CN111073696A - Method for reducing cloud point of base oil of high-viscosity lubricating oil and base oil of lubricating oil - Google Patents
Method for reducing cloud point of base oil of high-viscosity lubricating oil and base oil of lubricating oil Download PDFInfo
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
The invention discloses a method for reducing cloud point of base oil of high-viscosity lubricating oil and the base oil of the lubricating oil. The method comprises the following steps: adding a lubricating oil base oil raw material into a reaction device, wherein a first catalyst and a second catalyst are sequentially arranged in the reaction device from top to bottom; the first catalyst and the second catalyst are two different noble metal isodewaxing catalysts; the lubricating oil base oil raw material sequentially flows through a first catalyst and a second catalyst from top to bottom, the reaction temperature of the lubricating oil base oil raw material flowing through the second catalyst is lower than that of the lubricating oil base oil raw material flowing through the first catalyst, and after hydrofining, a vacuum tower bottom product obtained through normal and vacuum fractionation is the low-cloud-point high-viscosity lubricating oil base oil. The method has the advantages that the isomerization dewaxing reaction temperature is low through the grading of the catalyst, the reaction temperature close to the refining hydrogenation reaction temperature of noble metal is realized, the operation cost is reduced, and the high-viscosity lubricant base oil with low pour point and low cloud point is obtained.
Description
Technical Field
The invention relates to the field of petrochemical industry. More particularly, it relates to a method for reducing cloud point of base oil of high-viscosity lubricating oil and base oil of said lubricating oil.
Background
When the domestic lubricating oil high-pressure hydrogenation device is used for producing high-viscosity lubricating oil base oil through an isomerization dewaxing process, the phenomena of clouding of oil products and even a large amount of floccules in the long-term storage process exist, and the cloud point is tested to be about 16 ℃ generally. According to the standard of China Petroleum Universal lubricating oil base oil enterprises, the viscosity of the VHVI, HVIP and HVIH base oil at 100 ℃ is 8mm2S to 14mm2The cloud point is required to be not higher than-5 ℃ per second, and the cloud point index requirement is not required for base oil with the viscosity grade of more than 90 BS. Although there is no requirement for the cloud point index of a base oil of a large viscosity lubricant such as bright oil, there is also a requirement for the index of visual transparency. Users also make objections when they accept products with high cloud points due to their opaque appearance, especially when the temperature is low in winter.
For the research of reducing the cloud point of the base oil of the lubricating oil, the research is divided into two research directions of a composite molecular sieve isodewaxing catalyst and a combined process of solvent dewaxing. For example, patent CN 102085488A describes a method for lowering the cloud point of a base oil with high viscosity to-25 ℃ and below by using MFI-MCM composite molecular sieve; patent CN1690175A describes that a method of adding deflocculating auxiliary agent in acetone-benzol dewaxing can be used for producing base oil with large viscosity and cloud point of-10 ℃ or below; patent CN1690175A describes that the cloud point of 120BS can be reduced to below-10 ℃ by using hydrogenated base oil as a raw material and adding a deflocculating aid by solvent dewaxing; patent CN101191083A describes a method for reducing the cloud point of a lubricant using solvent dewaxing and a candle filter; patent CN101223262A describes a process for obtaining a kinematic viscosity at 100 ℃ of 10mm by means of a process comprising the separation of a high-freezing-point fraction by freezing and the subsequent re-isodewaxing of the high-freezing-point fraction2Base oil with low cloud point above s; patent CN102085487A describes a method for lowering the cloud point of high viscosity base oil to-8 ℃ and below by using AEL-MCM composite molecular sieve.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
One object of the present invention is to provide a method for reducing the cloud point of a high viscosity lubricant base oil. The method has the advantages that the reaction temperature is lower through the grading of the catalyst, the reaction temperature close to the reaction temperature of the complementary refining hydrogenation is realized, the cost is reduced, and the high-viscosity lubricating oil base oil with low pour point and low cloud point is obtained.
Another object of the present invention is to provide a low pour point, low cloud point high viscosity lubricant base stock.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of reducing the cloud point of a high viscosity lubricant base oil, the method comprising the steps of:
adding a lubricating oil base oil raw material into a reaction device, wherein a first catalyst and a second catalyst are sequentially arranged in the reaction device from top to bottom; the first catalyst and the second catalyst are two different noble metal isodewaxing catalysts;
the lubricating oil base oil raw material sequentially flows through a first catalyst and a second catalyst from top to bottom, the reaction temperature of the lubricating oil base oil raw material flowing through the second catalyst is lower than that of the lubricating oil base oil raw material flowing through the first catalyst, and after the lubricating oil base oil raw material is subjected to hydrogenation complementary refining, a vacuum tower bottom product obtained through normal and vacuum fractionation is the low-cloud-point high-viscosity lubricating oil base oil.
Preferably, the reaction temperature of the lubricating oil base oil raw material flowing through the first catalyst is 280-380 ℃, the reaction temperature of the lubricating oil base oil raw material flowing through the second catalyst is 200-340 ℃, and the temperature of the hydrofinishing is 200-280 ℃.
Preferably, the isomerization dewaxing shape-selective component of the first catalyst is ZSM-12 molecular sieve or ZSM-11 molecular sieve or ZSM-12/ZSM-11 composite molecular sieve; the isomerization dewaxing shape-selective component of the second catalyst is ZSM-5 molecular sieve; the active metal components used by the two catalysts are Pt and/or Pd.
Preferably, the first catalyst is one or more of Pt and/or Pd/ZSM-12, Pt and/or Pd/ZSM-11, Pt and/or Pd/ZSM-12/ZSM-11, wherein the content of noble metal is 0.1-1.0%; more preferably 0.4 to 0.8%;
the second catalyst is one or more of Pt/Pd/ZSM-5, Pt/ZSM-5 and Pd/ZSM-5, wherein the content of noble metal is 0.1-1%; more preferably 0.2 to 0.6%.
The filling ratio of the first catalyst to the second catalyst is 1: 0.5-4, and more preferably 1: 0.5-2.
Preferably, the lubricating oil base oil raw material comprises one or more of hydrotreating or hydrocracking produced oil of solvent deasphalting light deoiling, hydrotreating or cracking produced oil of heavy distillate oil such as paraffin-based minus four-line fraction, and the like, and the sulfur content is not higher than 10mg/kg, and the nitrogen content is not higher than 5 mg/kg.
Preferably, the first catalyst and the second catalyst are sequentially filled in an upper catalyst bed layer and a lower catalyst bed layer in the same reactor; or sequentially filling the reactors in different reactors;
when the first catalyst and the second catalyst are sequentially filled in an upper catalyst bed layer and a lower catalyst bed layer in the same reactor, the reaction temperature of the upper catalyst bed layer is 300-360 ℃, and the reaction temperature of the lower catalyst bed layer is 260-320 ℃;
when the first catalyst and the second catalyst are sequentially filled in different reactors, the reaction temperature of the reactor in which the first catalyst is positioned is 280-380 ℃, and the reaction temperature of the reactor in which the second catalyst is positioned is 220-280 ℃.
Preferably, when the first and second catalysts are sequentially loaded in the upper and lower catalyst beds in the same reactor, the operating conditions are as follows: the hydrogen partial pressure is 14.0MPa to 20.0 MPa; the total volume space velocity of the first catalyst and the second catalyst is 0.4h-1～1.6h-1(ii) a The volume ratio of hydrogen to oil is 400-800: 1.
preferably, when the first and second catalysts are sequentially loaded in different reactors,
the first catalyst is in the reactor operating conditions of: the hydrogen partial pressure is 14.0MPa to 20.0 MPa; the volume space velocity is 0.5h-1～3h-1(ii) a The volume ratio of hydrogen to oil is 400-800: 1;
the operating conditions of the reactor in which the second catalyst is present are: the hydrogen partial pressure is 14.0MPa to 20.0 MPa; the volume space velocity is 0.8h-1～2.0h-1(ii) a The volume ratio of hydrogen to oil is 400-800: 1.
preferably, when the first catalyst and the second catalyst are sequentially filled in an upper catalyst bed layer and a lower catalyst bed layer in the same reactor, cold hydrogen is arranged at the inlet of the lower catalyst bed layer to reduce the reaction temperature to within 40 ℃;
when the first catalyst and the second catalyst are sequentially filled in different reactors, a heat exchanger is arranged between the two reactors to reduce the reaction temperature to within 100 ℃.
The invention also discloses high-viscosity lubricating oil base oil which is prepared by the method.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
The invention has the following beneficial effects:
1) the invention takes the oil generated by hydrotreating or hydrocracking of heavy distillate oil such as solvent deasphalting light deasphalting oil and paraffin base minus quartzite fraction oil as a raw material, adopts the grading combination of two types of noble metal isodewaxing catalysts and respectively controls the reaction temperature, so that the reaction temperature of the subsequent isodewaxing catalyst is close to the reaction temperature of supplementary refining hydrogenation, and reduces the production cost while reducing the pour point and cloud point of a lubricating oil component.
2) In the method, two types of noble metal isodewaxing catalysts are filled in the same hydrogenation reactor or two reactors, and materials sequentially pass through the two types of isodewaxing catalysts; when two kinds of isodewaxing catalysts are filled in different beds of the same reactor, the reaction temperature of the next bed can be controlled and adjusted by using cold hydrogen quantity between beds; when two types of isodewaxing catalysts are filled in the two reactors, a heat exchanger can be arranged between the two reactors to control and adjust the temperature of the next reactor; because the isomerization dewaxing reaction temperature controlled by the heat exchanger is in the same range as the hydrogenation refining reaction temperature, the latter isomerization dewaxing catalyst and the hydrogenation refining catalyst can be filled in a reactor.
3) The isomerization dewaxing catalyst in the method adopts the combination technology of two types of isomerization dewaxing catalysts; ZSM-11, ZSM-12, ZSM-11 and ZSM-12 composite molecular sieves are used as a noble metal isomerization dewaxing catalyst of a shape selective component, ZSM-5 molecular sieves are used as a noble metal isomerization dewaxing catalyst of a shape selective component, the ZSM-5 molecular sieve noble metal isomerization dewaxing reaction temperature is lower and is close to the reaction temperature of supplementary hydrofining, and the quantity of supplementary hydrofining can be properly reduced, so that the catalyst cost is reduced.
4) The method of the invention shows excellent pour point and cloud point reducing performance aiming at various base oils with high viscosity, high pour point, high cloud point and the like, and can obtain qualified high-viscosity lubricating oil base oil by combining with a noble metal hydrofining catalyst. Compared with the base oil sample prepared by reference proportion, the cloud point of the base oil of the high-viscosity lubricating oil obtained by the method is lower, and the properties of other products are basically not different from those of the examples except that the yield of the target product is lower by less than 1%.
5) The reaction temperature of the second isodewaxing catalyst of the method is similar to that of the hydrofinishing, and the second isodewaxing catalyst and the noble metal hydrofinishing catalyst can share one reactor and are filled in an upper bed layer of the reactor in the specific industrial implementation process. The second isodewaxing catalyst has high noble metal hydrogenating performance and low reaction temperature, and can reduce the loading amount of the refined catalyst after hydrogenation greatly. And the isomerization dewaxing reaction temperature is low, the cloud point of the obtained product is low, and the process flow is simple.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The invention relates to a method for reducing cloud point of base oil of high-viscosity lubricating oil, which comprises the following steps:
adding a lubricating oil base oil raw material into a reaction device, wherein a first catalyst and a second catalyst are sequentially arranged in the reaction device from top to bottom; the first catalyst and the second catalyst are two different noble metal isodewaxing catalysts;
the lubricating oil base oil raw material sequentially flows through a first catalyst and a second catalyst from top to bottom, the reaction temperature of the lubricating oil base oil raw material flowing through the second catalyst is lower than that of the lubricating oil base oil raw material flowing through the first catalyst, and after precious metal hydrogenation complementary refining, a vacuum tower bottom product obtained through normal and reduced pressure fractionation is the low cloud point high viscosity lubricating oil base oil.
According to certain embodiments of the present disclosure, the reaction temperature of the lubricant base oil feedstock flowing over the first catalyst is 280 ℃ to 380 ℃, the reaction temperature of the lubricant base oil feedstock flowing over the second catalyst is 200 ℃ to 340 ℃, and the temperature of the hydrofinishing is 200 ℃ to 280 ℃.
Researches show that the reaction temperature of the isodewaxing catalyst is close to the reaction temperature of the complementary refining hydrogenation by adopting the grading combination of two types of noble metal isodewaxing catalysts and respectively controlling the reaction temperature, so that the production cost is reduced while the problem of high cloud point of various base oils with high viscosity, high pour point and high cloud point is solved.
According to certain embodiments of the present application, the shape selective component of the first catalyst is a ZSM-12 molecular sieve or a ZSM-11 molecular sieve or a ZSM-12/ZSM-11 composite molecular sieve. ZSM-12 or ZSM-11 is a one-dimensional straight-pore molecular sieve, has moderate acidity and is suitable to be used as a shape-selective molecular sieve component of an isomerization dewaxing catalyst.
According to certain embodiments of the present application, the shape selective component of the second catalyst is a ZSM-5 molecular sieve. The ZSM-5 molecular sieve is used as the main shape-selective molecular sieve component of the hydrodewaxing molecular sieve. In the application, noble metal active components such as Pt, Pd and the like are impregnated, so that the reaction temperature of the ZSM-5 dewaxing can be greatly reduced. The pore channels are three-dimensional cross pore channels, have strong acidity, are used as shape-selective components of the dewaxing catalyst, are combined with molecular sieves such as ZSM-12 and the like, can have complementary action on the acid strength and the shape selection of wax molecules, and can greatly reduce the cloud point of oil products.
The method adopts the combination of two isodewaxing catalysts, adopts a moderate-acidity shape-selective molecular sieve and a strong-acidity shape-selective molecular sieve, and improves the yield of a target product as much as possible under the condition that the target product solid paraffin passes through so as to reduce the operating temperature of subsequent fractionation; the acidity of the isomerization dewaxing catalyst is improved, so that the proper and ordered reduction of the reaction temperature is realized, the proper reaction temperature is provided for the subsequent noble metal hydrofining catalyst, and the product performance of the obtained food-grade white oil is not influenced.
According to certain embodiments of the present application, the active metal component used in the two catalysts is Pt and/or Pd. Noble metal active components such as Pt and/or Pd are selected to be matched with the molecular sieve of the isomerization dewaxing catalyst, the noble metal has very strong hydrogenation function, and unsaturated branched chain hydrocarbon generated by the isomerization dewaxing molecular sieve can be subjected to hydrogenation saturation in time, so that the cracking degree of the oil product is reduced, and the number of isomerization hydrocarbons of the oil product is reserved; secondly, noble metal active components such as Pt and/or Pd and the like are selected as the active components of the catalyst, so that the reaction temperature of the latter isodewaxing catalyst can be greatly reduced
According to certain embodiments of the present application, the first catalyst is one or more of 9 isodewaxing catalysts, such as Pt and/or Pd/ZSM-12, Pt and/or Pd/ZSM-11, Pt and/or Pd/ZSM-12/ZSM-11, with a precious metal content of 0.1% to 1.0%, specifically 0.4%, 0.6%, 0.7%, and preferably 0.6%. The noble metal is selected as an active component, so that the selectivity of isodewaxing and the yield of a target product can be ensured, meanwhile, the noble metal has stronger hydrofining capability, unsaturated hydrocarbons in an oil product can be saturated to the maximum extent, and the base oil of the lubricating oil has good oxidation stability and additive sensitivity. The content and type of the noble metal are matched with the performance of the isodewaxing molecular sieve, and the applicant finds that the content of the noble metal of 0.6 percent is more appropriate through a large amount of researches, so that the service life of the catalyst can be ensured, and the purchase cost is not increased due to the high content of the noble metal.
According to certain embodiments of the present application, the second catalyst is one or more of Pt/Pd/ZSM-5, Pt/ZSM-5, Pd/ZSM-5, wherein the noble metal content is 0.1% to 1%, and specifically may be 0.2%, 0.4%, 0.6%. The noble metal is selected to greatly reduce the isomerization dewaxing reaction temperature of the ZSM-5 molecular sieve, and the noble metal catalyst has stronger hydrogenation performance and has good catalytic action on promoting the hydrogenation of unsaturated hydrocarbons in oil products. Research shows that the content of noble metal is over 0.2%, ZSM-5 molecular sieve has ideal isodewaxing activity, the hydrorefining performance is improved when the content of metal is high, and the content of metal is not more than 0.6% considering the relationship between cost and performance.
According to certain embodiments of the present disclosure, the loading ratio of the first catalyst and the second catalyst is 1:0.5 to 4, and specifically may be 1:0.5, 1:1, 1:2, 1: 3.
Selecting two proper isomerization dewaxing ratios, which are mainly determined according to the wax content in the raw material, wherein when the condensation point of the raw material is high, such as above 30 ℃, the proportion of the first catalyst is high; when the condensation point of the raw material is low, such as below 10 ℃, the proportion of the second catalyst is high. The ratio of the two catalysts is adjusted, the total cost of the catalysts can be controlled according to the properties of the raw materials, and particularly, the quantity of the first catalyst can be greatly reduced aiming at the raw materials with lower condensation points, so that the total cost of the catalysts is reduced.
According to certain embodiments of the present application, the lubricant base oil feedstock comprises one or more of a hydrotreated or cracked product oil of solvent deasphalted light deoiled, or a hydrocracked product oil, a heavy distillate such as paraffin-based minus tetrads, and the like.
The method selects the hydrotreating or cracking produced oil of the solvent deasphalting light deasphalting or the hydrocracking produced oil, the paraffin base crude fraction and other heavy distillate oil to produce the high-viscosity lubricating oil base oil which comprises the kinematic viscosity of 7.0mm at 100 DEG C2(ii)/s and above, wherein the viscosity index is not lower than 80; and secondly, the oil generated by hydrotreating or hydrocracking heavy distillate oil such as solvent deasphalting light deasphalting and paraffin base tetralin reduction is selected to meet the feeding requirement of an isomerization dewaxing catalyst, and the sulfur content and the nitrogen content of the fed material are required to be not higher than 10mg/kg and not higher than 5 mg/kg. The isomerization dewaxing catalyst is poisoned by high content of sulfur and nitrogen, thereby losing activity, or the reaction temperature is required to be greatly increased after the isomerization dewaxing catalyst is deactivated, thereby losing selectivity.
According to certain embodiments of the present application, the first and second catalysts are sequentially packed in an upper catalyst bed and a lower catalyst bed in the same reactor; or sequentially packed in different reactors. When the first catalyst and the second catalyst are filled in different catalyst bed layers of the same reactor, the first catalyst is arranged above the second catalyst, and the filling mode is adopted, so that the yield of a target product can be improved, the reaction temperature of the two catalysts is within 20 ℃, the proper filling proportion of the two catalysts is required to be selected according to the condition of raw materials, the reaction temperature of the second catalyst can be controlled by cooling hydrogen, and the filling proportion of the two isodewaxing catalysts can be adjusted within a certain range, so that the requirements of different raw materials on pour point reduction and cloud point reduction can be met; when the first catalyst and the second catalyst are filled in different reactors, the reaction temperature of the second catalyst can be adjusted by the heat exchanger. At this time, the reaction temperature of the second catalyst is close to the reaction temperature of the hydrofinishing, and the process flow commonly used by the current industrial device can be adopted without newly adding or designing a larger reactor.
According to some embodiments of the present disclosure, when the first and second catalysts are sequentially loaded in the upper and lower catalyst beds in the same reactor, the reaction temperature of the upper catalyst bed is 300-360 ℃, and specifically 320-360 ℃; the reaction temperature of the lower catalyst bed layer is 260-320 ℃, and specifically can be 280-320 ℃. When the first catalyst and the second catalyst are sequentially filled in the upper catalyst bed layer and the lower catalyst bed layer in the same reactor, the reaction temperature difference of the two isodewaxing catalysts needs to be controlled within 40 ℃, the volume space velocity of the first catalyst is lower than that of the second catalyst bed layer, and particularly the oil product with higher condensation point. Because the first isodewaxing catalyst has better selectivity than the second isodewaxing catalyst, in order to ensure the yield of the target product, a packing mode of the first isodewaxing catalyst on the top and the second isodewaxing catalyst on the bottom is adopted.
According to some embodiments of the present disclosure, when the first catalyst and the second catalyst are sequentially loaded in different reactors, the reaction temperature of the reactor in which the first catalyst is located is 280 to 380 ℃, specifically 320 to 360 ℃, and the reaction temperature of the reactor in which the second catalyst is located is 220 to 280 ℃. When the first and second catalysts are sequentially filled in different reactors, the reaction temperature difference between the two isomerization dewaxing catalysts is controlled within 100 ℃. The filling ratio of the two isodewaxing catalysts can be adjusted according to the condensation point condition of the raw material. When the condensation point of the raw material is higher, the volume space velocity of the first catalyst is lower than that of the second catalyst bed layer. Because the first isodewaxing catalyst has better selectivity than the second isodewaxing catalyst, in order to ensure the yield of the target product, a filling mode that the first isodewaxing catalyst is arranged in front of the second isodewaxing catalyst is adopted. The second isomerization dewaxing catalyst has reaction temperature near the temperature of noble metal hydrofinishing and may be packed in one reactor to reduce the number of reactors.
According to certain embodiments of the present application, when the first and second catalysts are sequentially packed in the upper and lower catalyst beds in the same reactor, the operating conditions are: the hydrogen partial pressure is 14.0MPa to 20.0MPa, and can be specifically 15.0MPa or 16.0 MPa; the total volume space velocity of the first catalyst and the second catalyst is 0.4h-1～1.6h-1(ii) a The volume ratio of hydrogen to oil is 400-800: 1, specifically, 600: 1 or 800: 1. the hydrogen partial pressure is selected for the isodewaxing, the low reaction pressure is favorable for improving the selectivity and the reaction capacity of the isodewaxing, the isodewaxing reaction pressure is selected for the petroleum product with a wider viscosity range, the dewaxing capacity cannot be completely considered, and the service life of an isodewaxing catalyst can be prolonged due to the higher reaction pressure; for the application, because the sulfur and nitrogen contents of the raw material are required, 15MPa or 16.0MPa is selected as a relatively suitable reaction pressure and is also a reaction pressure commonly used for the isomerization and dewaxing of the lubricating oil of the current industrial device; for the selection of the total volume space velocity of the isomerization dewaxing catalyst, the application selects 0.4h due to the wide condensation point range of the raw material-1～1.0h-1The main purpose is to reduce the reaction temperature of isomerization dewaxing as much as possible and ensure the high selectivity of the target product; for hydrogenation reactions, the higher the hydrogen to oil ratio the more favorable the hydrogenation reaction and the catalyst life, 600: 1 or 800:1 is sufficient to meet the requirements of an isodewaxing catalyst.
According to certain embodiments of the present application, when the first and second catalysts are sequentially packed in different reactors,
the first catalyst is in the reactor operating conditions of: the hydrogen partial pressure is 14.0MPa to 20.0MPa, and can be specifically 15.0MPa or 16.0 MPa; the volume space velocity is 0.5h-1～3h-1Specifically, it can be 0.8h-1～1.6h-1、0.8h-1Or 1.0h-1(ii) a The volume ratio of hydrogen to oil is 400-800: 1, specifically, 600: 1 or 800: 1.
the operating conditions of the reactor in which the second catalyst is present are: the hydrogen partial pressure is 14.0-20.0 MPa, specifically 15.0MPa or16.0 MPa; the volume space velocity is 0.8h-1～2.0h-1Specifically, it can be 1.0h-1Or 1.6h-1Or 2.0h-1(ii) a The volume ratio of hydrogen to oil is 400-800: 1, specifically, 600: 1 or 800: 1.
the hydrogen partial pressure is selected for the isodewaxing, the low reaction pressure is favorable for improving the selectivity and the reaction capacity of the isodewaxing, the isodewaxing reaction pressure is selected for the petroleum product with a wider viscosity range, the dewaxing capacity cannot be completely considered, and the service life of an isodewaxing catalyst can be prolonged due to the higher reaction pressure; for the application, because the sulfur and nitrogen contents of the raw material are required, 15MPa or 16.0MPa is selected as a relatively suitable reaction pressure and is also a reaction pressure commonly used for the isomerization and dewaxing of the lubricating oil of the current industrial device; for the selection of the total volume space velocity of the isomerization dewaxing catalyst, the application selects 0.4h due to the wide condensation point range of the raw material-1～1.0h-1The main purpose is to reduce the reaction temperature of isomerization dewaxing as much as possible and ensure the high selectivity of the target product; for hydrogenation reactions, the higher the hydrogen to oil ratio the more favorable the hydrogenation reaction and the catalyst life, 600: 1 or 800:1 is sufficient to meet the requirements of an isodewaxing catalyst. The second catalyst and the noble metal hydrogenation refining catalyst can be filled in the same reactor due to the reduction of the reaction temperature, and the high reaction pressure is favorable for improving the oxidation stability of the lubricating oil base oil and the sensitivity of the lubricating oil base oil to additives.
According to some embodiments of the present application, when the first and second catalysts are sequentially loaded in the upper and lower catalyst beds in the same reactor, the inlet of the lower catalyst bed is provided with cold hydrogen to lower the reaction temperature by less than 40 ℃, preferably by less than 20 ℃. Since the second isodewaxing catalyst has a strong cracking activity, it is necessary to properly control the reaction temperature to increase the selectivity and the yield of the desired product. The temperature is reduced by 20 ℃, so that the flow of cold hydrogen can be greatly reduced, and the operation energy consumption is reduced.
According to some embodiments of the present application, when the first and second catalysts are sequentially loaded in different reactors, a heat exchanger is provided between the two reactors to reduce the reaction temperature to within 100 ℃, preferably to 60 ℃ to 80 ℃.
When the first and second catalysts are loaded in different reactors, the cracking activity of the second catalyst will be stronger, and the reaction temperature thereof needs to be properly controlled to improve the selectivity and the yield of the target product. The temperature is reduced to 100 ℃, and a heat exchanger can be adopted, so that the operation energy consumption is reduced. When the reaction temperature of the second catalyst is reduced, the process conditions of the second catalyst are the same as those of the noble metal hydrogenation complementary refining catalyst, and the second catalyst can be filled in a reactor so as to reduce the construction cost and the operation cost of the reactor.
The invention also discloses the high-viscosity lubricant base oil with low pour point and cloud point, which is prepared by the method.
The following examples further illustrate the invention.
Example 1
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes oil generated by light deoiling and hydrotreating as a raw material 1, and the properties are shown in Table 1. Filling two isodewaxing catalysts in a reactor; the catalyst of the upper catalyst bed layer is an isodewaxing catalyst which is loaded with Pt/Pd noble metal and has a shape-selective component of ZSM-12 molecular sieve, wherein the total mass content of the noble metal is 0.6 percent, and the mass ratio of the Pt/Pd noble metal is 1: 2; the catalyst of the lower catalyst bed layer is an isodewaxing catalyst which is loaded with Pt/Pd noble metal and has a shape-selective component of deeply modified ZSM-5, wherein the total mass content of the noble metal is 0.6%, and the mass ratio of the Pt/Pd noble metal is 1:1. Three volume ratios (1:1, 1:1.6, 1.6:1) were used for the two isodewaxing catalysts; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrogenation and additional refining, then a light component is pulled out from a often reduced pressure distillation tower, and the component with the temperature of more than or equal to 460 ℃ at the bottom of the reduced pressure tower is the low cloud point 150BS bright stock product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the space velocities of the catalyst volumes in the upper bed layers can be respectively 1.0h-1、1.6h-1The space velocity of the catalyst volume in the lower bed layer can be respectively1.0h-1、1.6h-1The total isomerization dewaxing volume space velocity is 0.5h-1～0.8h-1(ii) a The reaction temperature of the upper bed layer is 300 ℃, and the reaction temperature of the lower bed layer is 295 ℃.
Comparative example 1
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes naphthenic base light deoiling and hydrotreating generated oil as a raw material 1, and the properties are shown in Table 1. Filling a commercial isodewaxing catalyst, wherein the catalyst is a supported Pt/pd noble metal, the content of the noble metal is 0.6 percent, and the isodewaxing shape-selective component is a ZSM-23 molecular sieve; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrogenation and additional refining, then a light component is pulled out from a often reduced pressure distillation tower, and the component with the temperature of more than or equal to 460 ℃ at the bottom of the reduced pressure tower is the low cloud point 150BS bright stock product.
The operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the volume space velocity of the noble metal isodewaxing catalyst is respectively 0.5h-1、0.8h-1The reaction temperature was 320 ℃ at the same space velocity of the total volume as in the examples.
The properties of the 150BS bright stock samples produced under four conditions of inventive example 1 and two conditions of comparative example 1 are shown in Table 2.
TABLE 1 light deoiling and hydrotreating of 1-cycloalkyl feedstock to produce oily nature
TABLE 2 150BS sample Properties of high viscosity lube base oils prepared in example 1 and comparative example 1
Note: the total space velocity of the two isodewaxing catalysts combined is shown in parentheses.
As can be seen from Table 2, this embodiment is describedThe kinematic viscosity of the target product at 100 ℃ is 30mm2The 150BS bright stock per second shows excellent performance of reducing pour point and cloud point. Compared with 150BS bright stock prepared by the reference example technology, the base oil obtained by the method has no cloud point problem basically, and the yield and the property of the bright stock are basically not different from those of the examples; the reaction temperature of the method is lower than 20 ℃ of the reference ratio, and the creativity of the method of the embodiment is reflected.
Example 2
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes oil generated by paraffin-based light deoiling hydrogenation treatment or hydrocracking as a raw material 2, and the properties of the raw material are shown in a table 3. Filling two isodewaxing catalysts in a reactor; the catalyst of the upper catalyst bed layer is an isodewaxing catalyst which is loaded with Pt/Pd noble metal and has shape-selective components of ZSM-12 and ZSM-11 composite molecular sieves, wherein the total mass content of the noble metal is 0.7 percent, and the mass ratio of the Pt/Pd noble metal is 1: 2.5; the catalyst of the lower catalyst bed layer is an isodewaxing catalyst which is loaded with Pt noble metal and contains deeply modified ZSM-5 as a shape-selective component, wherein the content of the noble metal Pt is 0.3 percent; three volume ratios (1:1, 1:1.6, 1.6:1) were used for the two isodewaxing catalysts; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrogenation and additional refining, and then a light component is pulled out from a often reduced pressure distillation tower, and the component with the temperature of more than or equal to 465 ℃ at the bottom of the reduced pressure tower is the low cloud point 90BS bright stock product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the total space velocity of the catalyst in the upper bed layer can be respectively 1.0h-1、1.6h-1The space velocities of the catalyst volumes of the lower bed layers can be respectively 1.0h-1、1.6h-1The total volume space velocity of the isomerization dewaxing is 0.5h-1～0.8h-1(ii) a The reaction temperature of the upper bed layer is 330 ℃, and the reaction temperature of the lower bed layer is 325 ℃.
Comparative example 2
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes oil generated by paraffin-based light deoiling hydrogenation treatment or hydrocracking as a raw material 2, and the properties of the raw material are shown in a table 3. A commercial isodewaxing catalyst is filled, the catalyst is a Pt/Pd-loaded noble metal, and the total content of the noble metal is 0.7 percent; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrogenation and additional refining, then a light component is extracted from a often reduced pressure distillation tower, and the component with the temperature of more than or equal to 465 ℃ at the bottom of the reduced pressure tower is a 90BS bright stock product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the volume space velocity of the noble metal isodewaxing catalyst can be respectively 0.5h-1、0.8h-1The reaction temperature was 330 ℃ at the same space velocity of the total volume as in the examples.
The properties of 90BS samples of the high-viscosity lubricant base oil obtained under the four conditions of example 2 of the present invention and the two conditions of comparative example 2 are shown in Table 4.
TABLE 3 light deoiling hydrotreating or hydrocracking of feedstock 2-Paraffin based produced oil Properties
TABLE 4 90BS sample Properties of high viscosity lube base oils prepared in example 2 and comparative example 2
Note: the total space velocity of the two isodewaxing catalysts combined is shown in parentheses.
As can be seen from Table 4, the paraffin-based light deoiled and hydrotreated or hydrocracked product oil is used as the raw material, and compared with the 90BS bright stock prepared by the reference example technology, the cloud point of the high-viscosity lube base oil 90BS obtained by the method of the invention is lower, and the properties of other products are basically not different from those of the examples except that the yield of the 90BS bright stock is reduced by less than 2%, so that the creativity of the method of the invention is embodied.
Example 3
A method for reducing the cloud point of base oil of high-viscosity lubricating oil is to generate an oil raw material 3 by hydrotreating or hydrocracking paraffin-based four-line distillate oil, wherein the properties of the raw material are shown in a table 5. Filling two isodewaxing catalysts in a reactor; the upper bed catalyst is an isodewaxing catalyst which is loaded with Pt noble metal and has shape selective components of ZSM-12 and ZSM-11 composite molecular sieves, wherein the content of the noble metal Pt is 0.6 percent; the lower bed layer is an isodewaxing catalyst which is loaded with Pd noble metal and contains deeply modified ZSM-5 as a shape-selective component, wherein the content of the noble metal Pd is 0.6 percent; two isodewaxing catalysts are used in various volume ratios (1:1, 1:1.6, 1.6: 1); the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrogenation and additional refining, a light component is extracted from a often reduced pressure distillation tower, and a component with the temperature of more than or equal to 440 ℃ at the bottom of the reduced pressure tower is a low cloud point 8cst high viscosity lubricating oil base oil product.
The above operating conditions were: total hydrogen to oil volume ratio 800:1, the total space velocity of the catalyst in the upper bed layer can be respectively 1.0h-1、1.6h-1The space velocities of the catalyst volumes of the lower bed layers can be respectively 1.0h-1、1.6h-1The total volume space velocity of the isomerization dewaxing is 0.5h-1～0.8h-1(ii) a The reaction temperature of the upper bed layer is 335 ℃, and the reaction temperature of the lower bed layer is 325 ℃.
Comparative example 3
A method for reducing the cloud point of base oil of high-viscosity lubricating oil is to generate an oil raw material 3 by hydrotreating or hydrocracking paraffin-based four-line distillate oil, wherein the properties of the raw material are shown in a table 5. A reactor is adopted, a commercial isodewaxing catalyst is filled, the loaded noble metal is Pt, the content of the noble metal is 0.6 percent, and the isodewaxing shape-selective component is an SAPO-11 molecular sieve; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrofinishing, a light component is extracted from a often reduced pressure distillation tower, and the component with the temperature of more than or equal to 440 ℃ at the bottom of the reduced pressure tower is the 8cst high-viscosity lubricating oil base oil product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the space velocities of the catalyst volumes can be respectively 0.5h-1、0.8h-1The reaction temperature was 335 ℃ at the same space velocity of the total volume as in the examples.
The properties of the high viscosity lubricant base oil 8cst oil samples prepared under the four conditions of example 3 of the present invention and the two conditions of comparative example 3 are shown in table 6.
TABLE 5 hydrotreating or cracking of the 3-paraffinic minus tetralin distillate feedstock to produce an oily nature
TABLE 6 Properties of samples of high viscosity lube base oils prepared in example 3 and comparative example 3
As can be seen from Table 6, compared with the 8cst lubricating oil base oil prepared by the reference example technology, the heavy viscosity lubricating oil base oil obtained by the method of the present embodiment has a lower cloud point, and the properties of other products are basically not different from those of the embodiments except that the yield of the target product is reduced by less than 1%, so as to embody the creativity of the method of the present embodiment.
Example 4
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes naphthenic base light deoiling and hydrotreating generated oil as a raw material 1, and the properties are shown in Table 1. Two reactors are adopted and filled with two isodewaxing catalysts; the catalyst of the first reactor is an isomerization dewaxing catalyst which is loaded with Pt/Pd noble metal and has a shape-selective component of ZSM-12 molecular sieve, wherein the total mass content of the noble metal is 0.4 percent, and the mass ratio of the Pt/Pd noble metal is 1: 2; the catalyst of the second reactor is an isomerization dewaxing catalyst which is loaded with Pt/Pd noble metal and has shape-selective component of shallow modified ZSM-5, wherein the total mass content of the noble metal is 0.4 percent, and the mass ratio of the Pt/Pd noble metal is 1: 1; three volume ratios (1:1, 1:1.6, 1.6:1) were used for the two isodewaxing catalysts; the raw materials pass through the catalyst bed layers of the two reactors from top to bottom, and are subjected to hydrogenation complementary refining, and then a light component is extracted by a normal-pressure and reduced-pressure distillation tower, and the component with the temperature of more than or equal to 460 ℃ at the bottom of the reduced-pressure tower is the low cloud point 150BS bright stock product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen to oil volume ratio 600: 1, the catalyst volume space velocity of the first reactor can be respectively 1.0h-1、1.6h-1The catalyst volume space velocity of the second reactor can be respectively 1.0h-1、1.6h-1The reaction temperature of the first reactor is 300 ℃, and the reaction temperature of the second reactor is 240-280 ℃.
Comparative example 4
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes naphthenic base light deoiling and hydrotreating generated oil as a raw material 1, and the properties are shown in Table 1. Filling a commercial isodewaxing catalyst, wherein the catalyst is a Pt-loaded noble metal, the content of the noble metal is 0.4 percent, and an isodewaxing shape-selective molecular sieve is ZSM-23; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and is subjected to hydrogenation complementary refining, and then a light component is extracted through a normal-pressure and reduced-pressure distillation tower, wherein the component with the temperature of more than or equal to 460 ℃ at the bottom of the reduced-pressure tower is the low cloud point 150BS bright stock product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the volume space velocity of the noble metal isodewaxing catalyst is 0.5h-1、0.8h-1The reaction temperature was 325 ℃ at the same space velocity of the total volume as in the examples.
The properties of the 150BS bright stock samples prepared under the four conditions of inventive example 1 and the two conditions of comparative example 1 are shown in Table 7.
TABLE 7 150BS sample Properties of high viscosity lube base oils prepared in example 4 and comparative example 4
Note: the total space velocity of the two isodewaxing catalysts combined is shown in parentheses.
As can be seen from Table 7, the kinematic viscosity of the target product at 100 ℃ of the method of this example is 30mm2The 150BS bright stock per second shows excellent pour point reduction,Property of lowering cloud point. Compared with 150BS bright stock prepared by the reference example technology, the base oil obtained by the method has no cloud point problem basically, and the yield and the property of the bright stock are basically not different from those of the examples; by adopting the method of the embodiment, the reaction temperature of the first reactor is lower than the reference temperature of 25 ℃, the temperature of the second reactor is similar to that of the hydrofinishing, and the second isodewaxing catalyst and the noble metal hydrofinishing catalyst can share one reactor and are filled in the upper bed layer of the reactor in the specific industrial implementation process. The method has the advantages of low isomerization dewaxing reaction temperature, low cloud point of the obtained product and simple process flow, and embodies the creativity of the method.
Example 5
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes oil generated by paraffin-based light deoiling hydrogenation treatment or hydrocracking as a raw material 2, and the properties of the raw material are shown in a table 3. Two reactors are adopted and filled with two isodewaxing catalysts; the catalyst of the first reactor is an isomerization dewaxing catalyst which is loaded with Pt noble metal and has shape selective components of ZSM-12 and ZSM-11 composite molecular sieve, wherein the content of the noble metal Pt is 0.35 percent; the catalyst of the second reactor is an isodewaxing catalyst which is loaded with Pt noble metal and has a shape-selective component of lightly modified ZSM-5, wherein the content of the noble metal Pt is 0.35 percent; three volume ratios (1:1, 1:1.6, 1:2.0) were used for the two isodewaxing catalysts; the raw materials pass through the catalyst bed layers of the two reactors from top to bottom, and are subjected to hydrogenation complementary refining, and then a light component is extracted through a normal-pressure and reduced-pressure distillation tower, wherein the component at the bottom of the reduced-pressure tower is more than or equal to 465 ℃ and is the low cloud point 90BS bright stock product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the catalyst volume space velocity of the first reactor is 1.0h-1The catalyst volume space velocity of the second reactor can be respectively 1.0h-1、1.6h-1、2.0h-1The total volume space velocity of the two isodewaxing catalysts is 0.5h-1～0.67h-1(ii) a The reaction temperature of the first reactor is 330 ℃, and the reaction temperature of the second reactor is 260-300 ℃.
Comparative example 5
A method for reducing the cloud point of base oil of high-viscosity lubricating oil takes oil generated by paraffin-based light deoiling hydrogenation treatment or hydrocracking as a raw material 2, and the properties of the raw material are shown in a table 3. A commercial isodewaxing catalyst is filled, the catalyst is a Pt-loaded noble metal, the total content of the noble metal is 0.6 percent, and the isodewaxing shape-selective component is an SAPO-11 molecular sieve; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrogenation and additional refining, then a light component is extracted from a often reduced pressure distillation tower, and the component with the temperature of more than or equal to 465 ℃ at the bottom of the reduced pressure tower is a 90BS bright stock product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the volume space velocity of the noble metal isodewaxing catalyst can be respectively 0.5h-1、0.67h-1The reaction temperature was 330 ℃ at the same space velocity of the total volume as in the examples.
The properties of 90BS samples of the high-viscosity lubricant base oil prepared under the four conditions of example 2 of the present invention and the two conditions of comparative example 2 are shown in Table 8.
TABLE 8 90BS sample Properties of high viscosity lube base oils prepared in example 5 and comparative example 5
Note: the total space velocity of the two isodewaxing catalysts combined is shown in parentheses.
As can be seen from Table 8, the paraffin-based light deoiled and hydrotreated or hydrocracked product oil is used as the raw material, and compared with the 90BS bright stock prepared by the reference example technology, the cloud point of the high-viscosity lube base oil 90BS obtained by the method of the present embodiment is lower, and the product properties are basically not different from those of the examples except that the yield of the 90BS bright stock is reduced by less than 2%, so that the creativity of the method of the present invention is embodied.
Example 6
A method for reducing the cloud point of base oil of high-viscosity lubricating oil is to generate an oil raw material 3 by hydrotreating or hydrocracking paraffin-based four-line distillate oil, wherein the properties of the raw material are shown in a table 5. Two reactors are adopted and filled with two isodewaxing catalysts; the catalyst of the first reactor is an isomerization dewaxing catalyst which is loaded with Pt noble metal and has shape selective components of ZSM-12 and ZSM-11 composite molecular sieve, wherein the content of the noble metal Pt is 0.6 percent; the catalyst of the second reactor is an isomerization dewaxing catalyst loaded with noble metal, the shape-selective component of the catalyst is ZSM-5 molecular sieve, wherein the content of noble metal Pd is 0.6 percent; three volume ratios (1:1, 1:1.6, 1:2.0) were used for the two isodewaxing catalysts; the raw materials pass through the catalyst bed layers of the two reactors from top to bottom, and are subjected to hydrogenation and additional refining, and then the light component is extracted through a normal-pressure and reduced-pressure distillation tower, and the component with the temperature of more than or equal to 440 ℃ at the bottom of the reduced-pressure tower is the low cloud point 8cst high-viscosity lubricating oil base oil product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the space velocity of the catalyst volume of the first reactor is 1.0h-1The catalyst volume space velocity of the second reactor can be respectively 1.0h-1、1.6h-1、2.0h-1The total volume space velocity of the two isodewaxing catalysts is 0.5h-1～0.67h-1(ii) a The reaction temperature of the first reactor is 335 ℃, and the reaction temperature of the second reactor is 240-280 ℃.
Comparative example 6
A method for reducing the cloud point of base oil of high-viscosity lubricating oil is to generate an oil raw material 3 by hydrotreating or hydrocracking paraffin-based four-line distillate oil, wherein the properties of the raw material are shown in a table 5. A commercial isodewaxing catalyst is filled in the reactor, the supported noble metal is Pt, the content of the noble metal is 0.6 percent, and the isodewaxing shape-selective component is ZSM-12; the raw material passes through an isomerization dewaxing catalyst bed layer from top to bottom, and passes through another reactor again for hydrofinishing, a light component is extracted from a often reduced pressure distillation tower, and the component with the temperature of more than or equal to 440 ℃ at the bottom of the reduced pressure tower is the 8cst high-viscosity lubricating oil base oil product.
The above operating conditions were: total hydrogen partial pressure 15.0MPa, total hydrogen-oil volume ratio 800:1, the space velocity of the catalyst volume is 0.5h-1、0.67h-1The reaction temperature was 335 ℃ at the same space velocity of the total volume as in the examples.
The properties of the high viscosity lubricant base oil 8cst oil samples prepared under the four conditions of example 3 of the present invention and the two conditions of comparative example 3 are shown in table 9.
TABLE 9 Properties of samples of high viscosity lube base oils prepared in example 6 and comparative example 6
Note: the total space velocity of the two isodewaxing catalysts combined is shown in parentheses.
As can be seen from Table 9, the large viscosity lube base oil obtained by the method of this example has a lower cloud point than the 8cst lube base oil prepared by the reference example technique, and the properties of other products are not different from those of the examples except that the yield of the target product is reduced by less than 1%. And the temperature of the second reactor is similar to that of the hydrogenation complementary refining, and the second isomerization dewaxing catalyst and the noble metal hydrogenation refining catalyst can share one reactor and are filled in the upper bed layer of the reactor in the specific industrial implementation process. The isomerization dewaxing reaction temperature is low, the cloud point of the obtained product is low, the process flow is simple, and the creativity of the method is reflected.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A method for reducing the cloud point of a base oil of a high viscosity lubricating oil, comprising the steps of:
adding a lubricating oil base oil raw material into a reaction device, wherein a first catalyst and a second catalyst are sequentially arranged in the reaction device from top to bottom; the first catalyst and the second catalyst are two different noble metal isodewaxing catalysts;
the lubricating oil base oil raw material sequentially flows through a first catalyst and a second catalyst from top to bottom, the reaction temperature of the lubricating oil base oil raw material flowing through the second catalyst is lower than that of the lubricating oil base oil raw material flowing through the first catalyst, and after the lubricating oil base oil raw material is subjected to hydrogenation complementary refining, a vacuum tower bottom product obtained through normal and vacuum fractionation is the low-cloud-point high-viscosity lubricating oil base oil.
2. The method of reducing the cloud point of a basestock of a high viscosity lubricant according to claim 1, wherein:
the reaction temperature of the lubricating oil base oil raw material flowing through the first catalyst is 280-380 ℃, the reaction temperature of the lubricating oil base oil raw material flowing through the second catalyst is 200-340 ℃, and the temperature of the hydrofinishing is 200-280 ℃.
3. The method of reducing the cloud point of a basestock of a high viscosity lubricant according to claim 1, wherein:
the shape selective component of the first catalyst is a ZSM-12 molecular sieve or a ZSM-11 molecular sieve or a ZSM-12/ZSM-11 composite molecular sieve; the shape selective component of the second catalyst is a ZSM-5 molecular sieve; the active metal components used by the two catalysts are Pt and/or Pd.
4. The method of reducing the cloud point of a basestock of a high viscosity lubricant of claim 3, wherein:
the first catalyst is one or more of Pt and/or Pd/ZSM-12, Pt and/or Pd/ZSM-11, Pt and/or Pd/ZSM-12/ZSM-11, wherein the content of noble metal is 0.1-1.0%;
the second catalyst is one or more of Pt/Pd/ZSM-5, Pt/ZSM-5 and Pd/ZSM-5, wherein the content of noble metal is 0.1-1%;
the filling ratio of the first catalyst to the second catalyst is 1: 0.5-4.
5. The method of reducing the cloud point of a basestock of a high viscosity lubricant according to claim 1, wherein:
the raw material of the lubricating oil base oil comprises one or more of hydrotreating or hydrocracking generated oil of solvent deasphalting light deoiled oil and hydrotreating or cracking generated oil of heavy distillate oil.
6. The method for lowering cloud point of base oil of high viscosity lubricant according to any one of claims 1 to 5, wherein:
the first catalyst and the second catalyst are sequentially filled in an upper catalyst bed layer and a lower catalyst bed layer in the same reactor; or sequentially filling the reactors in different reactors;
when the first catalyst and the second catalyst are sequentially filled in an upper catalyst bed layer and a lower catalyst bed layer in the same reactor, the reaction temperature of the upper catalyst bed layer is 300-360 ℃, and the reaction temperature of the lower catalyst bed layer is 260-320 ℃;
when the first catalyst and the second catalyst are sequentially filled in different reactors, the reaction temperature of the reactor in which the first catalyst is positioned is 280-380 ℃, and the reaction temperature of the reactor in which the second catalyst is positioned is 220-280 ℃.
7. The method of lowering the cloud point of a basestock of a high viscosity lubricating oil of claim 6, wherein:
when the first catalyst and the second catalyst are sequentially filled in the upper catalyst bed layer and the lower catalyst bed layer in the same reactor, the operation conditions are as follows: the hydrogen partial pressure is 14.0MPa to 20.0 MPa; the total volume space velocity of the first catalyst and the second catalyst is 0.4h-1～1.6h-1(ii) a The volume ratio of the hydrogen to the oil is 400-800: 1.
8. The method of lowering the cloud point of a basestock of a high viscosity lubricating oil of claim 6, wherein:
when the first and second catalysts are sequentially loaded in different reactors,
the first catalyst is in the reactor operating conditions of: the hydrogen partial pressure is 14.0MPa to 20.0 MPa; the volume space velocity is 0.5h-1～3h-1(ii) a The volume ratio of hydrogen to oil is 400-800: 1;
the operating conditions of the reactor in which the second catalyst is present are: the hydrogen partial pressure is 14.0MPa to 20.0 MPa; the volume space velocity is 0.8h-1～2.0h-1Starting the process; the volume ratio of hydrogen to oil is 400-800: 1.
9. the method of lowering the cloud point of a basestock of a high viscosity lubricating oil of claim 6, wherein:
when the first catalyst and the second catalyst are sequentially filled in an upper catalyst bed layer and a lower catalyst bed layer in the same reactor, cold hydrogen is arranged at the inlet of the lower catalyst bed layer, so that the reaction temperature is reduced to within 40 ℃;
when the first catalyst and the second catalyst are sequentially filled in different reactors, a heat exchanger is arranged between the two reactors to reduce the reaction temperature to within 100 ℃.
10. A high-viscosity lubricating oil base oil is characterized in that: the lubricant base oil is prepared by the method as claimed in any one of claims 1 to 9.
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| CN106554820A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method for preparing lube base oil |
| CN106566589A (en) * | 2016-11-13 | 2017-04-19 | 中国海洋石油总公司 | Method for processing high-wax-content lubricant base oil |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114471681A (en) * | 2020-11-12 | 2022-05-13 | 中国石油天然气股份有限公司 | Method for producing low cloud point base oil, catalyst and preparation method of catalyst |
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