CN1352233A - Process for producing white oil from solvent refining oil - Google Patents
Process for producing white oil from solvent refining oil Download PDFInfo
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Abstract
The present invention is technological process of producing food level white oil by using refined solvent oil as material and including hydrogenation, hydrorefining, isomerization and dewaxing, and re-hydrorefining. During the hydrorefining and the re-hydrorefining, the same double catalyst system comprising two kinds of noble metal catalysts with different pore volume and loaded in different layers of one identical reactor is used to reduce the S, N2 and aromatic hydrocarbon contents of material to very low level in mild operation condition, avoid the competing adsorption of polar compound and normal alkane on the surface of the isomerization and dewaxing catalyst and thus imporved the isomerization performance of the catalyst for high base oil yield and long service life of the catalyst. Through the re-hydrorefining, food level and medicine level white oil with rich isomerized alkane may be produced.
Description
The present invention relates to a kind of is raw material with the solvent treatment hydrocarbon ils, and---hydrofining---isomerization dewaxing---hydrofinishing, a kind of like this technological process is produced the method for white oil by hydrotreatment.
White oil is to remove unsaturated hydrocarbons and non-hydrocarbons impurity in the lubricating oil distillate and the petroleum products that a class is colourless, tasteless, chemical property is stable that obtains through deep refining.Press the different of purposes and refining depth, can be divided into classifications such as technical grade, cosmetics-stage, food grade and pharmaceutical grade white oil.Wherein, the refining degree of food grade and pharmaceutical grade white oil is the darkest.
Traditional technology adopts acid treatment and clay-filtered method to produce white oil, and not only the white oil yield is low, also has problem of environmental pollution.Producing white oil by hydrogenation is pollution-free with it, white oil yield height, raw material sources are extensive, product category is complete, can process high viscosity white oil plurality of advantages and obtained significant progress.
Be to remove the most treating process that is present in sulphur, nitrogen, oxygen and aromatic hydroxy compound in the raw material on the process nature of producing white oil by hydrogenation.Because the white oil product is extremely strict to the restriction of aromaticity content, and the hydrogenation of aromatic hydrocarbons is subjected to thermodynamics equilibrium limit to be difficult at high temperature carry out, so will adopt higher pressure when using the non-noble metal hydrogenation catalyst for refining to produce white oil.According to the different of raw material and different to product requirement, adopt one-stage hydrogenation or multistage hydrogenation.For the lower charging of aromaticity content, as hydrocracking tail oil, can obtain industrial grade white oil through one-stage hydrogenation, even food grade, pharmaceutical grade white oil.For the higher lubricant base raw material of aromaticity content, as solvent treatment pressed oil, generally to pass through two-stage hydrogenation, one-stage hydrogenation can obtain industrial grade white oil, and secondary hydrogenation can obtain food grade and pharmaceutical grade white oil.
US5935416 and 5976353 discloses that a kind of------process of white oil is produced in demulcent hydrofining---dewaxing---hydrofinishing in the hydrofining of severe condition through hydrotreatment by solvent-refined oil, because hydrofining and post-refining section all adopt non-noble metal hydrogenation catalyst, can only the manufacture grade white oil.
The noble metal hydrogenation catalyst for refining has an incomparable high reactivity of non-precious metal catalyst for aromatic hydrogenation is saturated, can carry out post-refining to lubricant base under the demulcent condition and produce the extremely low white oil product of aromaticity content.But,, limited its use range because traditional employing noble metal catalyst nonacid or the slightly acidic carrier is very responsive to sulfide.In recent years, the anti-sulphur mechanism research of relevant noble metal catalyst has obtained breakthrough progress, the anti-sulfur poisoning character free from worldly cares that noble metal component showed that is supported on the acid carrier has not only obtained theoretically explaining more and more fully, and has obtained widespread use in the actual industrial reaction.
U.S. Pat 5,993,644 disclose the lubricant base oil fraction of a kind of precious metal aromatic hydrocarbon saturation catalyst that adopts anti-sulphur after to isomerization dewaxing carries out the method that base oil of high viscosity index lubricant is produced in hydrofining.
US5,993,644, US5,855,767, US5,879,539, US5, patents such as 976,354 have mentioned all that to adopt the lubricant base of noble metal catalyst after to dewaxing that contains acid carrier to carry out aromatic hydrocarbons saturated, improve its anti-oxidative stability.Though this noble metal catalyst that contains acid carrier has stronger anti-sulfur poisoning ability, sulphur content is up to hundreds of μ g/g in the permission charging, but because the isomerization dewaxing catalyst of the last period has adopted weakly acidic mesoporous molecular sieve to improve the selectivity of isomerization reaction, therefore anti-sulphur ability is relatively poor, requires sulphur in the charging, nitrogen content lower.In this case, be positioned at isomerization dewaxing section Hydrobon catalyst afterwards and can't give full play to its higher sulfur tolerance.
On the other hand, when being raw material with the higher solvent-refined oil of aromaticity content, although can make sulphur, nitrogen content be reduced to very low level through hydrotreatment,, still contain the aromatic hydrocarbons of 10-20% in the charging of isomerization dewaxing section.These aromatic hydroxy compounds and the competitive adsorption of wax component on isomerization dewaxing catalyst must cause the active and optionally decline of isomerization dewaxing catalyst.Even as US US5,976,354 adopt the precious metal/beta-molecular sieve catalyzer of anti-sulphur to carry out hydrocracking-isomerization dewaxing like that, can allow feed sulphur content up to 200 μ g/g, these sulfocompounds also can be on isomerization dewaxing catalyst and wax component generation competitive adsorption, isomerization dewaxing is reflected under the comparatively high temps carries out, thereby reduce the isomery selectivity.
Therefore, be necessary that fully the noble metal hydrogenation catalyst for refining with anti-sulphur places before the isomerization dewaxing catalyst, particularly when being raw material with the higher solvent-refined oil after hydrotreatment of aromaticity content, isomerization dewaxing after elder generation's hydrofining, sulphur, nitrogen, aromatic hydroxy compound in the isomerization dewaxing section feeding can be removed dramatically, make the activity of isomerization dewaxing catalyst obtain best performance, the lube oil base stocks after the dewaxing can be produced food grade and the cosmetics-stage white oil that is rich in isoparaffin through post-refining again.
US6030921 also discloses a kind of precious metal aromatic hydrocarbon saturation catalyst and the application in the hydrorefining basic oil lubricating oil process thereof of anti-sulphur, and has mentioned the hydrofining section is placed before the isomerization dewaxing section.But it is acid carrier that the employed Hydrobon catalyst of this patent has adopted amorphous silicon aluminium, comprises also that perhaps a part of Y zeolite improves the acidity of catalyzer.
Though contain the noble metal catalyst of amorphous silicon aluminium and the noble metal catalyst that contains Y zeolite and the mixture of the two all because of the acidity of its carrier has certain anti-sulfur poisoning ability, in the process that removes sulphur, nitrogen and aromatic hydroxy compound, have different effects because of the difference of pore volume by the catalyzer of different preparing carriers.The macroporous catalyst that contains amorphous silicon aluminium can remove the above polycyclic aromatic hydrocarbons of three rings and macromolecular organosulfur, nitrogen compound effectively, and the bigger polar compound of these volumes causes the obstruction or the carbon deposit in aperture because of the duct that can't enter Y zeolite, and then cause catalyst deactivation, need harsh reaction conditions in order to keep activity of such catalysts, the result causes the over-drastic cracking and shortens the life cycle of catalyzer.Even being carried out mechanically mixing, amorphous silicon aluminium and Y zeolite also can't protect the Y zeolite duct not stopped up effectively by the bigger polar compound of these volumes.
US5393408 mentions the precious metal/amorphous silicon aluminium catalyzer of a kind of macropore of employing and a kind of precious metal/amorphous silicon aluminium catalyzer of mesopore carries out hydrorefined process to the lubricant base after dewaxing.Macroporous catalyst can remove the above condensed-nuclei aromatics of three rings, and medium-pore catalyst has higher activity to one to the thrcylic aromatic hydrocarbon hydrogenation is saturated.When using separately, the activity of medium-pore catalyst is higher than macroporous catalyst, but inactivation is very fast.Two kinds of superimposed uses of catalyzer have activity and the better stability same with medium-pore catalyst.
The purpose of lube hydrofinishing is to remove alkene, diolefine, aromatic hydrocarbons and sulphur, nitrogen compound etc. to UV-light and the unsettled material of oxidizing medium and with look with the material of flavor is arranged.There are some researches show that wavelength is that the absorbancy of UV-light of 226nm-305nm is relevant to the content of UV-light and the unsettled material of oxidizing medium with polycyclic aromatic hydrocarbons and heterocyclic nitrogen compound etc., wherein, the 226nm absorbancy is relevant with readily oxidizable substance; And the 305nm absorbancy is relevant with bloom of lubricating oil and blackening.Also have research to think, the above polycyclic aromatic hydrocarbons of three rings is to cause lubricating oil to the light and the oxidizing medium factors of instability, and the macroporous catalyst that only contains amorphous silicon aluminium could remove the bigger polycyclic aromatic hydrocarbons of these volumes effectively; And the noble metal catalyst that contains Y zeolite has higher activity for one to the thrcylic aromatic hydrocarbon hydrogenation is saturated, when therefore the present invention is used for lube hydrofinishing, can can produce qualified food-level white oil, pharmaceutical grade white oil and cosmetics-stage white oil with alkene, diolefine, aromatic hydrocarbons and sulphur, nitrogen compound etc. to UV-light and the unsettled material of oxidizing medium and with look with there is the material of flavor to be removed to extremely low degree.
There are some researches show, in the food-level white oil normal paraffin content too high be to cause carbide accumulative major cause in tissue and the organ, therefore be necessary to improve the content of isoparaffin in the food-level white oil.US5,453,176 disclose and a kind ofly adopt hydrocracking-isomerization dewaxing-two-section hydrotreating production to be rich in the technological process of isoparaffin white oil, owing to adopted two sections noble metal catalyst hydrofinings that contain Y zeolite, aromaticity content in the product can be reduced to the level of food grade and cosmetics-stage white oil.But the catalyst runs cycle is short.
The purpose of this invention is to provide a kind of good product quality, yield height, catalyst life long be rich in the food grade of isoparaffin and the method for pharmaceutical grade white oil by solvent-refined oil production.
Implementation method of the present invention is to be raw material with the solvent treatment hydrocarbon ils, and---hydrofining---isomerization dewaxing---hydrofinishing, a kind of like this technological process is produced food-level white oil by hydrotreatment.Wherein, hydrofining section and hydrofinishing section adopt identical dual catalyst system, the macroporous catalyst that is about to the to contain amorphous silicon aluminium use of connecting with the catalyzer that contains Y zeolite.
Two kinds of catalyzer of the present invention do not have in two reactors of gas separation unit in the middle of can connecting yet and filling in, and improve the handiness of operation.First reactor charge contains the amorphous silicon aluminium catalyzer, and second reactor charge contains the catalyzer of Y zeolite.The operational condition of two reactors is except that temperature, and other is all identical.Because to contain the Y zeolite catalyst activity higher, therefore the temperature of second reactor will be lower than first reactor, and this temperature head still depends on feed properties and to the specification of quality of product.In general, the temperature head of two reactors is in 10-80 ℃ of scope.
The preferred scheme of the present invention is that two kinds of catalyzer layerings are filled in the same reactor, can reduce plant investment and process cost like this, it is 1 that top contains the volume ratio that amorphous silicon aluminium catalyzer and bottom contain the catalyzer of Y zeolite: 0-0: 1, be preferably 3: 1-1: 3.
The catalyzer pore volume that first bed on hydrofining reactor top is loaded is 0.6-1.0cm
3/ g.SiO in the macropore sial carrier that the first bed catalyzer is contained
2Content is 25-50wt%, and pore volume is 0.6-1.4cm
3/ g, specific surface area 300-500m
2/ g.Can prepare by the co-precipitation or the cogelled technology of routine.The first bed catalyzer contains a kind of adhesive oxides, is preferably aluminum oxide.The weight ratio of aluminum oxide and macropore sial carrier is 10: 90-40: 60.
The catalyzer that second bed is loaded contains Y zeolite.The SiO of this Y zeolite
2/ Al
2O
3Mol ratio is 12-40; Unit cell parameters is 2.422-2.445nm; Sodium oxide content is less than 0.15wt%; Relative crystallinity is preferably 98%-100% greater than 95%.
The second bed catalyzer contains a kind of adhesive oxides, is preferably aluminum oxide.The weight ratio of aluminum oxide and Y zeolite is 20: 80-40: 60.
Two kinds of catalyzer all contain at least a noble metal hydrogenation component, the preferably alloy of platinum and palladium.The amount that is supported on platinum on the carrier and palladium must be enough to guarantee the hydrogenation of lube oil base stocks, and the mol ratio of platinum and palladium is 2.5: 1-1: 2.5, be preferably 1: 1.5.The total amount of platinum and palladium is 0.2-1.2wt%.Two kinds of catalyzer all adopt certain density [Pt (NH
3)
4]
2+With [Pd (NH
3)
4]
2+The carrier of mixing solutions after to roasting pore volume impregnation or excess solution dipping such as carry out.The pH value of mixing solutions can obtain the preferred metal dispersity in the scope of 8-10 the time.
Being suitable for hydrocarbon oil crude material of the present invention and can being boiling point is higher than 250 ℃, preferably is higher than the solvent-refined oil of the hydrocarbon oil crude material of 310 ℃ vacuum distillate and vacuum residuum propane deasphalting oil and the contour aromaticity content of FCC heavy cycle oil.
The solvent treatment oil hydrogenating treatment catalyst is Mo (W)-Ni/ aluminum oxide (molecular sieve) catalyzer that general industry uses.The operational condition of hydrotreatment section is: reaction pressure 2.8-15.0Mpa, preferably 4.0-10.0Mpa.Temperature of reaction 340-420 ℃, be preferably 320-400 ℃, air speed (LHSV) is 0.2-3.0h
-1, be preferably 0.5-2.0h
-1Raw material in hydrotreatment section generation hydrogenating desulfurization, hydrodenitrification, aromatic hydrocarbons is saturated and ring-opening reaction, improves viscosity index.The effluent of first section hydrotreating reactor will pass through gas-liquid separation, fractionation plant and stripper plant, removes H
2S and NH
3, and from liquid stream, cut out boiling point and be higher than 250 ℃, preferably be higher than 310 ℃ cut as the charging of hydrofining section.The operational condition of hydrotreatment section will guarantee that sulphur, nitrogen content are preferably＜200 μ g/g and＜50 μ g/g respectively less than 500 μ g/g and 100 μ g/g in the hydrofining section feeding.
The hydrofining section is equipped with dual catalyst of the present invention, and hydrofining section operational condition is: reaction pressure 2.8-15.0Mpa, preferably 4.0-10.0Mpa.The temperature of reaction of temperature of reaction is 200-360 ℃, is preferably 220-320 ℃, and air speed (LHSV) is 0.2-2.0h
-1, be preferably 0.5-1.5h
-1
The effluent of hydrofining section can all enter the isomerization dewaxing section, if but remove H through gas-liquid separation, fractionation plant and stripper plant
2S and NH
3Be lower than 250 ℃ or be lower than 310 ℃ lighting end and will make the best use properties of isomerization dewaxing catalyst performance with boiling point.Isomerization dewaxing catalyst can contain mesoporous molecular sieve, comprises mesoporous molecular sieves such as SAPO-11, SAPO-31, SAPO-41, mordenite, ZSM-22, ZSM-23, SSZ-32, is preferably SAPO-11; The beta-molecular sieve that also can contain high silica alumina ratio, SiO
2/ Al
2O
3Greater than 100: 1, or greater than 200: 1, more preferably greater than 500: 1; The mixture that perhaps contains above-mentioned two molecular sieve analogs.The operational condition of isomerization dewaxing section is: reaction pressure 2.8-15.0Mpa, preferably 4.0-10.0Mpa.Temperature of reaction 280-420 ℃, be preferably 320-400 ℃, air speed (LHSV) is 0.2-2.0h
-1, be preferably 0.5-1.5h
-1
The effluent of isomerization dewaxing section directly enters the hydrofinishing section.The hydrofinishing section can adopt the catalyzer identical with the hydrofining section, can more operate reaction pressure 2.8-15.0Mpa, preferably 4.0-10.0Mpa under the demulcent condition.Temperature of reaction is 170-320 ℃, is preferably 190-280 ℃, and air speed (LHSV) is 0.2-4.0h
-1, be preferably 0.5-2.0h
-1
Compared with prior art, the inventive method has following advantage:
(1) quality product height.The white oil of producing according to the inventive method satisfies all index requests of food-level white oil, compares with catalytic dewaxing process with traditional solvent dewaxing, and the food-level white oil that the inventive method is produced is rich in isoparaffin.Because, adopt the noble metal catalyst of anti-sulphur, nitrogen in the hydrofining section, can under demulcent operational condition and feed sulfur, nitrogen content condition with higher, the sulphur in the isomerization dewaxing charging, nitrogen and aromaticity content be reduced to very low level, avoided polar compound and normal paraffin competitive adsorption, thereby the level the earth has improved the isomery performance of isomerization dewaxing catalyst on the isomerization dewaxing catalyst surface; Can make simultaneously that aromaticity content reaches quite low level in the isomerization dewaxing product, pass through hydrofinishing again, can produce the industrial grade white oil that is rich in isoparaffin and the food grade and the pharmaceutical grade white oil of aromatic free compound fully.Hydrofining and hydrofinishing adopt two kinds of catalyzer to work in coordination, polycyclic aromatic hydrocarbons removes on macropore amorphous silicon aluminium catalyzer, 1～3 Polycyclic aromatic hydrocarbons removes on the Y zeolite catalyzer, give full play to two kinds of catalyzer characteristics separately, reduced the aromaticity content in the product to greatest extent.
(2) low, the condition mitigation of cost, yield height, catalyst life are long.Adopt shallow degree solvent treatment, reduce process cost; Simultaneously, because hydrofining section catalyst system has higher anti-sulphur, nitrogen ability,, not only can improve the yield of lubricating oil distillate under lower severity so first section hydrotreatment reaction can be carried out, can also cut down the consumption of energy, prolong the life cycle of catalyzer.The macroporous catalyst that the hydrofining section will the contain amorphous silicon aluminium use of connecting with the catalyzer that contains Y zeolite, under the demulcent operational condition, hydrofining is carried out in the lubricant base charging before dewaxing, can be produced high-quality white oil product by sulphur, nitrogen, the higher lubricant base charging of aromaticity content.Because dual catalyst system has stronger anti-sulphur, nitrogen ability and stronger inhibition green coke ability, and active higher can under the mitigation condition, the operation, so the work-ing life of catalyzer is longer.Can also improve simultaneously the use properties of isomerization dewaxing catalyst, delay the heterogeneous catalyst inactivation.In sum, the inventive method can be operated whole hydrogenation system under the mitigation condition, and whole hydrogenation system has the advantages that process cost is low, product yield is high, catalyst life is long.
In a word, the higher arene saturating activity of dual catalyst system of unifining process of the present invention and hydrofinishing process is to make the inventive method to be rich in the food grade of isoparaffin and the important assurance of pharmaceutical grade white oil by solvent-refined oil production.
Embodiment
The operational condition of each conversion zone can require suitably to regulate according to a conventional method according to feedstock property, foreign matter content and quality product.The following examples only describe preferred version of the present invention with regard to a kind of raw material, do not constitute limiting the scope of the invention.
Embodiment 1
The catalyst A l that contains the macropore sial is equipped with on hydrofining reactor of the present invention top, and its preparation method is: with SiO
2/ Al
2O
3Weight ratio is 45/55, pore volume is that 1.204ml/g, specific surface area are 467m
2The macropore sial of/g mixes in 65/35 ratio (weight ratio) with gama-alumina, add the concentrated nitric acid of 5wt% (accounting for the carrier total amount) and an amount of water mix pinch, extruded moulding, after drying, the roasting with certain density [Pt (NH
3)
4] Cl
2[Pd (NH
3)
4] (NO
3)
2Mixing solutions flood, the pH value of steeping fluid is 9, the steeping fluid volume is two times of carrier bulk.2 hours after-filtration after 8 hours, carry out the segmentation roasting through 110 ℃ of dryings, 150 ℃ 2 hours, 280 ℃ 2 hours, 480 ℃ 4 hours.Make catalyst A l, pore volume is that 0.820ml/g, specific surface area are 346m
2/ g, bulk density are 0.45g/ml.Platinum content is 0.28wt% in the catalyzer, and palladium content is 0.31wt%.
The catalyst B 1 that contains Y zeolite is equipped with in hydrofining reactor of the present invention bottom, and its preparation method is: with SiO
2/ Al
2O
3Mol ratio is 12, unit cell parameters is 2.438nm, sodium oxide content is less than 0.15wt%, relative crystallinity is that 98% Y zeolite mixes in 65/35 ratio (weight ratio) with gama-alumina, add the concentrated nitric acid of 5wt% (accounting for the carrier total amount) and an amount of water mix pinch, extruded moulding, after drying, the roasting with certain density [Pt (NH
3)
4] Cl
2[Pd (NH
3)
4] (NO
3)
2Mixing solutions flood, the pH value of steeping fluid is 9, the steeping fluid volume is two times of carrier bulk.2 hours after-filtration after 8 hours, carry out the segmentation roasting through 110 ℃ of dryings, 150 ℃ 2 hours, 280 ℃ 2 hours, 480 ℃ 4 hours.Make catalyst B 1, pore volume is that 0.478ml/g, specific surface area are 532m
2/ g, bulk density are 0.72g/ml.Platinum content is 0.34wt% in the catalyzer, and palladium content is 0.32wt%.Prepare catalyzer in the table 1,2 with same procedure.
Table 1 contains the amorphous silicon aluminium catalyzer and forms and character
| Contain the amorphous silicon aluminium catalyzer | ????A2 | ????A3 | |
| Pore volume, ml/g | ????0.595 | ????0.95 | |
| Specific surface area, m 2/g | ????216 | ????425 | |
| Silicon-aluminium | ??SiO 2/Al 2O 3Weight ratio | ????45/55 | ????25/75 |
| Pore volume, ml/g | ????0.663 | ????1.23 | |
| Specific surface area, m 2/g | ????247 | ????463 | |
| Content, wt% | ????70 | ????80 | |
| Metal | Platinum/palladium mol ratio | ????1.5/1 | ????1/1.8 |
| Total content, wt% | ????0.9 | ????1.0 | |
Table 2 contains the Y zeolite catalyzer and forms and character
| Contain the Y zeolite catalyzer | ????B2 | ????B3 | |
| Pore volume, ml/g | ????0.421 | ????0.397 | |
| Specific surface area, m 2/g | ????482 | ????435 | |
| Molecular sieve | ??SiO 2/Al 2O 3Mol ratio | ????25 | ????35 |
| Lattice constant, nm | ????2.428 | ????2.423 | |
| Relative crystallinity, % | ????100 | ????98 | |
| Content, wt% | ????65 | ????75 | |
| Metal | The Pt/Pd mol ratio | ????1.5/1 | ????1/2.3 |
| Total content, wt% | ????0.6 | ????0.6 | |
Embodiment 2
With a kind of solvent treatment hydrocarbon ils is raw material, be to have carried out following test on the small hydrogenation device of 200ml at loaded catalyst: with raw material and purity is that 95% plant hydrogen contacts with 3934/3935 hydrotreating catalyst that Fushun No.3 Petroleum Factory produces together, effluent cuts through true boiling point, getting the cut that boiling point is higher than 420 ℃ adopts dual catalyst system of the present invention to carry out hydrofining
Catalyst A 1 described in the embodiment 1 is filled in the hydrofining reactor with catalyst B 1 layering.The catalyst A 1 on reactor top is 70: 30 with the volume ratio of the catalyst B 1 of bottom.Catalyzer is warming up to 260 ℃ of constant temperature reduction 4 hours in the presence of hydrogen, be cooled to 170 ℃ and begin into stock oil.Hydrogen and stock oil enter by reactor top.
Effluent after the hydrofining is removed H through stripping
2S and NH
3, all product liquid carries out isomerization dewaxing, and isomerization dewaxing catalyst is a kind of Pd/SAPO-11 catalyzer, and wherein (Si/Si+Al+P) mol ratio of SAPO-11 is 0.21, and content is 65wt%, and Pd content is 0.5wt%, and all the other are the tackiness agent aluminum oxide.
The isomerization dewaxing product all enters the hydrofinishing section, and the hydrofinishing section is equipped with catalyst A identical with the hydrofining section 1 and catalyst B 1, and the volume ratio of the two is 30: 70.The white oil that a kind of like this technological process is produced satisfies whole index requests of petrochemical industry food-level white oil.
All the operational condition and the feed properties of each section reactor of technical process see Table 3.The white oil product property that finally obtains sees Table 4.
The operational condition and the feed properties of each section of table 3 reactor
| Operational condition | The hydrotreatment section | The hydrofining section | The isomerization dewaxing section | The hydrofinishing section |
| Pressure, Mpa | ??10.0 | ??8.0 | ??8.0 | ??8.0 |
| Temperature, ℃ | ??340 | ??260 | ??360 | ??220 |
| Liquid hourly space velocity, h -1 | ??0.5 | ??1.0 | ??0.6 | ??1.0 |
| Hydrogen-oil ratio (v/v) | ??800 | ??800 | ??600 | ??500 |
| Feed properties | ||||
| Sulphur, μ g/g | ??13700 | ??215 | ??9.0 | ??＜1 |
| Nitrogen, μ g/g | ??124 | ??1.54 | ??0.42 | ??＜0.1 |
| Aromatic hydrocarbons, wt% | ??46.0 | ??26.5 | ??3.8 | ??1.2 |
| Viscosity, 100 ℃, mm 2/s | ??8.466 | ??7.449 | ??6.406 | ??6.002 |
| Viscosity index (pressed oil) | ??86 | ??94 | ??104 | ??107 |
| Pour point, ℃ | ??41 | ??39 | ??40 | ??-18 |
| Boiling range, D1160, v% | ||||
| ????10％ | ??433 | ??413 | ??399 | ??392 |
| ????50％ | ??474 | ??467 | ??462 | ??463 |
| ????90％ | ??514 | ??513 | ??512 | ??511 |
Table 4 white oil product property
| Viscosity, 40 ℃, mm 2/s | ????36.31 | ????GB/T265 |
| Pour point, ℃ | ????-12 | ????GB/T3535 |
| Flash-point (opening), ℃ | ????220 | ????GB/T3536 |
| Colourity, number (Sai Shi) | ????＞+30 | ????GB/T3555 |
| Heavy metal, μ g/g | ????＜10 | ????GB/T8451 |
| Arsenic, μ g/g | ????＜1 | ????GB/T8450 |
| Lead, μ g/g | ????＜1 | ????GB/T8449 |
| Solid paraffin | By | ????SH/T0134 |
| Readily carbonizable substance | By | ????GB/T11079 |
| Ultraviolet absorptivity/cm 260nm 270nm 280nm 290nm 300nm 320nm 340nm 360nm 380nm 400nm 420nm | ????0.064 ????0.059 ????0.054 ????0.053 ????0.052 ????0.039 ????0.035 ????0.034 ????0.023 ????0.021 ????0.014 | ????GB/T11081 |
Embodiment 3
Under the constant situation of hydrotreatment segment process condition, hydrofining section and hydrofinishing section adopt different technology conditions, and the solvent-refined oil among the embodiment 2 is handled, and processing condition and product property are listed in table 5.
Product property under table 5 different condition
| Operational condition | ??????????????????1 | ?????????????????2 | |||||
| Hydrofining | Isomerization dewaxing | Post-refining | Hydrofining | Isomerization dewaxing | Post-refining | ||
| Pressure, Mpa | ????8.0 | ??8.0 | ??8.0 | ??4.5 | ??4.5 | ??4.5 | |
| Temperature, ℃ | ????275 | ??367 | ??220 | ??295 | ??363 | ??236 | |
| Liquid hourly space velocity, h -1 | ????1.5 | ??0.4 | ??2.0 | ??1.0 | ??0.6 | ??1.5 | |
| Hydrogen-oil ratio (v/v) | ????800 | ??600 | ??500 | ??800 | ??600 | ??500 | |
| Catalyzer | Kind | ????A3/B2 | ??Pd/SAP ??O-11 | ??A3/B2 | ??A2/B3 | ??Pd/SAP ??O-11 | ??A2/B3 |
| Volume ratio | ????1∶1 | ??1∶2 | ??1∶1 | ??1∶1 | |||
| 36# white oil product property | |||||||
| 40 ℃ of viscosity, mm 2/s | ????39.16 | ????37.58 | |||||
| Pour point, ℃ | ????-12 | ????-10 | |||||
| Viscosity index | ????126 | ????124 | |||||
| Colourity, number (Sai Shi) | ????＞+30 | ????＞+30 | |||||
| Ultraviolet absorptivity/cm (260～420nm) | ????＜0.1 | ????＜0.1 | |||||
| Flash-point, ℃ | ????271 | ????268 | |||||
| Readily carbonizable substance | By | By | |||||
Embodiment 4
The embodiment of the invention 2 and alternative comparing result, the hydrofining section of alternative is used the single catalyzer (with catalyzer identical among the embodiment 2) that contains Y zeolite with the hydrofinishing section, and other condition is identical with embodiment 2.Comparative result sees Table 6.
Table 6 the inventive method and control methods comparative result
| Runtime, hour | ????200 | ????1000 | ????2000 | |
| Temperature, refining/post-refining, ℃ | Embodiment 2 | ????260/220 | ????262/223 | ????263/225 |
| Relatively | ????257/215 | ????260/220 | ????263/225 | |
| Yield, weight % | Embodiment 2 | ????74.2 | ????74.0 | ????73.9 |
| Relatively | ????72.8 | ????71.5 | ????68.5 | |
| Ultraviolet absorptivity, cm (260～420nm) | Embodiment 2 | ????＜0.1 | ????＜0.1 | ????＜0.1 |
| Relatively | ????＜0.1 | ????0.105 | ????0.112 | |
Claims (19)
1, a kind of is the method for raw material production white oil with the solvent treatment hydrocarbon ils, in the presence of catalyzer,---hydrofining---isomerization dewaxing---hydrofinishing with raw material and hydrogen successively by hydrotreatment, wherein hydrotreatment adopts non-noble metal hydrogenation to handle catalyzer, the isomerization dewaxing section adopts the isomerization dewaxing catalyst contain the mesoporous silicon aluminophosphate molecular sieve, it is characterized in that hydrofining section and hydrofinishing section that lubricating oil distillate that the hydrotreatment section obtains enters next unit use two kinds of catalyzer that contain the macropore amorphous silicon aluminium and contain Y zeolite simultaneously.
2, in accordance with the method for claim 1, it is characterized in that described solvent treatment hydrocarbon oil crude material is the solvent-refined oil that boiling point is higher than 250 ℃ vacuum distillate, vacuum residuum propane deasphalting oil or FCC heavy cycle oil.
3, in accordance with the method for claim 1, it is characterized in that described hydrotreating catalyst is Mo or W-Ni/ aluminum oxide or molecular sieve catalyst.
4, in accordance with the method for claim 1, the effluent that it is characterized in that the hydrotreatment section is through gas-liquid separation, fractionation plant and stripper plant, and from liquid stream, cut out boiling point and be higher than the charging of 250 ℃ of cuts as the hydrofining section, the sulphur of charging, nitrogen content are lower than 500 μ g/g and 100 μ g/g respectively.
5, in accordance with the method for claim 4, it is characterized in that the described charging boiling point that enters the hydrofining section is higher than 310 ℃, sulphur, nitrogen content are lower than 200 μ g/g and 50 μ g/g respectively.
6, in accordance with the method for claim 1, first bed that it is characterized in that described hydrofining section and hydrofinishing section uses precious metal-macropore amorphous silicon aluminium catalyzer, second bed uses precious metal-Y zeolite catalyzer, and charging is successively by first bed and second bed.
7, in accordance with the method for claim 6, it is characterized in that the catalyzer pore volume that described first bed is loaded is 0.6-1.0cm
3/ g.
8, in accordance with the method for claim 6, it is characterized in that SiO in the macropore amorphous silicon aluminium that the described first bed catalyzer contained
2Content is 25-50wt%, and pore volume is 0.6-1.4cm
3/ g, specific surface area 300-500m
2/ g.
9, in accordance with the method for claim 6, it is characterized in that the described first bed catalyzer contains a kind of adhesive oxides, the weight ratio of binding agent and macropore silica-alumina supports is 20: 80-40: 60.
10, in accordance with the method for claim 6, it is characterized in that the catalyzer that described second bed is loaded contains Y zeolite, the SiO of molecular sieve
2/ Al
2O
3Mol ratio is 10-40; Unit cell parameters is 2.422-2.445nm; Sodium oxide content is less than 0.15wt%; Relative crystallinity is greater than 95%.
11, in accordance with the method for claim 10, the relative crystallinity that it is characterized in that described Y zeolite is 98%-100%.
12, in accordance with the method for claim 6, it is characterized in that the described second bed catalyzer contains a kind of adhesive oxides, the weight ratio of binding agent and macropore silica-alumina supports is 20: 80-40: 60.
13, in accordance with the method for claim 6, it is characterized in that described two kinds of catalyzer all contain at least a noble metal hydrogenation component, metal content is 0.2-1.2wt%.
14, in accordance with the method for claim 13, it is characterized in that described precious metal is platinum and palladium, the mol ratio of platinum and palladium is 2.5: 1-1: 2.5.
15, in accordance with the method for claim 6, the volume ratio that it is characterized in that the described first bed catalyzer and the second bed catalyzer is 3: 1-1: 3.
16, in accordance with the method for claim 1, each section reactor that it is characterized in that described hydrogenation technique process is all depressed at 2.8-15.0Mpa hydrogen branch and is operated, and the temperature of reaction of hydrofining section is 200-360 ℃, and liquid hourly space velocity is 0.2-2.0h
-1
17, in accordance with the method for claim 1, it is characterized in that described hydrofining section operational condition is: hydrogen dividing potential drop 4.0-10.0Mpa, temperature of reaction 220-320 ℃, liquid hourly space velocity 0.5-1.5h
-1
18, in accordance with the method for claim 1, it is characterized in that the operational condition of described hydrofinishing section is, temperature of reaction 170-320 ℃, liquid hourly space velocity 0.2-4.0h
-1
19, in accordance with the method for claim 1, its feature in the operational condition of described hydrofinishing section is, temperature of reaction 190-280 ℃, and liquid hourly space velocity 0.5-2.0h
-1
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|---|---|---|---|
| CNB001232193A CN1160440C (en) | 2000-11-08 | 2000-11-08 | Process for producing white oil from solvent refining oil |
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|---|---|---|---|
| CNB001232193A CN1160440C (en) | 2000-11-08 | 2000-11-08 | Process for producing white oil from solvent refining oil |
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| CN1160440C CN1160440C (en) | 2004-08-04 |
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|---|---|---|---|
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Cited By (12)
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|---|---|---|---|---|
| CN100400625C (en) * | 2005-10-19 | 2008-07-09 | 中国石油化工股份有限公司 | Hydrogenation process of producing food-level white oil |
| CN100457862C (en) * | 2004-10-29 | 2009-02-04 | 中国石油化工股份有限公司 | One-step hydrogenation method for producing super white oil |
| CN101148606B (en) * | 2006-09-20 | 2010-08-18 | 中国石油化工股份有限公司 | One-stage hydrogenation method for producing food-level white oil |
| CN101074393B (en) * | 2006-05-17 | 2011-04-20 | 中国石油化工股份有限公司 | Method for producing petroleum wax and high-viscosity index lube-oil base oil simultaneously |
| CN101429457B (en) * | 2007-11-08 | 2012-05-09 | 中国石油化工股份有限公司 | Method for distillate hydrogenation for feracity of white oil |
| CN101392186B (en) * | 2007-09-17 | 2012-08-08 | 贾中佑 | White mineral oil for polystyrol |
| CN102971402A (en) * | 2010-05-07 | 2013-03-13 | Sk新技术株式会社 | Method of simultaneously manufacturing high quality naphthenic base oil and heavy base oil |
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| CN107987881A (en) * | 2017-11-30 | 2018-05-04 | 中海沥青股份有限公司 | A kind of preparation method of thick white oil |
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| CN100457862C (en) * | 2004-10-29 | 2009-02-04 | 中国石油化工股份有限公司 | One-step hydrogenation method for producing super white oil |
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| CN101148606B (en) * | 2006-09-20 | 2010-08-18 | 中国石油化工股份有限公司 | One-stage hydrogenation method for producing food-level white oil |
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| CN101429457B (en) * | 2007-11-08 | 2012-05-09 | 中国石油化工股份有限公司 | Method for distillate hydrogenation for feracity of white oil |
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| CN102971402B (en) * | 2010-05-07 | 2015-03-25 | Sk新技术株式会社 | Method of simultaneously manufacturing high quality naphthenic base oil and heavy base oil |
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| CN106479565A (en) * | 2016-11-16 | 2017-03-08 | 中国海洋石油总公司 | Special white oil of a kind of polystyrene and preparation method thereof |
| CN106479565B (en) * | 2016-11-16 | 2018-01-26 | 中国海洋石油总公司 | A kind of special white oil of polystyrene and preparation method thereof |
| CN107987881A (en) * | 2017-11-30 | 2018-05-04 | 中海沥青股份有限公司 | A kind of preparation method of thick white oil |
| CN107987881B (en) * | 2017-11-30 | 2020-04-17 | 中海沥青股份有限公司 | Preparation method of crude white oil |
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