Naphthenic base oil for high viscosity adhesive and method for producing the same, and adhesive

Abstract

This invention provides a naphthenic oil for high-viscosity adhesives, its preparation method, and the adhesive, relating to the technical field of petrochemicals, including: (a) subjecting naphthenic vacuum residue to vacuum distillation to obtain a heavy distillate oil with a kinematic viscosity of 39 mmHg at 100°C. 2 (a) Hydrotreating heavy distillate oil to obtain hydrotreated product oil, wherein the active metal impregnation depth in the catalyst is not higher than 0.5 mm; and / or, the maximum thickness of the support in the catalyst is not higher than 0.5 mm; (c) Isomerizing and hydrorefining the hydrotreated product oil, followed by fractionation, to obtain a high-viscosity naphthenic oil for adhesives, with a kinematic viscosity of 19 mm at 100 °C. 2 / s or more, C N The value is not less than 40%. This invention resolves the contradiction between product yield and kinematic viscosity, effectively improving product viscosity and thus increasing its yield, filling the gap in kinematic viscosity >19 mmHg at 100°C. 2 Blank of cycloalkyl oil / s.

Description

Technical Field

[0001] This invention relates to the technical field of petrochemicals, and in particular to a naphthenic oil for high-viscosity adhesives, its preparation method, and the adhesive itself. Background Technology

[0002] Synthetic adhesives, as a new type of material, are seeing their applications expand rapidly from traditional sectors such as wood processing and construction to areas like packaging and hygiene. Their widespread use in domestic trademarks and advertising stickers has accelerated the development of adhesive varieties. With increasing environmental awareness and stricter environmental regulations, environmentally friendly adhesives are becoming the trend. Among these, hot melt adhesives and hot melt pressure-sensitive adhesives are experiencing the fastest growth.

[0003] Hot melt pressure-sensitive adhesive is a thermoplastic elastomer rubber that combines the characteristics of hot melt adhesive and pressure-sensitive adhesive. It is applied in a molten state and can be quickly bonded by applying light finger pressure after cooling and hardening. Due to its advantages such as being solvent-free, pollution-free, and requiring simple and convenient application equipment, it is currently widely used in various labeling industries.

[0004] Adhesive softening oil is added to hot melt pressure-sensitive adhesives as a plasticizer or softener. By weakening the secondary valence bonds between polymer molecules, it improves the fluidity of the adhesive, reduces the modulus, imparts plasticity to the hot melt pressure-sensitive adhesive, improves its initial tack, and at the same time reduces the melt viscosity of the hot melt pressure-sensitive adhesive, maintains the viscoelasticity of the pressure-sensitive adhesive at room temperature, and improves its processing performance.

[0005] Based on their hydrocarbon composition and structure, softening oils are classified into paraffinic oils, naphthenic oils, and aromatic oils. Aromatic oils have the best compatibility with rubber, but they are dark in color, highly polluting, and contain a large amount of polycyclic aromatic hydrocarbons, posing a potential carcinogenic risk. Paraffinic oils are prone to exudation and exhibit wax precipitation at low temperatures. Naphthenic oils possess cycloalkanes similar to aromatic carbons and branched structures similar to straight-chain carbons, offering better rubber compatibility than paraffinic oils. Furthermore, their predominantly cyclic saturated hydrocarbon structure provides good aging resistance, overcomes the polluting properties of aromatic oils, and offers better health and safety, making them generally suitable for various types of rubber. Naphthenic oils maintain good fluidity even at low temperatures, ensuring the performance of adhesives. Therefore, naphthenic oils are currently considered ideal plasticizers or softeners for hot-melt pressure-sensitive adhesives. Naphthenic crude oil is characterized by high density, high viscosity, low wax content, low pour point, as well as low sulfur, low pour point, and low carbon residue. The distillate oils obtained from the vacuum distillation of naphthenic crude oil often have very low pour points, and carbon structure analysis shows a high percentage of carbon atoms (C) in the cycloane phase. N The values ​​are all very high, indicating a very low content of n-alkanes and a very high content of cycloalkanes, making it a high-quality raw material for producing adhesive softening oil.

[0006] Traditionally produced naphthenic oils are darker in color, often yellow, and contain sulfur, nitrogen, and oxygen compounds, as well as polar substances. These substances are unstable and have poor resistance to photo-oxidation and heat aging, affecting product usability. Naphthenic raw materials undergo deep desulfurization, denitrification, and aromatic saturation through a high-pressure hydrogenation process, resulting in a high-grade adhesive softening oil that is water-white in color, has good photo- and heat stability, extremely low aromatic content, minimal toxicity, and no potential carcinogenic risks—making it a safe and healthy option.

[0007] Karamay Petrochemical Company uses Karamay heavy oil and a high-pressure hydrogenation process to produce the KG series of environmentally friendly naphthenic adhesive softening oils. These oils not only have excellent appearance but also good light and heat stability, as well as good rubber compatibility. They also offer good safety and environmental performance. Among them, KG17 has the highest kinematic viscosity at 100℃, with a kinematic viscosity of 15 mmHg. 2 / s~19mm 2 Between / s, the open flash point is ≥230℃, and the sulfur content is ≤-10℃; the kinematic viscosity at 100℃ for KG series environmentally friendly naphthenic adhesive softening oil does not exceed 19mm. 2 / s.

[0008] In view of this, the present invention is hereby proposed. Summary of the Invention

[0009] One objective of this invention is to provide a method for preparing naphthenic oils for high-viscosity adhesives, which utilizes high-quality marine naphthenic heavy oil resources and employs a full hydrogenation process to produce oils with a kinematic viscosity >19 mmHg at 100°C. 2 The naphthenic oil, at a concentration of / s, resolved the conflict between product yield and kinematic viscosity, effectively increasing the viscosity of the target product and improving its yield, thus filling the gap in kinematic viscosity >19mm at 100℃. 2 Blank of cycloalkyl oil / s.

[0010] The second objective of this invention is to provide a naphthenic oil for high-viscosity adhesives.

[0011] A third objective of this invention is to provide an adhesive.

[0012] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: In a first aspect, a method for preparing a naphthenic oil for high-viscosity adhesives includes the following steps: (a) Deep vacuum distillation of naphthenic vacuum residue to obtain heavy distillate; The heavy distillate oil has a kinematic viscosity of 39 mmHg at 100°C. 2 / s or more; (b) Hydrotreating the heavy distillate oil to obtain hydrotreated product oil; The active metal impregnation depth in the catalyst used for the hydrogenation treatment is no higher than 0.5 mm; And / or, the maximum thickness of the support in the catalyst used for the hydrogenation treatment is not higher than 0.5 mm; (c) The hydrotreated oil is subjected to isomerization dewaxing and hydrorefining, followed by fractionation, to obtain the naphthenic oil for high-viscosity adhesives; The kinematic viscosity of the naphthenic oil at 100°C is 19 mm. 2 / s or more, C N The value is not less than 40%.

[0013] Furthermore, the naphthenic vacuum residue includes Suizhong 36-1 vacuum residue.

[0014] Furthermore, the heavy distillate oil has a distillation range of 460℃ to 520℃ and a kinematic viscosity of 39 mmHg at 100℃. 2 / s or more.

[0015] Furthermore, the heavy distillate oil has a distillation range of 500℃ to 560℃ and a kinematic viscosity of 60 mmHg at 100℃. 2 / s or more.

[0016] Furthermore, the partial pressure of hydrogen in the hydrogenation treatment is not less than 15 MPa, preferably 15 MPa to 22 MPa; Preferably, the reaction temperature for the hydrogenation treatment is 370℃~395℃, and more preferably 380℃~390℃; Preferably, the volume ratio of hydrogen to oil in the hydrotreating reaction is not less than 1000:1; Preferably, the volume hourly space velocity (VHSV) of the hydrogenation treatment is 0.2 h⁻¹. -1 ~0.5h -1 Preferably 0.35h -1 .

[0017] Furthermore, the nitrogen content in the oil produced by the hydrotreating process is below 5 mg / kg.

[0018] Furthermore, the reaction hydrogen partial pressures of the isomerization dewaxing and hydrorefining processes are each independently not less than 15 MPa; Preferably, the reaction temperature for isomerization dewaxing is 335℃~360℃; Preferably, the reaction temperature for the hydrorefining is 250°C to 280°C; Preferably, the volume hourly space velocity (VHSV) for both the isomerization dewaxing and hydrorefining is independently 0.8 h⁻¹. -1 ~1.0h -1 .

[0019] Secondly, a cycloalkyl oil prepared by any of the above-described preparation methods.

[0020] Furthermore, the kinematic viscosity of the naphthenic oil at 100°C is 20.5 mm. 2 / s, pour point is -15℃, C N The value is 41.5%, and the Cybert color is greater than +30.

[0021] Thirdly, an adhesive comprising the aforementioned naphthenic oil.

[0022] Compared with the prior art, the present invention has at least the following beneficial effects: The method for preparing high-viscosity adhesive naphthenic oil provided by this invention can use CNOOC naphthenic vacuum residue as raw material, and obtain a kinematic viscosity of 39 mmHg at 100°C through a vacuum deep drawing process. 2 Heavy distillate oil with a carbon residue of no more than 0.55% is subjected to hydrotreating. The catalyst used in the hydrotreating process (with an active metal impregnation depth of no more than 0.5 mm; and / or a maximum support thickness of no more than 0.5 mm) has a short diffusion path and the ability to retain product viscosity, resulting in a hydrotreated product oil. This hydrotreated product oil is then subjected to isomerization dewaxing and hydrorefining to produce a hydrotreated product oil with a lower pour point. This product is then subjected to vacuum fractionation (with a cut-off temperature converted to atmospheric pressure of no less than 470°C and a yield of no less than 30%), and the resulting bottom product is a high-viscosity naphthenic oil for adhesives, with a kinematic viscosity of 19 mmHg at 100°C. 2 / s or higher, far exceeding the levels of common high-viscosity naphthenic oils on the market, C N With a value of not less than 40%, the yield accounts for more than 30% of heavy distillate oil, which is much higher than the yield of similar products. It solves the contradiction between product yield and kinematic viscosity, and has very good product performance and economy. Detailed Implementation

[0023] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] According to a first aspect of the present invention, a method for preparing a naphthenic oil for high-viscosity adhesives is provided, comprising the following steps: (a) Deep vacuum distillation of naphthenic vacuum residue to obtain heavy distillate; The kinematic viscosity of heavy distillate oil at 100°C is 39 mm. 2 / s or more; (b) The heavy distillate oil is hydrotreated to obtain hydrotreated product oil; The active metal impregnation depth in the catalyst used for hydrotreating shall not exceed 0.5 mm; And / or, the maximum thickness of the support in the catalyst used for hydrotreating is not higher than 0.5 mm; (c) The hydrotreated oil is subjected to isomerization dewaxing and hydrorefining, followed by fractionation to obtain a high-viscosity naphthenic oil for adhesives; The kinematic viscosity of this naphthenic oil at 100°C is 19 mm. 2 / s or more, C N The value is not less than 40%.

[0025] The method for preparing naphthenic oil of this invention can use CNOOC naphthenic vacuum residue as raw material, and obtain a kinematic viscosity of 39 mmHg at 100°C through a vacuum deep drawing process. 2 Heavy distillate oil with a carbon residue of no more than 0.55% is subjected to hydrotreating. The catalyst used in the hydrotreating process (with an active metal impregnation depth of no more than 0.5 mm; and / or a maximum support thickness of no more than 0.5 mm) has a short diffusion path and the ability to retain product viscosity, resulting in a hydrotreated product oil. This hydrotreated product oil is then subjected to isomerization dewaxing and hydrorefining to produce a hydrotreated product oil with a lower pour point. This product is then subjected to vacuum fractionation (with a cut-off temperature converted to atmospheric pressure of no less than 470°C and a yield of no less than 30%), and the resulting bottom product is a high-viscosity naphthenic oil for adhesives, with a kinematic viscosity of 19 mmHg at 100°C. 2 / s or higher, far exceeding the levels of common high-viscosity naphthenic oils on the market, C N With a value of not less than 40%, the yield accounts for more than 30% of heavy distillate oil, which is much higher than the yield of similar products. It solves the contradiction between product yield and kinematic viscosity, and has very good product performance and economy.

[0026] In a preferred embodiment, the naphthenic vacuum residue can be a naphthenic vacuum residue unique to CNOOC, including but not limited to Suizhong 36-1 vacuum residue, with a penetration of about 90 (1 / 10 mm). After deep vacuum extraction, the penetration can be reduced to about 12 (1 / 10 mm).

[0027] In a preferred embodiment, the heavy distillate oil has a distillation range of 460°C to 520°C and a kinematic viscosity of 39 mmHg at 100°C. 2 With a yield of over 14.5% of vacuum residue and a carbon residue of 0.43%, the yield can reach 14.5% of vacuum residue.

[0028] In a preferred embodiment, the heavy distillate oil has a distillation range of 500°C to 560°C and a kinematic viscosity of 60 mmHg at 100°C. 2 With a yield of over 24.5% of vacuum residue and a carbon residue of 0.52%, the yield can reach 24.5% of vacuum residue.

[0029] In this invention, an eggshell-type hydrotreating catalyst can be used to hydrotreat heavy distillate oil. This hydrotreating catalyst has active centers with low diffusion radius, which can reduce the influence of diffusion on the reaction, thereby reducing side reactions such as cracking, maximizing the retention of the viscosity of the target product and improving the yield of the target product.

[0030] The active components of the hydrotreating catalyst are controlled by an eggshell-type active center control method, and the impregnation depth of the active metal is controlled to be no more than 0.5 mm.

[0031] A method for preparing an eggshell-shaped hydrotreating catalyst includes the following steps: (1) A catalyst support is obtained by mixing boehmite, extrusion aid, nitric acid and water, followed by molding, drying and calcination; (2) The catalyst support was treated with a water-soluble polymer and then dried; (3) Mix nickel salt, tungsten salt, competing adsorbent and water to prepare impregnation solution; (4) The catalyst support obtained in step (2) is impregnated with the impregnation solution obtained in step (3), and then dried and calcined to obtain an eggshell-type hydrogenation catalyst.

[0032] In step (1), the pore volume of the pseudoboehmite is ≥1.0 mL / g, and the specific surface area of ​​the pseudoboehmite is ≥300 m². 2 / g; the extrusion aid includes at least one of guar gum powder, starch and methylcellulose; the drying temperature is 80℃~150℃; the calcination temperature is 500℃~750℃; the calcination time is 3h~4h; the cross-sectional shape of the catalyst support is any one of circular, clover-shaped or four-leaf clover-shaped.

[0033] In step (2), the water-soluble polymer is dissolved and adsorbed into the catalyst support pores by an equal volume impregnation method; the dry mass of the polymer occupies one-quarter to one-half of the catalyst support pores; after impregnation, the polymer is dried at 80℃~150℃ with a heating rate ≤10℃ / hour to promote the diffusion of the polymer into the catalyst support. In step (3), the impregnation solution is prepared according to the fact that the weight of the active component of the catalyst (calculated according to oxides) accounts for 15% to 22.5% of the weight of the catalyst; the nickel salt in the impregnation solution includes at least one of nickel nitrate and basic nickel carbonate; the tungsten salt includes at least one of ammonium tungstate, ammonium metatungstate or ammonium paratungstate; the impregnation amount of nickel salt and tungsten salt is controlled according to the weight ratio of nickel atoms to tungsten atoms in the range of 1:10 to 1:6. In step (4), the impregnation is carried out by equal volume impregnation. After the impregnation is completed, the active metal of the catalyst is anchored according to the steps of drying and calcination of the hydrogenation catalyst. The drying is carried out by a rapid drying method with a heating rate of ≥50℃ / hour to quickly leave the metal salt on the outer layer of the catalyst. After the drying is completed, the calcination stage is entered, and the calcination temperature is 400℃~500℃.

[0034] In a preferred embodiment, the hydrogen partial pressure of the hydrogenation treatment reaction is not less than 15 MPa, and more preferably 15 MPa to 22 MPa. Typical but non-limiting hydrogen partial pressures are, for example, 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa, 20 MPa, 21 MPa, and 22 MPa, which is more conducive to improving the hydrogenation treatment effect and better maintaining the viscosity and yield of the product.

[0035] In a preferred embodiment, the reaction temperature for hydrogenation treatment can be 370°C to 395°C, and more preferably 380°C to 390°C. Typical but non-limiting reaction temperatures, such as 380°C, 382°C, 384°C, 386°C, 388°C, and 390°C, are more conducive to improving the hydrogenation treatment effect and better maintaining the viscosity and yield of the product.

[0036] In a preferred embodiment, the hydrogen-to-oil volume ratio in the hydrotreating reaction is not less than 1000:1, and the volume hourly space velocity (VHSV) can be 0.2 h⁻¹. -1 ~0.5h -1 It can be further preferred to be 0.35h -1 This helps maintain the product's viscosity and yield.

[0037] In a preferred embodiment, the nitrogen content in the hydrotreated oil is below 5 mg / kg.

[0038] In this invention, commercial catalysts can be used to perform precious metal isomerization dewaxing and precious metal hydrorefining on the hydrotreated oil, which can further reduce the pour point, improve the stability of the product and improve its color.

[0039] In a preferred embodiment, the hydrogen partial pressure of both the isomerization dewaxing and hydrorefining reactions is independently not less than 15 MPa, which is more conducive to lowering the pour point, improving the stability of the product and improving its color.

[0040] In a preferred embodiment, the reaction temperature for isomerization dewaxing can be 335°C to 360°C, with typical but non-limiting reaction temperatures such as 335°C, 340°C, 345°C, 350°C, 355°C, and 360°C, which is more conducive to lowering the pour point, improving the stability of the product, and improving its color.

[0041] In a preferred embodiment, the hydrorefining reaction temperature can be 250°C to 280°C, with typical but non-limiting reaction temperatures such as 250°C, 260°C, 270°C, and 280°C. The hydrogen-to-oil volume ratio can be 600:1, and the volume hourly space velocity (VHSV) can be independently 0.8 h⁻¹. -1 ~1.0h -1 Its typical, but not limiting, volumetric space velocity is, for example, 0.8 h⁻¹. -1 0.85h -1 0.9h -1 0.95h -1 1.0h -1 This is more conducive to lowering the pour point, improving product stability, and enhancing its color.

[0042] According to a second aspect of the present invention, a cycloalkyl oil prepared by any of the above-described preparation methods is provided.

[0043] In a preferred embodiment, the kinematic viscosity of the naphthenic oil at 100°C can be 20.5 mm. 2 / s, pour point can be -15℃, C N The value can be 41.5%, and the Cybert color is greater than +30.

[0044] According to a third aspect of the invention, an adhesive is provided comprising the naphthenic oil described above.

[0045] The present invention will be further illustrated by the following examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or purchased directly from the market.

[0046] Example 1 A method for preparing a naphthenic oil for high-viscosity adhesives includes the following steps: (a) Using Suizhong 36-1 vacuum residue as raw material, the properties of which are shown in Table 1, vacuum deep drawing was performed to obtain heavy distillate oil, denoted as heavy distillate oil 1, with a kinematic viscosity of 39 mm at 100°C. 2 For values ​​above / s, their properties are shown in Table 2; (b) The obtained heavy distillate oil was subjected to hydrotreating at a reaction pressure of 15 MPa, a reaction temperature of 395 °C, and a volume hourly space velocity of 0.35 h⁻¹. -1The hydrogen-to-oil volume ratio was 1000:1, resulting in hydrotreated oil, denoted as hydrotreated oil 1, the properties of which are shown in Table 3. The catalyst used in the hydrotreating process is an eggshell-type hydrotreating catalyst, wherein the active metal impregnation depth is no more than 0.5 mm; (c) The resulting hydrotreated oil was subjected to isomerization dewaxing and hydrorefining, both at a reaction pressure of 15 MPa, a reaction temperature of 335 °C for isomerization dewaxing, and a reaction temperature of 260 °C for hydrorefining, with a volume hourly space velocity of 0.8 h⁻¹. -1 A hydrogen-to-oil volume ratio of 600:1 was fractionated to obtain a high-viscosity naphthenic oil for adhesives, denoted as naphthenic oil 1, with a kinematic viscosity of 19 mmHg at 100°C. 2 / s or more, C N The yield is not less than 40%, and its yield and properties are shown in Table 4.

[0047] Example 2 A method for preparing a naphthenic oil for high-viscosity adhesives includes the following steps: (a) Using Suizhong 36-1 vacuum residue as raw material, the properties of which are shown in Table 1, vacuum distillation was performed to obtain heavy distillate oil, denoted as heavy distillate oil 1 and heavy distillate oil 2. The two were mixed to obtain mixed distillate oil, the kinematic viscosity at 100℃ being 39 mm. 2 For values ​​above / s, their properties are shown in Table 2; (b) The resulting mixed distillate oil was subjected to hydrotreating at a reaction pressure of 15 MPa, a reaction temperature of 393 °C, and a volume hourly space velocity of 0.35 h⁻¹. -1 With a hydrogen-to-oil volume ratio of 1000:1, hydrotreated oil was obtained, denoted as hydrotreated oil 2, and its properties are shown in Table 3. The catalyst used in the hydrotreating process is an eggshell-type hydrotreating catalyst, wherein the active metal impregnation depth is no more than 0.5 mm; (c) The resulting hydrotreated oil was subjected to isomerization dewaxing and hydrorefining, both at a reaction pressure of 15 MPa, a reaction temperature of 340 °C for isomerization dewaxing, and a reaction temperature of 260 °C for hydrorefining, with a volume hourly space velocity of 0.8 h⁻¹. -1 A hydrogen-to-oil volume ratio of 600:1 was fractionated to obtain a high-viscosity naphthenic oil for adhesives, denoted as naphthenic oil 2, with a kinematic viscosity of 19 mmHg at 100°C. 2 / s or more, C N The yield is not less than 40%, and its yield and properties are shown in Table 4.

[0048] Example 3 A method for preparing a naphthenic oil for high-viscosity adhesives includes the following steps: (a) Using Suizhong 36-1 vacuum residue as raw material, the properties of which are shown in Table 1, vacuum deep drawing was performed to obtain heavy distillate oil, denoted as heavy distillate oil 1, with a kinematic viscosity of 39 mm at 100°C. 2 For values ​​above / s, their properties are shown in Table 2; (b) The obtained heavy distillate oil was subjected to hydrotreating at a reaction pressure of 18 MPa, a reaction temperature of 383 °C, and a volume hourly space velocity of 0.35 h⁻¹. -1 The hydrogen-to-oil volume ratio was 1000:1, resulting in hydrotreated oil, denoted as hydrotreated oil 3, the properties of which are shown in Table 3. The catalyst used in the hydrotreating process is an eggshell-type hydrotreating catalyst, wherein the active metal impregnation depth is no more than 0.5 mm; (c) The resulting hydrotreated oil was subjected to isomerization dewaxing and hydrorefining at a reaction pressure of 18 MPa, a reaction temperature of 340 °C for isomerization dewaxing, and a reaction temperature of 255 °C for hydrorefining, with a volume hourly space velocity of 0.8 h⁻¹. -1 A hydrogen-to-oil volume ratio of 600:1 was fractionated to obtain a high-viscosity naphthenic oil for adhesives, designated as naphthenic oil 3, with a kinematic viscosity of 19 mmHg at 100°C. 2 / s or more, C N The yield is not less than 40%, and its yield and properties are shown in Table 4.

[0049] Example 4 A method for preparing a naphthenic oil for high-viscosity adhesives includes the following steps: (a) Using Suizhong 36-1 vacuum residue as raw material, the properties of which are shown in Table 1, vacuum distillation was performed to obtain heavy distillate oil, denoted as heavy distillate oil 1 and heavy distillate oil 2. The two were mixed to obtain mixed distillate oil, the kinematic viscosity at 100℃ being 39 mm. 2 For values ​​above / s, their properties are shown in Table 2; (b) The resulting mixed distillate oil was subjected to hydrotreating at a reaction pressure of 18 MPa, a reaction temperature of 381 °C, and a volume hourly space velocity of 0.35 h⁻¹. -1 The hydrogen-to-oil volume ratio was 1000:1, resulting in hydrotreated oil, denoted as hydrotreated oil 4, the properties of which are shown in Table 3. The catalyst used in the hydrotreating process is an eggshell-type hydrotreating catalyst, wherein the active metal impregnation depth is no more than 0.5 mm; (c) The resulting hydrotreated oil was subjected to isomerization dewaxing and hydrorefining, both at a reaction pressure of 18 MPa, a reaction temperature of 345 °C for isomerization dewaxing, and a reaction temperature of 260 °C for hydrorefining, with a volume hourly space velocity of 0.8 h⁻¹. -1 A hydrogen-to-oil volume ratio of 600:1 was fractionated to obtain a high-viscosity naphthenic oil for adhesives, designated as naphthenic oil 4, with a kinematic viscosity of 19 mmHg at 100°C. 2 / s or more, C N The yield is not less than 40%, and its yield and properties are shown in Table 4.

[0050] Table 1 Properties of vacuum residue

[0051] Table 2 Properties of Heavy Distillate Oils

[0052] Table 3 Properties of oils produced by hydrotreating

[0053] Table 4 Properties of Naphthenic Oils

[0054] Comparative Example 1 The difference between this comparative example and Example 4 is that the Suizhong 36-1 vacuum residue oil was not subjected to deep vacuum extraction, but was directly hydrotreated. The remaining steps are the same as in Example 4.

[0055] Compared with Example 4, the drawback of this comparative example is that the residual carbon, asphaltene and other indicators seriously exceed the feed requirements of the distillate oil hydrotreating unit; vacuum residue cannot be directly fed into the distillate oil hydrotreating unit.

[0056] Comparative Example 2 The difference between this comparative example and Example 4 is that the catalyst used for the hydrogenation treatment is a conventional clover-shaped catalyst. The remaining steps are the same as in Example 4.

[0057] Compared with Example 4, the drawback of this comparative example is that the diffusion efficiency will decrease due to the influence of the diffusion path, which will ultimately affect the hydrogenation depth; while Example 4 uses an eggshell-type hydrogenation treatment catalyst, which reduces the limitation of the raw material diffusion path and improves the hydrogenation reaction efficiency.

[0058] Comparative Example 3 The difference between this comparative example and Example 4 is that the mixed distillate oil was not hydrotreated, but was directly subjected to isomerization dewaxing and hydrorefining. The remaining steps are the same as in Example 4.

[0059] Compared with Example 4, the drawback of this comparative example is that the sulfur and nitrogen contents are both above 1000 μg / g, which will directly lead to poisoning and deactivation of the isomerization dewaxing catalyst.

[0060] Comparative Example 4 The difference between this comparative example and Example 4 is that the oil produced by hydrotreating was not hydrorefined, but only underwent isomerization dewaxing; The remaining steps are the same as in Example 4.

[0061] Compared with Example 4, the drawback of this comparative example is that the light and heat stability of the target product does not meet the requirements.

[0062] In summary, this invention resolves the contradiction between product yield and kinematic viscosity, effectively improving product viscosity and thus increasing yield, filling the gap in kinematic viscosity >19 mmHg at 100°C. 2 Blank of cycloalkyl oil / s.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a naphthenic oil for high-viscosity adhesives, characterized in that, Includes the following steps: (a) Deep vacuum distillation of naphthenic vacuum residue to obtain heavy distillate; The heavy distillate oil has a kinematic viscosity of 39 mmHg at 100°C. 2 / s or more; (b) Hydrotreating the heavy distillate oil to obtain hydrotreated product oil; The active metal impregnation depth in the catalyst used for the hydrogenation treatment is no higher than 0.5 mm; And / or, the maximum thickness of the support in the catalyst used for the hydrogenation treatment is not higher than 0.5 mm; (c) The hydrotreated oil is subjected to isomerization dewaxing and hydrorefining, followed by fractionation, to obtain the naphthenic oil for high-viscosity adhesives; The kinematic viscosity of the naphthenic oil at 100°C is 19 mm. 2 / s or more, C N The value is not less than 40%.

2. The preparation method according to claim 1, characterized in that, The naphthenic vacuum residue includes Suizhong 36-1 vacuum residue.

3. The preparation method according to claim 1, characterized in that, The heavy distillate oil has a distillation range of 460℃ to 520℃ and a kinematic viscosity of 39 mmHg at 100℃. 2 / s or more.

4. The preparation method according to claim 1, characterized in that, The heavy distillate oil has a distillation range of 500℃ to 560℃ and a kinematic viscosity of 60 mmHg at 100℃. 2 / s or more.

5. The preparation method according to any one of claims 1-4, characterized in that, The partial pressure of hydrogen in the hydrogenation treatment is not less than 15 MPa, preferably 15 MPa to 22 MPa. Preferably, the reaction temperature for the hydrogenation treatment is 370℃~395℃, and more preferably 380℃~390℃; Preferably, the volume ratio of hydrogen to oil in the hydrotreating reaction is not less than 1000:1; Preferably, the volume hourly space velocity (VHSV) of the hydrogenation treatment is 0.2 h⁻¹. -1 ~0.5h -1 Preferably 0.35h -1 .

6. The preparation method according to claim 5, characterized in that, The nitrogen content in the oil produced by the hydrotreating process is below 5 mg / kg.

7. The preparation method according to any one of claims 1-4, characterized in that, The hydrogen partial pressure of the reactions in the isomerization dewaxing and hydrorefining processes is independently not less than 15 MPa; Preferably, the reaction temperature for isomerization dewaxing is 335℃~360℃; Preferably, the reaction temperature for the hydrorefining is 250°C to 280°C; Preferably, the volume hourly space velocity (VHSV) for both the isomerization dewaxing and hydrorefining is 0.8 h⁻¹. -1 ~1.0h -1 .

8. A cycloalkyl oil prepared by the preparation method according to any one of claims 1-7.

9. The naphthenic oil according to claim 8, characterized in that, The kinematic viscosity of the naphthenic oil at 100°C is 20.5 mm. 2 / s, pour point is -15℃, C N The value is 41.5%, and the Cybert color is greater than +30.

10. An adhesive, characterized in that, Including the naphthenic oils as described in claim 8 or 9.

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