Mo-Ni/Al after mixing
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction product
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
The main character of hydro-upgrading stock oil 2 sees Table 3, has also listed the processing condition of hydro-upgrading in the table 3 and has given birth to olefiant main character.
On the true boiling point distillation device, the product liquid behind the above-mentioned hydro-upgrading is carried out fractionation by distillation, the main character of the plastic plasticizer that obtains sees Table 4.
The character of table 3 stock oil 2 and hydrogenated oil thereof
| The main character analytic density of stock oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, the processing condition hydrogen dividing potential drop of μ g/g smell hydro-upgrading, MPa temperature of reaction (R 1/R 2), ℃ volume space velocity (R 1/R 2)，h -1The main character analytic density of hydrogen to oil volume ratio hydrogenated oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, μ g/g smell | 1118.2 0.92 3.972 6,592 8526 pungent odour, 13.0 380/380 1.25/0.83,1,200 985.3 0.04 2.279 73 229 frees from extraneous odour |
The plastic plasticizer main character that table 4 is produced by stock oil 2 is analyzed
| Density, 20 ℃, kg/m 3Open flash point, ℃ pour point, ℃ viscosity, 40 ℃, mm 2/ s acid number, the mgKOH/g copper corrosion; (100 ℃, 3h) carbon residue, the m% aniline point, ℃ colourity moisture, v% smell outward appearance | 1029.3＞180＜-15 20.41 0.015 1b＜0.01＜10＜6 trace frees from extraneous odour are orange red transparent |
Embodiment 3:
On medium-sized fixed bed hydrogenation testing apparatus, with W-Ni/Al
2O
3Type is hydrogenation pre-refining (R1) catalyzer (WO wherein
3Account for 24.79% of total catalyst weight, NiO account for total catalyst weight 3.05%), with W-Mo-Ni/Al
2O
3Type is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 3: 7 (weight), two reactors in series operations are adopted and greater than 420 ℃ last running round-robin operating method stock oil 1 (character sees Table 1) have been carried out hydro-upgrading.Catalyzer adopts conventional pre-vulcanization process to carry out prevulcanized before use, treat that catalyst activity is stable after, carry out processing condition again and investigate test.
Stock oil 1 and hydrogen enter hydrogenator, elder generation and W-Ni/Al after mixing
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction product
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
Stock oil 1 on this hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading, carry out hydro-upgrading the main technique condition and give birth to olefiant main character and see Table 5.
On the true boiling point distillation device, the product liquid behind the above-mentioned hydro-upgrading is carried out fractionation by distillation, the main character of the plastic plasticizer that obtains sees Table 6.
Operational condition under the table 5 hydrogenation heavy oil cycling condition and generation oil nature
| The main character analytic density of stock oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, the processing condition hydrogen dividing potential drop of μ g/g smell hydro-upgrading, MPa temperature of reaction (R 1/R 2), ℃ volume space velocity (R 1/R 2)，h -1The main character analytic density of hydrogen to oil volume ratio hydrogenated oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, μ g/g smell | 1140.1 1.05 4.126 7,082 8955 pungent odours, 13.0 375/375 1.67/0.71,1,200 976.3 0.04 2.231 79 207 frees from extraneous odour |
Plastic plasticizer main character under the table 6 hydrogenation heavy oil cycling condition is analyzed
| Density, 20 ℃, kg/m 3Open flash point, ℃ pour point, ℃ viscosity, 40 ℃, mm 2/ s acid number, the mgKOH/g copper corrosion; (100 ℃, 3h) carbon residue; The m% aniline point, ℃ colourity moisture, the v% smell, outward appearance | 1013.6＞165＜-20 18.27 0.016 1a＜0.01＜10＜6 trace frees from extraneous odour are orange red transparent |
Embodiment 4:
On medium-sized fixed bed hydrogenation testing apparatus, with W-Ni/Al
2O
3Type is hydrogenation pre-refining (R1) catalyzer (WO wherein
3Account for 24.79% of total catalyst weight, NiO account for total catalyst weight 3.05%), with W-Mo-Ni/Al
2O
3Type is hydro-upgrading (R2) catalyzer (WO wherein
3Account for 21.27% of total catalyst weight, MoO
3Account for 5.91% of total catalyst weight, NiO account for total catalyst weight 2.84%), the filling ratio of hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1: 4 (weight), two reactors in series, and adopt the 20% hydrogenation full distillate oil round-robin operating method that accounts for device fresh feed amount that test raw material oil 2 has been carried out hydro-upgrading.Catalyzer adopts conventional pre-vulcanization process to carry out prevulcanized before use, treat that catalyst activity is stable after, carry out processing condition again and investigate test.
Mix with hydrogen again after stock oil 2 and its hydrogenation full distillate oil of 20% mix, then enter hydrogenator, elder generation and W-Ni/Al
2O
3The contact of hydrogenation pre-refining catalyzer removes impurity such as sulphur, nitrogen, the direct and W-Mo-Ni/Al of reaction product
2O
3The catalyst for hydro-upgrading contact is carried out the saturated reaction of part aromatic ring, and is removed impurity such as sulphur, nitrogen.Reaction product is isolated gaseous fraction through separator, stabilizer, obtains the liquid ingredient behind the upgrading; The hydrogen-rich gas that removes behind the impurity such as hydrogen sulfide, ammonia recycles.
Stock oil 2 carries out the hydro-upgrading main technique condition of partial hydrogenation generation oil (20%) and gives birth to olefiant main character seeing Table 7 on this hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading.
On the true boiling point distillation device, to the product liquid behind the above-mentioned hydro-upgrading carry out fractionation by distillation, the main character of the plastic plasticizer that obtains sees Table 8.
Table 7 partial hydrogenation generates operational condition and the hydrogenated oil character under the oil circulation condition
| The main character analytic density of stock oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, the processing condition hydrogen dividing potential drop of μ g/g smell hydro-upgrading, MPa temperature of reaction (R 1/R 2), ℃ volume space velocity (R 1/R 2)，h -1The main character analytic density of hydrogen to oil volume ratio hydrogenated oil, 20 ℃, kg/m 3Carbon residue, m% viscosity (80 ℃), mm 2/ s sulphur content, μ g/g nitrogen content, μ g/g smell | 1118.2 0.92 3.972 6,592 8526 pungent odour, 13.0 375/375 2.50/0.625,1,200 972.6 0.03 2.153 49 192 frees from extraneous odour |
Table 8 partial hydrogenation generate under the oil circulation condition the analysis of plastic plasticizer main character
| Density, 20 ℃, kg/m 3Open flash point, ℃ pour point, ℃ viscosity, 40 ℃, mm 2/ s acid number, the mgKOH/g copper corrosion, (100 ℃, 3h) carbon residue, the m% aniline point, ℃ colourity moisture, v% smell outward appearance | 1010.2＞165＜-20 17.96 0.011 1a＜0.01＜10＜6 trace frees from extraneous odour are orange red transparent |
Embodiment 5:
Narrow fraction (320 ℃～360 ℃, 360 ℃～400 ℃, 400 ℃～450 ℃) or its mixing oil that the hydrogenated oil that is obtained by example 1 obtains after distillation can be used as the plastic plasticizer product, and its character sees Table 9.
Table 9 is by the main character analysis of each plastic plasticizer of stock oil 1 production
| Project name | 320～360 ℃ | 360～400 ℃ | 400～450 ℃ | Mixing oil |
| Density, 20 ℃, kg/m 3Open flash point, ℃ pour point, ℃ viscosity, 40 ℃, mm 2/ s acid number, the mgKOH/g copper corrosion, (100 ℃, 3h) carbon residue, the m% aniline point, ℃ colourity moisture, v% smell outward appearance | 1019.6 162＜-30 16.35 0.021 2a＜0.01＜10 2.0 trace frees from extraneous odour are orange transparent | 1033.7 194＜-20 22.52 0.017 1b＜0.01＜10 4.9 trace frees from extraneous odour are orange red transparent | 1046.2 213＜-15 25.39 0.015 1b＜0.01＜10 7.2 trace frees from extraneous odour are reddish brown transparent | 1035.8＞180＜-15 21.26 0.018 1b＜0.01＜10＜6 trace frees from extraneous odour are orange red transparent |
Claims (2)
1. the production method of a plastic plasticizer is characterized in that this method comprises the steps:
(1) stock oil contacts with hydrogenation pre-refining catalyzer earlier in hydro-upgrading unit with hydrogen, remove impurity such as sulphur, nitrogen, the reaction product of hydrogenation pre-refining contacts with catalyst for hydro-upgrading again reacts, and remove impurity such as sulphur, nitrogen, described stock oil is the mixing oil of dead oil, preparing ethylene by steam cracking tar or dead oil and other heavy arene distillate, when adopting the mixing oil of dead oil and other heavy arene distillate, the amount of mixing of other heavy arene distillate is 0～60 weight %, in the mixing oil gross weight; The weight ratio of described hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading is 1～6: 4～9, and the operational condition of hydrogenation pre-refining and hydro-upgrading is, the hydrogen dividing potential drop is 8.0～18.0Mpa, and volume space velocity is 0.1～2.5h during liquid
-1Temperature of reaction is 300～450 ℃, the volume ratio of hydrogen and stock oil is 500～4000, described hydrogenation pre-refining catalyzer and catalyst for hydro-upgrading mainly are made up of carrier and active ingredient, wherein carrier is the resistant to elevated temperatures inorganic oxide of porous, and active ingredient is the oxide compound of group vib and/or VIII family metal;
(2) hydrogenated oil that step (1) is obtained is delivered to separation column and is carried out air distillation and underpressure distillation, the overhead oil of atmospheric tower is a boiling point less than 320 ℃ distillate, the overhead oil of vacuum distillation tower is a boiling range at 320～450 ℃ distillate, be the plastic plasticizer product, oil is got back to as rubber filling oil or as turning oil and is carried out hydrogenation reaction in the hydro-upgrading unit again at the bottom of the tower of vacuum distillation tower; Or the hydrogenated oil that obtains of step (1) carries out cutting and separating in a stage casing is provided with the separation column of one or several side line, cat head goes out boiling point less than 320 ℃ distillate, the distillate that the side line extraction is 320 ℃～450 ℃ is the plastic plasticizer product, and oil is got back to as rubber filling oil or as turning oil and carried out hydrogenation reaction in the hydro-upgrading unit again at the bottom of the tower.
2. method according to claim 1 is characterized in that: the operational condition of described hydrogenation pre-refining and hydro-upgrading is: the hydrogen dividing potential drop is 9.0～15.0Mpa; Volume space velocity is 0.2～1.0h during liquid
-1Temperature of reaction is 350～420 ℃; The volume ratio of hydrogen and stock oil is 800～2000.
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- 2005-12-02 CN CN 200510107236 patent/CN1775919A/en active Pending
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