CN1524929A - Method for reducing lubricating oil basic oil cloud point - Google Patents
Method for reducing lubricating oil basic oil cloud point Download PDFInfo
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- CN1524929A CN1524929A CNA03105398XA CN03105398A CN1524929A CN 1524929 A CN1524929 A CN 1524929A CN A03105398X A CNA03105398X A CN A03105398XA CN 03105398 A CN03105398 A CN 03105398A CN 1524929 A CN1524929 A CN 1524929A
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Abstract
A method for lowering lubricating oil basic oil turbidity point, wherein the pour point of the dewaxed oil is -5 deg. C - 15 deg. C after the lubricating oil is dewaxed through the solvent, the pre-dewaxed oil is hydrotreated for lowering its sulfur and nitrogen content, the hydrotreated pre-dewaxed oil is dewaxed through isomerous process, obtaining lubricating oil basic with lowered oil turbidity point.
Description
Technical field
The present invention relates to treating process under the situation that does not have hydrogen of a kind of usefulness and at least one hydroprocessing technique process and handle the method for hydrocarbon ils.
Background technology
Produce lubricant base from lube stock and remove wherein sulphur, nitrogen compound and some polycyclic aromatic hydrocarbons except that need are refining, also must remove wherein hydrocarbon solid to reduce its zero pour or pour point to improve its viscosity index and the oxidation stability.Contained hydrocarbon solid is referred to as wax usually in the lube stock, and it is made up of straight-chain paraffin and some non-straight-chain paraffins.Remove that institute's the most frequently used method of the content of wax is solvent dewaxing in the lube stock, solvent dewaxing is that lube stock is in the presence of dewaxing solvent, reducing temperature makes wax form solid crystal, and by solvent to oil dissolving and the characteristic of or minimal amounts of dissolved insoluble to wax, form the solid-liquid two-phase, reach oil, wax separating process after filtration.
When solvent dewaxing,, need solvent and lube stock are cooled to the temperature lower than base oil pour point, therefore need expensive refrigerating apparatus, also be more difficult to get the very low base oil product of pour point simultaneously in order to obtain the base oil of certain pour point.Therefore from eighties of last century since the sixties, external many companies have developed the technology of catalysis pour point depression in succession.
Catalysis pour point depression technology is divided into two types of catalytic dewaxing and isomerization dewaxings according to the catalyst system therefor difference.
It is the catalyzer of carrier that catalytic dewaxing is adopted with the molecular sieve, because the well-regulated pore structure of molecular sieve, this catalyzer repels the oil molecule of lubricant base in the molecular sieve pore passage outside, only allow the wax molecule of straight-chain paraffin and some isoparaffin to enter its inside, make them in molecular sieve pore passage, become low molecule alkane by hydrocracking reaction, and it is separating of oil with lube base, thereby reach the purpose of dewaxing, molecular sieve as catalytic dewaxing catalyst has: ZRP, ZSM-5, mordenite etc.
The shortcoming of catalytic dewaxing is that the viscosity index and the yield of resulting lubricant base is lower than solvent dewaxing.For overcoming this shortcoming, therefore developed the isomerization dewaxing technology, isomerization dewaxing is to make the high straight-chain paraffin hydroisomerizing of pour point change the low isoparaffin of pour point into, so the viscosity index of isomerization dewaxing lubricant base and yield are all higher than solvent dewaxing and catalytic dewaxing.
It is the catalyzer of carrier that isomerization dewaxing also adopts with the molecular sieve, this kind catalyzer has very strong hydrogenation performance, the rapid hydrogenation of the intermediate that the straight-chain paraffin isomerization is obtained generates isoparaffin, to avoid further hydrocracking to generate the low molecular hydrocarbon of low value, also the molecular sieve than catalytic dewaxing catalyst is little for its molecular sieve bore diameter simultaneously, to avoid generating many isoparaffins of easy hydrocracking.Molecular sieve as isomerization dewaxing catalyst has: ZAP, SAPO-11, SAPO-41, SAPO-48, ZSM-22, ZSM-23, SSZ-32 etc.
Because isomerization dewaxing catalyst has very high selectivity, so it can not transform the baroque wax molecule in some special lube stock.The isomerization dewaxing lubricant base that contains these wax molecules, after at room temperature placing certain hour, above-mentioned wax molecule can be separated out from oil with the form of floss, these flosss not only influence the outward appearance of isomerization dewaxing lubricant base, simultaneously its quality also there is certain influence, the characteristic of floss appears in the isomerization dewaxing lubricant base, usually show note of the ancient Chinese with the height of cloud point, therefore reducing the cloud point of isomerization dewaxing lubricant base, is the problem that development isomerization dewaxing Technology Need solves.
In order to reduce the cloud point of isomerization dewaxing lubricant base, more external patents adopt the combined method of dewaxing by molecular sieve catalyzer in different apertures, promptly at the little dewaxing by molecular sieve catalyzer in the filling aperture, top of dewaxing reactor, then load some aperture in its underpart bigger, help the dewaxing by molecular sieve catalyzer that baroque wax molecule transforms, for example WO99/32581 is at the top of its dewaxing reactor filling SSZ-32 dewaxing by molecular sieve catalyzer, ZSM-5 dewaxing by molecular sieve catalyzer is then loaded in the bottom, US6051129 then adopts ZSM-48 or SSZ-32 dewaxing by molecular sieve catalyzer and EU-1 dewaxing by molecular sieve catalyzer combined, and US5951847 then proposes to handle with the magnesium base molecule sieve catalyst that contains hydrogenation component for the high pressed oil of cloud point.
In order to reduce the cloud point of isomerization dewaxing lubricant base, external other patent then adopts the method for refining with adsorbents, US6468417 for example, US6468418 introduces and makes sorbent treatment isomerization dewaxing lubricant base to reduce its cloud point with acidic white earth or aluminum oxide.
The method of above-mentioned reduction isomerization dewaxing lube base valenta value is not very effective, for example US4428819 carries out the catalytic dewaxing of some heavy grease material with ZSM-5 dewaxing by molecular sieve catalyzer, discovery can not remove some petroleum wax, there is the high problem of pressed oil cloud point equally, with the residual wax in acidic white earth or the alumina removal isomerization dewaxing lubricant base, because there is the competitive adsorption effect of some oil molecule, so its effect that reduces isomerization dewaxing lube base valenta value is also very limited.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method that effectively reduces the lube base valenta value more.
Method provided by the invention comprises:
(1), the pour point of lube stock pressed oil after solvent dewaxes in advance is-5 ℃～15 ℃;
(2), pre-pressed oil reduces its sulphur, nitrogen content through hydrotreatment;
(3), the pre-pressed oil after the hydrotreatment obtains the lubricant base of low cloud point through isomerization dewaxing.
Method provided by the invention can reduce the cloud point of lubricant base effectively.
Embodiment
The used lube stock of the present invention is vacuum distillate, deasphalted oil or its mixture of paraffinic base or intermediate base crude oil, and its boiling point should be higher than 400 ℃, preferably can be higher than 450 ℃, if can be higher than 500 ℃ and then more can show effect of the present invention.
The first step of the present invention is that the solvent of lube stock dewaxes in advance:
The pre-dewaxing of the solvent of lube stock utilizes the difference of solvent to oil and wax solubleness, cools off having under the situation of solvent cut, makes wax and separating of oil with filter method then.Solvent reclaims through heating evaporation and reuses.Solvent for use is ketone-benzene class mixed solvent, and wherein ketones solvent is acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or its mixture, and benzene kind solvent is benzene, toluene or its mixture, and the volume ratio of ketones solvent and benzene kind solvent is 4: 6～7: 3.The temperature of the pre-dewaxing of solvent is-10 ℃～20 ℃.
In the pre-dewaxing process of solvent, lube stock dewaxed to pour point be-5 ℃～15 ℃.The pour point of pre-pressed oil is minimum should not to be lower than-5 ℃, if the pour point of pre-pressed oil is low excessively, then can influence the yield and the viscosity index of last isomerization dewaxing lubricant base; But the pour point of pre-pressed oil should not be higher than 15 ℃ yet, if the pour point of pre-pressed oil is too high, then can make the cloud point of isomerization dewaxing lubricant base inaccessible below 0 ℃, even inaccessible below 5 ℃.
The pre-dewaxing of solvent preferably can be adopted the solvent dewaxing and de-oiling process integration, adopt this technology decapacitation direct production to go out outside the qualified paraffin of oleaginousness, the sweat oil that degreasing process produces, can mix charging with pre-pressed oil, thereby can further improve the yield of isomerization dewaxing lubricant base as isomerization dewaxing.
Second step of the present invention is the hydrotreatment of pre-pressed oil:
Lube stock, hydrogen after the pre-dewaxing of solvent contact with hydrogenation catalyst, and the hydroprocessing technique condition is: pressure 10～20MPa, 350～420 ℃ of temperature, air speed 0.5～1.0h
-1, hydrogen-oil ratio 500～2000v/v, reaction effluent is through separating, and the gained hydrogenated oil is as the raw material of the 3rd step isomerization dewaxing; Rich hydrogen hydrogen recycle is used.This hydrogenation catalyst is generally industrial hydrotreating catalyst or the hydrocracking catalyst that is used to produce lubricating oil or middle runnings, or the Hydrobon catalyst with deep desulfuration, denitrogenation ability.As W-Ni, Mo-Ni, the W-Mo-Ni catalyzer of making carrier with Si-Al, or with the Al of F modification
2O
3Make W-Ni, Mo-Ni, the W-Mo-Ni catalyzer of carrier.
Through the generation oil of hydrotreatment, its sulphur content should be lower than 50 μ g/g preferably can be lower than 10 μ g/g, and its nitrogen content should be lower than 10 μ g/g preferably can be lower than 2 μ g/g.
The 3rd step of the present invention is the isomerization dewaxing of hydrogenated oil:
Pre-pressed oil after the hydrotreatment is that hydrogenated oil, hydrogen contact with isomerization dewaxing catalyst, and the processing condition of isomerization dewaxing are: pressure 10～20MPa, 300～420 ℃ of temperature, air speed 0.5～2.0h
-1, hydrogen-oil ratio 500～1000v/v, reaction effluent is through separating, and gained isomerization dewaxing oil is the lubricant base of low cloud point; Rich hydrogen hydrogen recycle is used.The used isomerization dewaxing catalyst of isomerization dewaxing is ZAP, SAPO-11, SAPO-41, SAPO-48, ZSM-22, ZSM-23, the SSZ-32 dewaxing by molecular sieve catalyzer that is loaded with precious metal.
Method provided by the invention can be effectively be reduced to the cloud point of lubricant base below 0 ℃.
The following examples will give further instruction to present method, but therefore not limit present method.
Used lube stock is the deasphalted oil through furfural treatment in embodiment and the Comparative Examples, and its character sees Table 1.The trade mark of used hydrogenation catalyst and isomerization dewaxing catalyst is respectively the Al with the F modification in embodiment and the Comparative Examples
2O
3Make the W-Ni catalyzer and the SAPO-11 catalyzer that is loaded with precious metal of carrier.
Comparative Examples
In Comparative Examples, lube stock dewaxes in advance without solvent, but the catalytic dewaxing again of first isomerization dewaxing.Reaction conditions and test-results are listed in table 2.As can be seen from Table 2, the cloud point of isomerization dewaxing oil is up to 21 ℃, and isomerization dewaxing oil is through further dewaxing with ZSM-5 dewaxing by molecular sieve catalyzer, and its cloud point is still more than 10 ℃.
Embodiment
In an embodiment, lube stock dewaxes in advance through solvent earlier, and pre-pressed oil is successively through the hydrotreatment isomerization dewaxing.Operational condition and test-results are listed in table 3.As can be seen from Table 3, the cloud point of last isomerization dewaxing oil is reduced to-1 ℃.
Table 1
| Density (20 ℃), g/cm 3 | ????0.897 |
| Sulphur content, μ g/g | ????800 |
| Nitrogen content, μ g/g | ????710 |
| Carbon residue, % | ????0.4 |
| Viscosity (100 ℃), mm 2/s | ????25.1 |
| Initial boiling point, ℃ | ????460 |
Table 2
| The isomerization dewaxing processing condition | |
| Pressure, MPa | ????13.5 |
| Temperature, ℃ | ????385 |
| Air speed, h -1 | ????0.7 |
| Hydrogen-oil ratio, v/v | ????500 |
| The isomerization dewaxing oil nature | |
| Density (20 ℃), g/cm 3 | ????0.8539 |
| Viscosity (100 ℃), mm 2/s | ????18.67 |
| Viscosity index | ????134 |
| Pour point, ℃ | ????-15 |
| Cloud point, ℃ | ????21 |
| The WITH CATALYTIC DEWAXING TECHNIQUE condition | |
| Pressure, MPa | ????12 |
| Temperature, ℃ | ????350 |
| Air speed, h -1 | ????1 |
| Hydrogen-oil ratio, v/v | ????500 |
| The catalytic dewaxing oil nature | |
| Viscosity (100 ℃), mm 2/s | ????18.6 |
| Viscosity index | ????132 |
| Pour point, ℃ | ????-27 |
| Cloud point, ℃ | ????13 |
Table 3
| The pre-dewaxing technique condition of solvent | |
| Dewaxing temperature, ℃ | ????5 |
| Solvent (ketone/benzene class) (volume ratio) | Methyl ethyl ketone/toluene (50/50) |
| Pre-pressed oil character | |
| Viscosity (100 ℃), mm 2/s | ????17.47 |
| Pour point, ℃ | ????6 |
| The hydroprocessing technique condition | |
| Pressure, MPa | ????12 |
| Temperature, ℃ | ????370 |
| Air speed, h -1 | ????0.6 |
| Hydrogen-oil ratio, v/v | ????600 |
| The isomerization dewaxing processing condition | |
| Pressure, MPa | ????12 |
| Temperature, ℃ | ????370 |
| Air speed, h -1 | ????0.7 |
| Hydrogen-oil ratio, v/v | ????500 |
| Isomerization dewaxing oil production character | |
| Viscosity (100 ℃), mm 2/s | ????17.3 |
| Viscosity index | ????131 |
| Pour point, ℃ | ????-24 |
| Cloud point, ℃ | ????-1 |
Claims (9)
1, a kind of method that reduces the lube base valenta value is characterized in that this method comprises:
(1), the pour point of lube stock pressed oil after solvent dewaxes in advance is-5 ℃～15 ℃;
(2), pre-pressed oil reduces its sulphur, nitrogen content through hydrotreatment;
(3), the pre-pressed oil after the hydrotreatment obtains the lubricant base of low cloud point through isomerization dewaxing.
2, according to the method for claim 1, it is characterized in that described lube stock is vacuum distillate, deasphalted oil or its mixture of paraffinic base or intermediate base crude oil, its boiling point is greater than 400 ℃.
3, according to the method for claim 1, it is characterized in that step (1) solvent for use is ketone-benzene class mixed solvent, wherein ketones solvent is acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or its mixture, benzene kind solvent is benzene, toluene or its mixture, and the volume ratio of ketones solvent and benzene kind solvent is 4: 6～7: 3.
4,, it is characterized in that dewaxing temperature is-10 ℃～20 ℃ in the step (1) according to the method for claim 1.
5,, it is characterized in that the hydroprocessing technique condition is in the step (2): pressure 10～20MPa, 350～420 ℃ of temperature, air speed 0.5～1.0h according to the method for claim 1
-1
6, according to the method for claim 1, it is characterized in that hydrogenation catalyst used therein is the hydrotreating catalyst or the hydrocracking catalyst of production lubricating oil or middle runnings in the step (2), or the Hydrobon catalyst with deep desulfuration, denitrogenation ability.
7, according to the method for claim 6, it is characterized in that in the step (2) hydrogenation catalyst used therein for making W-Ni, Mo-Ni, the W-Mo-Ni catalyzer of carrier with Si-Al, or with the Al of F modification
2O
3Make W-Ni, Mo-Ni, the W-Mo-Ni catalyzer of carrier.
8,, it is characterized in that the processing condition of isomerization dewaxing in the step (3) are: pressure 10～20MPa, 300～420 ℃ of temperature, air speed 0.5～2.0h according to the method for claim 1
-1
9,, it is characterized in that isomerization dewaxing catalyst used in the step (3) is ZAP, SAPO-11, SAPO-41, SAPO-48, ZSM-22, ZSM-23, the SSZ-32 dewaxing by molecular sieve catalyzer that is loaded with precious metal according to the method for claim 1.
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| CN 03105398 CN1286954C (en) | 2003-02-28 | 2003-02-28 | Method for reducing lubricating oil basic oil cloud point |
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| CN 03105398 CN1286954C (en) | 2003-02-28 | 2003-02-28 | Method for reducing lubricating oil basic oil cloud point |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942336A (en) * | 2010-09-07 | 2011-01-12 | 中国石油天然气股份有限公司 | Method for producing lube base oil having low cloud point and high viscosity index |
| CN113388426A (en) * | 2020-03-12 | 2021-09-14 | 中国石油天然气股份有限公司 | Dewaxing agent and natural gas dewaxing treatment method |
| CN114479915A (en) * | 2020-11-12 | 2022-05-13 | 中国石油天然气股份有限公司 | Production method of low-cloud-point lubricating oil base oil |
-
2003
- 2003-02-28 CN CN 03105398 patent/CN1286954C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942336A (en) * | 2010-09-07 | 2011-01-12 | 中国石油天然气股份有限公司 | Method for producing lube base oil having low cloud point and high viscosity index |
| WO2012031449A1 (en) | 2010-09-07 | 2012-03-15 | 中国石油天然气股份有限公司 | Method for producing lubricating base oil with low cloud point and high viscosity index |
| CN113388426A (en) * | 2020-03-12 | 2021-09-14 | 中国石油天然气股份有限公司 | Dewaxing agent and natural gas dewaxing treatment method |
| CN114479915A (en) * | 2020-11-12 | 2022-05-13 | 中国石油天然气股份有限公司 | Production method of low-cloud-point lubricating oil base oil |
| CN114479915B (en) * | 2020-11-12 | 2023-08-22 | 中国石油天然气股份有限公司 | Production method of low-cloud-point lubricating oil base oil |
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