Process for passivation and process for the hydroisomerisation of fischer-tropsch waxes to produce lube base oils

Abstract

The application provides a passivation method and a method for producing lubricating base oil by Fischer-Tropsch wax hydrogenation isomerization, and based on the passivation method provided by the application, good passivation effect can be achieved with lower passivation agent dosage, and based on the passivation method, the Fischer-Tropsch wax hydrogenation isomerization is used to produce lubricating base oil, the temperature rise after passivation is small, and the start-up time can be greatly shortened. The passivation method comprises the following steps: using Fischer-Tropsch product oil with a distillation range of 430 DEG C or below as a passivation carrying oil, using alkyl amine free of oxygen atoms as a passivation agent, and passivating the hydrogenation isomerization catalyst in the presence of hydrogen; the passivation treatment conditions comprise the following steps: heating to 300-350 DEG C at a heating rate of 5-20 DEG C / h, and then keeping the temperature constant for 10-30 h, preferably 10-24 h; based on the mass of the passivation carrying oil, the dosage of the passivation agent is 10-500 ppm in terms of nitrogen element in the passivation agent.

Description

TECHNICAL FIELD

[0001] The present application relates to a passivation method of a hydroisomerization catalyst for producing lubricating base oil from Fischer-Tropsch wax by hydroisomerization and a method for producing lubricating base oil from Fischer-Tropsch wax by hydroisomerization based on the passivation method. BACKGROUND

[0002] Currently, the hydroisomerization catalysts for preparing lubricating base oil from Fischer-Tropsch wax (referred to as "Fischer-Tropsch wax" for short) mainly include noble metal molecular sieve catalysts, and the noble metals include Pt and the like. The active metal has strong hydrogenation activity, the carrier is molecular sieve and alumina, the content of the molecular sieve is high, and the catalyst has very high hydrocracking activity. Before the feedstock oil is introduced, measures must be taken to passivate the catalyst to inhibit its excessively high initial activity and prevent the occurrence of "flying temperature" phenomenon during the oil reaction process, thereby causing the activity and selectivity of the catalyst to decrease.

[0003] CN 103789008A discloses a start-up method of a hydrocracking device, wherein the passivation method is to introduce a light fraction oil containing nitrogen when the temperature of the catalyst bed is about 245℃, and to replace the light fraction oil containing nitrogen with a heavy fraction oil containing nitrogen when the temperature of the bed is increased to 290℃, so as to passivate the acid sites of the catalyst by means of the generated ammonia.

[0004] CN 109957419 A discloses a start-up method of a hydrocracking process, which introduces gaseous nitrogen compounds such as pyridine and quinoline after the sulfurization of the catalyst is completed and performs passivation at 420℃-550℃. The start-up method adopts high-temperature passivation, and the passivation agent used has strong toxicity and is easy to pollute the environment.

[0005] CN 103059969 A discloses a start-up passivation method of a hydrocracking catalyst, wherein the refined feedstock oil is high-nitrogen oil, and the high-nitrogen gas generated after refining is used to passivate the cracking catalyst without introducing a passivation agent.

[0006] The above documents do not involve the start-up passivation technology for producing lubricating base oil from Fischer-Tropsch wax by hydroisomerization. In addition, the existing start-up passivation methods often need to introduce a passivation agent in a high amount, and the passivation carrying oil is often difficult to be directly output as a product after the reaction and can only be used as the next start-up oil. Moreover, the passivation effect is not good, the reaction temperature rise after passivation is large (for example, the temperature rise is >18℃), and the like, which is not conducive to the control of the temperature of the reactor and the smooth start-up. SUMMARY

[0007] This invention provides a passivation method for a Fischer-Tropsch wax hydroisomerization catalyst and a method for producing lubricating oil base oil through Fischer-Tropsch wax hydroisomerization. The passivation method provided by this invention, particularly for Fischer-Tropsch wax hydroisomerization catalysts based on ten-membered ring molecular sieves and precious metals used in the production of lubricating oil base oils, achieves good passivation results with a lower amount of passivating agent. When using this passivation method for producing lubricating oil base oils through Fischer-Tropsch wax hydroisomerization, the temperature rise after passivation is small, and the start-up time is significantly shortened.

[0008] To achieve its objective, the present invention provides the following technical solution:

[0009] This invention provides a passivation method for a Fischer-Tropsch wax hydroisomerization catalyst, wherein the hydroisomerization catalyst comprises a support and a noble metal element supported on the support, the support comprising a ten-membered ring molecular sieve, and the passivation method comprises:

[0010] The hydroisomerization catalyst was passivated using Fischer-Tropsch product oil with a distillation range of less than 430°C as the passivation carrier oil and alkane amines without oxygen atoms as the passivating agent in the presence of hydrogen.

[0011] The passivation treatment conditions include: heating to 300-350℃ at a heating rate of 5-20℃ / h, and then holding the temperature at that temperature for 10-30h, preferably 10-24h; based on the mass of the passivation carrier oil, the amount of the passivating agent, calculated by nitrogen element in the passivating agent, is 10-500ppm, preferably 50-200ppm, more preferably 50-150ppm, and even more preferably 60-100ppm.

[0012] In some embodiments, the passivating agent is selected from one or more of ethylenediamine, butylamine, n-butylamine, and tri-n-butylamine, with n-butylamine being preferred.

[0013] In some embodiments, the pore size of the hydroisomerization catalyst is 0.4-0.53 nm.

[0014] In some embodiments, the Fischer-Tropsch product oil is selected from one or more of light white oil, direct coal liquefaction diesel, Fischer-Tropsch diesel with a distillation range of 300-390°C, Fischer-Tropsch hydrocracking oil, and petroleum-based diesel; preferably, the Fischer-Tropsch hydrocracking oil is Fischer-Tropsch hydrocracking reduced-second-line oil and / or Fischer-Tropsch hydrocracking reduced-third-line oil.

[0015] In some embodiments, the passivation conditions involve heating to 300-350°C at a heating rate of 8-12°C / h, preferably to 330-350°C.

[0016] In some embodiments, the initial temperature for the heating is 100-250°C, preferably 150-200°C.

[0017] In some embodiments, the passivation conditions further include: a pressure of 3-10 MPa and a volume hourly space velocity of 0.5-2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300:1-800:1;

[0018] Preferably, the pressure is 3-6 MPa and the volumetric hourly space velocity is 0.5-1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1-600:1.

[0019] In some embodiments, the ten-membered ring molecule is selected from one or more of ZSM-22, ZSM-23, ZSM-48 and ZSM-35, with ZSM-48 being preferred;

[0020] The precious metal element is selected from Pd and / or Pt;

[0021] The carrier also includes aluminum oxide and / or silicon oxide.

[0022] In some embodiments, the content of the ten-membered ring molecular sieve in the hydroisomerization catalyst is 60-90 wt%.

[0023] The content of the precious metal element is 0.1-0.5 wt%.

[0024] In some embodiments, after passivation is completed, a product oil is obtained by reacting the passivation-carrying oil during the passivation process. Preferably, the product oil is white oil or lubricating oil base oil.

[0025] A second aspect of the present invention provides a method for producing lubricating oil base oil by hydroisomerization of Fischer-Tropsch wax, comprising the following steps:

[0026] 1) The hydroisomerization catalyst is passivated using the passivation method described above;

[0027] 2) Fischer-Tropsch wax is subjected to hydroisomerization reaction in the presence of the hydroisomerization catalyst after passivation treatment in step 1) to produce lubricating oil base oil.

[0028] In some embodiments, the reaction conditions for the hydroisomerization reaction in step 2) include: pressure 3-10 MPa, temperature 300-360 °C, and volume hourly space velocity 0.5-2 h⁻¹. -1 Hydrogen-to-oil volume ratio 300:1-800:1;

[0029] Preferably, the reaction conditions for the hydroisomerization reaction include: pressure 3-6 MPa, temperature 320-350 °C, and volume hourly space velocity (VHSV) 0.5-1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1-600:1.

[0030] Furthermore, in step 1), after the passivation treatment is performed, the product oil is output, which is transformed from the passivation-carrying oil through reaction during the passivation process.

[0031] The technical solution provided by this invention has the following beneficial effects:

[0032] This invention proposes a passivation method for hydroisomerization catalysts based on noble metal elements and ten-membered ring molecular sieves used in the hydroisomerization of Fischer-Tropsch wax. Using Fischer-Tropsch product oil as the passivation carrier oil and an oxygen-free alkane amine as the passivating agent, good passivation results can be achieved with a relatively low amount of passivating agent. The passivation carrier oil can be directly converted into the product oil after passivation. Applying this passivation method to the process of producing lubricating oil base oil through the hydroisomerization of Fischer-Tropsch wax results in a low reaction temperature rise after passivation, which facilitates stable subsequent start-up, significantly shortens start-up time, improves start-up efficiency, and achieves a high product yield. Detailed Implementation

[0033] To facilitate understanding of the present invention, the following description, in conjunction with embodiments, will further illustrate the invention. It should be understood that the following embodiments are merely for a better understanding of the invention and do not imply that the invention is limited to these embodiments.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The term "and / or" may be used herein to include any and all combinations of one or more of the associated listed items.

[0035] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in this technical field can be followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0036] This invention proposes a passivation method and a method for producing lubricating oil base oil through Fischer-Tropsch wax hydroisomerization reactions (particularly for the production of lubricating oil base oils from Fischer-Tropsch wax) using Fischer-Tropsch wax-based hydroisomerization catalysts with ten-membered ring molecular sieves and precious metal elements. The passivation method of this invention achieves excellent passivation results for the hydroisomerization catalyst and converts the passivated oil into high-value-added product oil.

[0037] The passivation method for Fischer-Tropsch wax hydroisomerization catalyst provided by this invention includes a support and a noble metal element supported on the support. The support includes a ten-membered ring molecular sieve. The passivation method mainly includes the following steps:

[0038] Using Fischer-Tropsch product oil with a distillation range below 430℃ as the passivation carrier oil and an oxygen-free alkane amine as the passivating agent, the hydroisomerization catalyst was passivated in the presence of hydrogen. The passivation conditions included heating to 300-350℃ (e.g., 300, 320, 330, 340, 350℃) at a heating rate of 5-20℃ / h (e.g., 5, 8, 12, 15, 18, 20℃ / h), and then holding at that temperature for 10-30 hours. The temperature is preferably constant for 10-24 hours. Based on the mass of the passivation carrier oil, the amount of passivating agent is 10-500 ppm (e.g., 10, 20, 50, 60, 80, 100, 150, 180, 200, 250, 300, 350, 400, 450, 500 ppm, etc.), preferably 50-200 ppm, more preferably 50-150 ppm, and even more preferably 60-100 ppm.

[0039] The passivation method described above enables hydroisomerization catalysts based on ten-membered ring molecular sieves and precious metal elements, suitable for Fischer-Tropsch wax hydroisomerization (especially for producing lubricating oil base oils), to achieve excellent passivation results. Passivation results in a small temperature rise, facilitating reaction control and stable reaction, while also shortening start-up time and increasing product yield. Furthermore, the passivation carrier oil can be converted into high-value-added product oil. Using the passivation method of this invention, alkane amines without oxygen atoms are used as passivating agents, combined with Fischer-Tropsch product oils with a distillation range below 430°C, and under the passivation conditions of this invention, the hydroisomerization catalyst is passivated. During the passivation process, no water is generated, metal aggregation does not occur, and catalyst pulverization is less likely, which helps maintain the stability of catalyst activity and selectivity, extends catalyst lifespan, and thus shortens the start-up time of subsequent reactions. Simultaneously, the passivation reaction of this invention is not vigorous, and the heat of reaction is low.

[0040] In the passivation method of this invention, good passivation effect can be achieved with a relatively low amount of passivating agent. Based on the mass of the passivation carrier oil, the amount of passivating agent is 10-500 ppm, calculated by nitrogen element in the passivating agent. Preferably, the amount of passivating agent is 50-200 ppm, more preferably 50-150 ppm, and even more preferably 60-100 ppm. This invention uses a low amount of passivating agent for passivation treatment, which can reduce the processing load of subsequent ammonia units. There are no particular limitations on the amount of passivation carrier oil, as long as it is sufficient to at least wet the catalyst.

[0041] In some preferred embodiments, the passivating agent used in the passivation method of the present invention is selected from one or more of ethylenediamine, butylamine, n-butylamine, and tri-n-butylamine, more preferably n-butylamine. The inventors have found that using these preferred passivating agents in combination with Fischer-Tropsch product oils with a distillation range below 430°C for the passivation of hydroisomerization catalysts based on ten-membered ring molecular sieves and noble metal elements in the production of lubricating oil base oils via Fischer-Tropsch wax hydroisomerization can achieve better passivation results. Furthermore, the aforementioned alkane amine passivating agents have low toxicity and, when used in combination with Fischer-Tropsch product oils with a distillation range below 430°C at lower dosages, provide good passivation effects for Fischer-Tropsch wax hydroisomerization cracking agents.

[0042] In some preferred embodiments, the passivating agent used is selected from one or more of ethylenediamine, butylamine, n-butylamine, and tri-n-butylamine, preferably n-butylamine; the pore size of the hydroisomerization catalyst used is 0.4-0.53 nm; the inventors have found that when these preferred passivating agents are combined with Fischer-Tropsch product oil with a distillation range of less than 430°C for the passivation of the above-mentioned hydroisomerization catalyst with specific pore size requirements, the passivating agent can easily enter the pores of the catalyst, resulting in a better passivation effect.

[0043] In a preferred embodiment, in the passivation method of the present invention, the Fischer-Tropsch product oil used as the passivation carrier oil is selected from one or more of light white oil, direct coal liquefaction diesel, Fischer-Tropsch diesel (distillation range 300-390°C), Fischer-Tropsch hydrocracking oil, and petroleum-based diesel; preferably Fischer-Tropsch hydrocracking oil, which is preferably Fischer-Tropsch hydrocracking reduced-pressure oil (P2) and / or Fischer-Tropsch hydrocracking reduced-pressure oil (P3). The Fischer-Tropsch hydrocracking reduced-pressure oil (P3) is preferably a low-nitrogen, low-sulfur cracked reduced-pressure oil, where "low-nitrogen, low-sulfur" means a nitrogen content of less than 2 ppm and a sulfur content of less than 10 ppm.

[0044] In the passivation method of the present invention, the passivation conditions include: heating to 300-350°C at a heating rate of 5-20°C / h, and then holding at that temperature for 10-30h, preferably 10-24h. Passivation under these conditions facilitates reaction diffusion, retains basic nitrogen within the molecular acid channels, stabilizes the acidity, inhibits the initial activity of the catalyst, and helps reduce the reaction temperature rise after passivation; for example, in some preferred embodiments, the temperature rise can be kept below 11°C. Preferably, the temperature is increased to 300-350℃, preferably 330-350℃, at a heating rate of 8-12℃ / h. The inventors have found that using the preferred passivation conditions results in a better passivation effect, helps to maintain the stable activity of the catalyst, facilitates a shorter start-up time, and ensures complete passivation. More preferably, the temperature is increased to 330-350℃ at a heating rate of 8-12℃ / h. The inventors have found that when the passivation temperature is higher than 350℃, the catalyst is prone to carbon deposition, which reduces the activity of the catalyst and is not conducive to the normal performance of the catalyst's isomerism. Controlling the passivation temperature at 330-350℃ helps to ensure complete passivation and obtain a better passivation effect.

[0045] In some preferred embodiments, based on the mass of the passivation carrier oil, the amount of passivating agent is 50-200 ppm, more preferably 50-150 ppm, and even more preferably 60-100 ppm, calculated by nitrogen element in the passivating agent. During the passivation overtreatment, the temperature is increased to 300-350℃, preferably 330-350℃, at a heating rate of 8-12℃ / h. Using the above combination of passivating agent dosage and passivation conditions for passivation is beneficial to obtaining a better passivation effect, and is beneficial to taking into account shorter start-up time, higher lubricating oil base oil yield, and lower reaction temperature rise.

[0046] In some implementations, the passivation conditions also include: a pressure of 3-10 MPa and a volumetric hourly space velocity of 0.5-2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300:1-800:1; preferably, the pressure is 3-6 MPa and the volume hourly space velocity is 0.5-1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1-600:1.

[0047] Preferably, the initial temperature for heating during passivation is 100-250°C, more preferably 150-200°C. In some embodiments, the hydroisomerization catalyst is reduced before passivation, preferably after reduction and before passivation, and the temperature is controlled at 100-250°C, more preferably 150-200°C, before the passivation operation.

[0048] In some embodiments, the hydroisomerization catalyst used for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil base oil contains a ten-membered ring molecule selected from one or more of ZSM-22, ZSM-23, ZSM-48, and ZSM-35, preferably ZSM-48; and / or, the noble metal element is selected from Pd and / or Pt; the support also includes alumina and / or silica.

[0049] In some embodiments, the hydroisomerization catalyst contains 60-90 wt% ten-membered ring molecular sieves, 0.1-0.5 wt% precious metal elements, and the balance is alumina and / or silicon oxide. Hydroisomerization catalysts with a ten-membered ring molecular sieve content as high as 60-90% exhibit high activity. However, when used in the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil base oil, they easily cause large temperature rises and overheating of the equipment during the reaction, adversely affecting the maintenance of catalyst activity and selectivity. The passivation method of this invention has a very good passivation effect on this type of hydroisomerization catalyst. After passivation, the reaction temperature rise is low, the reaction proceeds smoothly, and a high yield of product is obtained within a short start-up time.

[0050] The hydroisomerization catalyst used for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil base oil is conventionally used or existing in the art, or can be prepared using existing catalyst preparation methods. Taking the ten-membered ring molecular sieve ZSM-48 as an example, it can be directly obtained using methods disclosed in the prior art, such as those disclosed in CN103332703A and CN20181067095.0, and then a catalyst loaded with noble metal elements can be prepared based on this molecular sieve. Specifically, the hydroisomerization catalyst can be obtained by referring to the preparation methods disclosed in Examples 1-4 of CN20181067095.0. For reference, for example, a ten-membered ring molecular sieve is mixed with other support components (alumina and / or silica, the specific amount of which is determined according to the catalyst composition, for example, the mass ratio of molecular sieve to other support components is 65:35), and 5-20 wt% dilute nitric acid (the amount of which is, for example, but not limited to, 2% of the powder weight, for example, 1.5-4%) is added as a binder. The mixture is then extruded, aged, dried, and calcined (for example, calcined at 550°C for 2 hours, or calcined at 450-550°C for 1.5-4 hours) to obtain a support. Then, a noble metal element is loaded using an impregnation method (for example, pore saturation impregnation method), and the catalyst is dried and calcined (for example, calcined at 500°C for 2 hours, or calcined at 450-550°C for 1.5-4 hours) to obtain the catalyst with the desired noble metal element loading.

[0051] In the passivation method of the present invention, the passivation-carrying oil is converted into product oil through reaction during the passivation process. For example, the product oil is white oil or lubricating oil base oil.

[0052] The passivation method of this invention can achieve good passivation results when used to passivate Fischer-Tropsch wax hydroisomerization catalysts based on ten-membered ring molecular sieves and precious metal elements (especially hydroisomerization catalysts for the production of lubricating oil base oils through Fischer-Tropsch wax hydroisomerization). By using a specific combination of passivation carrier oil and passivating agent, and performing isothermal passivation at a heating rate of 5-20℃ / h (preferably 8-12℃ / h) to 300-350℃ (preferably 330-350℃), a good passivation effect can be achieved with relatively low passivating agent dosage. During the passivation process, basic nitrogen remains in the molecular sieve channels through reactive diffusion, passivating the acidic neutrality and reducing the acid strength. After passivation, when Fischer-Tropsch wax hydroisomerization is carried out to produce lubricating oil base oils, the reaction temperature rise is small, the reaction proceeds smoothly, the catalyst stabilization time is shortened, a stable product is obtained in a shorter start-up time, and the yield of lubricating oil base oil can be improved (e.g., by 2-3%).

[0053] A second aspect of the present invention also provides a method for producing lubricating oil base oil by hydroisomerization of Fischer-Tropsch wax, which mainly includes the following steps:

[0054] 1) The passivation method described above is used to passivate the hydroisomerization catalyst; after passivation, the product oil is output, which is converted from the passivation-carrying oil through reaction during the passivation process; the hydroisomerization catalyst is the hydroisomerization catalyst for producing lubricating oil base oil by Fischer-Tropsch wax hydroisomerization. For details about the catalyst, please refer to the above description.

[0055] 2) Fischer-Tropsch wax is subjected to hydroisomerization reaction in the presence of the hydroisomerization catalyst after passivation treatment in step 1) to produce lubricating oil base oil.

[0056] In step 2), the hydroisomerization reaction can be carried out under conventional reaction conditions in the art. In some embodiments, the reaction conditions for the hydroisomerization reaction in step 2) include: pressure 3-10 MPa, temperature 300-360 °C, and volume hourly space velocity 0.5-2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300:1-800:1; preferably, the reaction conditions for the hydroisomerization reaction include: pressure 3-6 MPa, temperature 320-350℃, and volume hourly space velocity 0.5-1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 400:1-600:1.

[0057] Example 1:

[0058] In this embodiment, Fischer-Tropsch 70# wax (the properties of the raw material are shown in Table 1 below) is used as the raw material, and hydroisomerization is carried out in the presence of a Fischer-Tropsch hydroisomerization catalyst to produce lubricating oil base oil.

[0059] Table 1 Properties of Fischer-Tropsch Wax (raw material)

[0060] Item Value Density, g / cm 3 ]] 0.82 Distillation range (D2887) / °C IBP / 5% 430 / 449 10％ / 30％ 458 / 482 50％ / 70％ 501 / 517 90％ / 95％ 540 / 550 99.5％ 574

[0061] The Fischer-Tropsch hydroisomerization catalyst is obtained through the following steps:

[0062] ZSM-48 molecular sieve was prepared according to the preparation process of Example 1 in patent document CN103332703A. Then, ZSM-48 molecular sieve and Al2O3 were mixed at a mass ratio of 65:35, and 10wt% dilute nitric acid was added as a binder. The mixture was extruded into strips. During the extrusion process, the amount of dilute nitric acid added accounted for 2% of the mass of the powder (the sum of molecular sieve and alumina, the same below), and the amount of water added accounted for 0.7% of the mass of the powder. The obtained support sample was aged at room temperature for 4 hours, dried at 80℃ for 5 hours, and calcined at 550℃ for 2 hours to obtain the support. Pt element was impregnated using a pore saturation impregnation method, dried at 80℃ for 4 hours, and calcined at 500℃ for 2 hours to obtain the catalyst. The mass fraction of Pt loading was 0.35%, the mass fraction of ZSM-48 was approximately 65%, and the pore size of the obtained catalyst was 0.5 nm.

[0063] The previously prepared 80 ml catalyst was loaded into the reaction apparatus and reduced for 5 h at 240 °C, 4 MPa and a hydrogen flow rate of 70 NL / h.

[0064] The reduced catalyst was passivated using Fischer-Tropsch hydrocracking oil (300-400℃ distillation range) as the passivation carrier oil and n-butylamine as the passivating agent. Based on the mass of the passivation carrier oil, the amount of passivating agent added, calculated as nitrogen, was 80 ppm. The passivation conditions included: an initial passivation temperature of 150℃, a heating rate of 10℃ / h, heating to 350℃, isothermal passivation for 24 h, a pressure (hydrogen pressure) of 4 MPa, and a volume hourly space velocity (VHSV) of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500:1.

[0065] After discharging the product oil converted from the passivation carrier oil (which, upon testing, meets the requirements for W1-TB light white oil), Fischer-Tropsch 70# wax is introduced into the reaction apparatus for a hydroisomerization reaction. The reaction pressure is 4 MPa, the reaction temperature is 325℃, and the volume hourly space velocity is 1 h⁻¹. -1 The hydrogen-to-oil volume ratio was 500:1, and the reaction was carried out for 3 days (corresponding to the "stabilization time" in the table below). A product with stable properties (i.e., stable density, distillation range, pour point, and kinematic viscosity) was obtained. The yield of lubricating oil base oil was 76.5 wt%, and the temperature rise during the reaction was 10 °C.

[0066] Comparative Example 1:

[0067] Lubricating oil base oil was prepared according to Example 1, except that the catalyst was not passivated. After the catalyst was reduced, the temperature was directly increased to 325°C at 10°C / h and the reaction was carried out for 20 days to obtain a stable product. The yield of lubricating oil base oil was 74.1 wt%, and the temperature rise during the reaction was 20°C.

[0068] Table 2: Comparison of experimental results between Example 1 and Comparative Example 1

[0069]

[0070] Example 2

[0071] This embodiment is based on Embodiment 1. The following mainly describes the differences from Embodiment 1:

[0072] The catalyst was packed into the reaction apparatus and reduced under conditions of 4 MPa and a hydrogen flow rate of 70 NL / h.

[0073] The reduced catalyst was passivated using Fischer-Tropsch hydrocracking oil (300-400℃ distillation range) as the passivation carrier oil and n-butylamine as the passivating agent. Based on the mass of the passivation carrier oil, the amount of passivating agent added, calculated as nitrogen, was 80 ppm. The passivation conditions included: an initial passivation temperature of 150℃, a heating rate of 5℃ / h, heating to 350℃, isothermal passivation for 24 h, a pressure (hydrogen pressure) of 4 MPa, and a volume hourly space velocity (VHSV) of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500:1. The product oil converted from the passivation-carrying oil is discharged (meeting the W1-TB requirements for light white oil).

[0074] After passivation, the Fischer-Tropsch wax underwent a hydroisomerization reaction as described in Example 1. The reaction lasted for 5 days, yielding a stable product. The temperature rise during the reaction was 12°C. The results are shown in Table 3.

[0075] Table 3. Experimental Results

[0076]

[0077] Example 3

[0078] This embodiment is based on Embodiment 1. The following mainly describes the differences from Embodiment 1:

[0079] The catalyst was packed into the reaction apparatus and reduced under conditions of 4 MPa and a hydrogen flow rate of 70 NL / h.

[0080] The reduced catalyst was passivated using Fischer-Tropsch hydrocracking oil (300-400℃ distillation range) as the passivation carrier oil and n-butylamine as the passivating agent. Based on the mass of the carrier oil, the amount of passivating agent added, calculated as nitrogen, was 10 ppm. The passivation conditions included: an initial passivation temperature of 150℃, a heating rate of 10℃ / h, heating to 350℃, isothermal passivation for 24 h, a pressure (hydrogen pressure) of 4 MPa, and a volume hourly space velocity (VHSV) of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500:1. The product oil converted from the passivation-carrying oil is discharged (meeting the W1-TB requirements for light white oil).

[0081] After passivation, the Fischer-Tropsch wax underwent a hydroisomerization reaction as described in Example 1. The reaction lasted for 7 days, yielding a stable product. The temperature rise during the reaction was 14°C. The results are shown in Table 4.

[0082] Table 4. Test Results

[0083]

[0084] Comparative Example 2

[0085] This embodiment is based on Embodiment 1. The main difference between this embodiment and Embodiment 1 is that the passivation conditions are different.

[0086] The following mainly describes the differences from Example 1:

[0087] The catalyst was packed into the reaction apparatus and reduced under conditions of 4 MPa and a hydrogen flow rate of 70 NL / h.

[0088] The reduced catalyst was passivated: Fischer-Tropsch hydrocracking oil (distillation range 300-400℃) was used as the passivation carrier oil, and n-butylamine was used as the passivating agent. Based on the mass of the passivation carrier oil, the amount of passivating agent added, calculated as nitrogen, was 80 ppm. The passivation conditions included: an initial passivation temperature of 150℃, a heating rate of 10℃ / h, heating to 360℃, isothermal passivation for 24 h, a pressure (hydrogen pressure) of 4 MPa, and a volume hourly space velocity (VHSV) of 1 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500:1.

[0089] After passivation, the Fischer-Tropsch wax underwent a hydroisomerization reaction as described in Example 1. The reaction lasted for 10 days, yielding a stable product, although the temperature rise during the reaction reached 17°C. The results are shown in Table 5.

[0090] Table 5. Test Results

[0091]

[0092] It is readily understood that the above embodiments are merely illustrative examples for clear explanation and do not imply that the invention is limited thereto. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for passivating a Fischer-Tropsch wax hydroisomerization catalyst, said hydroisomerization catalyst comprising a support and a noble metal element supported on the support, said support comprising a ten-membered ring molecular sieve, characterized in that, The passivation method comprises: The passivation treatment is carried out on the hydroisomerization catalyst in the presence of hydrogen, using a Fischer-Tropsch product oil or coal direct liquefaction diesel or petroleum-based diesel with a distillation range of 430℃ or lower as a passivation carrier oil, and an alkylamine containing no oxygen atom as a passivation agent; the passivation agent is selected from one or more of ethylenediamine, butylamine, n-butylamine, and tri-n-butylamine; The passivation treatment conditions include: temperature rising at a temperature rising rate of 5-20℃ / h to 300-350℃, and then constant temperature for 10-30h; based on the mass of the passivation carrier oil, the amount of the passivation agent is 10-500ppm in terms of nitrogen element in the passivation agent.

2. The passivation method according to claim 1, characterized in that, The passivation agent is n-butylamine.

3. The passivation method according to claim 2, characterized in that, The pore size of the hydroisomerization catalyst is 0.4-0.53nm.

4. The passivation method of claim 1, wherein, The constant temperature time is 10-24h.

5. The passivation method of claim 1, wherein, The amount of the passivation agent is 50-200ppm in terms of nitrogen element in the passivation agent.

6. The passivation method according to claim 5, characterized in that, The amount of the passivation agent is 50-150ppm in terms of nitrogen element in the passivation agent.

7. The passivation method according to claim 6, characterized in that, The amount of the passivation agent is 60-100ppm in terms of nitrogen element in the passivation agent.

8. The passivation method according to any one of claims 1 to 7, characterized in that, The Fischer-Tropsch product oil is selected from one or more of Fischer-Tropsch diesel with a distillation range of 300-390℃, and Fischer-Tropsch hydrocracked oil.

9. The passivation method according to claim 8, characterized in that, The Fischer-Tropsch hydrocracked oil is Fischer-Tropsch hydrocracked vacuum gas oil and / or Fischer-Tropsch hydrocracked vacuum gas oil.

10. The passivation method according to any one of claims 1 to 7, characterized in that, In the passivation conditions, the temperature rising is to 330-350℃ at a temperature rising rate of 8-12℃ / h; And / or, the starting temperature for the temperature rising is 100-250℃.

11. The passivation method according to claim 10, characterized in that, In the passivation conditions, the temperature rising is to 330-350℃ at a temperature rising rate of 8-12℃ / h; And / or, the starting temperature for the temperature rising is 100-250℃.

12. The passivation method according to any one of claims 1 to 7, characterized in that, The passivation conditions further include: pressure of 3-10 MPa, volume space velocity of 0.5-2 h -1 , hydrogen to oil volume ratio of 300:1-800:

1.

13. The passivation method according to claim 12, characterized in that, The pressure is 3-6 MPa, the volume space velocity is 0.5-1.2 h -1 , and the hydrogen-oil volume ratio is 400:1-600:

1.

14. The passivation method according to any one of claims 1 to 7, characterized in that, The ten-membered ring molecular sieve is selected from one or more of ZSM-22, ZSM-23, ZSM-48, and ZSM-35; The noble metal element is selected from Pd and / or Pt; The carrier further comprises alumina and / or silica.

15. The passivation method according to claim 14, characterized in that, The ten-membered ring molecular sieve is ZSM-48.

16. The passivation method of claim 14, wherein, In the hydroisomerization catalyst, the content of the ten-membered ring molecular sieve is 60-90wt%; The content of the noble metal element is 0.1-0.5wt%.

17. The passivation method according to any one of claims 1 to 7, characterized in that, After the passivation, a product oil converted from the passivation carrier oil in the passivation process is obtained.

18. The passivation method according to claim 17, characterized in that, The product oil is white oil or lubricating oil base oil.

19. A process for the hydroisomerization of Fischer-Tropsch waxes to produce lube base oil, characterized in that, The method comprises the following steps: 1) passivation treatment of the hydroisomerization catalyst by the passivation method of any one of claims 1-18; 2) hydroisomerization reaction of Fischer-Tropsch wax in the presence of the hydroisomerization catalyst after the passivation treatment of step 1) to produce lubricating oil base oil.

20. The method of claim 19, wherein, The reaction conditions of the hydroisomerization reaction in Step 2) include a pressure of 3-10 MPa, a temperature of 300-360°C, a volume space velocity of 0.5-2 h -1 , and a hydrogen / oil volume ratio of 300:1-800:

1.

21. The method of claim 20, wherein, The reaction conditions of the hydroisomerization reaction include: pressure 3-6 MPa, temperature 320-350℃, volume space velocity 0.5-1.2 h -1 , hydrogen oil volume ratio 400:1-600:

1.

22. The method of claim 19, wherein, In step 1), after the passivation treatment, a product oil converted from the passivation carrier oil in the passivation process is output.

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