Method for preparing C9 petroleum hydrogenated resin through hydrogenation in loop reactor and application of C9 petroleum hydrogenated resin

Abstract

The invention relates to a method for preparing C9 petroleum hydrogenated resin through hydrogenation in a loop reactor and application. Comprising the following steps: S1, rectifying and cutting ethylene cracking C9 to obtain a fraction with a distillation range of 80-230 DEG C, and carrying out polymerization reaction to obtain a polymerization solution; s2, carrying out reduced pressure rectification on the polymerization liquid to obtain a resin liquid A; s3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B; s4, adding the resin liquid B into a loop hydrogenation reactor loaded with a catalyst, and carrying out hydrogenation reaction on the resin liquid B and hydrogen to obtain resin liquid C; and S4, rectifying the resin liquid C to obtain the product. A loop hydrogenation technology is adopted, the process is simple, catalyst loading and consumption are lower, selectivity is higher, a reactor is smaller, heat transfer capacity is very high, and the obtained hydrogenated resin is excellent in performance and has excellent compatibility with styrene elastomers such as SBS and SIS.

Description

Technical Field

[0001] The present invention relates to the technical field of petroleum resins, in particular to the field of IPC C08F 8, and more specifically to a method and application of preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor. Background Art

[0002] At present, there are three main methods for hydrogenating resins in China: kettle hydrogenation, fixed bed hydrogenation, and loop reactor hydrogenation. Among them, kettle hydrogenation has the disadvantages of low production efficiency, high labor intensity, and short catalyst life.

[0003] Chinese invention patent CN101538350A discloses an industrial manufacturing process and equipment for hydrogenated C5 / C9 petroleum resin, which adopts a hydrogenation reactor and is intermittently operated, and is not suitable for mass production. However, fixed bed hydrogenation has the disadvantages of high hydrogenation temperature, high hydrogenation pressure, low production efficiency, large equipment investment, and complex process. Chinese invention patent CN114516926A discloses a preparation method for hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin, selects a suitable fraction segment, obtains a polymer liquid through polymerization, removes oligomers from the polymer liquid, and performs fixed bed one-stage and fixed bed two-stage hydrogenation. This process is complex to operate and requires large investment; Chinese invention patent CN111592617A discloses a preparation method for high aromatic hydrogenated resin, which adopts fixed bed one-stage and two-stage hydrogenation, and its hydrogenation pressure reaches 18mPa, and the hydrogenation temperature is 350℃, and the hydrogenated resin Gardner color number 1.4-4.0 is obtained. Summary of the invention

[0004] The first aspect of the present invention provides a method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor, comprising the following steps:

[0005] S1, cracking ethylene C9 to obtain a fraction with a distillation range of 80-230° C., and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0006] S2, distilling the polymer solution under reduced pressure to obtain resin solution A;

[0007] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0008] S4, adding the resin liquid B into a catalyst-loaded loop hydrogenation reactor to carry out a hydrogenation reaction with hydrogen to obtain a resin liquid C;

[0009] S5, distilling the resin liquid C to obtain.

[0010] Calculated by percentage, the fraction includes: 1-3wt% of cyclopentadiene, 1-5wt% of styrene, 7-13wt% of methylstyrene, 30-45wt% of dicyclopentadiene, 5-10wt% of indene, 2-5wt% of methylindene, and the remainder is inert components.

[0011] Preferably, in percentage, the fraction comprises: 1-2 wt% cyclopentadiene, 1-3 wt% styrene, 7-9 wt% methylstyrene, 30-45 wt% dicyclopentadiene, 5-8 wt% indene, 2-4 wt% methylindene, and the remainder being inert components.

[0012] Further preferably, the content of dicyclopentadiene in the fraction is 30-40 wt %.

[0013] More preferably, the content of dicyclopentadiene in the fraction is 40 wt %.

[0014] The applicant has found that the fraction includes: 1-3wt% cyclopentadiene, 1-5wt% styrene, 7-13wt% methyl styrene, 30-45wt% dicyclopentadiene, 5-10wt% indene, 2-5wt% methyl indene, and the remainder is inert components. A resin with a low color number and a softening point higher than 80°C can be obtained. Further research has found that by adjusting the content of dicyclopentadiene in the fraction to 30-40wt%, and the polymerization temperature to 180-280°C and the time to 5-8h, a resin with a softening point of 95-115°C and a color number less than 8 can be obtained, and the product odor is reduced at the same time. It may be that the specific raw material selection and polymerization process reduce the generation of by-products.

[0015] The inert component includes at least one of naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene and trimethylbenzene.

[0016] Preferably, the inert components include naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0017] The polymerization reaction temperature is 180-280° C. and the reaction time is 5-8 hours.

[0018] Preferably, the polymerization reaction temperature is 180-240° C. and the time is 5-8 hours.

[0019] More preferably, the polymerization reaction is carried out at a temperature of 180° C. and for 5 hours.

[0020] Preferably, the pressure of the vacuum distillation is -0.090-0.095 MPa, and the temperature is 150-180°C.

[0021] Further preferably, the pressure of the vacuum distillation is -0.090 MPa and the temperature is 120°C.

[0022] The solvent includes at least one of cyclohexane, methylcyclohexane, n-octane, n-heptane, toluene, xylene, and C9 inert oil.

[0023] Preferably, the solvent includes at least one of cyclohexane, methylcyclohexane, n-octane and n-heptane.

[0024] Further preferably, the solvent comprises n-heptane.

[0025] The adsorbent includes at least one of diatomaceous earth, acidic clay and neutral clay.

[0026] Preferably, the adsorbent comprises neutral clay.

[0027] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst. The nickel content of the nickel-based catalyst is 1-20 wt %, and the palladium content of the palladium-carbon catalyst is 1-20 wt %.

[0028] Preferably, the weight ratio of the nickel-based catalyst to the palladium-carbon catalyst is 1:(0.5-2).

[0029] More preferably, the weight ratio of the nickel-based catalyst to the palladium-carbon catalyst is 1:(0.5-1).

[0030] Preferably, the nickel content in the nickel-based catalyst can be 1wt%, 5wt%, 10wt%, and 20wt%, and the palladium content in the palladium-carbon catalyst can be 1wt%, 5wt%, 0wt%, and 20wt%.

[0031] More preferably, the nickel content in the nickel-based catalyst is 10 wt %, and the palladium content in the palladium-carbon catalyst is 1 wt %.

[0032] The specific surface area of ​​the nickel catalyst is 150-300m 2 / g, pore volume is 0.1-0.9cm 3 / g, and the average particle size is 3-12mm.

[0033] Preferably, the specific surface area of ​​the nickel-based catalyst is 160-190 m 2 / g, pore volume is 0.3-0.5cm 3 / g, and the average particle size is 6-9mm.

[0034] The temperature of the hydrogenation reaction is 180-250° C., the pressure is 4-7 MPa, and the time is 3-6 hours.

[0035] Preferably, the hydrogenation reaction is carried out at a temperature of 220-250° C., a pressure of 5-7 MPa, and a time of 4-6 h.

[0036] Further preferably, the hydrogenation reaction is carried out at a temperature of 240-250° C., a pressure of 5-6 MPa, and a time of 4-5 h.

[0037] The second aspect of the present invention provides an application of a method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor, which is applied to the fields of hot melt adhesives, sanitary materials, coatings, and rubber modification.

[0038] Beneficial Effects

[0039] 1. The fraction includes: 1-3 wt% of cyclopentadiene, 1-5 wt% of styrene, 7-13 wt% of methyl styrene, 30-45 wt% of dicyclopentadiene, 5-10 wt% of indene, 2-5 wt% of methyl indene, and the remainder is inert components. A resin with low color number and softening point above 80°C can be obtained.

[0040] 2. The content of dicyclopentadiene in the fraction is regulated to be 30-40wt%, and the polymerization temperature is 180-280°C, and the time is 5-8h, so that a resin with a softening point of 95-115°C and a color number less than 8 can be obtained, and the odor of the product is reduced.

[0041] 3. The content of dicyclopentadiene in the fraction is regulated to 40wt%, and the temperature of the hydrogenation reaction is 180-250°C, which can further reduce the resin color number to 0-2, while improving the compatibility with elastomers to meet the application in the adhesive field.

[0042] 4. Adjust the temperature of hydrogenation reaction to 250℃, which can further reduce the resin color to 0 and the bromine value to

[0043] 0.4gBr / 100g, and also has excellent aging resistance.

[0044] 5. The present invention adopts loop hydrogenation to prepare C9 hydrogenated petroleum resin, with mild and controllable conditions, strong industrial operability, continuous production and stable product quality.

[0045] 6. The present invention uses an adsorbent to pretreat the hydrogenation raw material, which effectively protects the service life of the catalyst, ensures the long-term operation of the experimental device and reduces the cost of the catalyst.

[0046] 7. The catalyst used in the present invention is nickel and palladium loaded alumina, which has high strength, large specific surface area, high catalytic efficiency, and good resistance to colloids and sulfur, and is suitable for the hydrogenation process of complex components. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1It is a schematic diagram of a loop hydrogenation reactor, in which resin liquid B is fed from the upper left arrow and resin liquid C is discharged from the lower right arrow.

[0048] Figure 2 1 is C9 petroleum hydrogenated resin before aging, and corresponds to Example 4, Example 7, Example 8 and Example 9 from left to right.

[0049] Figure 3 The C9 petroleum hydrogenated resin after aging corresponds to Example 4, Example 7, Example 8 and Example 9 from left to right. DETAILED DESCRIPTION

[0050] Example 1

[0051] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0052] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0053] S2, the polymer solution is subjected to vacuum distillation to 230°C to remove oligomers to obtain resin solution A;

[0054] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0055] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0056] S5, distilling the resin liquid C to obtain.

[0057] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 30 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0058] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0059] The polymerization reaction was carried out at a temperature of 200° C. and for 5 hours.

[0060] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0061] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0062] The catalyst includes a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, the nickel content of the nickel-based catalyst is 10wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst. The nickel-based catalyst and the palladium-carbon catalyst are both purchased from Liaoning Haitai Technology Development Co., Ltd.

[0063] The temperature of the hydrogenation reaction is 250° C., the pressure is 6 MPa, and the time is 5 hours.

[0064] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0065] Example 2

[0066] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0067] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0068] S2, after vacuum distillation of the polymer solution to 230°C, remove oligomers to obtain resin solution A;

[0069] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0070] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0071] S5, distilling the resin liquid C to obtain.

[0072] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 35 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0073] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0074] The polymerization reaction was carried out at a temperature of 200° C. and for 5 hours.

[0075] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0076] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0077] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0078] The temperature of the hydrogenation reaction is 250° C., the pressure is 6 MPa, and the time is 5 hours.

[0079] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0080] Example 3

[0081] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0082] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0083] S2, the polymer solution is subjected to vacuum distillation to 230°C to remove oligomers to obtain resin solution A;

[0084] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0085] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0086] S5, distilling the resin liquid C to obtain.

[0087] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0088] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0089] The polymerization reaction was carried out at a temperature of 200° C. and for 5 hours.

[0090] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0091] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0092] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0093] The temperature of the hydrogenation reaction is 250° C., the pressure is 6 MPa, and the time is 5 hours.

[0094] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0095] Example 4

[0096] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0097] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0098] S2, the polymer solution is subjected to vacuum distillation to 230°C to remove oligomers to obtain resin solution A;

[0099] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0100] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0101] S5, distilling the resin liquid C to obtain.

[0102] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0103] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0104] The polymerization reaction was carried out at a temperature of 180° C. and for 5 hours.

[0105] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0106] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0107] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0108] The temperature of the hydrogenation reaction is 250° C., the pressure is 6 MPa, and the time is 5 hours.

[0109] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0110] Example 5

[0111] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0112] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0113] S2, the polymer solution is subjected to vacuum distillation to 230°C to remove oligomers to obtain resin solution A;

[0114] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0115] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0116] S5, distilling the resin liquid C to obtain.

[0117] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0118] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0119] The polymerization reaction was carried out at a temperature of 220° C. and for a period of 5 hours.

[0120] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0121] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0122] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0123] The temperature of the hydrogenation reaction is 250° C., the pressure is 6 MPa, and the time is 5 hours.

[0124] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0125] Example 6

[0126] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0127] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0128] S2, after vacuum distillation of the polymer solution to 230°C, remove oligomers to obtain resin solution A;

[0129] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0130] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0131] S5, distilling the resin liquid C to obtain.

[0132] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0133] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0134] The polymerization reaction was carried out at a temperature of 240° C. and for a period of 5 hours.

[0135] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0136] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0137] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0138] The temperature of the hydrogenation reaction is 250° C., the pressure is 6 MPa, and the time is 5 hours.

[0139] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0140] Example 7

[0141] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0142] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0143] S2, the polymer solution is subjected to vacuum distillation to 230°C to remove oligomers to obtain resin solution A;

[0144] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0145] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0146] S5, distilling the resin liquid C to obtain.

[0147] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0148] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0149] The polymerization reaction was carried out at a temperature of 180° C. and for 5 hours.

[0150] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0151] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0152] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0153] The hydrogenation reaction was carried out at a temperature of 180° C., a pressure of 6 MPa and a time of 5 h.

[0154] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0155] Example 8

[0156] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0157] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0158] S2, after vacuum distillation of the polymer solution to 230°C, remove oligomers to obtain resin solution A;

[0159] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0160] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0161] S5, distilling the resin liquid C to obtain.

[0162] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0163] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0164] The polymerization reaction was carried out at a temperature of 180° C. and for 5 hours.

[0165] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0166] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0167] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0168] The temperature of the hydrogenation reaction is 220° C., the pressure is 6 MPa, and the time is 5 hours.

[0169] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0170] Example 9

[0171] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0172] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0173] S2, the polymer solution is subjected to vacuum distillation to 230°C to remove oligomers to obtain resin solution A;

[0174] S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B;

[0175] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0176] S5, distilling the resin liquid C to obtain.

[0177] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0178] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0179] The polymerization reaction was carried out at a temperature of 180° C. and for 5 hours.

[0180] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0181] The weight ratio of the resin liquid A, the solvent and the adsorbent is 1:3:0.05, the solvent is n-heptane, and the adsorbent is neutral clay.

[0182] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0183] The hydrogenation reaction was carried out at a temperature of 240° C., a pressure of 6 MPa and a time of 5 h.

[0184] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0185] Example 10

[0186] A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor:

[0187] S1, cracking ethylene and distilling C9 to obtain a fraction, and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid;

[0188] S2, the polymer solution is subjected to vacuum distillation to 230°C to remove oligomers to obtain resin solution A;

[0189] S3, dissolving the resin liquid A with a solvent, and filtering to obtain a resin liquid B;

[0190] S4, adding resin liquid B to a loop hydrogenation reactor loaded with 400 mL of catalyst ( Figure 1 ) is subjected to hydrogenation reaction with hydrogen to obtain resin liquid C;

[0191] S5, distilling the resin liquid C to obtain.

[0192] Calculated by percentage, the fractions include: 1 wt% of cyclopentadiene, 2 wt% of styrene, 7 wt% of methylstyrene, 40 wt% of dicyclopentadiene, 8 wt% of indene, 2 wt% of methylindene, and the remainder is inert components.

[0193] The inert components do not participate in the reaction, and the content of the specific components of the inert components is not limited. The inert components include: naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene, and trimethylbenzene.

[0194] The polymerization reaction was carried out at a temperature of 180° C. and for 5 hours.

[0195] The pressure of the vacuum distillation in step S2 is -0.090 MPa and the temperature is 120°C.

[0196] The weight ratio of the resin liquid A to the solvent is 1:3, and the solvent is n-heptane.

[0197] The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst in a volume ratio of 1:1, wherein the nickel content of the nickel-based catalyst is 10 wt%, and the product model is: C9RH-20S nickel-based loaded alumina catalyst; the palladium content of the palladium-carbon catalyst is 1 wt%, and the product model is: PDC-01 palladium-carbon loaded alumina catalyst.

[0198] The temperature of the hydrogenation reaction is 250° C., the pressure is 6 MPa, and the time is 5 hours.

[0199] The pressure of the vacuum distillation in step S5 is -0.095 MPa and the temperature is 210°C.

[0200] Performance Testing Methods and Data

[0201] The softening point, hue and yield of the resin solution A prepared in Examples 1-6 were tested. The test data are listed in Table 1.

[0202] The softening point, hue and bromine value of the C9 petroleum hydrogenated resin prepared in Examples 4 and 7-9 were tested. The test data are listed in Table 2.

[0203] The resin liquid A treated with kaolin in Example 4 weighs m grams, and the resin liquid A not treated with kaolin in Example 10 is analyzed for colloid content. The colloid method is: add a certain amount of kaolin that has been constant weight at high temperature to Example 4, record the weight as m1, after adsorption filtration, dry the filter cake obtained above to constant weight, and record the weight as m2.

[0204] Calculation method of resin colloid content: (m2-m1) / m.

[0205] The catalyst life test method is as follows: subject the above treated materials to loop hydrogenation, adjust parameters such as pressure and temperature, and start timing when the product hue is 0. When the product hue is greater than 0, it is the final life of the catalyst.

[0206] The prepared resin liquid A was subjected to colloid analysis and catalyst life test, and the test data are listed in Table 3.

[0207] The C9 petroleum hydrogenated resin prepared in Examples 1-3 was applied to the adhesive, and the aromatic content (%), compatibility with SIS and tape holding force (seconds) were tested. The test data are listed in Table 4. The adhesive was prepared by: 10.0 g of C9 petroleum hydrogenated resin, 10.0 g of SIS, 10.0 g of cyclohexane oil, and 0.05 g of antioxidant, and heated and mixed evenly.

[0208] 15.0 g of each of the C9 petroleum hydrogenated resins prepared in Examples 4 and 7-9 were placed in an oven at 180°C for 5 h for aging, and the change in resin hue was tested. If the increase in resin hue was no more than 0.5, it was excellent; 0.5-1.5 was medium; 1.5-3 was poor; and more than 3 was poor. The test results are as follows: Figure 2-3 And shown in Table 5.

[0209] The compatibility method between the resin and SIS is as follows: take 10.0g of C9 petroleum hydrogenated resin, 10.0g of SIS, and 10.0g of cyclohexane oil, dissolve and mix them evenly at 150°C, place them in a clean watch glass to cool down, and when it cools to room temperature, inspect its appearance visually. If it is transparent, it indicates good compatibility with SIS. Otherwise, if it is opaque and turbid, it indicates poor compatibility with SIS.

[0210] The tape holding force method refers to the standard GB / T4851.

[0211] Table 1

[0212] Example Resin softening point / ℃ Resin hue / # Resin yield (total feed) / % Example 1 85 10 48 Example 2 90 9 53 Example 3 99 8 58 Example 4 96 7 56 Example 5 101 9 60 Example 6 105 10 62

[0213] Table 2

[0214]

[0215]

[0216] Table 3

[0217] Example Gum content Catalyst single service life Example 4 <10ppm ＞600h Example 10 >200ppm ＜200h

[0218] Table 4

[0219] Example Aromatic content (%) Compatibility with SIS Tape holding force (seconds) Example 1 75 Difference 25 Example 2 88 generally 68 Example 3 93 Better 320

[0220] Table 5

[0221] Example Increase color number Thermal stability Example 4 0.1 excellent Example 7 1.2 middle Example 8 2.3 Poor Example 9 4.4 Difference

Claims

1. A method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor, characterized in that: The following steps are involved: S1, cracking ethylene C9 to obtain a fraction with a distillation range of 80-230° C., and subjecting the fraction to a polymerization reaction to obtain a polymerization liquid; S2, distilling the polymer solution under reduced pressure to obtain resin solution A; S3, dissolving the resin liquid A with a solvent, adding an adsorbent for treatment, and filtering to obtain a resin liquid B; S4, adding the resin liquid B into a catalyst-loaded loop hydrogenation reactor to carry out a hydrogenation reaction with hydrogen to obtain a resin liquid C; S5, distilling the resin liquid C to obtain.

2. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 1, characterized in that: Calculated by percentage, the fraction includes: 1-3wt% of cyclopentadiene, 1-5wt% of styrene, 7-13wt% of methylstyrene, 30-45wt% of dicyclopentadiene, 5-10wt% of indene, 2-5wt% of methylindene, and the remainder is inert components.

3. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 2, characterized in that: The inert component includes at least one of naphthalene, toluene, isopropylbenzene, o-xylene, m-xylene, p-xylene, methylpropylbenzene, dimethylethylbenzene, methyldiethylbenzene and trimethylbenzene.

4. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 3, characterized in that: The polymerization reaction temperature is 180-280° C. and the reaction time is 5-8 hours.

5. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 4, characterized in that: The pressure of the vacuum distillation is 0.090-0.095 MPa, and the temperature is 120-180°C.

6. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 5, characterized in that: The solvent includes at least one of cyclohexane, methylcyclohexane, n-octane, n-heptane, toluene and xylene.

7. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 1 or 6, characterized in that: The temperature of the hydrogenation reaction is 180-250° C., the pressure is 4-7 MPa, and the time is 3-6 hours.

8. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 1, characterized in that: The catalyst comprises a nickel-based catalyst and a palladium-carbon catalyst. The nickel content of the nickel-based catalyst is 1-20 wt %, and the palladium content of the palladium-carbon catalyst is 1-20 wt %.

9. The method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to claim 8, characterized in that: The specific surface area of ​​the nickel catalyst is 150-300m 2 / g, pore volume is 0.1-0.9cm 3 / g, and the average particle size is 3-12mm.

10. An application of the method for preparing C9 petroleum hydrogenated resin by hydrogenation in a loop reactor according to any one of claims 1 to 6, characterized in that: Used in hot melt adhesives, sanitary materials, coatings, and rubber modification fields.

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