Sulfur-containing isodewaxing catalyst as well as preparation method and application thereof

Abstract

The invention provides a sulfur-containing isodewaxing catalyst as well as a preparation method and application thereof, in sulfurized active components of the catalyst, in terms of elements, the molar ratio of S to Pt exposed on the surface of the catalyst is (0.8-1.2): 1 or (1.8-2.2): 1; the content of the Pt exposed on the surface of the catalyst is the product of the content of the Pt in the catalyst and the metal dispersity of the Pt. The sulfur-containing isodewaxing catalyst provided by the invention has high selectivity and high activity.

Description

Technical Field

[0001] The present invention relates to a method for producing lubricating oil base oil by isodewaxing, in particular to a hydroisomerization dewaxing catalyst treated by sulfidation, a preparation method thereof, and an application thereof in the production of lubricating oil base oil. Background Art

[0002] The lubricating oil hydroisomerization technology is the mainstream technology for producing type II and type III base oils. The core of this technology, the hydroisomerization dewaxing catalyst, is continuously developed towards higher activity and higher isomerization selectivity. The metals used in the hydroisomerization dewaxing catalyst generally include noble metals such as Pt and Pd. Since Pt and Pd have high activity, they are widely used in isomerization reactions, reforming reactions, and various organic synthesis reactions. However, their excessive catalytic activity often causes over-hydrogenation in the reaction, failing to meet the requirements of high selectivity. A large number of studies have shown that sulfiding noble metal catalysts is an effective way to improve the selectivity of noble metal catalysts. Such catalysts exhibit better selectivity and stability in hydrogenation reactions. However, there is usually a problem of reduced catalyst activity when noble metals are sulfided.

[0003] Chinese Patent CN 116099571 A discloses a catalyst for isomerization and pour point reduction of Fischer-Tropsch synthetic oil, a preparation method and an application thereof, and a method for isomerization and pour point reduction of Fischer-Tropsch synthetic oil. The method is characterized in that the catalyst comprises a carrier and a sulfided active component supported on the carrier. The carrier contains mesoporous molecular sieve and binder, and the sulfided active component is a sulfide of noble metal. Among the sulfided active components, in terms of elements, the weight ratio of S to noble metal is (0.001 - 0.3):1. This invention proposes that different from the traditional view that S shows toxicity to hydroisomerization catalysts, when S and noble metals satisfy a certain quantitative relationship, the hydroisomerization activity and selectivity of the catalyst can be improved simultaneously. However, this invention does not disclose the corresponding relationship between S and the special sulfided active component formed by combining with effective active noble metals, resulting in the inability of operators to accurately control the sulfidation range.

[0004] Chinese Patent CN 105647574 B discloses a method for producing lubricating oil base oil from high-wax feedstock. In this method, a pretreatment solution including sulfide, nitride, and organic solvent is mixed with an isodewaxing catalyst for pretreatment to obtain a pretreated isodewaxing catalyst. The obtained pretreated isodewaxing catalyst is loaded into a reactor for hydrogen activation. The sulfide dosage in this invention is 0.2 - 10% of the catalyst weight. By adsorbing hydrogen sulfide on the noble metal active centers, the activity of the isodewaxing catalyst is reduced, thereby reducing its cracking activity and increasing the base oil yield.

[0005] Lei Yuanjin pointed out in the article "Sulfidation Method and Mechanism of Pt-Sn Catalysts" that using (NH4 ) 2 Sulfurize the Pt-Sn long-chain paraffin dehydrogenation catalyst. Use 0.2% (NH 4 ) 2 S impregnate the catalyst and reduce it with hydrogen. The initial activity and stability of the catalyst are improved synchronously. This study did not reveal the corresponding relationship between the dosage of the sulfurizing agent and the formation of a special sulfurized active component of the effective active noble metal, resulting in the operator being unable to accurately perform the sulfurization operation. Summary of the Invention

[0006] The technical problem to be solved by the present invention is that the sulfurization of the noble metal isomerization dewaxing catalyst easily leads to a decrease in the catalyst activity. The present invention combines the metal dispersion properties of the catalyst and, by precisely and effectively controlling the sulfurization range, enables the sulfurized isomerization dewaxing catalyst to have both high selectivity and high activity.

[0007] The present invention provides a sulfur-containing isomerization dewaxing catalyst. In the sulfurized active component of the catalyst, by element, the molar ratio of S to Pt exposed on the catalyst surface is 0.8-1.2:1 or 1.8-2.2:1; the content of the Pt exposed on the catalyst surface is the product of the Pt content in the catalyst and the metal dispersion of Pt.

[0008] The present invention also provides a preparation method of a sulfur-containing isomerization dewaxing catalyst. The preparation method includes the following steps:

[0009] (1) Hydrogen-activate the isomerization dewaxing catalyst;

[0010] (2) Sulfurize the hydrogen-activated catalyst to obtain a sulfur-containing isomerization dewaxing catalyst;

[0011] Among them, the sulfurization treatment includes:

[0012] (A) Add a sulfur species to the sulfurization solvent oil to obtain a sulfurization reagent;

[0013] (B) Sulfurize the hydrogen-activated catalyst in the presence of the sulfurization reagent and hydrogen to obtain a sulfurized active component;

[0014] Among them, in the sulfurized active component, by element, the molar ratio of S to Pt exposed on the catalyst surface is 0.8-1.2:1 or 1.8-2.2:1; the content of the Pt exposed on the catalyst surface is the product of the Pt content in the catalyst and the metal dispersion of Pt.

[0015] In the preparation method of the present invention, in step (2), the sulfurization solvent oil is selected from at least one of naphtha fractions, kerosene fractions, diesel fractions, and lubricating oil fractions with a sulfur content of less than 2 μg / g and a nitrogen content of less than 2 μg / g obtained by a hydrotreating process.

[0016] In the preparation method of the present invention, in step (2), the sulfur species is a substance that can react with hydrogen to generate H 2 S, including at least one of carbon disulfide, dimethyl disulfide, organic mercaptan, organic sulfide, and ammonium thiosulfate, preferably carbon disulfide and / or dimethyl disulfide.

[0017] In the preparation method of the present invention, in step (2), the content of sulfur species in the sulfiding reagent in terms of S element is 1-120 ppm, preferably 15-100 ppm.

[0018] In the preparation method of the present invention, in step (2), the sulfiding conditions include: hydrogen partial pressure of 0.1-20 Mpa, preferably 5-15 Mpa; volumetric space velocity of 0.25-2 h -1 , preferably 0.5-1.5 h -1 ; hydrogen-oil volume ratio of (100-1000):1, preferably (200-800):1; reaction temperature of 150-450 °C, preferably 200-300 °C.

[0019] In the sulfur-containing isomerization dewaxing catalyst and its preparation method of the present invention, in the sulfided active component, in terms of elements, the molar ratio of S to Pt exposed on the catalyst surface is 0.85-1.15:1 or 1.85-2.15:1.

[0020] In the sulfur-containing isomerization dewaxing catalyst and its preparation method of the present invention, the preparation method of the isomerization dewaxing catalyst is not particularly limited. The isomerization dewaxing catalyst is a commonly used lubricating oil hydroisomerization catalyst in the art. Commercial hydroisomerization catalysts can be used, or it can be prepared according to general knowledge in the art.

[0021] In the sulfur-containing isomerization dewaxing catalyst and its preparation method of the present invention, the carrier of the isomerization dewaxing catalyst is generally a mesoporous molecular sieve and a binder.

[0022] In the sulfur-containing isomerization dewaxing catalyst and its preparation method of the present invention, the mesoporous molecular sieve is selected from at least one of molecular sieves with a pore diameter of 0.4-0.7 nm, but is not limited to the types of molecular sieves described in the present invention. It includes silicoaluminophosphate molecular sieves, such as SAPO-11, SAPO-31, SAPO-41; zeolite molecular sieves with an MTT framework structure, such as ZSM-23, SSZ-32, EU-13, ISI-4, and KZ-1; zeolite molecular sieves with a TON framework structure, such as θ-1, ISI-1, KZ-2, NU-10, and ZSM-22; the content of the mesoporous molecular sieve in the catalyst is 30 wt%-80 wt%.

[0023] In the sulfur-containing isomerization dewaxing catalyst and its preparation method of the present invention, the binder is selected from at least one of alumina, aluminum hydroxide, pseudo-boehmite, aluminum sol or silica sol.

[0024] In the sulfur-containing isomerization dewaxing catalyst and its preparation method of the present invention, the active metal component is at least one of Pt, Pd, Ru and Rh, preferably Pt, and its content in the catalyst is 0.1 wt% to 1.0 wt%. The metal salt of Pt can be at least one of chloroplatinic acid, tetraammineplatinum acetate, tetraammineplatinum nitrate, tetraammineplatinum nitrite, tetraammineplatinum sulfate or tetraammineplatinum chloride.

[0025] The present invention also provides an application of the sulfur-containing isomerization dewaxing catalyst in the production of lubricating base oil.

[0026] Some scholars believe that the sulfidation of noble metal catalysts is a kind of temporary poisoning. During sulfidation, a small amount of sulfur is adsorbed on the most active active centers of the catalyst, inhibiting the initial activity and hydrocracking reaction of the catalyst. As the reaction proceeds, these active centers temporarily poisoned by sulfur gradually play a role to improve the stability of the catalyst. The inventors of the present invention found in the study of sulfidation of noble metal catalysts that usually, the sulfidation treatment makes the lubricating oil hydroisomerization dewaxing catalyst show a phenomenon of reduced activity. However, when S and Pt exposed on the catalyst surface satisfy a certain quantitative relationship, the isomerization selectivity and reaction activity of the catalyst can be improved simultaneously. Based on the above research findings, an optimized sulfidation range is obtained. The beneficial effects of the present invention are as follows:

[0027] (1) The present invention reveals the corresponding relationship between S and the effective active Pt metal exposed on the catalyst surface, which is beneficial to the precise control of the sulfidation operation process of noble metal catalysts.

[0028] (2) The present invention obtains a sulfided active component with both high activity and high selectivity. At a lower reaction temperature (more than 5 °C lower than the general reaction temperature), a lower pour point and cloud point of the base oil can be obtained, and at the same time, the liquid yield is higher (the yield can be increased by more than 3%). Specific Embodiments

[0029] The isomerization dewaxing catalyst involved in the present invention can select a commercial catalyst according to its properties or can be prepared according to the knowledge in the art. For example, according to the method described in CN201180022390.7, zeolite SSZ-32 is compounded with alumina to provide a mixture containing 75 wt% zeolite, and the mixture is extruded, dried and calcined. The dried and calcined extrudate is impregnated with a solution containing both platinum and magnesium, and then the co-impregnated catalyst is dried and calcined.

[0030] The Pt metal dispersion in the present invention is the ratio of the number of Pt atoms exposed on the surface of platinum grains to the total number of Pt atoms in the catalyst. The specific test method is as follows: Weigh a certain amount of the catalyst, and use the static chemisorption method with CO as the probe molecule to obtain two isothermal adsorption curves. The first isothermal adsorption curve measures the total amount of reversible chemisorption, irreversible chemisorption, and physical adsorption of CO on the catalyst surface; by evacuating, the reversibly chemisorbed and physically adsorbed CO is removed, leaving the irreversibly chemisorbed CO on the metal surface; finally, the second adsorption isotherm is tested under the same experimental conditions; since the irreversible chemisorption sites have been occupied, only reversible chemisorption and physical adsorption can occur this time. The difference between the two adsorption isotherms is the amount of irreversible chemisorption. With the stoichiometric ratio of irreversibly adsorbed CO to Pt being 1:1, the total amount of Pt exposed on the surface is obtained, and the ratio of the amount of Pt exposed on the surface to the total amount of Pt in the sample is the metal dispersion of Pt in this sample.

[0031] The following examples will further illustrate the method provided by the present invention, but do not limit the scope of the present invention thereby.

[0032] Example 1

[0033] Mix 90 g of ZSM-23 molecular sieve (silica-alumina ratio of 60:1), 40 g of pseudo-boehmite (Al 2 O 3 content about 75 wt%) with dilute nitric acid, and roll and extrude into shape. After drying at 120 °C for 12 h and calcining at 350 °C for 6 h, a support is obtained. The molecular sieve content in the support is about 75 wt%, and the Al 2 O 3 content is about 25 wt%. The support is impregnated with an aqueous solution of magnesium nitrate and tetraammineplatinum nitrate, and after drying at 120 °C for 12 h and calcining at 350 °C for 6 h, an isomerization dewaxing catalyst is obtained and denoted as C1. The C1 catalyst contains about 0.5 wt% of Pt and about 1 wt% of Mg. The metal dispersion of the C1 catalyst is measured to be 73%.

[0034] Charge 19.5 g of the C1 catalyst (volume 30 mL) into a fixed-bed reactor for hydrogen activation, and subject the hydrogen-activated catalyst to sulfidation treatment. The sulfidation treatment steps are as follows: (A) Add dimethyl disulfide to hydrotreated jet fuel (density 0.79 kg / m 3 ) to obtain a sulfiding reagent with a sulfur content of 15 ppm; (B) Pass hydrogen and the sulfiding reagent into the fixed-bed reactor for sulfidation, with conditions including a hydrogen partial pressure of 12 MPa and a volume space velocity of 1.5 h -1, the hydrogen-oil volume ratio is 360:1, the reaction temperature is 230 °C, and the reaction time is 18.62 h. The above sulfidation operation makes the molar ratio of S to Pt exposed on the catalyst surface in the sulfided isodewaxing catalyst (denoted as S1) 0.85:1.

[0035] Example 2

[0036] Using the C1 catalyst prepared in Example 1, 19.5 g of the C1 catalyst (volume 30 mL) was loaded into a fixed-bed reactor for hydrogen activation, and the hydrogen-activated catalyst was subjected to sulfidation treatment. The sulfidation treatment steps are as follows: (A) Carbon disulfide was added to hydrotreated jet fuel (density 0.79 kg / m 3 ) to obtain a sulfiding reagent with a sulfur content of 30 ppm; (B) Hydrogen and the sulfiding reagent were introduced into the fixed-bed reactor for sulfidation, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 1.0 h -1 , the hydrogen-oil volume ratio is 360:1, the reaction temperature is 230 °C, and the reaction time is 18.9 h. The above sulfidation operation makes the molar ratio of S to Pt exposed on the catalyst surface in the sulfided isodewaxing catalyst (denoted as S2) 1.15:1.

[0037] Example 3

[0038] Using the C1 catalyst prepared in Example 1, 19.5 g of the C1 catalyst (volume 30 mL) was loaded into a fixed-bed reactor for hydrogen activation, and the hydrogen-activated catalyst was subjected to sulfidation treatment. The sulfidation treatment steps are as follows: (A) Dimethyl disulfide was added to hydrotreated diesel (density 0.83 kg / m 3 ) to obtain a sulfiding reagent with a sulfur content of 60 ppm; (B) Hydrogen and the sulfiding reagent were introduced into the fixed-bed reactor for sulfidation, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 1.0 h -1 , the hydrogen-oil volume ratio is 360:1, the reaction temperature is 230 °C, and the reaction time is 14.46 h. The above sulfidation operation makes the molar ratio of S to Pt exposed on the catalyst surface in the sulfided isodewaxing catalyst (denoted as S3) 1.85:1.

[0039] Example 4

[0040] Using the C1 catalyst prepared in Example 1, 19.5 g of the C1 catalyst (volume 30 mL) was loaded into a fixed-bed reactor for hydrogen activation, and the hydrogen-activated catalyst was subjected to sulfidation treatment. The sulfidation treatment steps are as follows: (A) Dimethyl disulfide was added to hydrotreated diesel (density 0.83 kg / m 3Carbon disulfide was added thereto to obtain a sulfiding reagent with a sulfur content of 100 ppm; (B) Hydrogen and the sulfiding reagent were introduced into a fixed-bed reactor for sulfiding, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 0.75 h -1 , a hydrogen-oil volume ratio of 240:1, a reaction temperature of 230 °C, and a reaction time of 13.44 h. The above sulfiding operation made the molar ratio of S to Pt exposed on the surface of the catalyst in the sulfided isodewaxing catalyst (denoted as S4) 2.15:1.

[0041] Example 5

[0042] 90 g of ZSM-23 molecular sieve (silica-alumina ratio of 60:1), 40 g of pseudo-boehmite (Al 2 O 3 content about 75 wt%) were mixed with dilute nitric acid, rolled and extruded into pellets. After drying at 120 °C for 12 h and calcining at 500 °C for 6 h, a support was obtained. The support had a molecular sieve content of about 75 wt% and an Al 2 O 3 content of about 25 wt%. The support was impregnated with an aqueous solution of magnesium nitrate and tetraammineplatinum nitrate, and after drying at 120 °C for 12 h and calcining at 500 °C for 6 h, an isodewaxing catalyst denoted as C2 was obtained. The C2 catalyst contained about 0.5 wt% of Pt and 1 wt% of Mg. The metal dispersion of the C2 catalyst was measured to be 62%.

[0043] 19.5 g of the C2 catalyst (volume 30 mL) was loaded into a fixed-bed reactor for hydrogen activation, and the hydrogen-activated catalyst was subjected to a sulfiding treatment. The sulfiding treatment steps were as follows: (A) Dimethyl disulfide was added to 2 cSt base oil (density 0.85 kg / m 3 ) to obtain a sulfiding reagent with a sulfur content of 50 ppm; (B) Hydrogen and the sulfiding reagent were introduced into the fixed-bed reactor for sulfiding, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 1.0 h -1 , a hydrogen-oil volume ratio of 500:1, a reaction temperature of 240 °C, and a reaction time of 7.76 h. The above sulfiding operation made the molar ratio of S to Pt exposed on the surface of the catalyst in the sulfided isodewaxing catalyst (denoted as S5) 1:1.

[0044] Example 6

[0045] Using the C2 catalyst prepared in Example 5, 19.5 g of the C2 catalyst (volume 30 mL) was loaded into a fixed-bed reactor for hydrogen activation, and the hydrogen-activated catalyst was subjected to a sulfiding treatment. The sulfiding treatment steps were as follows: (A) Dimethyl disulfide was added to 2 cSt base oil (density 0.85 kg / m 3Carbon disulfide was added to obtain a sulfiding reagent with a sulfur content of 90 ppm; (B) Hydrogen and the sulfiding reagent were introduced into a fixed-bed reactor for sulfiding, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 0.8 h -1 , a hydrogen-to-oil volume ratio of 300:1, a reaction temperature of 240 °C, and a reaction time of 10.78 h. The above sulfiding operation made the molar ratio of S to Pt exposed on the surface of the isodewaxing catalyst (denoted as S6) in the sulfided active component 2:1.

[0046] Comparative Example 1

[0047] The C1 catalyst prepared in Example 1 was used. 19.5 g of the C1 catalyst (with a volume of 30 mL) was loaded into a fixed-bed reactor for hydrogen activation. The hydrogen-activated catalyst was not sulfided to obtain catalyst D1.

[0048] Comparative Example 2

[0049] The C2 catalyst prepared in Example 5 was used. 19.5 g of the C2 catalyst (with a volume of 30 mL) was loaded into a fixed-bed reactor for hydrogen activation. The hydrogen-activated catalyst was not sulfided to obtain catalyst D2.

[0050] Comparative Example 3

[0051] The C1 catalyst prepared in Example 1 was used. 19.5 g of the C1 catalyst (with a volume of 30 mL) was loaded into a fixed-bed reactor for hydrogen activation. The hydrogen-activated catalyst was sulfided. The sulfiding treatment steps were as follows: (A) Dimethyl disulfide was added to hydrotreated jet fuel (with a density of 0.79 kg / m 3 ) to obtain a sulfiding reagent with a sulfur content of 60 ppm; (B) Hydrogen and the sulfiding reagent were introduced into a fixed-bed reactor for sulfiding, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 1.0 h -1 , a hydrogen-to-oil volume ratio of 360:1, a reaction temperature of 230 °C, and a reaction time of 4.09 h. The above sulfiding operation made the molar ratio of S to Pt exposed on the surface of the isodewaxing catalyst (denoted as D3) in the sulfided active component 0.5:1.

[0052] Comparative Example 4

[0053] The C1 catalyst prepared in Example 1 was used. 19.5 g of the C1 catalyst (with a volume of 30 mL) was loaded into a fixed-bed reactor for hydrogen activation. The hydrogen-activated catalyst was sulfided. The sulfiding treatment steps were as follows: (A) Dimethyl disulfide was added to hydrotreated jet fuel (with a density of 0.79 kg / m 3Dimethyl disulfide was added thereto to obtain a sulfiding reagent with a sulfur content of 60 ppm; (B) Hydrogen and the sulfiding reagent were introduced into a fixed bed reactor for sulfiding, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 1.0 h -1 , a hydrogen-oil volume ratio of 360:1, a reaction temperature of 230 °C, and a reaction time of 12.28 h. The above sulfiding operation made the molar ratio of S to Pt exposed on the catalyst surface in the sulfided isodewaxing catalyst (denoted as D4) 1.5:1.

[0054] Comparative Example 5

[0055] The C1 catalyst prepared in Example 1 was used. 19.5 g of the C1 catalyst (with a volume of 30 mL) was loaded into a fixed bed reactor for hydrogen activation, and the hydrogen-activated catalyst was subjected to a sulfiding treatment. The sulfiding treatment steps were as follows: (A) Dimethyl disulfide was added to hydrotreated jet fuel (with a density of 0.79 kg / m 3 ) to obtain a sulfiding reagent with a sulfur content of 60 ppm; (B) Hydrogen and the sulfiding reagent were introduced into a fixed bed reactor for sulfiding, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 1.0 h -1 , a hydrogen-oil volume ratio of 360:1, a reaction temperature of 230 °C, and a reaction time of 20.45 h. The above sulfiding operation made the molar ratio of S to Pt exposed on the catalyst surface in the sulfided isodewaxing catalyst (denoted as D5) 2.5:1.

[0056] Comparative Example 6

[0057] The C1 catalyst prepared in Example 1 was used. 19.5 g of the C1 catalyst (with a volume of 30 mL) was loaded into a fixed bed reactor for hydrogen activation, and the hydrogen-activated catalyst was subjected to a sulfiding treatment. The sulfiding treatment steps were as follows: (A) Dimethyl disulfide was added to hydrotreated jet fuel (with a density of 0.79 kg / m 3 ) to obtain a sulfiding reagent with a sulfur content of 140 ppm; (B) Hydrogen and the sulfiding reagent were introduced into a fixed bed reactor for sulfiding, and the conditions included a hydrogen partial pressure of 12 MPa, a volumetric space velocity of 1.0 h -1 , a hydrogen-oil volume ratio of 360:1, a reaction temperature of 230 °C, and a reaction time of 7.05 h. The above sulfiding operation made the molar ratio of S to Pt exposed on the catalyst surface in the sulfided isodewaxing catalyst (denoted as D6) 2.0:1.

[0058] The physical and chemical properties of the catalysts C1 and C2 obtained in the present invention are shown in Table 1, and the properties of the feedstock oil treated in the present invention are shown in Table 2.

[0059] Table 1 Catalyst Properties

[0060]

[0061]

[0062] Table 2 Properties of feedstock oil

[0063] Feedstock oil Paraffin-based vacuum gas oil refined oil <![CDATA[Density, kg / m 3 > 0.8575 Distillation range, °C 394～550 <![CDATA[Kinematic viscosity at 100 °C, mm 2 / S]]> 9.820 Viscosity index 149 Sulfur content, μg / g ＜2 Nitrogen content, μg / g ＜2 Pour point, °C 60

[0064] The catalysts prepared in Examples 1-6 and Comparative Examples 1-6 were respectively used in the isodewaxing reaction of paraffin-based reduced fourth-line refined oil, and the reaction liquid yield and the pour point, cloud point and yield of the obtained lubricating oil base oil were compared. The isodewaxing reaction conditions included a hydrogen partial pressure of 12 MPa, a volume space velocity of 0.75 h -1 , a hydrogen-oil volume ratio of 560:1, and a reaction temperature of 370-390 °C. The reaction temperatures and reaction results of the examples and comparative examples are shown in Table 3.

[0065] Table 3 Reaction temperature and reaction results

[0066]

[0067]

[0068] As can be seen from Table 3, within the appropriate sulfidation range, the catalyst provided by the present invention has higher hydroisomerization catalytic activity and selectivity in the lubricating oil isodewaxing reaction. D1 and D2 are conventional catalysts of the prior art. Compared with D1, S1, S2, S3, and S4, and compared with D2, S5 and S6 have higher reaction activity and can obtain lower pour points and cloud points at lower reaction temperatures. At the same time, the liquid yield also increases significantly. The reaction results of D3, D4, D5, and D6 show that when the dosage of the sulfiding agent is inappropriate and the concentration of the sulfiding oil is too high, the catalyst shows a decrease in activity or deactivation.

[0069] Of course, the present invention may also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformations should all fall within the protection scope of the claims of the present invention.

Claims

1. A sulfur-containing isomerization dewaxing catalyst, characterized in that, in the sulfided active components of the catalyst, by element, the molar ratio of S to Pt exposed on the catalyst surface is 0.8 - 1.2:1 or 1.8 - 2.2:1; the content of the Pt exposed on the catalyst surface is the product of the Pt content in the catalyst and the metal dispersion of Pt.

2. A preparation method of a sulfur-containing isomerization dewaxing catalyst, characterized in that, comprises the following steps: (1) Hydrogen-activate the isomerization dewaxing catalyst; (2) Sulfurize the hydrogen-activated catalyst to obtain a sulfur-containing isomerization dewaxing catalyst; wherein, the sulfurization treatment includes: (A) Add a sulfur species to a sulfurization solvent oil to obtain a sulfurization reagent; (B) Sulfurize the hydrogen-activated catalyst in the presence of the sulfurization reagent and hydrogen to obtain sulfided active components; wherein, in the sulfided active components, by element, the molar ratio of S to Pt exposed on the catalyst surface is 0.8 - 1.2:1 or 1.8 - 2.2:1; the content of the Pt exposed on the catalyst surface is the product of the Pt content in the catalyst and the metal dispersion of Pt.

3. The preparation method according to claim 2, characterized in that, in step (2), the sulfurization solvent oil is selected from at least one of naphtha fraction, kerosene fraction, diesel fraction, and lubricating oil fraction with a sulfur content less than 2 μg / g and a nitrogen content less than 2 μg / g obtained by a hydrotreating process.

4. The preparation method according to claim 2, characterized in that, in step (2), the sulfur species includes at least one of carbon disulfide, dimethyl disulfide, organic mercaptan, organic sulfide, and ammonium thiosulfate.

5. The preparation method according to claim 2, characterized in that, in step (2), the content of the sulfur species in the sulfurization reagent in terms of S element is 1 - 120 ppm.

6. The preparation method according to claim 2, characterized in that, In step (2), the conditions for vulcanization include: hydrogen partial pressure of 0.1 to 20 Mpa; volumetric space velocity of 0.25 to 2 h -1 ; hydrogen-oil volume ratio of (100 to 1000):1; reaction temperature of 150 to 450 °C.

7. The sulfur-containing isomerization dewaxing catalyst according to claim 1 or the preparation method according to claim 2, characterized in that, in the sulfided active components, by element, the molar ratio of S to Pt exposed on the catalyst surface is 0.85 - 1.15:1 or 1.85 - 2.15:

1.

8. The sulfur-containing isomerization dewaxing catalyst according to claim 1 or the preparation method according to claim 2, characterized in that, the carrier of the isomerization dewaxing catalyst is a mesoporous molecular sieve and a binder.

9. The sulfur-containing isomerization dewaxing catalyst according to claim 1 or the preparation method according to claim 2, characterized in that, the mesoporous molecular sieve is selected from at least one of molecular sieves with a pore diameter of 0.4 - 0.7 nm, and is selected from at least one of SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, EU-13, ISI-4, KZ-1, θ-1, ISI-1, KZ-2, NU-10, and ZSM-22; the content of the mesoporous molecular sieve in the catalyst is 30 wt% - 80 wt%.

10. The sulfur-containing isomerization dewaxing catalyst according to claim 1 or the preparation method according to claim 2, characterized in that, the binder is selected from at least one of alumina, aluminum hydroxide, pseudo-boehmite, aluminum sol or silica sol.

11. The sulfur-containing isomerization dewaxing catalyst according to claim 1 or the preparation method according to claim 2, characterized in that, the content of Pt in the catalyst is 0.1 wt% to 1.0 wt%.

12. Use of the sulfur-containing isomerization dewaxing catalyst according to claim 1 in the production of lubricating base oil.

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