Naphthenic rubber filling oil and preparation method thereof

Abstract

The invention relates to the technical field of preparation of naphthenic oil, and discloses naphthenic rubber filling oil and a preparation method thereof. The method comprises the following steps: (1) in the presence of a non-noble metal hydrogenation catalyst, carrying out first hydrofining on the direct coal liquefaction oil, and then fractionating the obtained product to obtain a fraction A with the distillation range of more than 350 DEG C; (2) in the presence of a hydroisomerization catalyst, carrying out hydroisomerization on the indirect coal liquefaction oil, and then fractionating the obtained product to obtain a fraction B with the distillation range of more than 370 DEG C; and (3) mixing the fraction A and the fraction B, and carrying out second hydrofining on the obtained mixture in the presence of a noble metal hydrogenation catalyst. The prepared naphthenic rubber filling oil has the characteristics of low pour point and low aromatic hydrocarbon content. And the method has the advantages of small hydrofining load, high yield, abundant raw materials and low cost, highly meets the requirements of large-scale industrial production, and shows significant economic value and wide industrial application prospects.

Description

Technical Field

[0001] This invention relates to the field of cycloalkyl oil preparation technology, specifically to a cycloalkyl rubber filler oil and its preparation method. Background Technology

[0002] From a resource endowment perspective, the scarcity of naphthenic crude oil is particularly pronounced—its global reserves account for only 2%, making it a typical strategic and scarce energy resource. Focusing on the domestic market, it not only faces the rigid constraint of insufficient total supply of naphthenic crude oil, but also a significant gap in related refining and processing capacity. Under these dual constraints, the actual output of downstream products using naphthenic oil as the core raw material (such as specialty lubricants and rubber filler oils) has long been at a low level, and the contradiction between market supply and demand continues to intensify. The supply-demand imbalance has become a key bottleneck restricting the high-quality development of industries such as rubber and high-end lubricants.

[0003] Based on my country's fundamental energy structure of "abundant coal, scarce oil, and abundant gas," this unique resource endowment provides a natural guide for energy substitution pathways. Meanwhile, after years of continuous technological breakthroughs, my country's coal liquefaction technology has achieved significant progress, with the entire process system from direct to indirect liquefaction becoming increasingly mature, laying a solid technical foundation for the development and industrial application of high-value-added downstream products of coal liquefaction oil. However, against this backdrop, a critical issue urgently needing to be addressed has become increasingly prominent: how to efficiently produce naphthenic rubber filler oils that meet the core needs of rubber processing, relying on the coal liquefaction technology route. Solving this problem will not only effectively alleviate the supply pressure caused by the scarcity of naphthenic crude oil resources but will also inject strong momentum into the diversified upgrading and independent controllable development of my country's rubber industry raw material system. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of high pour point and aromatic hydrocarbon content, as well as low yield, in existing naphthenic rubber filler oil preparation processes. This invention provides a naphthenic rubber filler oil and its preparation method. This method efficiently prepares naphthenic rubber filler oil with low pour point and low aromatic hydrocarbon content by coupling direct coal liquefaction oil and indirect coal liquefaction oil through process coupling. Furthermore, this method has a low hydrorefining load, high yield, abundant raw materials, and low production cost, highly meeting the needs of large-scale industrial production and demonstrating significant economic value and broad industrial application prospects.

[0005] To achieve the above objectives, the present invention provides a method for preparing a cycloalkyl rubber filler oil, the method comprising the following steps:

[0006] (1) In the presence of a non-precious metal hydrogenation catalyst, coal direct liquefaction oil is subjected to first hydrogenation refining, and then the obtained product is fractionated to obtain fraction A with a distillation range > 350℃.

[0007] (2) In the presence of a hydroisomerization catalyst, coal indirect liquefaction oil is hydroisomerized, and then the obtained product is fractionated to obtain fraction B with a distillation range > 370℃.

[0008] (3) The fraction A and the fraction B are mixed, and the resulting mixture is subjected to a second hydrogenation refining in the presence of a noble metal hydrogenation catalyst.

[0009] Preferably, in step (1), the conditions for the first hydrorefining include: a hydrogen-to-oil volume ratio of 500-1500:1, and a volume hourly space velocity (VHSV) of 0.1-2 h⁻¹ for the direct coal liquefaction oil. -1 The temperature is 340-385℃ and the pressure is 5-20MPa.

[0010] Preferably, the direct coal liquefaction oil has a distillation range of 220-450℃, and the direct coal liquefaction oil contains ≥10wt% cycloalkanes and ≥80wt% aromatic hydrocarbons.

[0011] Preferably, in step (1), the support for the non-precious metal hydrogenation catalyst is alumina and / or silica-alumina.

[0012] Preferably, the active metal component of the non-precious metal hydrogenation catalyst is selected from at least one of WO3, MoO3 and NiO, and the content of the active metal component in the non-precious metal hydrogenation catalyst is 10-45 wt%.

[0013] Preferably, the specific surface area of ​​the non-precious metal hydrogenation catalyst is ≥100 m². 2 / g, pore volume ≥0.2cm³ 2 / g, crushing strength ≥15N / mm.

[0014] Preferably, in step (1), the fraction A contains ≥85wt% aromatic hydrocarbons, ≤10wt% alkanes, and ≥5wt% cycloalkanes.

[0015] Preferably, in step (2), the conditions for hydroisomerization include: a hydrogen-to-oil volume ratio of 500-1500:1, and a volume hourly space velocity (VHSV) of 0.1-2 h⁻¹ for the coal-to-oil indirect liquefaction oil. -1 The temperature is 320-350℃ and the pressure is 1-10MPa.

[0016] Preferably, the coal-to-liquids oil is a Fischer-Tropsch hydrorefined wax with a distillation range of 400-600℃, and the saturated hydrocarbon content in the coal-to-liquids oil is ≥95wt%.

[0017] Preferably, the alkanes in fraction B contain ≥98 wt%.

[0018] Preferably, in step (2), the support for the hydroisomerization catalyst is a ten-membered ring molecular sieve.

[0019] Preferably, the support for the hydroisomerization catalyst is selected from at least one of ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-48 molecular sieve and SAPO-11 molecular sieve.

[0020] Preferably, the active metal component of the hydroisomerization catalyst is Pt and / or Pd, and the content of the active metal component in the hydroisomerization catalyst, calculated as metal element, is 0.2-1 wt%.

[0021] Preferably, the specific surface area of ​​the hydroisomerization catalyst is ≥150 m². 2 / g, pore volume ≤0.5cm³ 2 / g, crushing strength ≥10N / mm.

[0022] Preferably, in step (3), the weight ratio of fraction A to fraction B is 0.9-2:1, more preferably 0.95-1.8:1.

[0023] Preferably, in step (3), the support for the noble metal hydrogenation catalyst is alumina.

[0024] Preferably, the active metal component of the noble metal hydrogenation catalyst contains Pt and / or Pd, and the content of the active metal component in the noble metal hydrogenation catalyst, calculated as metal element, is 0.2-1 wt%.

[0025] Preferably, the specific surface area of ​​the noble metal hydrogenation catalyst is ≥150 m². 2 / g, pore volume ≥0.2cm³ 2 / g, crushing strength ≥15N / mm.

[0026] Preferably, in step (3), the conditions for the second hydrorefining include: a hydrogen-to-oil volume ratio of 500-1500:1, and a volume hourly space velocity (VHSV) of 0.1-2 h⁻¹ for the mixture. -1 The temperature is 200-280℃ and the pressure is 5-20MPa.

[0027] A second aspect of the present invention provides a cycloalkyl rubber filler oil prepared by the above method.

[0028] The method described in this invention uses coal liquefaction oil as raw material. Based on the characteristics of direct coal liquefaction oil being rich in aromatics, which can be desulfurized and have nitrogen heteroatoms removed through hydrorefining, and which saturates aromatics to form cycloalkanes, and the high alkane content and near absence of aromatics, sulfur, nitrogen, and other impurities in indirect coal liquefaction oil, this invention develops hydrorefining and upgrading technologies for direct coal liquefaction oil and hydroisomerization and upgrading technologies for indirect coal liquefaction oil. The product with a distillation range >350℃ obtained after hydrorefining and fractionating direct coal liquefaction oil is mixed with the product with a distillation range >370℃ obtained after hydroisomerization and fractionating indirect coal liquefaction oil, and then subjected to further hydrorefining to obtain a cycloalkyl rubber filler oil with a low pour point and low aromatic content. Furthermore, this method has a low hydrorefining load, high yield, abundant raw materials, and low production cost, highly meeting the needs of large-scale industrial production, demonstrating significant economic value and broad industrial application prospects. Attached Figure Description

[0029] Figure 1 This is a schematic flowchart of the method for preparing cycloalkyl rubber filler oil according to the present invention. Detailed Implementation

[0030] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0031] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] The process flow diagram of the method for preparing cycloalkyl rubber filler oil according to the present invention is as follows: Figure 1 As shown, the method includes the following steps:

[0033] (1) In the presence of a non-precious metal hydrogenation catalyst, coal direct liquefaction oil is subjected to first hydrogenation refining, and then the obtained product is fractionated to obtain fraction A with a distillation range > 350℃.

[0034] (2) In the presence of a hydroisomerization catalyst, coal indirect liquefaction oil is hydroisomerized, and then the obtained product is fractionated to obtain fraction B with a distillation range > 370℃.

[0035] (3) The fraction A and the fraction B are mixed, and the resulting mixture is subjected to a second hydrogenation refining in the presence of a noble metal hydrogenation catalyst.

[0036] In the method described in this invention, in step (1), in order to obtain a naphthenic rubber filler oil with a low pour point and low aromatic hydrocarbon content, it is necessary to limit the distillation range and composition of the direct coal liquefaction oil. Specifically, the distillation range of the direct coal liquefaction oil is 220-450℃, and the naphthenic hydrocarbon content in the direct coal liquefaction oil is ≥10wt%, and the aromatic hydrocarbon content is ≥80wt%. In a preferred embodiment, the naphthenic hydrocarbon content in the direct coal liquefaction oil is 10-20wt%, and the aromatic hydrocarbon content is 80-90wt%.

[0037] In the method described in this invention, in step (1), the non-precious metal hydrogenation catalyst contains a support and an active metal component. The support of the non-precious metal hydrogenation catalyst is alumina and / or silica-alumina; the active metal component of the non-precious metal hydrogenation catalyst is selected from at least one of WO3, MoO3, and NiO. Preferably, the support of the non-precious metal hydrogenation catalyst is alumina; the active metal component of the non-precious metal hydrogenation catalyst is a combination of WO3, MoO3, and NiO, and the weight ratio of WO3, MoO3, and NiO is (3-20):(0.5-1.5):1.

[0038] In some preferred embodiments, in step (1), in order to further improve the hydrorefining efficiency of the direct coal liquefaction oil and thus increase the yield of epoxy-based rubber-filled oil, it is necessary to limit the content of the active metal component in the non-precious metal hydrogenation catalyst. Specifically, in the non-precious metal hydrogenation catalyst, the content of the active metal component is preferably 10-45 wt%, more preferably 15-40 wt%, and even more preferably 20-35 wt%.

[0039] In some preferred embodiments, in step (1), to further improve the hydrorefining efficiency of the direct coal liquefaction oil, it is necessary to limit the specific surface area, pore volume, and crushing strength of the non-precious metal hydrogenation catalyst. Specifically, the specific surface area of ​​the non-precious metal hydrogenation catalyst is ≥100 m². 2 / g, pore volume ≥0.2cm³ 2 / g, crushing strength ≥15N / mm. Preferably, the specific surface area of ​​the non-precious metal hydrogenation catalyst is 100-200m². 2 / g, pore volume 0.2-0.5cm³ 2 / g, crushing strength is 15-20N / mm.

[0040] In some specific embodiments, in step (1), in order to further improve the hydrorefining efficiency of the direct coal liquefaction oil and thus increase the yield of epoxy-based rubber filler oil, it is necessary to limit the hydrogen-to-oil volume ratio in the first hydrorefining. Specifically, the hydrogen-to-oil volume ratio in the first hydrorefining is preferably 500-1500:1, more preferably 550-1300:1, and even more preferably 600-1200:1. As a specific example, the hydrogen-to-oil volume ratio in the first hydrorefining can be 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, or 1200:1. In this invention, the hydrogen-to-oil volume ratio in the first hydrorefining is the volume ratio of hydrogen to the amount of direct coal liquefaction oil used in the first hydrorefining process.

[0041] In some specific embodiments, in step (1), in order to further improve the hydrorefining efficiency of the direct coal liquefaction oil and thus increase the yield of epoxy-based rubber-filled oil, it is necessary to limit the volume hourly space velocity (VHSV) of the direct coal liquefaction oil. Specifically, the VHSV of the direct coal liquefaction oil is preferably 0.1-2 h⁻¹. -1 More preferably 0.5-1.5h -1 .

[0042] In some specific embodiments, in step (1), the conditions for the first hydrorefining include: a temperature of 340-385°C, preferably 345-380°C; and a pressure of 5-20 MPa, preferably 8-15 MPa. In this invention, the pressure is gauge pressure.

[0043] In some embodiments, in step (1), fraction A is a fraction with a distillation range > 350°C, and the aromatic hydrocarbon content (C) of fraction A is... A ≥85wt%, Alkane content (C P ≤10wt%, cycloalkanes content (C N ≥5wt%. In this invention, the fraction with a distillation range ≤350℃ can produce naphtha and jet fuel as byproducts.

[0044] In the method described in this invention, in step (2), the coal-to-liquids oil can be a Fischer-Tropsch hydrorefined wax with a distillation range of 400-600℃, and the saturated hydrocarbon content in the coal-to-liquids oil is ≥95wt%. Preferably, the coal-to-liquids oil can be a Fischer-Tropsch hydrorefined wax with a distillation range of 450-550℃, and the saturated hydrocarbon content in the coal-to-liquids oil is 95-99wt%.

[0045] In the method described in this invention, in step (2), the hydroisomerization catalyst contains a support and an active metal component. The support for the hydroisomerization catalyst is a ten-membered ring molecular sieve; the metal element in the active metal component of the hydroisomerization catalyst is Pt and / or Pd. Preferably, the support for the hydroisomerization catalyst is selected from at least one of ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-48 molecular sieve, and SAPO-11 molecular sieve; the metal element in the active metal component of the hydroisomerization catalyst is Pt. In a further preferred embodiment, the support for the hydroisomerization catalyst is ZSM-48 molecular sieve.

[0046] In some preferred embodiments, in step (2), in order to further improve the efficiency of the hydroisomerization and thus increase the yield of the epoxy-based rubber filler oil, it is necessary to limit the content of the active metal component in the hydroisomerization catalyst. Specifically, in the hydroisomerization catalyst, the content of the active metal component, calculated as metal element, is preferably 0.2-1 wt%, more preferably 0.2-0.8 wt%, and even more preferably 0.2-0.5 wt%.

[0047] In some preferred embodiments, in step (2), to further improve the efficiency of the hydroisomerization and thus increase the yield of the epoxy-based rubber filler oil, it is necessary to limit the specific surface area, pore volume, and crushing strength of the hydroisomerization catalyst. Specifically, the specific surface area of ​​the hydroisomerization catalyst is ≥150 m². 2 / g, pore volume ≤0.5cm³ 2 / g, crushing strength ≥10N / mm. Preferably, the specific surface area of ​​the hydroisomerization catalyst is 150-240m². 2 / g, pore volume 0.2-0.5cm³ 2 / g, crushing strength is 10-15N / mm.

[0048] In some specific embodiments, in step (2), in order to further improve the efficiency of the hydroisomerization and thus increase the yield of the epoxy-based rubber filler oil, it is necessary to limit the hydrogen-to-oil volume ratio of the hydroisomerization. Specifically, the hydrogen-to-oil volume ratio of the hydroisomerization is preferably 500-1500:1, more preferably 600-1200:1. As a specific example, the hydrogen-to-oil volume ratio of the hydroisomerization can be 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, or 1200:1. In this invention, the hydrogen-to-oil volume ratio of the hydroisomerization is the volume ratio of hydrogen to the amount of coal-to-oil indirect liquefaction oil used in the hydroisomerization process.

[0049] In some specific embodiments, in step (2), in order to further improve the efficiency of the hydroisomerization and thus increase the yield of the epoxy-based rubber filler oil, it is necessary to limit the volume hourly space velocity (VHSV) of the coal-to-liquids oil. Specifically, the VHSV of the coal-to-liquids oil is preferably 0.1-2 h⁻¹. -1 More preferably 0.5-1.5h -1 .

[0050] In some specific embodiments, in step (2), the conditions for the hydroisomerization include: a temperature of 320-350°C, preferably 330-340°C; and a pressure of 1-10 MPa, preferably 3-8 MPa.

[0051] In some embodiments, in step (2), fraction B is a fraction with a distillation range > 370°C, and the alkanes content in fraction B is ≥ 98 wt%. In this invention, fractions with a distillation range ≤ 370°C can be used as naphtha, jet fuel, white oil, and other special oil products.

[0052] In some embodiments, in step (3), in order to obtain a naphthenic rubber filler oil with a low pour point and low aromatic hydrocarbon content, and to further improve the yield of the naphthenic rubber filler oil, it is necessary to limit the weight ratio of fraction A to fraction B. Specifically, the weight ratio of fraction A to fraction B is preferably 0.9-2:1, more preferably 0.95-1.8:1, and even more preferably 1-1.5:1. As a specific example, the weight ratio of fraction A to fraction B can be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, or 1.5:1.

[0053] In the method described in this invention, in step (3), the noble metal hydrogenation catalyst contains a support and an active metal component. The support of the noble metal hydrogenation catalyst is alumina; the metal element in the active metal component of the noble metal hydrogenation catalyst is Pt and / or Pd. Preferably, the metal element in the active metal component of the noble metal hydrogenation catalyst is a combination of Pt and Pd, and the weight ratio of Pt to Pd is 0.2-1:1.

[0054] In some preferred embodiments, in step (3), in order to further improve the efficiency of the second hydrorefining and the yield of the naphthenic rubber filler oil, it is necessary to limit the content of the active metal component in the noble metal hydrogenation catalyst. Specifically, in the noble metal hydrogenation catalyst, the content of the active metal component, calculated as a metal element, is preferably 0.2-1 wt%, more preferably 0.2-0.8 wt%, and even more preferably 0.2-0.5 wt%.

[0055] In some specific embodiments, in step (3), in order to further improve the efficiency of the second hydrorefining and the yield of the naphthenic rubber filler oil, it is necessary to limit the specific surface area, pore volume, and crushing strength of the noble metal hydrogenation catalyst. Specifically, the specific surface area of ​​the noble metal hydrogenation catalyst is ≥150 m². 2 / g, pore volume ≥0.2cm³ 2 / g, crushing strength ≥15N / mm. Preferably, the specific surface area of ​​the noble metal hydrogenation catalyst is 150-230m². 2 / g, pore volume 0.2-0.5cm³ 2 / g, crushing strength is 15-20N / mm.

[0056] In some specific embodiments, in step (3), in order to obtain a naphthenic rubber filler oil with a low pour point and low aromatic hydrocarbon content, and to further improve the yield of the naphthenic rubber filler oil, it is necessary to limit the volume ratio of hydrogen oil in the second hydrorefining process. Specifically, the volume ratio of hydrogen oil in the second hydrorefining process is preferably 500-1500:1, more preferably 600-1200:1. As a specific example, the volume ratio of hydrogen oil in the second hydrorefining process can be 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, or 1200:1. In this invention, the volume ratio of hydrogen oil in the second hydrorefining process is the volume ratio of hydrogen to the mixture used in the second hydrorefining process.

[0057] In some specific embodiments, in step (3), in order to obtain a naphthenic rubber filler oil with a low pour point and low aromatic hydrocarbon content, and to further improve the yield of the naphthenic rubber filler oil, it is necessary to limit the volume hourly space velocity (VHSV) of the mixture. Specifically, the VHSV of the mixture is preferably 0.1-2 h⁻¹. -1 More preferably 0.5-1.5h -1 .

[0058] In some specific embodiments, in step (3), the conditions for the second hydrorefining include: a temperature of 200-280°C, preferably 220-260°C; and a pressure of 5-20 MPa, preferably 8-15 MPa.

[0059] The present invention also provides a cycloalkyl rubber filler oil prepared by the above method, which has the characteristics of low pour point and low aromatic hydrocarbon content, and has broad application prospects in rubber production enterprises as filler oil, as well as in rubber product factories as rubber processing oil and softener.

[0060] The following examples further illustrate the naphthenic rubber filler oil and its preparation method according to the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0061] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0062] In the following examples and comparative examples, the direct coal liquefaction oil has a distillation range of 220-450°C, a cycloalkanes content of 10 wt%, an alkanes content of 5 wt%, and an aromatics content of 85 wt%.

[0063] The coal-to-liquid oil is a Fischer-Tropsch hydrorefined wax with a distillation range of 450-550℃ and a saturated hydrocarbon content of 98 wt%.

[0064] Example 1

[0065] (1) In a non-metallic hydrogenation catalyst (the support is alumina, the active metal components are WO3, MoO3 and NiO, and the weight ratio of WO3, MoO3 and NiO is 25:3:3, the content of the active metal components is 35wt%, and the specific surface area is 163m²), 2 / g, pore volume is 0.26cm³ 2 In the presence of a hydrogen-to-oil ratio of 1000:1 and a crushing strength of 18 N / mm, coal direct liquefaction oil is subjected to a first hydrorefining process at 360℃ and 15 MPa. The first hydrorefining product is then distilled, and the fraction with a distillation range >350℃ is collected and designated as fraction A1. The hydrogen-to-oil volume ratio in the first hydrorefining process is 1000:1, and the volume hourly space velocity (VHSV) of the coal direct liquefaction oil is 0.8 h⁻¹. -1 The fraction A1 contains 10 wt% cycloalkanes, 5 wt% alkanes, and 85 wt% aromatic hydrocarbons.

[0066] (2) In the hydroisomerization catalyst (supported by ZSM-48 molecular sieve, the active metal component is Pt, the Pt content is 0.4wt%, and the specific surface area is 220m²), the catalyst is used for hydroisomerization. 2 / g, pore volume is 0.26cm³ 2 In the presence of a sample with a crushing strength of 12 N / mm², coal-to-oil indirect liquefaction oil was hydroisomerized at 330℃ and 4 MPa. The hydroisomerized product was then distilled, and the fraction with a distillation range >370℃ was collected and designated as fraction B1. The hydrogen-to-oil volume ratio in the hydroisomerization was 600:1, and the volume hourly space velocity (VHSV) of the coal-to-oil indirect liquefaction oil was 0.8 h⁻¹. -1 The alkanes content in fraction B1 was 98 wt%.

[0067] (3) Mix fractions A1 and B1 at a weight ratio of 1:1 to obtain a mixture, and then add it to a noble metal hydrogenation catalyst (the support is alumina, the active metal components are Pt and Pd, the content of the active metal components based on metal elements is 0.3wt%, the weight ratio of Pt and Pd is 0.3:1, and the specific surface area is 180m²). 2 / g, pore volume is 0.24cm³ 2 In the presence of a hydrogen-to-oil ratio of 800:1 and a crushing strength of 16 N / mm, the mixture is subjected to a second hydrorefining process at a temperature of 240°C and a pressure of 8 MPa to obtain cycloalkyl rubber filler oil S1. The hydrogen-to-oil volume ratio in the second hydrorefining process is 800:1, and the volume hourly space velocity (VHSV) of the mixture is 1 h⁻¹. -1 .

[0068] Example 2

[0069] (1) In a non-metallic hydrogenation catalyst (the support is alumina, the active metal components are WO3, MoO3 and NiO, and the weight ratio of WO3, MoO3 and NiO is 28:6:5, the content of the active metal components is 28wt%, and the specific surface area is 155m²), 2 / g, pore volume is 0.22cm³ 2 In the presence of a sample with a crushing strength of 17 N / mm², coal direct liquefaction oil was subjected to a first hydrorefining process at 345℃ and 8 MPa. The first hydrorefining product was then distilled, and the fraction with a distillation range >350℃ was collected and designated as fraction A2. The hydrogen-to-oil volume ratio in the first hydrorefining process was 600:1, and the volume hourly space velocity (VHSV) of the coal direct liquefaction oil was 0.5 h⁻¹. -1 The A2 fraction contained 7 wt% cycloalkanes, 5 wt% alkanes, and 88 wt% aromatic hydrocarbons.

[0070] (2) In the hydroisomerization catalyst (supported by ZSM-48 molecular sieve, the active metal component is Pt, the Pt content is 0.3wt%, and the specific surface area is 180m²), the catalyst is used for hydroisomerization. 2 / g, pore volume 0.25cm³ 2 In the presence of a sample with a crushing strength of 12 N / mm², coal-to-oil indirect liquefaction oil was hydroisomerized at 335℃ and 3 MPa. The hydroisomerized product was then distilled, and the fraction with a distillation range >370℃ was collected and designated as fraction B2. The hydrogen-to-oil volume ratio in the hydroisomerization was 800:1, and the volume hourly space velocity (VHSV) of the coal-to-oil indirect liquefaction oil was 0.5 h⁻¹. -1 The alkanes content in fraction B2 was 98.5 wt%.

[0071] (3) Mix fractions A2 and B2 at a weight ratio of 1.2:1 to obtain a mixture, and then add it to a noble metal hydrogenation catalyst (the support is alumina, the active metal component consists of Pt and Pd, the content of the active metal component is 0.4 wt% based on metal elements, the weight ratio of Pt and Pd is 0.5:1, and the specific surface area is 176 m²). 2 / g, pore volume is 0.23cm³ 2 In the presence of a sample with a crushing strength of 18 N / mm², the mixture is subjected to a second hydrorefining process at a temperature of 220°C and a pressure of 10 MPa to obtain cycloalkyl rubber filler oil S2. The hydrogen-to-oil volume ratio in the second hydrorefining process is 600:1, and the volume hourly space velocity (VHSV) of the mixture is 0.5 h⁻¹. -1 .

[0072] Example 3

[0073] (1) In a non-metallic hydrogenation catalyst (the support is alumina, the active metal components are WO3, MoO3 and NiO, and the weight ratio of WO3, MoO3 and NiO is 25:3:2, the content of the active metal components is 20wt%, and the specific surface area is 170m²), 2 / g, pore volume is 0.28cm³ 2 In the presence of a sample containing 20 N / mm³ of hydrogen peroxide (crushing strength 20 N / mm²), coal direct liquefaction oil underwent a first hydrorefining process at 380 °C and 10 MPa. The first hydrorefining product was then distilled, and the fraction with a distillation range >350 °C was collected and designated as fraction A3. The hydrogen-to-oil volume ratio in the first hydrorefining process was 1200:1, and the volume hourly space velocity (VHSV) of the coal direct liquefaction oil was 1.5 h⁻¹. -1 The A3 fraction contains 5 wt% cycloalkanes, 10 wt% alkanes, and 85 wt% aromatic hydrocarbons.

[0074] (2) In the hydroisomerization catalyst (supported by ZSM-48 molecular sieve, the active metal component is Pt, the Pt content is 0.5wt%, and the specific surface area is 206m²), the catalyst is used to prepare the catalyst. 2 / g, pore volume is 0.36cm³ 2 In the presence of a sample with a crushing strength of 14 N / mm, coal-to-oil indirect liquefaction oil was hydroisomerized at 340℃ and 8 MPa. The hydroisomerized product was then distilled, and the fraction with a distillation range >370℃ was collected and designated as fraction B3. The hydrogen-to-oil volume ratio in the hydroisomerization was 1200:1, and the volume hourly space velocity (VHSV) of the coal-to-oil indirect liquefaction oil was 1.5 h⁻¹. -1 The alkanes content in fraction B3 was 99 wt%.

[0075] (3) Mix fractions A3 and B3 at a weight ratio of 1.5:1 to obtain a mixture, and then add it to a noble metal hydrogenation catalyst (the support is alumina, the active metal components are Pt and Pd, the content of the active metal components based on metal elements is 0.5wt%, the weight ratio of Pt and Pd is 1:1, and the specific surface area is 200m²). 2 / g, pore volume is 0.29cm³ 2 In the presence of a sample with a crushing strength of 18 N / mm², the mixture is subjected to a second hydrorefining process at a temperature of 260°C and a pressure of 15 MPa to obtain cycloalkyl rubber filler oil S3. The hydrogen-to-oil volume ratio in the second hydrorefining process is 1200:1, and the volume hourly space velocity (VHSV) of the mixture is 1.5 h⁻¹. -1 .

[0076] Example 4

[0077] (1) In a non-metallic hydrogenation catalyst (the support is alumina, the active metal components are WO3, MoO3 and NiO, and the weight ratio of WO3, MoO3 and NiO is 30:3:2, the content of the active metal components is 26wt%, and the specific surface area is 190m²), 2 / g, pore volume is 0.32cm³ 2 In the presence of a sample with a crushing strength of 17 N / mm, coal direct liquefaction oil was subjected to a first hydrorefining process at 370℃ and 12 MPa. The first hydrorefining product was then distilled, and the fraction with a distillation range >350℃ was collected and designated as fraction A4. The hydrogen-to-oil volume ratio in the first hydrorefining process was 800:1, and the volume hourly space velocity (VHSV) of the coal direct liquefaction oil was 0.8 h⁻¹. -1 The fraction A4 contained 6 wt% cycloalkanes, 6 wt% alkanes, and 88 wt% aromatic hydrocarbons.

[0078] (2) In the hydroisomerization catalyst (supported by ZSM-23 molecular sieve, the active metal component is Pt, the Pt content is 0.32wt%, and the specific surface area is 210m²), the catalyst is used for hydroisomerization. 2 / g, pore volume is 0.32cm³ 2 In the presence of a sample containing 14 N / mm³ of coal (with a crushing strength of 14 N / mm²), coal-to-oil indirect liquefaction was hydroisomerized at 335 °C and 3 MPa. The hydroisomerized product was then distilled, and the fraction with a distillation range >370 °C was collected and designated as fraction B4. The hydrogen-to-oil volume ratio in the hydroisomerization was 800:1, and the volume hourly space velocity (VHSV) of the coal-to-oil indirect liquefaction was 1.2 h⁻¹. -1 The alkanes in fraction B4 were 98 wt%.

[0079] (3) Mix fractions A4 and B4 at a weight ratio of 1.22:1 to obtain a mixture, and then add it to a noble metal hydrogenation catalyst (the support is alumina, the active metal component consists of Pt and Pd, the content of the active metal component is 0.4 wt% based on metal elements, the weight ratio of Pt and Pd is 0.3:1, and the specific surface area is 180 m²). 2 / g, pore volume is 0.26cm³ 2 In the presence of a sample with a crushing strength of 17 N / mm² (g), the mixture was subjected to a second hydrorefining process at a temperature of 230°C and a pressure of 10 MPa to obtain cycloalkyl rubber filler oil S4. The hydrogen-to-oil volume ratio in the second hydrorefining process was 800:1, and the volume hourly space velocity (VHSV) of the mixture was 0.8 h⁻¹. -1 .

[0080] Example 5

[0081] (1) In a non-metallic hydrogenation catalyst (the support is alumina, the active metal components are WO3, MoO3 and NiO, and the weight ratio of WO3, MoO3 and NiO is 20:3:3, the content of the active metal components is 30wt%, and the specific surface area is 185m²), 2 / g, pore volume is 0.27cm³ 2 In the presence of a sample with a crushing strength of 18 N / mm², coal direct liquefaction oil was subjected to a first hydrorefining process at 380℃ and 10 MPa. The first hydrorefining product was then distilled, and the fraction with a distillation range >350℃ was collected and designated as fraction A5. The hydrogen-to-oil volume ratio in the first hydrorefining process was 600:1, and the volume hourly space velocity (VHSV) of the coal direct liquefaction oil was 1.2 h⁻¹. -1 The A5 fraction contained 8 wt% cycloalkanes, 6 wt% alkanes, and 86 wt% aromatic hydrocarbons.

[0082] (2) In the hydroisomerization catalyst (supported by ZSM-22 molecular sieve, the active metal component is Pt, the Pt content is 0.4wt%, and the specific surface area is 210m²), the catalyst is used as a support. 2 / g, pore volume is 0.38cm³ 2 In the presence of a sample with a crushing strength of 13 N / mm, coal-to-oil indirect liquefaction oil was hydroisomerized at 330℃ and 5 MPa. The hydroisomerized product was then distilled, and the fraction with a distillation range >370℃ was collected and designated as fraction B5. The hydrogen-to-oil volume ratio in the hydroisomerization was 600:1, and the volume hourly space velocity (VHSV) of the coal-to-oil indirect liquefaction oil was 1 h⁻¹. -1 The alkanes content in fraction B5 was 98.5 wt%.

[0083] (3) Mix fractions A5 and B5 at a weight ratio of 1.5:1 to obtain a mixture, and then add it to a noble metal hydrogenation catalyst (the support is alumina, the active metal component consists of Pt and Pd, the content of the active metal component based on metal elements is 0.35wt%, the weight ratio of Pt and Pd is 0.6:1, and the specific surface area is 220m²). 2 / g, pore volume is 0.43cm³ 2 In the presence of a hydrogen-to-oil ratio of 1000:1 and a crushing strength of 16 N / mm, the mixture is subjected to a second hydrorefining process at a temperature of 250°C and a pressure of 12 MPa to obtain cycloalkyl rubber filler oil S5. The second hydrorefining process involves a hydrogen-to-oil volume ratio of 1000:1 and a volume hourly space velocity (VHSV) of 1.25 h⁻¹. -1 .

[0084] Example 6

[0085] (1) In a non-metallic hydrogenation catalyst (the support is alumina, the active metal components are WO3, MoO3 and NiO, and the weight ratio of WO3, MoO3 and NiO is 20:5:5, the content of the active metal components is 28wt%, and the specific surface area is 185m²), 2 / g, pore volume 0.25cm³ 2 In the presence of a sample with a crushing strength of 19 N / mm², coal direct liquefaction oil was subjected to a first hydrorefining process at a temperature of 385℃ and a pressure of 8 MPa. The first hydrorefining product was then distilled, and the fraction with a distillation range >350℃ was collected and designated as fraction A6. The hydrogen-to-oil volume ratio in the first hydrorefining process was 1000:1, and the volume hourly space velocity (VHSV) of the coal direct liquefaction oil was 1.5 h⁻¹. -1 The A6 fraction contained 5 wt% cycloalkanes, 6 wt% alkanes, and 89 wt% aromatic hydrocarbons.

[0086] (2) In the hydroisomerization catalyst (supported by SAPO-11 molecular sieve, the active metal component is Pt, the Pt content is 0.4wt%, and the specific surface area is 185m²), the catalyst is used for hydroisomerization. 2 / g, pore volume is 0.22cm³ 2 In the presence of a sample with a crushing strength of 16 N / mm, coal-to-oil indirect liquefaction oil was hydroisomerized at 340℃ and 8 MPa. The hydroisomerized product was then distilled, and the fraction with a distillation range >370℃ was collected and designated as fraction B6. The hydrogen-to-oil volume ratio in the hydroisomerization was 800:1, and the volume hourly space velocity (VHSV) of the coal-to-oil indirect liquefaction oil was 1.5 h⁻¹. -1 The alkanes content in fraction B6 was 98 wt%.

[0087] (3) Mix fractions A6 and B6 at a weight ratio of 1.22:1 to obtain a mixture, and then add it to a noble metal hydrogenation catalyst (the support is alumina, the active metal components are Pt and Pd, the content of the active metal components based on metal elements is 0.46wt%, the weight ratio of Pt and Pd is 0.7:1, and the specific surface area is 205m²). 2 / g, pore volume is 0.32cm³ 2 In the presence of a hydrogen-to-oil ratio of 600:1 and a crushing strength of 17 N / mm, the mixture was subjected to a second hydrorefining process at a temperature of 260°C and a pressure of 10 MPa to obtain cycloalkyl rubber filler oil S6. The second hydrorefining process involved a hydrogen-to-oil volume ratio of 600:1 and a volume hourly space velocity (VHSV) of 1.5 h⁻¹. -1 .

[0088] Example 7

[0089] The method described in Example 1 is implemented, except that in step (3), fraction A1 and fraction B1 are mixed in a weight ratio of 0.9:1 to finally obtain cycloalkyl rubber filler oil S7.

[0090] Example 8

[0091] The method described in Example 1 is implemented, except that in step (3), fraction A1 and fraction B1 are mixed in a weight ratio of 2.5:1 to finally obtain cycloalkyl rubber filler oil S8.

[0092] Comparative Example 1

[0093] The method described in Example 1 was carried out, except that step (2) was not performed, and cycloalkyl rubber filler oil D1 was finally obtained.

[0094] Comparative Example 2

[0095] The method described in Example 1 was carried out, except that step (1) was omitted, and cycloalkyl rubber filler oil D2 was finally obtained.

[0096] Test case

[0097] (1) The pour point of the cycloalkyl rubber filler oil prepared in the examples and comparative examples was tested using the method of GB / T 3535. The results are shown in Table 1.

[0098] (2) The kinematic viscosity of the naphthenic rubber filler oil prepared in the examples and comparative examples at 100°C was tested using the method of GB / T 265. The results are shown in Table 1.

[0099] (3) The present invention uses the method of NB / SH / T 0838 to test the polycyclic aromatic hydrocarbon content of the cycloalkyl rubber filler oil prepared in the examples and comparative examples, and the results are shown in Table 1.

[0100] (4) The carbon form distribution of the cycloalkyl rubber filler oils prepared in the examples and comparative examples was tested using the method of SH / T 0725. The results are shown in Table 1. Wherein, C N It is a cycloalkanes, C P It is an alkane, C A It is an aromatic hydrocarbon.

[0101] (5) The yield of the cycloalkyl rubber filler oil prepared in the examples and comparative examples was calculated by the method of (yield of component A × proportion of component A in the mixture + yield of component B × proportion of component B in the mixture) × yield of the second hydrogenation refining liquid. The results are shown in Table 1.

[0102] Table 1

[0103]

[0104] As can be seen from the results in Table 1, since the cycloalkanes content in the product prepared in Comparative Example 2 is 0, it does not belong to cycloalkyl rubber filler oil.

[0105] The cycloalkyl rubber filler oil prepared by the method described in this invention has the advantages of flexible process. By changing the ratio of direct liquefaction and indirect liquefaction oil, the content of cycloalkanes in the product can be controlled. The produced product has the characteristics of low pour point, low aromatic content and high yield.

[0106] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing cycloalkyl rubber filler oil, characterized in that, The method includes the following steps: (1) In the presence of a non-precious metal hydrogenation catalyst, coal direct liquefaction oil is subjected to first hydrogenation refining, and then the obtained product is fractionated to obtain fraction A with a distillation range > 350℃. (2) In the presence of a hydroisomerization catalyst, coal indirect liquefaction oil is hydroisomerized, and then the obtained product is fractionated to obtain fraction B with a distillation range > 370℃. (3) The fraction A and the fraction B are mixed, and the resulting mixture is subjected to a second hydrogenation refining in the presence of a noble metal hydrogenation catalyst.

2. The method according to claim 1, characterized in that, In step (1), the conditions for the first hydrorefining include: a hydrogen-to-oil volume ratio of 500-1500:1, and a volume hourly space velocity (VHSV) of 0.1-2 h⁻¹ for the direct coal liquefaction oil. -1 Temperature: 340-385℃; Pressure: 5-20MPa; Preferably, the direct coal liquefaction oil has a distillation range of 220-450℃, and the direct coal liquefaction oil contains ≥10wt% cycloalkanes and ≥80wt% aromatic hydrocarbons.

3. The method according to claim 1, characterized in that, In step (1), the support for the non-noble metal hydrogenation catalyst is alumina and / or silica-alumina; and / or The active metal component of the non-precious metal hydrogenation catalyst is selected from at least one of WO3, MoO3, and NiO, and the content of the active metal component in the non-precious metal hydrogenation catalyst is 10-45 wt%; and / or The specific surface area of ​​the non-precious metal hydrogenation catalyst is ≥100 m². 2 / g, pore volume ≥0.2cm³ 2 / g, crushing strength ≥15N / mm.

4. The method according to claim 1, characterized in that, In step (1), the aromatic hydrocarbon content in fraction A is ≥85wt%, the alkanes content is ≤10wt%, and the cycloalkanes content is ≥5wt%.

5. The method according to claim 1, characterized in that, In step (2), the conditions for hydroisomerization include: a hydrogen-to-oil volume ratio of 500-1500:1, and a volume hourly space velocity (VHSV) of 0.1-2 h⁻¹ for the coal-to-oil indirect liquefaction oil. -1 Temperature: 320-350℃; Pressure: 1-10MPa; Preferably, the coal-to-liquids oil has a distillation range of 400-600℃ and is a Fischer-Tropsch hydrorefined wax, and the coal-to-liquids oil contains ≥95wt% saturated hydrocarbons. Preferably, the alkanes in fraction B contain ≥98 wt%.

6. The method according to claim 1, characterized in that, In step (2), the support for the hydroisomerization catalyst is a ten-membered ring molecular sieve; Preferably, the support for the hydroisomerization catalyst is selected from at least one of ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-48 molecular sieve and SAPO-11 molecular sieve; The active metal component of the hydroisomerization catalyst is Pt and / or Pd, and the content of the active metal component in the hydroisomerization catalyst, calculated as metal element, is 0.2-1 wt%. and / or The specific surface area of ​​the hydroisomerization catalyst is ≥150 m². 2 / g, pore volume ≤0.5cm³ 2 / g, crushing strength ≥10N / mm.

7. The method according to claim 1, characterized in that, In step (3), the weight ratio of fraction A to fraction B is 0.9-2:1, preferably 0.95-1.8:

1.

8. The method according to claim 1, characterized in that, In step (3), the support for the noble metal hydrogenation catalyst is alumina; and / or The active metal component of the noble metal hydrogenation catalyst is Pt and / or Pd, and the content of the active metal component in the noble metal hydrogenation catalyst, calculated as metal element, is 0.2-1 wt%. and / or The specific surface area of ​​the noble metal hydrogenation catalyst is ≥150 m². 2 / g, pore volume ≥0.2cm³ 2 / g, crushing strength ≥15N / mm.

9. The method according to claim 1, 7 or 8, characterized in that, In step (3), the conditions for the second hydrorefining include: a hydrogen-to-oil volume ratio of 500-1500:1, and a volume hourly space velocity (VHSV) of 0.1-2 h⁻¹ for the mixture. -1 The temperature is 200-280℃ and the pressure is 5-20MPa.

10. A cycloalkyl rubber filler oil prepared by the method according to any one of claims 1-9.

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