CN101089136A - White oil producing hydrofining process - Google Patents
White oil producing hydrofining process Download PDFInfo
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- CN101089136A CN101089136A CN 200610046935 CN200610046935A CN101089136A CN 101089136 A CN101089136 A CN 101089136A CN 200610046935 CN200610046935 CN 200610046935 CN 200610046935 A CN200610046935 A CN 200610046935A CN 101089136 A CN101089136 A CN 101089136A
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Abstract
The present invention relates to white oil hydrofining production process. Base oil for lubricating oil as the material is hydrogenated in a two-stage process, including the first stage with the dual function catalyst for isomerizing to lower pour point and hydrofining and the second stage with reduced state catalyst. Through the first stage, high quality industrial level white oil may be produced, and through the second stage, high quality food level white oil may be produced. Compared with available technology, the present invention has the advantages of high liquid product yield, high product quality, etc.
Description
Technical field
The present invention relates to a kind of hydrofining and produce the method for white oil, feature is with lube base oils raw material hydrogenation, the method for production high-quality white oil.
Background technology
Fields such as that white oil is widely used in is daily, food, chemical industry, weaving, electronics, metallurgy, agricultural, military project, light industry.White oil is with the petroleum oil fractions deep refining, the product that obtains to almost completely removing desulfuration nitrogen aromatic hydrocarbons, and its main component is isoparaffin and naphthenic hydrocarbon.
The early stage white oil of producing adopts sulfonation method, and it is seriously polluted that this method produces a large amount of acid sludges.The main method of modern production white oil is hydrofining, and its raw material and technology have multiple.As to adopt hydrocracking tail oil be raw material, through the refining white oil that obtains of hydrodewaxing restock; Or through adopting precious metal heterogeneous catalyst isomerization dewaxing/post-refining one-stage serial to produce white oil etc.; With the lubricant base is raw material, through two to three sections white oils that hydrofining also can be produced.But because the pour point reversion after than higher (usually at-6～-12 ℃) and aromatic hydrogenation of the pour point of base oil itself wherein needs the pour point depression operation.
Chinese patent 96120125.8 provides a kind of method of producing white oil by the direct hydrogenation of cycloalkyl straight run.Adopt the single hop tandem process, first reactor is operated under hydrogenating desulfurization, denitrogenation condition, and second reactor is operated under the hydrogenation aromatics-removing condition.Adopt non-precious metal catalyst.Chinese patent 98114344.X uses impurity such as sulphur, nitrogen and higher lubricant base or the worse distillate of quality of aromaticity content to be raw material, adopts one-stage hydrogenation technology, can produce the industrial white oil of top grade product.More than two kinds of methods all have the problem of hydrogenated products pour point reversion, when the pour point of raw material is not enough to reach product requirement, just need replenish processing with the technology of further reduction pour point.
Chinese patent 99113287.4 is a lubricating oil hydrogenation supplementing refining method, and by the dual catalyst bed, wherein a kind of catalyzer contains ZSM-5 or ZSM-8 etc. to this method with lubricating oil.This method also can be used to reduce the pour point of white oil.
In Hydrodewaxing catalyst, contain zeolite component such as ZSM-5, ZSM-8 usually.Because this class zeolite component only allows the small molecules straight-chain paraffin to enter and and scission reaction takes place, it is more to produce gas.In pour point depression-process for refining, its total liquid yield is relatively low like this, and product distributes also more single.
And adopt precious metal heterogeneous catalyst isomerization dewaxing/post-refining to produce white oil; Sulphur, nitrogen content to raw material have strict demand, do not reach requirement through the common base oil of furfural, ketone benzene and the old three covering device productions of carclazyte usually, and need carry out could be as raw material after the hydrofining again.
Summary of the invention
The invention provides and a kind ofly can improve the method that the white oil yield reduces the production white oil of pour point simultaneously, the inventive method can obtain industrial white oil, also can obtain food-level white oil.
The method of manufacture grade white oil of the present invention is specific as follows: be raw material with the lubricant base, under optimum conditions, raw material and hydrogen are by containing the beds of β zeolite hydrotreating catalyst, and product can obtain industrial grade white oil through separating.
The present invention produces the method for food-level white oil and specifically gives: be raw material with the lubricant base, under optimum conditions, raw material and hydrogen are by containing the beds of β zeolite hydrotreating catalyst.Process contains product and the hydrogen process post-refining beds behind the β zeolite hydrotreating catalyst bed, obtains food-level white oil.
The hydrotreating catalyst of the described β of containing zeolite has following character: contain β modified zeolite 1～9wt% in the catalyzer, preferably contain β zeolite 1～7wt%, 2.0～5.0wt% more preferably, infrared acidity 0.05～0.8mmol/g, preferred 0.1～0.4mmol/g, average grain size is 0-1～0.5 micron, and preferred 0.1～0.3 micron, the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume.β zeolite General N a
2The O weight content is less than 0.15wt%, preferably less than 0.10wt%, and SiO
2/ Al
2O
3Weight ratio is 50～90, preferred 60～80.Other carrier component can be one or more in the various inorganic refractory oxides such as mixture of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, zirconium white and above several oxide compounds, and commonly used is aluminum oxide and/or amorphous silicon aluminium.Amorphous aluminum silicide content is 29w%～34w%, 32w%～47w% preferably, and alumina content is a surplus, the specific surface area 160～230m of catalyzer
2/ g, pore volume 0.32～0.45ml/g.The hydrogenation metal component can be selected from one or more in group vib and the group VIII base metal, and one or more that commonly used is among W, Mo, Ni, the Co are generally 15.0～40.0wt% in the oxide compound metal content, preferred 20.0～35.0wt%.Usually contain group vib metal and group VIII metal simultaneously, as contain W and/or Mo 15.0～30.0wt% in oxide compound, preferred 18.0～26.0wt% contains Ni and/or Co 3.0～9.0wt%, preferred 5.0～7.0wt% in oxide compound.
Before containing β zeolite hydrotreating catalyst bed and/or conventional Hydrobon catalyst bed can be set afterwards, conventional Hydrobon catalyst is 10: 90～90: 10 with the volume ratio that contains β zeolite hydrotreating catalyst.The hydrotreatment conversion zone and the conventional Hydrobon catalyst conversion zone that contain the β zeolite are called first conversion zone, and two types catalyzer can be seated in the same reactor, also can be seated in the different reactors.Hydrofinishing through material after first section processing is called second conversion zone.
Raw material by the operational condition that contains β zeolite hydrotreating catalyst is: reaction pressure 8.0～20.0MPa, hydrogen to oil volume ratio 300～2000, volume space velocity 0.2～2.0h
-1, 280～400 ℃ of temperature of reaction.Being preferably reaction conditions is reaction pressure 10.0～16.0MPa, 300～360 ℃ of temperature of reaction, volume space velocity 0.6～1.0h
-1, hydrogen to oil volume ratio 500～1000.As first conversion zone a plurality of reaction zones are arranged, raw material can be identical with the condition by β zeolite hydrotreating catalyst by the condition of conventional Hydrobon catalyst layer reaction zone, also can be different.Can be conventional hydroprocessing condition, general reaction conditions be reaction pressure 5～20.0MPa, 280～400 ℃ of temperature, hydrogen to oil volume ratio 200～1500, air speed 0.5～5.0h
-1, preferably in passing through the operational condition scope of β zeolite hydrotreating catalyst.
The reaction conditions of second conversion zone is generally reaction pressure 12～20.0MPa, hydrogen to oil volume ratio 300～1500, volume space velocity 0.2～2.0h
-1, 150～330 ℃ of temperature of reaction.Being preferably reaction conditions is reaction pressure 15.0～20.0MPa, 180～260 ℃ of temperature of reaction, volume space velocity 0.6～1.0h
-1, hydrogen to oil volume ratio 500～1000.Catalyzer can be selected conventional hydrocatalyst for saturating, as going back the ortho states high-nickel catalyst, also can be noble metal catalyst etc.
The present invention takes all factors into consideration the white oil index request, selects suitable technical process and optimizes processing condition, determines suitable catalyzer, can be the high quality white oil production with the raw material time processing, also can be with first section product as the second section feeding repeated hydrogenation.The inventive method can remove the impurity such as sulfide, nitride, oxide compound, organic acid, phenol, alkene and aromatic hydrocarbons in the raw material, appropriate regulation viscosity, density; The pour point appropriateness reduces, and does not have gas substantially and produces, and white oil yield and pure hydrofining are basic identical, and the low on a small quantity aromatic hydrocarbons low-sulfur high-quality light oil of by-product can be used as specialty oil products, as the super low sulfur solvent oil, does not have fragrant solvent wet goods.
Advantages such as it is simple that the inventive method has flow process, and stable operation, lower, catalyst runs cycle of investment are long.The catalyzer that the inventive method is selected uses the non-noble metal hydrogenation component, and the cost of catalyzer is low, and adaptability is strong, and good stability is applicable to single hop or series process flow.The β zeolite hydrotreating catalyst that contains that the inventive method is used has characteristics such as crystal grain is little, acidity is low, secondary pore is many, after effectively carrying out isomery, taking off the impurity reaction, can reduce cracking reaction and secondary reaction effectively, help improving product yield.Compare with general refining-pour point depression technology, the written or printed documents characteristic feature of an invention is a liquid oils yield height, and flexibility of operation is bigger, can use white oil and the extraordinary refined oil of the degree of depth with the multiple viscosity of a kind of raw material production.Can adapt to the market seasonal demand preferably.
Embodiment
Adopt the two-stage hydrogenation technical process to produce make up level and/or food-level white oil.Wherein first section hydrogenation catalyst bed comprises a hydrogenation catalyst bed that contains the β zeolite at least.Under optimum conditions, raw material and hydrogen obtain sulphur nitrogen and aromaticity content very low and the satisfactory industrial grade white oil product of pour point and a small amount of low aromatic hydrocarbons light oil by beds.Second section hydrogenation then is that the aromatic hydrocarbons deep hydrogenation is saturated.
Wherein raw material can be the base oil of producing through furfural, ketone benzene and old three covering devices of carclazyte, or through the treated oil of furfural, ketone benzene, or base oil or the intermediates produced through peracid carclazyte process.Or one or more mixing oil in the above stock oil.Also can contain a small amount of light ends.
First section hydrogenation can adopt single beds in the inventive method, also can adopt a plurality of beds.Each bed can use a kind of type catalyst, and can the supplementary protection agent etc., or use catalyzer to form two or several different reaction zones more than one type.Can in same reactor or in two or more tandem reactor, realize.When multi-reaction-area, look raw material condition and to the requirement of product, raw material can at first pass through conventional Hydrobon catalyst layer, then by containing the hydrotreating catalyst layer of β zeolite, otherwise or, or the hydrotreating catalyst layer is mediated.
The β zeolite that the present invention contains in the hydrogenation catalyst of β zeolite is a modified beta zeolite, and preparation process may further comprise the steps:
(1) the beta-molecular sieve slurries after the crystallization directly carry out ammonium exchange, filtration, washing, drying and roasting;
(2) beta-molecular sieve that takes off behind the ammonium of roasting carries out acid treatment;
(3) the intact beta-molecular sieve of acid treatment carries out hydrothermal treatment consists again.
Beta-molecular sieve after the above-mentioned crystallization generally is to be template with organic ammonium (as tetraethyl ammonium hydroxide), uses the hydrothermal crystallization method synthetic.Its SiO
2/ Al
2O
3Weight ratio is generally 25～30, Na
2The content of O is 3.0wt%～4.0wt%.Beta-molecular sieve slurries after the crystallization directly carry out the ammonium salt exchange, and the concentration of ammonium salt in slurries is 0.5～5.0mol/l, and several is carried out in the ammonium exchange, make Na in the molecular sieve of exchange back
2The O weight content is not more than 0.5%, and general ammonium exchange 1～4 time can reach requirement.Beta-molecular sieve after the ammonium salt exchange filters, washes, drying and roasting, and wherein maturing temperature is controlled at 450 ℃～650 ℃, and the time is 5.0～15.0 hours.The beta-molecular sieve that roasting is taken off behind the ammonium carries out acid treatment, filters, and wherein acid treatment condition is for being that the mineral acid of 0.1～5.0mol/l is carrying out acid treatment with concentration under abundant agitation condition, 20 ℃～100 ℃ of treatment temps, and the treatment time is 0.5～5.0 hour.The intact beta-molecular sieve of acid treatment carries out pressurized thermal water to be handled, the hydrothermal treatment consists condition for 100% water vapor at 500 ℃～800 ℃, be preferably 550 ℃～700 ℃, system pressure is 0.05～1.0MPa, be preferably 0.1～0.5MPa, handled preferably 1～2 hour 0.5～5.0 hour.
Three β zeolites of following mask body modification are used for hydrotreating catalyst of the present invention.
β 1 character is: molecular sieve SiO
2/ Al
2O
3Weight ratio 70, relative crystallinity are 107, specific surface 570m
2/ g, infrared acidity 0.25mmol/g, the secondary pore pore volume of 2～10nm accounts for 45% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve of O 3.65wt% synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 85 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 550 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 1.2M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 85 ℃, and constant temperature stirred 2 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 600 ℃, control pressure 0.3MPa, and the treatment time is 2 hours.
β 2 character are: molecular sieve SiO
2/ Al
2O
3Weight ratio 60, specific surface 600m
2/ g, relative crystallinity are 105, infrared acidity 0.35mmol/g, and the secondary pore pore volume of 2～10nm accounts for 38% of total pore volume, average crystal grain diameter 0.3 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve of O 3.65wt% synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 3 hours, was cooled to 50 ℃ of filtrations, wet cake carries out second and third time exchange again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 500 ℃, constant temperature 12 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 0.8M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 4 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 570 ℃, control pressure 0.1MPa, and the treatment time is 3 hours.
β 3 character are: molecular sieve SiO
2/ Al
2O
3Weight ratio 85, specific surface 530m
2/ g, relative crystallinity are 100, infrared acidity 0.15mmol/g, and the secondary pore pore volume of 2～10nm accounts for 52% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2O
3.65wt% Na beta-molecular sieve synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 3.5M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 600 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 2.5M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 3 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 650 ℃, control pressure 0.4MPa, and the treatment time is 4 hours.
Further specify the present invention below in conjunction with embodiment.The per-cent that relates to is weight percentage.Specific surface area is measured for the BDE method, and pore volume is that low-temperature nitrogen adsorption method is measured, and infrared acidity is that 160 ℃ of infrared external spectrum methods of pyridine adsorption are measured, and other index is that ordinary method or standard method are measured.
Feedstock property used among the embodiment sees Table 1.
Table 1 feedstock property
| Project | Stock oil A | Stock oil B |
| Density (20 ℃)/g.cm 3 | 0.860 | 0.862 |
| Pour point/℃ | -12 | -6 |
| Color (GB6540)/number | 3.0 | 3.5 |
| Viscosity (40 ℃)/mm 2.s -1 | 29.90 | 28.35 |
| Acid number/mgKOH.g -1 | 0.02 | 0.02 |
| S/μg·g -1 | 341 | 675 |
| Aromatic hydrocarbons/% | 14.3 | 6.2 |
| Boiling range/℃ | ||
| 10％ | 381 | 390 |
| 50％ | 413 | 417 |
| 90％ | 436 | 448 |
| 95％ | 442 | 463 |
The catalyzer that the hydrofining reaction district uses among the embodiment is the commercial hydrotreating catalyst 3996 of commercial Hydrobon catalyst FV or the production of Fushun Petrochemical Company catalyst plant, and character sees Table 2-1.The hydrotreating catalyst character that contains the β zeolite sees Table 2-2.The operational condition of embodiment and the results are shown in Table 3, as can be seen from Table 3, the one-stage hydrogenation by the inventive method can obtain the fine industrial grade white oil.
The main composition and the character of table 2-1 Hydrobon catalyst
| Catalyzer | FV | 3996 |
| Reactive metal composition/wt% | ||
| WO 3 | 30.0 | / |
| MoO 3 | / | 24.5 |
| NiO | 4.5 | 4.5 |
| Pore volume/mlg -1 | 0.30 | 0.38 |
| Specific surface area/m 2·g -1 | 140 | 165 |
Table 2-2 contains the composition and the character of β zeolite hydrotreating catalyst
| Catalyzer | A-1 | A-2 |
| Carrier | γ-Al 2O 3 | Amorphous silicon aluminium * |
| The β zeolite | β1 | β 2/ β 3 weight 1: 1 |
| β zeolite content/wt% | 5 | 3 |
| Chemical constitution/wt% | ||
| WO 3 | 25 | 22 |
| MoO 3 | 5 | / |
| NiO | 3 | 5 |
| Pore volume/mlg -1 | 0.36 | 0.48 |
| Specific surface area/m 2·g -1 | 168 | 194 |
Comparative example 1～2
Catalyzer is replaced with the catalyst A-3 that contains β zeolite 20wt% among comparative example 1: the embodiment 1, and other is identical with embodiment 1, and test-results sees Table 4, data as can be seen from table, use the hydrotreating catalyst of high zeolite content, yield of lubricating oil is reduced greatly, it is more that cracking produces lighter hydrocarbons.
The contained β zeolite of catalyzer is changed to commercially available β zeolite among comparative example 2: the embodiment 1, obtains the Hydrogen β zeolite of sodium oxide content 0.1% for 4 times through ammonium exchange, and main character is: molecular sieve SiO
2/ Al
2O
3Weight ratio 30, infrared acidity 1.2mmol/g, the secondary pore pore volume of 2～10nm accounts for below 5% of total pore volume, average crystal grain diameter 0.8 μ m, catalyzer is A-4.Other is identical with embodiment 1.Test-results sees Table 4, and data are used common Hydrogen β zeolite as can be seen from table, because acidity is strong, secondary pore is less, crystal grain is bigger, and yield of lubricating oil is reduced greatly, it is more that cracking produces lighter hydrocarbons.
Table 3 embodiment 1～4 operational condition and result
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Stock oil A | Stock oil A | Stock oil B | Stock oil B |
| Catalyzer | A-1/FV | A-2 | A-2/3996 | FV/A-1 |
| The catalyst volume ratio | 1∶1 | / | 5∶1 | 4∶1 |
| Processing condition | ||||
| Temperature of reaction/℃ | 340 | 320 | 340 | 330 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| The volume of hydrogen oil ratio | 500 | 500 | 1200 | 800 |
| Cumulative volume air speed/h -1 | 0.6 | 1.0 | 0.6 | 0.8 |
| Total liquid yield, % | 100.3 | 100.1 | 100.1 | 100.4 |
| ＞300 ℃. the cut product property | ||||
| Yield % | 92.3 | 90.9 | 88.6 | 90.5 |
| Color (Sai Shi) | +30 | +30 | +30 | +30 |
| Pour point/℃ | -15 | -16 | -12 | -9 |
| Viscosity (40 ℃)/mm 2.s -1 | 28.7 | 28.6 | 29.1 | 29.0 |
| Aromatic hydrocarbons/% | 1.0 | 1.0 | 0.8 | 0.8 |
| S/μg·g -1 | 2.1 | 2.1 | 2.1 | 2.5 |
| N/μg·g -1 | 1.0 | 1.0 | 1.0 | 1.0 |
Table 4 comparative example 1 operational condition and result
| Embodiment | Comparative example 1 | Comparative example 2 |
| Stock oil | Stock oil A | Stock oil A |
| Catalyzer | A-3/FV | A-4/FV |
| The catalyst volume ratio | 1∶1 | 1∶1 |
| Processing condition | ||
| Temperature of reaction/℃ | 330 | 320 |
| Reaction pressure/MPa | 15.0 | 15.0 |
| The volume of hydrogen oil ratio | 500 | 500 |
| Cumulative volume air speed/h 1 | 0.6 | 0.6 |
| Total liquid yield | 95.5 | 85.5 |
| ＞300 ℃. the cut product property | ||
| Yield % | 79.5 | 70.5 |
| Color (Sai Shi) | +30 | +30 |
| Pour point/℃ | -16 | -19 |
| Viscosity (40 ℃)/mm 2.s -1 | 28.6 | 27.9 |
| Aromatic hydrocarbons/% | 1.0 | 1.0 |
| S/μg·g -1 | 2.0 | 2.0 |
| N/μg·g -1 | 1.0 | 1.0 |
In the comparative example 3～4 of following table 5, adopt the commercial catalysts B-1 contain the ZSM-5 molecular sieve (3881 catalyzer of Fushun Petrochemical Company catalyst plant production, mainly to contain non-amine method synthetic ZSM-5 molecular sieve, pore volume 0.18～0.22ml/g, specific surface area 250～300m
2/ g) carry out the hydrogenation pour point depression.Processing condition and table 3 are approaching.Contrast table 3 and table 5 as seen, when processing condition were close, the total liquid yield of hydrogenated products of the present invention was than higher.
Table 5 comparative example 3～4 operational conditions and result
| Comparative example | Comparative example 2 | Comparative example 3 |
| Stock oil | Stock oil A | Stock oil B |
| Catalyzer | FV/B-1 | B-1/FV |
| The catalyst volume ratio | 1∶1 | 1∶1 |
| Processing condition | ||
| Temperature of reaction/℃ | 340 | 330 |
| Reaction pressure/MPa | 15.0 | 15.0 |
| The volume of hydrogen oil ratio | 500 | 500 |
| Cumulative volume air speed/h -1 | 0.6 | 0.6 |
| Total liquid yield | 95.2 | 97.0 |
| ＞300 ℃. the cut product property | ||
| Yield (to raw material) | 90.7 | 93.2 |
| Pour point/℃ | -15 | -12 |
| Viscosity (40 ℃)/mm 2.s -1 | 28.6 | 28.72 |
| Aromatic hydrocarbons/% | 1.2 | 1.0 |
| S/μg·g -1 | 2.1 | 2.4 |
| N/μg·g -1 | 1.0 | 1.0 |
The processing condition such as the table 6 of second section hydrogenation: hydrogenated products all meet state food grade white oil specification of quality.Wherein C-1 is industrial high-nickel catalyst, and C-2 is the palladium catalyst of prepared in laboratory.C-1 and C-2 used 300/250 ℃ of reduction in back 10 hours.(the C-1 catalyzer is formed: NiO49%, specific surface area 138m
2/ g, pore volume 0.30ml/g; C-2 catalyst P d 2%, specific surface area 227m
2/ g, pore volume 0.41ml/g.Surplus is an aluminum oxide.)
Table 6 embodiment 5～7 operational conditions and result
| Embodiment | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Stock oil | The product of embodiment 2＞300 ℃. cut | The product of embodiment 3＞300 ℃. cut | The product of embodiment 3＞300 ℃. cut |
| Catalyzer | C-1 | C-1 | C-2 |
| Processing condition | |||
| Temperature of reaction/℃ | 230 | 240 | 230 |
| Reaction pressure/MPa | 15.0 | 15.0 | 15.0 |
| The volume of hydrogen oil ratio | 500 | 500 | 500 |
| Cumulative volume air speed/h -1 | 0.3 | 0.5 | 1.0 |
| Product property | |||
| Yield % | 100.0 | 100.0 | 100.0 |
| Pour point/℃ | -15 | -12 | -12 |
| Viscosity (40 ℃)/mm 2.s -1 | 28.8 | 29.3 | 29.4 |
| Condensed-nuclei aromatics | By | By | By |
| Readily carbonizable substance | By | By | By |
Claims (13)
1, the method for white oil is produced in a kind of hydrofining, is raw material with the lubricant base, and under optimum conditions, raw material and hydrogen are by containing the beds of β zeolite hydrotreating catalyst, and product can obtain industrial grade white oil through separating; The content of wherein said β zeolite is 1～9wt%, the infrared acidity 0.05～0.8mmol/g of β zeolite, and average grain size is 0.1～0.5 micron, the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume.
2, in accordance with the method for claim 1, it is characterized in that product and hydrogen process post-refining beds after described process contains β zeolite hydrotreating catalyst bed, obtain food-level white oil.
3, in accordance with the method for claim 1, it is characterized in that the hydrotreating catalyst of the described β of containing zeolite has following character: contain β modified zeolite 1～7wt% in the catalyzer, SiO
2/ Al
2O
3Weight ratio is 50～90, and infrared acidity 0.1～0.4mmol/g, average grain size are 0.1～0.3 micron.
4, in accordance with the method for claim 1, the hydrotreating catalyst that it is characterized in that the described β of containing zeolite contains one or more in the mixture of carrier component aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, zirconium white and above several oxide compounds.
5, in accordance with the method for claim 1, the hydrogenation component that it is characterized in that the hydrotreating catalyst of the described β of containing zeolite is one or more among W, Mo, Ni and the Co, is 15.0～40.0wt% in the oxide compound metal content.
6, in accordance with the method for claim 1, it is characterized in that before containing β zeolite hydrotreating catalyst bed and/or conventional Hydrobon catalyst be set afterwards that conventional Hydrobon catalyst is 10: 90～10: 90 with the volume ratio that contains β zeolite hydrotreating catalyst.
7, in accordance with the method for claim 1, it is characterized in that raw material by the operational condition that contains β zeolite hydrotreating catalyst is: reaction pressure 8.0～20.0MPa, hydrogen to oil volume ratio 300～2000, volume space velocity 0.2～2.0h
-1, 280～400 ℃ of temperature of reaction.
8, in accordance with the method for claim 1, it is characterized in that raw material by the operational condition that contains β zeolite hydrotreating catalyst is: reaction pressure 10.0～16.0MPa, 300～360 ℃ of temperature of reaction, volume space velocity 0.6～1.0h
-1, hydrogen to oil volume ratio 500～1000.
9, in accordance with the method for claim 6, it is characterized in that the operational condition when raw material passes through Hydrobon catalyst is: reaction pressure 5～20.0MPa, 280～400 ℃ of temperature, hydrogen to oil volume ratio 200～1500, air speed 0.5～5.0h
-1
10, in accordance with the method for claim 2, it is characterized in that described post-refining condition is: reaction pressure 12～20.0MPa, hydrogen to oil volume ratio 300～1500, volume space velocity 0.2～2.0h
-1, 150～330 ℃ of temperature of reaction.
11, in accordance with the method for claim 10, it is characterized in that described post-refining condition is: reaction pressure 15.0～20.0MPa, 180～260 ℃ of temperature of reaction, volume space velocity 0.6～1.0h
-1, hydrogen to oil volume ratio 500～1000.
12, in accordance with the method for claim 2, it is characterized in that described post-refining catalyzer for going back the ortho states high-nickel catalyst, or noble metal catalyst.
13, in accordance with the method for claim 1, it is characterized in that described lubricant base raw material is the base oil of producing through furfural, ketone benzene and carclazyte device, or through the treated oil of furfural, ketone benzene, or base oil or the intermediates produced through peracid carclazyte process, or one or more mixing oil in the above stock oil.
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| CN103059975A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreatment method for producing solvent naphtha in flexible mode |
| CN106753550A (en) * | 2016-11-16 | 2017-05-31 | 中国海洋石油总公司 | A kind of food-level white oil 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 |
| CN109261153A (en) * | 2017-12-27 | 2019-01-25 | 上海迅凯新材料科技有限公司 | A kind of loading type nickel-based catalyst and its preparation method and application |
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2006
- 2006-06-16 CN CNB2006100469359A patent/CN100558862C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059975A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreatment method for producing solvent naphtha in flexible mode |
| CN103059975B (en) * | 2011-10-18 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of hydroprocessing process of flexible production solvent oil |
| CN106753550A (en) * | 2016-11-16 | 2017-05-31 | 中国海洋石油总公司 | A kind of food-level white oil and preparation method thereof |
| CN106753550B (en) * | 2016-11-16 | 2018-07-20 | 中国海洋石油集团有限公司 | A kind of food-level white oil 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 |
| CN109261153A (en) * | 2017-12-27 | 2019-01-25 | 上海迅凯新材料科技有限公司 | A kind of loading type nickel-based catalyst and its preparation method and application |
| CN109261153B (en) * | 2017-12-27 | 2021-08-03 | 上海迅凯新材料科技有限公司 | Supported nickel-based catalyst and preparation method and application thereof |
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| CN100558862C (en) | 2009-11-11 |
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