CN103695028A - Method for producing white oil - Google Patents
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Abstract
The invention provides a method for producing white oil. The method comprises the following steps: mixing first tail oil and second tail oil according to a mass ratio of (15-35):(85-65), and adding hydrogen so as to obtain white oil. The quality of the white oil obtained by using the method is higher than the quality of white oil prepared by adding hydrogen into single tail oil. The white oil prepared by using the method provided by the invention can be the food grade, and in addition, by adopting the method, the requirements on the quality of the tail oil are reduced, and meanwhile the situation that a production method of a hydrogenation reaction catalyst needs to be changed because of the difference of the tail oil is avoided, so that the cost is saved, the production process is simplified, and long-term and stable operation of the production process is ensured.
Description
Technical field
The present invention relates to Petroleum Processing Technology field, relate in particular to a kind of production method of white oil.
Background technology
White oil is the slab oil after deep refining, and it basic composition is saturated hydrocarbon structure, has good chemical stability and light stability.Be widely used in the fields such as daily use chemicals industry, pharmaceutical production, food-processing, fiber and weaving, polystyrene resin, petrochemical industry, plastics and Rubber processing, leather processing, instrument, electric power and agricultural.The production technique of white oil mainly contains: old three cover methods, sulfonation method and hydrogenation method.Old three cover methods are furfural treatment, solvent dewaxing and clay-filtered, the method complex process, and cost is high, and can only produce general industry grade white oil; It is sulphonating agent that sulfonation method be take oleum or sulphur trioxide, and the white oil yield of this explained hereafter is lower, and acid sludge and spent bleaching clay are difficult to process, and environmental pollution is serious; The advantages such as that the technique of producing white oil by hydrogenation has is pollution-free, yield is high and raw material sources are extensive, have obtained development rapidly.And along with rapid development of economy, the demand straight line of white oil rises, particularly high-quality, high-level high-quality white oil.
The raw material of producing white oil by hydrogenation is mainly hydrocracking tail oil, through solvent dewaxing or isomerization dewaxing, then through the saturated production white oil of reduction catalyst high-pressure hydrogenation.In actual production, for improving the quality of white oil, usually need the catalyzer in optimization production process, because the cost of catalyzer is higher, thereby the cost of producing white oil is also improved greatly.The one-stage hydrogenation method of production top grade product white oil as disclosed in CN1769380A, by stock oil successively by have hydrofining function catalyst reaction district, there is the catalyst reaction district of pour point depression function and there is the catalyst reaction district of the saturated function of hydrogenation, different catalyzer need be added in these three reaction zones, this method is used catalyzer many, and cost is also high.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of production method of white oil, under the catalyzer condition of method provided by the invention in not changing WHITE OIL PRODUCTION process, produces high-quality white oil.
The production method that the invention provides a kind of white oil, comprising:
The first tail oil and the second tail oil be take to mass percent as (15～35): mix (85～65), carries out hydrogenation reaction, obtains white oil;
The initial boiling point of described the first tail oil is 330～360 ℃, and final boiling point is 485～505 ℃, and the density in the time of 20 ℃ is 845～855kg/m
3, the viscosity of 40 ℃ is 20～35mm
2/ s, condensation point is-10～+ 10 ℃;
The initial boiling point of described the second tail oil is 305～325 ℃, and final boiling point is 510～540 ℃, and the density in the time of 20 ℃ is 825～840kg/m
3, the viscosity of 100 ℃ is 5.0～6.0mm
2/ s, condensation point is+20～+ 45 ℃.
Preferably, described the first tail oil is for adopting the tail oil of the hydrocracking of FF-20 and the series connection of FC-14 dual catalyst.
Preferably, described the second tail oil is for adopting the tail oil of the hydrocracking of FZC-100 protective material, FZC-105 protective material, FZC-106 protective material, tooth ball-type FF-46 pretreating catalyst by hydrocracking and tooth ball-type FC-16B hydrocracking catalyst.
Preferably, the mass percent of described the first tail oil and the second tail oil is (20～30): (80～70).
Preferably, described method is specially: the first tail oil and the second tail oil be take to mass ratio as (15～35): mix (85～65), carries out hydroisomerization dewax, and the white oil cut after refining is collected in hydrofining, obtains white oil.
Preferably, the pressure of described hydroisomerization dewax is 14MPa～16.8MPa.
Preferably, the pressure of described hydroisomerization dewax is 15MPa～16MPa.
Preferably, the temperature of described hydroisomerization dewax is 320 ℃～360 ℃.
Preferably, the temperature of described hydroisomerization dewax is 330 ℃～350 ℃.
Preferably, the pressure of the white oil cut of described collection after refining is 1.10MPa～1.60MPa.
Compared with prior art, the invention provides a kind of production method of white oil, comprising: the first tail oil and the second tail oil be take to mass percent as (15～35): mix (85～65), and hydrogenation, obtains white oil; The initial boiling point of described the first tail oil is 330～360 ℃, and final boiling point is 485～505 ℃, and the density in the time of 20 ℃ is 845～855kg/m
3, the viscosity of 40 ℃ is 20～35mm
2/ s, condensation point is-10～+ 10 ℃; The initial boiling point of described the second tail oil is 305～325 ℃, and final boiling point is 510～540 ℃, and the density in the time of 20 ℃ is 825～840kg/m
3, the viscosity of 100 ℃ is 5.0～6.0mm
2/ s, condensation point is+20～+ 45 ℃.Wherein, the first tail oil be take to mass percent with the second tail oil as (15～35): (85～65) mix, the quality of the white oil obtaining by Hydrogenation is higher than the quality of the white oil obtaining with single tail oil Hydrogenation, and the white oil that method provided by the invention makes can reach cosmetics-stage white oil.Experimental result shows, in the white oil making by method provided by the invention, it subtracts top and follows oil viscosity index up to 82, and condensation point is low to moderate-46 ℃, subtracts one, the viscosity index of two wires mixing oil is up to 107, and condensation point is low to moderate-24 ℃; In addition, the method has also reduced the requirement to tail oil quality, and also avoided, because tail oil is different, needs to change the production method of catalyst for hydrogenation, and then saved cost simultaneously, has simplified production technique, guarantees the operation that production technique can be steady in a long-term.
Embodiment
The production method that the invention provides a kind of white oil, comprising:
The first tail oil and the second tail oil be take to mass percent as (15～35): mix (85～65), carries out hydrogenation reaction, obtains white oil;
The initial boiling point of described the first tail oil is 330～360 ℃, and final boiling point is 485～505 ℃, and the density in the time of 20 ℃ is 845～855kg/m
3, the viscosity of 40 ℃ is 20～35mm
2/ s, condensation point is-10～+ 10 ℃;
The initial boiling point of described the second tail oil is 305～325 ℃, and final boiling point is 510～540 ℃, and the density in the time of 20 ℃ is 825～840kg/m
3, the viscosity of 100 ℃ is 5.0～6.0mm
2/ s, condensation point is+25～+ 45 ℃.
In the present invention, the first tail oil and the second tail oil are mixed, obtain mixing tail oil, the initial boiling point of described the first tail oil is 330～360 ℃, and final boiling point is 485～505 ℃, and the density in the time of 20 ℃ is 845～855kg/m
3, the viscosity of 40 ℃ is 20～35mm
2/ s, condensation point is-10～+ 10 ℃; Being preferably initial boiling point is 335～355 ℃, and final boiling point is 490～500 ℃, and the density in the time of 20 ℃ is 848～853kg/m
3, the viscosity of 40 ℃ is 22～30mm
2/ s, condensation point is-8～+ 8 ℃; More preferably initial boiling point is 340～350 ℃, and final boiling point is 491～495 ℃, and the density in the time of 20 ℃ is 849～851kg/m
3, the viscosity of 40 ℃ is 23～25mm
2/ s, condensation point is+4～+ 6 ℃, most preferably is the tail oil of the hydrocracking that adopts FF-20 and the series connection of FC-14 dual catalyst, and it is 345 ℃ that described tail oil is preferably initial boiling point, and final boiling point is 493 ℃, and the density in the time of 20 ℃ is 849.9kg/m
3, the viscosity of 40 ℃ is 24.22mm
2/ s, the viscosity of 100 ℃ is 4.573mm
2/ s, viscosity index is 103, and flash-point (opening) is 208 ℃, and condensation point is+5 ℃, and colourity is less than 3.0, and sulphur content is 2.81 μ g/g, and nitrogen content is 0.57 μ g/g, and iron level is 1.9 μ g/g; The initial boiling point of described the second tail oil is 305～325 ℃, and final boiling point is 510～540 ℃, and the density in the time of 20 ℃ is 825～840kg/m
3, the viscosity of 100 ℃ is 5.0～6.0mm
2/ s, condensation point is+25～+ 45 ℃, and being preferably initial boiling point is 310～322 ℃, and final boiling point is 520～538 ℃, and the density in the time of 20 ℃ is 830～838kg/m
3, the viscosity of 100 ℃ is 5.2～5.8mm
2/ s, condensation point is+30～+ 40 ℃, and more preferably initial boiling point is 315～320 ℃, and final boiling point is 525～535 ℃, and the density in the time of 20 ℃ is 832～836kg/m
3, the viscosity of 100 ℃ is 5.4～5.7mm
2/ s; condensation point is+35～+ 49 ℃; most preferably be the tail oil of the hydrocracking that adopts FZC-100 protective material, FZC-105 protective material, FZC-106 protective material, tooth ball-type FF-46 pretreating catalyst by hydrocracking and tooth ball-type FC-16B hydrocracking catalyst; it is 320 ℃ that described tail oil is preferably initial boiling point; final boiling point is 535 ℃, and the density in the time of 20 ℃ is 835.1kg/m
3, the viscosity of 100 ℃ is 5.679mm
2/ s, viscosity index is 139, and flash-point (opening) is 224 ℃, and condensation point is+38 ℃, and colourity is less than 1.0, and sulphur content is 10.5 μ g/g, and nitrogen content is 0.37 μ g/g, and iron level is 1.8 μ g/g; The mass percent of described the first tail oil and the second tail oil is (15～35): (85～65), are preferably (20～30): (80～70), more preferably (22～28): (78～72).
The present invention carries out hydrogenation reaction by mixing tail oil, obtains white oil.The present invention is not particularly limited the catalyzer of hydrogenation reaction, the conventional catalyst for hydrogenation using in this area, as can be carrier for one or more of take in aluminum oxide, silicon oxide, amorphous aluminum silicide, titanium oxide and zirconium white, one or more metals of usining in group vib and group VIII element, as activeconstituents, can contain the catalyzer of the auxiliary agents such as P, Ti, B and Zr.The present invention does not have particular requirement to described hydrogenation reaction, can be one-stage process hydrogenation reaction, two-stage method hydrogenation reaction or three-stage process hydrogenation reaction.
In order to obtain high-quality white oil, the present invention preferably uses two-stage method hydrogenation reaction, being about to mix tail oil fully contacts after mixing with hydrogen, through hydroisomerization reactor, carry out hydroisomerization dewax reaction again, through hydrofining reactor, carry out hydrofining again, collect the white oil cut after refining, obtain white oil; The present invention does not have particular requirement to hydroisomerization catalyst, the conventional hydroisomerization catalyst using in this area, as can be carrier for one or more of take in aluminum oxide, silicon oxide, amorphous aluminum silicide, titanium oxide and zirconium white, one or more metals of usining in group vib and group VIII element, as activeconstituents, can contain the catalyzer of the auxiliary agents such as P, Ti, B and Zr; The Pt that to be preferably mass percent be 0.32～0.38 is as the FIW-1 catalyzer of metal active catalyzer; The present invention does not have particular requirement to hydrorefined catalyzer yet, the conventional hydrorefined catalyzer using in this area, and as can be active metal for take nickel or group VIII metal, Al
2o
3or Al
2o
3-SiO
2for carrier, the catalyzer that contains the auxiliary agents such as P, Ti, B and Zr, the Pd that the Pt that to be preferably mass percent be 0.18～0.20 and mass percent are 0.26～0.30% is as the FHDA-1 catalyzer of metal active catalyzer.
In order to make aromatic hydrocarbons in tail oil fully saturated and can fully remove sulphur, nitrogen and oxygen, and then oxidation stability and the light stability of raising product, the pressure of hydroisomerization dewax of the present invention is preferably 14MPa～16.8MPa, more preferably 15MPa～16MPa; In order to guarantee fully carrying out of isomerization reaction, and then the viscosity of the pour point of reduction white oil product and assurance white oil product, the temperature of hydroisomerization dewax of the present invention is preferably 320 ℃～360 ℃, more preferably 330 ℃～350 ℃.
In order to improve the treatment capacity of single unit system and the energy consumption of reduction Sweet natural gas, the present invention preferably will collect the required pressure-controlling of white oil cut at 1.20MPa～1.60MPa, more preferably 1.20MPa～1.40MPa.
The production method that the invention provides a kind of white oil, comprising: the first tail oil and the second tail oil be take to mass percent as (15～35): mix (85～65), and hydrogenation, obtains white oil; The initial boiling point of described the first tail oil is 330～360 ℃, and final boiling point is 485～505 ℃, and the density in the time of 20 ℃ is 845～855kg/m
3, the viscosity of 40 ℃ is 20～35mm
2/ s, condensation point is-10～+ 10 ℃; The initial boiling point of described the second tail oil is 305～325 ℃, and final boiling point is 510～540 ℃, and the density in the time of 20 ℃ is 825～840kg/m
3, the viscosity of 100 ℃ is 5.0～6.0mm
2/ s, condensation point is+25～+ 45 ℃.Wherein, the first tail oil be take to mass percent with the second tail oil as (15～35): (85～65) mix, the quality of the white oil obtaining by Hydrogenation is higher than the quality of the white oil obtaining with single tail oil Hydrogenation, and the white oil that method provided by the invention makes can reach cosmetics-stage white oil.In addition, the method has also been avoided, because tail oil is different, needing the production method of the catalyzer of change hydrogenation reaction, and then having saved cost, has simplified production technique, guarantees the operation that production technique can be steady in a long-term.
In order further to understand the present invention, below in conjunction with embodiment, the production method of white oil provided by the invention is described in detail.
Embodiment 1
Mass percent that the first tail oil be take with the second tail oil is mixed as 25:75, obtain mixing tail oil, to mix tail oil is 15.45MPa in reaction pressure, temperature of reaction is under 335 ℃ of conditions, by the development and production of hydroisomerization catalyst FIW-1(Fushun Petrochemical Research Institute) catalysis, carry out hydroisomerization dewax reaction, in temperature of reaction, be under 260 ℃ of conditions again, by the development and production of Hydrobon catalyst FHDA-1(Fushun Petrochemical Research Institute) catalysis, carry out hydrofining reaction, after completion of the reaction, by normal decompression fractionation unit, collect the white oil cut under 1.2MPa, obtain white oil product.
Described the first tail oil is for adopting the tail oil of the hydrocracking of FF-20 and the series connection of FC-14 dual catalyst, and its technical indicator is as shown in table 2, the tail oil properties that table 2 provides for the embodiment of the present invention and comparative example; Described the second tail oil is for adopting the tail oil of the hydrocracking of FZC-100 protective material, FZC-105 protective material, FZC-106 protective material, tooth ball-type FF-46 pretreating catalyst by hydrocracking and tooth ball-type FC-16B hydrocracking catalyst, its technical indicator is as shown in table 2, the tail oil properties that table 2 provides for the embodiment of the present invention and comparative example; The technical indicator of described mixing tail oil is as shown in table 2 in shown, the tail oil properties that table 2 provides for the embodiment of the present invention and comparative example; The main physical and chemical of described catalyzer FIW-1 and FHDA-1 is as shown in table 1, the main physical and chemical index of the catalyzer that table 1 provides for the embodiment of the present invention and comparative example.
The character of described white oil product is as shown in table 3, the character of the white oil product that table 3 provides for the embodiment of the present invention and comparative example
Comparative example 1
By the first tail oil, in reaction pressure, be 15.45MPa, temperature of reaction is under the condition of 335 ℃, by the development and production of hydroisomerization catalyst FIW-1(Fushun Petrochemical Research Institute) catalysis, carry out hydroisomerization dewax reaction, in temperature of reaction, be under 260 ℃ of conditions again, by the development and production of Hydrobon catalyst FHDA-1(Fushun Petrochemical Research Institute) catalysis carries out hydrofining reaction, after completion of the reaction, by collecting the white oil cut under 1.2MPa in normal decompression fractionation unit, obtain white oil product.
Described the first tail oil is for adopting the tail oil of the hydrocracking of FF-20 and the series connection of FC-14 dual catalyst, and its technical indicator is as shown in table 2, the tail oil properties that table 2 provides for the embodiment of the present invention and comparative example; The main physical and chemical of described catalyzer FIW-1 and FHDA-1 is as shown in table 1, the main physical and chemical index of the catalyzer that table 1 provides for the embodiment of the present invention and comparative example.
The character of described white oil product is as shown in table 3, the character of the white oil product that table 3 provides for the embodiment of the present invention and comparative example
The main physical and chemical index of the catalyzer that table 1 embodiment of the present invention and comparative example provide
The tail oil properties that table 2 embodiment of the present invention and comparative example provide
| Project | The first tail oil | The second tail oil | Mix tail oil |
| Density kg/m 3（20℃） | 849.9 | 835.1 | 850.2 |
| Initial boiling point (℃) | 345 | 320 | 338 |
| 10%/30% | 380/400 | 391/412 | 383/405 |
| 50%/70% | 415/432 | 430/453 | 432/465 |
| 90%/95% | 464/479 | 515/-- | 500/515 |
| Do (℃) | 493 | 535 | 523 |
| 40 ℃ of (mm of viscosity 2/s） | 24.22 | -- | 31.39 |
| 100 ℃ of (mm of viscosity 2/s） | 4.573 | 5.679 | 5.431 |
| Viscosity index | 103 | 139 | 108 |
| Lightning (opening) ℃ | 208 | 224 | 216 |
| Condensation point ℃ | +5 | +38 | +14 |
| Colourity | <3.0 | <1.0 | <1.5 |
| Sulphur (μ g/g) | 2.81 | 10.5 | ? |
| Nitrogen (μ g/g) | 0.57 | 0.37 | ? |
| Iron (μ g/g) | 1.9 | 1.8 | ? |
The character of the white oil product that table 2 embodiment of the present invention and comparative example provide
As shown in Table 2, its quality of white oil product being made by mixing tail oil is higher than the quality of the white oil product making with single tail oil, and the white oil that method provided by the invention makes has reached the standard of cosmetics-stage white oil.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a production method for white oil, comprising:
The first tail oil and the second tail oil be take to mass percent as (15～35): mix (85～65), carries out hydrogenation reaction, obtains white oil;
The initial boiling point of described the first tail oil is 330～360 ℃, and final boiling point is 485～505 ℃, and the density in the time of 20 ℃ is 845～855kg/m
3, the viscosity of 40 ℃ is 20～35mm
2/ s, condensation point is-10～+ 10 ℃;
The initial boiling point of described the second tail oil is 305～325 ℃, and final boiling point is 510～540 ℃, and the density in the time of 20 ℃ is 825～840kg/m
3, the viscosity of 100 ℃ is 5.0～6.0mm
2/ s, condensation point is+20～+ 45 ℃.
2. method according to claim 1, is characterized in that, described the first tail oil is for adopting the tail oil of the hydrocracking of FF-20 and the series connection of FC-14 dual catalyst.
3. method according to claim 1; it is characterized in that, described the second tail oil is for adopting the tail oil of the hydrocracking of FZC-100 protective material, FZC-105 protective material, FZC-106 protective material, tooth ball-type FF-46 pretreating catalyst by hydrocracking and tooth ball-type FC-16B hydrocracking catalyst.
4. method according to claim 1, is characterized in that, the mass ratio of described the first tail oil and the second tail oil is (20～30): (80～70).
5. method according to claim 1, is characterized in that, described method is specially: the first tail oil and the second tail oil be take to mass percent as (15～35): (85～65) evenly mix, carry out hydroisomerization dewax, hydrofining, collects the white oil cut after refining, and obtains white oil.
6. method according to claim 3, is characterized in that, the working pressure of described hydroisomerization dewax is 14MPa～16.8MPa.
7. method according to claim 3, is characterized in that, the pressure of described hydroisomerization dewax is 15MPa～16MPa.
8. method according to claim 3, is characterized in that, the temperature of described hydroisomerization dewax is 320 ℃～360 ℃.
9. method according to claim 3, is characterized in that, the temperature of described hydroisomerization dewax is 330 ℃～350 ℃.
10. method according to claim 3, is characterized in that, the pressure of the white oil cut after described collection is refining is 1.10MPa～1.60MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266388A (en) * | 2018-10-30 | 2019-01-25 | 东营奥星石油化工有限公司 | A kind of white oil Hydrogenation production method based on composite catalyst |
| CN113667513A (en) * | 2020-05-15 | 2021-11-19 | 山东清沂山石化科技有限公司 | Production process of cosmetic-grade white oil |
| CN114686258A (en) * | 2022-02-25 | 2022-07-01 | 海南汉地阳光石油化工有限公司 | Oil special for food coating agent and preparation process thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510110A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Production of high viscosity food grade white oil |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510110A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Production of high viscosity food grade white oil |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266388A (en) * | 2018-10-30 | 2019-01-25 | 东营奥星石油化工有限公司 | A kind of white oil Hydrogenation production method based on composite catalyst |
| CN113667513A (en) * | 2020-05-15 | 2021-11-19 | 山东清沂山石化科技有限公司 | Production process of cosmetic-grade white oil |
| CN114686258A (en) * | 2022-02-25 | 2022-07-01 | 海南汉地阳光石油化工有限公司 | Oil special for food coating agent and preparation process thereof |
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Denomination of invention: Production method of white oil Effective date of registration: 20230823 Granted publication date: 20160120 Pledgee: Industrial Bank Co.,Ltd. Haikou Branch Pledgor: HAINAN HANDI SUNSHINE PETROCHEMICAL Co.,Ltd. Registration number: Y2023980053471 |
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