Preparation method of hydrogenated petroleum resin

Abstract

The invention belongs to the technical field of petrochemical engineering. More specifically, the invention relates to a preparation method of hydrogenated petroleum resin. The preparation method comprises the following steps: blending and mixing C5 petroleum resin and C9 petroleum resin to obtain blended petroleum resin; mixing the blended petroleum resin and a solvent, stirring and dissolving to obtain a blended petroleum resin solution; aluminum chloride is used as a catalyst and is filled in a fixed bed reactor; the preparation method comprises the following steps: adding a blended petroleum resin solution, preheating, mixing with hydrogen, entering a first-stage hydrogenation reactor, and carrying out hydrogenation reaction under the conditions that the pressure is 2.2-2.5 MPa, the air speed is 0.8-1.2 h <-1 >, the temperature is 280-300 DEG C and the volume ratio of hydrogen to oil is 180-200 to obtain a first-stage hydrogenation material; preheating the first-stage hydrogenation material again, mixing with hydrogen, feeding into a tail-stage hydrogenation reactor, and carrying out hydrogenation reaction under the conditions that the pressure is 12-15MPa, the air speed is 1.8-2.0 h <-1 >, the temperature is 320-330 DEG C and the volume ratio of hydrogen to oil is 230-250 to obtain a tail-stage hydrogenation material; and separating the tail-section hydrogenated material to obtain the hydrogenated petroleum resin.

Description

Technical Field

[0001] The present invention belongs to the technical field of petrochemical industry and more specifically relates to a method for preparing hydrogenated petroleum resin. Background Art

[0002] At present, the common preparation process of hydrogenated petroleum resin includes the following steps: S1, raw material pretreatment, by pretreating C9 petroleum resin or C5 petroleum resin produced as a by-product of ethylene cracking to remove impurities; S2, catalyst selection, selecting a suitable hydrogenation catalyst is the key, and a suitable catalyst can effectively catalyze the hydrogenation reaction of petroleum resin and improve the color and stability of the product; S3, hydrogenation reaction, in the presence of a hydrogenation catalyst, the pretreated raw material is hydrogenated at a certain temperature and pressure; S4, post-treatment, after the hydrogenation reaction, the product may require further post-treatment, such as removing unreacted hydrogen, recovering and reusing the catalyst, etc.

[0003] For the above conventional hydrogenation steps, the technical difficulties that the industry is still trying to overcome include: how to improve the hydrogenation efficiency, etc. For the improvement of hydrogenation efficiency, we can consider optimizing the catalyst. The key to this technology is to develop efficient and stable catalysts. The performance of the catalyst can be improved by changing the composition of the metal active components, geometric and electronic structure, carrier morphology and pore structure design of the catalyst. However, the mechanism of this method is relatively complex, and it will lead to higher costs. In addition, since the catalyst needs to be recycled and regenerated, the recycling and regeneration of new catalysts will also be a bottleneck restricting the widespread use of this method.

[0004] Based on this, how to develop a relatively more convenient preparation method to improve the efficiency of the hydrogenation reaction is one of the technical challenges that technicians in this field still need to continue to face. Summary of the invention

[0005] The technical problem to be solved by the present invention is: in view of the problem that the hydrogenation efficiency cannot be effectively improved in the current petroleum resin hydrogenation process, the present invention provides a method for preparing hydrogenated petroleum resin.

[0006] The object of the present invention is to provide a method for preparing hydrogenated petroleum resin.

[0007] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0008] A method for preparing hydrogenated petroleum resin, the specific preparation steps comprising:

[0009] C5 petroleum resin and C9 petroleum resin are blended and mixed in a mass ratio of 1:(4-4.5) to obtain a blended petroleum resin;

[0010] The blended petroleum resin and the solvent are mixed in a mass ratio of 1:(5-6), and stirred to dissolve to obtain a blended petroleum resin solution;

[0011] Aluminum chloride is used as a catalyst and filled into a fixed bed reactor;

[0012] After preheating the blended petroleum resin solution, it is mixed with hydrogen and enters the first stage hydrogenation reactor at a pressure of 2.2-2.5MPa and a space velocity of 0.8-1.2h -1 , the temperature is 280-300℃, the volume ratio of hydrogen to oil is 180-200, after hydrogenation reaction, the first stage hydrogenation material is obtained;

[0013] The first stage hydrogenation material is preheated again, mixed with hydrogen, and enters the final stage hydrogenation reactor at a pressure of 12-15MPa and a space velocity of 1.8-2.0h -1 , the temperature is 320-330℃, the hydrogen-to-oil volume ratio is 230-250, after hydrogenation reaction, the final hydrogenation material is obtained;

[0014] The final hydrogenation material is separated to obtain hydrogenated petroleum resin.

[0015] In order to ensure that a higher degree of hydrogenation can be obtained during the preparation process, the above technical solution starts from the perspective of raw material selection and achieves this goal by cleverly using two different petroleum resins for physical blending.

[0016] Specifically, due to the different molecular structures and molecular weights of C5 petroleum resin and C9 petroleum resin, physical blending and compounding of the two can effectively improve the fluidity and dispersibility of the petroleum resin on the catalyst surface; more importantly, the two different types of petroleum resins may contain different types and numbers of unsaturated bonds in their molecular structures, thereby increasing the diversity of the active sites of the petroleum resin, thereby improving the activity and selectivity of the hydrogenation reaction, and ultimately improving the efficiency of the hydrogenation reaction. From the product perspective, the hydrogenation rate of the product is improved.

[0017] Furthermore, the specific preparation steps also include:

[0018] When the blended petroleum resin and the solvent are stirred and dissolved, a surfactant is added in an amount of 2-4% by weight of the blended petroleum resin;

[0019] The surfactant is selected from any one of a cationic surfactant, an anionic surfactant or a nonionic surfactant.

[0020] Furthermore, the surfactant is selected from anionic surfactants.

[0021] In addition, the inventors have found that for a hydrogenation reaction system using aluminum chloride as a catalyst, if a certain amount of surfactant is added, it will be beneficial to the uniform mixing of two different types of petroleum resins. At the same time, it can further enhance the wetting and spreading of the petroleum resin on the catalyst surface, so that the two can effectively contact during the reaction process; in particular, the inventors have further found that when anionic surfactants are selected, they can form mutual adsorption forces with aluminum ions in the aluminum chloride catalyst, thereby forming a stable liquid film layer on the surface of the aluminum chloride catalyst. The liquid film layer can prevent substances in the system that are toxic to the catalyst from depositing on the catalyst surface to a certain extent, thereby stabilizing the catalytic effect of the catalyst and ultimately improving the efficiency of the hydrogenation reaction of the product as a whole.

[0022] Furthermore, the anionic surfactant is selected from any one of alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfonate, succinate sulfonate, lignin sulfonate, alkyl glyceryl ether sulfonate, and fatty alcohol sulfate.

[0023] Furthermore, the solvent is selected from any one of cyclohexane oil, ethyl acetate, butyrate, phenylpropionate, methyl ethyl ketone and xylene.

[0024] Further, the aluminum chloride catalyst is a spherical aluminum chloride catalyst;

[0025] The sphericity of the spherical aluminum chloride catalyst is 9.2-9.4;

[0026] Moreover, the particle size distribution range of the spherical aluminum chloride catalyst is 10-30 nm.

[0027] By selecting aluminum chloride with high sphericity and narrow particle size distribution as the catalyst, when it is filled in a fixed bed reactor, on the one hand, the reaction system after the overall filling and stacking is a relatively more uniform system. For example, the gaps between particles, which are used for fluid to pass through, are relatively uniform, so the contact during the reaction is more uniform; on the other hand, after the sphericity of a single catalyst is high, its contact with the petroleum resin at different angles is also uniform, so that the low reaction efficiency caused by local defects can be avoided.

[0028] Furthermore, the filling amount of the aluminum chloride catalyst is 25-30% of the volume of the fixed bed reactor.

[0029] Furthermore, the fixed bed reactor is also filled with reduced graphene in an amount of 10-12% of the mass of the aluminum chloride catalyst.

[0030] Furthermore, the particle size distribution range of the reduced graphene is 80-100 nm.

[0031] By further adding reduced graphene and filling reduced graphene and aluminum chloride together, a more complex mass transfer channel is constructed, thereby increasing the contact time between the petroleum resin and the catalyst system, so that efficient hydrogenation effect can be obtained even at a relatively low catalyst filling amount. DETAILED DESCRIPTION

[0032] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0033] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0034] Example 1

[0035] C5 petroleum resin and C9 petroleum resin were mixed in a mass ratio of 1:4, and stirred with a stirrer at a speed of 300 r / min for 80 minutes to obtain a blended petroleum resin;

[0036] The blended petroleum resin and the solvent are mixed in a mass ratio of 1:5, and then a surfactant of 2% by mass of the blended petroleum resin is added, and then a stirrer is used to continuously stir and dissolve at a speed of 300 r / min and a temperature of 45° C. for 4 hours to obtain a blended petroleum resin solution;

[0037] The surfactant is selected from anionic surfactants;

[0038] The anionic surfactant is selected from alkylbenzene sulfonate;

[0039] The solvent is selected from naphthenic oil;

[0040] Aluminum chloride is used as a catalyst and filled into a fixed bed reactor;

[0041] The aluminum chloride catalyst is a spherical aluminum chloride catalyst;

[0042] The sphericity of the spherical aluminum chloride catalyst is 9.2;

[0043] The particle size distribution range of the spherical aluminum chloride catalyst is 10-30nm;

[0044] The filling amount of the aluminum chloride catalyst is 25% of the volume of the fixed bed reactor;

[0045] The fixed bed reactor is also filled with reduced graphene in an amount of 10% of the mass of the aluminum chloride catalyst;

[0046] The particle size distribution range of the reduced graphene is 80-100 nm;

[0047] After preheating, the blended petroleum resin solution is mixed with hydrogen and enters the first stage hydrogenation reactor at a pressure of 2.2 MPa and a space velocity of 0.8 h -1 , the temperature is 280℃, the hydrogen-to-oil volume ratio is 180, after hydrogenation reaction, the first stage hydrogenation material is obtained;

[0048] The first stage hydrogenation material is preheated again, mixed with hydrogen, and enters the final stage hydrogenation reactor at a pressure of 12 MPa and a space velocity of 1.8 h -1 , the temperature is 320℃, the hydrogen-to-oil volume ratio is 230, after hydrogenation reaction, the final hydrogenation material is obtained;

[0049] The final hydrogenation material is separated to obtain hydrogenated petroleum resin.

[0050] Example 2

[0051] C5 petroleum resin and C9 petroleum resin were mixed in a mass ratio of 1:4.3, and stirred with a stirrer at a speed of 300 r / min for 80 min to obtain a blended petroleum resin;

[0052] The blended petroleum resin and the solvent are mixed in a mass ratio of 1:5.4, and then a surfactant of 3% by mass of the blended petroleum resin is added, and then a stirrer is used to continuously stir and dissolve for 5 hours at a speed of 300 r / min and a temperature of 48° C. to obtain a blended petroleum resin solution;

[0053] The surfactant is selected from anionic surfactants;

[0054] The anionic surfactant is selected from α-olefin sulfonates;

[0055] The solvent is selected from ethyl acetate;

[0056] Aluminum chloride is used as a catalyst and filled into a fixed bed reactor;

[0057] The aluminum chloride catalyst is a spherical aluminum chloride catalyst;

[0058] The sphericity of the spherical aluminum chloride catalyst is 9.3;

[0059] The particle size distribution range of the spherical aluminum chloride catalyst is 10-30nm;

[0060] The filling amount of the aluminum chloride catalyst is 27% of the volume of the fixed bed reactor;

[0061] The fixed bed reactor is also filled with reduced graphene at 11% of the mass of the aluminum chloride catalyst;

[0062] The particle size distribution range of the reduced graphene is 80-100 nm;

[0063] After preheating the blended petroleum resin solution, it is mixed with hydrogen and enters the first stage hydrogenation reactor at a pressure of 2.4 MPa and a space velocity of 1.0 h -1 , the temperature is 290℃, the hydrogen-to-oil volume ratio is 190, after hydrogenation reaction, the first stage hydrogenation material is obtained;

[0064] The first stage hydrogenation material is preheated again, mixed with hydrogen, and enters the final stage hydrogenation reactor at a pressure of 14 MPa and a space velocity of 1.9 h -1 , the temperature is 325℃, the hydrogen-to-oil volume ratio is 240, after hydrogenation reaction, the final hydrogenation material is obtained;

[0065] The final hydrogenation material is separated to obtain hydrogenated petroleum resin.

[0066] Example 3

[0067] C5 petroleum resin and C9 petroleum resin were mixed in a mass ratio of 1:4.5, and stirred with a stirrer at a speed of 300 r / min for 80 minutes to obtain a blended petroleum resin;

[0068] The blended petroleum resin and the solvent are mixed in a mass ratio of 1:6, and then a surfactant of 4% by mass of the blended petroleum resin is added, and then a stirrer is used to continuously stir and dissolve for 6 hours at a speed of 300 r / min and a temperature of 55° C. to obtain a blended petroleum resin solution;

[0069] The surfactant is selected from anionic surfactants;

[0070] The anionic surfactant is selected from succinate sulfonates;

[0071] The solvent is selected from butyrate;

[0072] Aluminum chloride is used as a catalyst and filled into a fixed bed reactor;

[0073] The aluminum chloride catalyst is a spherical aluminum chloride catalyst;

[0074] The sphericity of the spherical aluminum chloride catalyst is 9.4;

[0075] The particle size distribution range of the spherical aluminum chloride catalyst is 10-30nm;

[0076] The filling amount of the aluminum chloride catalyst is 30% of the volume of the fixed bed reactor;

[0077] The fixed bed reactor is also filled with reduced graphene in an amount of 12% of the mass of the aluminum chloride catalyst;

[0078] The particle size distribution range of the reduced graphene is 80-100 nm;

[0079] After preheating the blended petroleum resin solution, it is mixed with hydrogen and enters the first stage hydrogenation reactor at a pressure of 2.5 MPa and a space velocity of 1.2 h -1 , the temperature is 300℃, the hydrogen-to-oil volume ratio is 200, after hydrogenation reaction, the first stage hydrogenation material is obtained;

[0080] The first stage hydrogenation material is preheated again, mixed with hydrogen, and enters the final stage hydrogenation reactor at a pressure of 15 MPa and a space velocity of 2.0 h -1 , the temperature is 330℃, the hydrogen-to-oil volume ratio is 250, after hydrogenation reaction, the final hydrogenation material is obtained;

[0081] The final hydrogenation material is separated to obtain hydrogenated petroleum resin.

[0082] Example 4

[0083] Compared with Example 1, this embodiment is different in that:

[0084] An equal amount of hexadecyltrimethylammonium chloride was used to replace the alkylbenzene sulfonate, and the other conditions remained unchanged.

[0085] Example 5

[0086] Compared with Example 1, this embodiment is different in that:

[0087] No alkylbenzene sulfonate was added and the other conditions remained unchanged.

[0088] Example 6

[0089] Compared with Example 1, this embodiment is different in that:

[0090] The sphericity of the aluminum chloride is 8.5, and the other conditions remain unchanged.

[0091] Example 7

[0092] Compared with Example 1, this embodiment is different in that:

[0093] The particle size distribution range of the aluminum chloride is 1-50 nm, and the other conditions remain unchanged.

[0094] Example 8

[0095] Compared with Example 1, this embodiment is different in that:

[0096] No reduced graphene was added, and the other conditions remained unchanged.

[0097] Example 9

[0098] Compared with Example 1, this embodiment is different in that:

[0099] The particle size distribution range of the reduced graphene is 20-150 nm, and the other conditions remain unchanged.

[0100] Comparative Example 1

[0101] The difference between this comparative example and Example 1 is that no C5 petroleum resin is added, and other conditions remain unchanged.

[0102] Comparative Example 2

[0103] The difference between this comparative example and Example 1 is that no C9 petroleum resin is added, and other conditions remain unchanged.

[0104] The hydrogenation rates of the preparation processes of the above embodiments and comparative examples were tested, and the specific testing method was carried out as follows:

[0105] Among them, the hydrogenation rate is used to measure the degree of hydrogenation of petroleum resin;

[0106] Hydrogenation rate = (bromine value of raw petroleum resin - bromine value of hydrogenated petroleum resin product) / bromine value of raw petroleum resin

[0107] The bromine value of raw petroleum resin and hydrogenated petroleum resin products refers to the number of grams of bromine consumed by 100g of petroleum resin reacting with bromine under certain conditions. The bromine value can be used to reflect the performance of petroleum resin and measure the degree of unsaturation of polymer petroleum resin.

[0108] The specific testing process is:

[0109] (1) Preparation of electrolyte: Dissolve 100g LiBr·H2O in 100mL deionized water to prepare a solution for later use. Next, add 5mL of the above LiBr solution, 45mL CH3CH2OH, 40mL C6H6 and 10mL CH3COOH into a 200mL volumetric flask, mix well and set aside; (2) Use a standard bromine solution to calibrate the electrolyte, the bromine value of the standard bromine solution is 1.0gBr / 100g; (3) Inject the petroleum resin solution into the above electrolyte, and the carbon-carbon double bond in the petroleum resin and Br2 undergo an addition reaction: R-CH=CH+Br2→R-CHBrCHBr, and the consumed Br2 is replenished by anode electrolysis: 2Br--2e→Br2. According to Faraday's law of electrolysis, the electrical signal is converted by a bromine value meter, and the resulting value is the bromine value.

[0110] The specific test results are shown in Table 1:

[0111] Table 1: Hydrogenation rate test results of different examples or comparative examples

[0112]

[0113]

[0114] It can be seen from the test results in Table 1 that the preparation method of the present invention has a higher degree of hydrogenation when preparing hydrogenated petroleum resin.

[0115] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a hydrogenated petroleum resin, characterized in that: The specific preparation steps include: C5 petroleum resin and C9 petroleum resin are blended and mixed in a mass ratio of 1:(4-4.5) to obtain a blended petroleum resin; The blended petroleum resin and the solvent are mixed in a mass ratio of 1:(5-6), and stirred to dissolve to obtain a blended petroleum resin solution; Aluminum chloride is used as a catalyst and filled into a fixed bed reactor; After preheating the blended petroleum resin solution, it is mixed with hydrogen and enters the first stage hydrogenation reactor at a pressure of 2.2-2.5MPa and a space velocity of 0.8-1.2h -1 , the temperature is 280-300℃, the volume ratio of hydrogen to oil is 180-200, after hydrogenation reaction, the first stage hydrogenation material is obtained; The first stage hydrogenation material is preheated again, mixed with hydrogen, and enters the final stage hydrogenation reactor at a pressure of 12-15MPa and a space velocity of 1.8-2.0h -1 , the temperature is 320-330℃, the hydrogen-to-oil volume ratio is 230-250, after hydrogenation reaction, the final hydrogenation material is obtained; The final hydrogenation material is separated to obtain hydrogenated petroleum resin.

2. The method for preparing a hydrogenated petroleum resin according to claim 1, characterized in that: The specific preparation steps also include: When the blended petroleum resin and the solvent are stirred and dissolved, a surfactant is added in an amount of 2-4% by weight of the blended petroleum resin; The surfactant is selected from any one of a cationic surfactant, an anionic surfactant or a nonionic surfactant.

3. The method for preparing a hydrogenated petroleum resin according to claim 2, characterized in that: The surfactant is selected from anionic surfactants.

4. The method for preparing a hydrogenated petroleum resin according to claim 3, characterized in that: The anionic surfactant is selected from any one of alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfonate, succinate sulfonate, lignin sulfonate, alkyl glyceryl ether sulfonate and fatty alcohol sulfate.

5. The method for preparing a hydrogenated petroleum resin according to claim 1, characterized in that: The solvent is selected from any one of naphthenic oil, ethyl acetate, butyrate, phenylpropionate, methyl ethyl ketone and xylene.

6. The method for preparing a hydrogenated petroleum resin according to claim 1, characterized in that: The aluminum chloride catalyst is a spherical aluminum chloride catalyst; The sphericity of the spherical aluminum chloride catalyst is 9.2-9.4; Moreover, the particle size distribution range of the spherical aluminum chloride catalyst is 10-30 nm.

7. The method for preparing a hydrogenated petroleum resin according to claim 6, characterized in that: The filling amount of the aluminum chloride catalyst is 25-30% of the volume of the fixed bed reactor.

8. The method for preparing a hydrogenated petroleum resin according to claim 7, characterized in that: The fixed bed reactor is also filled with reduced graphene in an amount of 10-12% of the mass of the aluminum chloride catalyst.

9. The method for preparing a hydrogenated petroleum resin according to claim 8, characterized in that: The particle size distribution range of the reduced graphene is 80-100 nm.

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