Treatment method suitable for dicyclopentadiene cracking kettle residues

Abstract

The invention discloses a treatment method suitable for dicyclopentadiene cracking kettle residues, and belongs to the technical field of chemical engineering. According to the invention, the specific auxiliary agent is introduced into the kettle residue, and the properties of the kettle residue can be effectively changed in the mixing and heating process of the specific auxiliary agent and the kettle residue, so that the kettle residue falls off from the inner wall of the reaction kettle, the flowability of the kettle residue is improved, and the kettle residue can be smoothly removed; the auxiliary agent with a specific structure not only plays a role of a solvent, but also permeates into the cross-linked chain structure of the polycyclopentadiene through the intermolecular force, so that the flowability of the molecular chain is promoted, a certain chemical reaction possibly exists between the auxiliary agent and the polycyclopentadiene, and the polycyclopentadiene is promoted to fall off from the kettle wall by changing the chemical structure of the auxiliary agent. On the basis, the polycyclopentadiene kettle residue can be completely removed under the condition of ensuring the treatment cost by limiting the use amount of the auxiliary agent and the reaction temperature.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical industry, and in particular relates to a method for treating dicyclopentadiene cracking kettle residue. Background Art

[0002] Cyclopentadiene (R n Cyclopentadiene is an active raw material in organic synthesis industry. It is becoming more and more important as an important raw material in organic synthesis industry. The preparation method of cyclopentadiene monomer is mainly to crack dicyclopentadiene at high temperature. Cyclopentadiene monomer is a colorless and highly chemically active alicyclic olefin with a special odor. Because it contains active methylene, it is easy to polymerize into dicyclopentadiene at room temperature.

[0003] Dicyclopentadiene is a colorless crystal at room temperature, with a freezing point of 31.5°C, a boiling point of 170°C (decomposition), and is soluble in alcohol. The physical properties of cyclopentadiene and dicyclopentadiene are quite different. The process for producing monomer cyclopentadiene is to obtain the target product monomer cyclopentadiene by pyrolysis and distillation of dicyclopentadiene at a temperature of 200-220°C. Under this process, the pyrolysis of dicyclopentadiene is prone to coking due to long-term high temperature, resulting in a large amount of production residues, and the treatment of the remaining residues has the following difficulties: after the residue in the pyrolysis kettle is cooled, polycyclopentadiene solids with different polymerization degrees will be formed, including dicyclopentadiene, tricyclopentadiene or polycyclopentadiene, etc. These solids are difficult to melt at high temperatures and are easy to block the discharge valve, making it difficult to discharge the kettle residue.

[0004] Therefore, an effective treatment method is urgently needed to solve the above problems. Summary of the invention

[0005] The object of the present invention is to provide a method for treating dicyclopentadiene cracking kettle residue, so as to solve the problem that the residue produced by cracking dicyclopentadiene to prepare cyclopentadiene is difficult to treat.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for treating dicyclopentadiene cracking still residue comprises the following steps: adding an auxiliary agent to the dicyclopentadiene cracking still residue and heating the still residue for reaction, wherein the auxiliary agent is selected from at least one of the following structural formulas:

[0008] Formula (I): Wherein, R1 and R2 are independently selected from H, C1-5 alkyl or substituted alkyl, X is C or N, and n=1 or 2;

[0009] Formula (II): Wherein, R3 and R4 are independently selected from H, C1-5 alkyl or substituted alkyl, R5 is selected from any one of H, C1-5 alkyl or substituted alkyl, -NR3R4, Y is C or P, and m is 1 or 2;

[0010] Formula (III): Wherein, R6 and R7 are independently selected from C1-5 alkyl or substituted alkyl, C1-5 alkoxy or substituted alkoxy; or R6R7 form a cyclic structure.

[0011] Formula (IV): Wherein, R8 and R9 are independently selected from H, C1-C10 alkyl, -OH, RCOO-, RCO-, wherein R is selected from C1-C5 alkyl or substituted alkyl, and s is an integer of 2-6.

[0012] Unless otherwise specified, the cyclopentadiene described in the present invention is substituted or unsubstituted cyclopentadiene, and the structure is represented by: R n Cp, n is an integer of 0-5, and each R substituent is independently selected from a C1-15 straight chain or branched alkyl group. Accordingly, the polycyclopentadiene is a substituted or unsubstituted polycyclopentadiene.

[0013] Furthermore, the boiling point of the auxiliary agent having the structure of formula (I) to formula (IV) is greater than 150°C; preferably, the boiling point of the auxiliary agent is greater than 180°C; more preferably, the boiling point of the auxiliary agent is greater than 200°C.

[0014] In one embodiment, the optional auxiliary agent of formula (I) includes but is not limited to:

[0015]

[0016] In one embodiment, the optional auxiliary agent of formula (II) includes but is not limited to:

[0017]

[0018] In one embodiment, the optional auxiliary agent of formula (III) includes but is not limited to:

[0019]

[0020] In one embodiment, the optional auxiliary agent of formula (IV) includes but is not limited to:

[0021]

[0022]

[0023] Preferably, the auxiliary agent is a substance represented by formula (III).

[0024] Preferably, the auxiliary agent is a substance represented by formula (IV).

[0025] Furthermore, the reaction temperature of the heating reaction is ≤200°C; preferably, the reaction temperature is 130-200°C.

[0026] Furthermore, the dosage of the auxiliary agent is at least 3 times the weight of the dicyclopentadiene cracking kettle residue.

[0027] Furthermore, the mass ratio of the auxiliary agent to the dicyclopentadiene cracking still residue is 3-7:1; preferably, the mass ratio of the auxiliary agent to the dicyclopentadiene cracking still residue is 4-6:1.

[0028] The preparation method of cyclopentadiene monomer comprises the following steps: adding a certain amount of dicyclopentadiene into a cracking tower, turning on the heating, maintaining the temperature in the cracking tower at 150-180°C, and in the process of receiving cyclopentadiene, controlling the top temperature of the cracking tower outlet between 38-43°C, and the condenser temperature ≤0°C. The cracking time varies according to the feed amount, and the cracking is stopped when the top temperature of the cracking tower outlet is less than 38°C. The dicyclopentadiene cracking kettle residue is the polycyclopentadiene with different polymerization degrees in a highly viscous waxy state remaining in the reactor after the high-temperature cracking of dicyclopentadiene. By adding an additive at least 3 times the amount of the kettle residue, the residue can be effectively promoted to melt, thereby improving production efficiency and safety.

[0029] Specifically, the present invention provides a method for treating dicyclopentadiene cracking still residue, comprising the following steps:

[0030] Step 1. After the cracking of dicyclopentadiene is completed, the temperature in the cracking tower kettle is reduced to below the initial temperature of 100° C., and then an additive at least 3 times the mass of the kettle residue is added to the kettle; the mass of the kettle residue polycyclopentadiene in the cracking tower is calculated according to the theoretical mass, specifically the difference between the amount of dicyclopentadiene used and the yield of cyclopentadiene in the preparation of cyclopentadiene by cracking dicyclopentadiene;

[0031] Step 2. Under normal pressure, start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 130-200°C;

[0032] Step 3. After the temperature reaches 130-200°C, continue stirring at normal pressure until the reaction is complete;

[0033] Step 4. After the reaction is completed, when the temperature in the pyrolysis tower kettle drops below 50°C, the mixture residue in the kettle can be discharged from the bottom valve of the pyrolysis tower kettle.

[0034] Furthermore, in step 1, the initial temperature in the cracking tower kettle is reduced to 60-80°C.

[0035] Furthermore, in step 2, the reaction temperature is 140-190°C, and preferably, the reaction temperature is 150-180°C.

[0036] Furthermore, the reaction time in step 3 is 4-6 hours.

[0037] Furthermore, the additive can be a pure product or a recycled product.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The still residue produced by the high-temperature cracking of dicyclopentadiene to prepare cyclopentadiene monomer includes high-viscosity polymers (i.e., polycyclopentadiene) such as dicyclopentadiene, tricyclopentadiene or polycyclopentadiene, which are difficult to flow out through the discharge valve and easily block the pipeline, and are also difficult to handle manually; the present invention introduces an auxiliary agent of a specific structure, and heats and mixes with the still residue, which can effectively change the properties of the still residue, so that it falls off from the inner wall of the reactor and improves its fluidity, and the still residue can be removed smoothly; the auxiliary agent of a specific structure is not only used as a solvent, but also can penetrate into the cross-linked chain structure of polycyclopentadiene through intermolecular forces, promote the fluidity of its molecular chain, and there may also be a certain chemical reaction between the two, which promotes the falling off of polycyclopentadiene on the still wall by changing its chemical structure. On this basis, by limiting the usage amount of the auxiliary agent and the temperature of the reaction, the complete removal of the still residue of polycyclopentadiene can be achieved under the condition of ensuring the processing cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The drawings described herein are used to provide further understanding of the present invention and constitute a part of this application. The illustrative embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0041] In the attached picture:

[0042] Figure 1 This is a schematic diagram of the process flow of treating dicyclopentadiene cracking kettle residue of the present invention;

[0043] Figure 2 This is a schematic diagram of the reactor before the dicyclopentadiene cracking reactor residue treatment of the present invention;

[0044] Figure 3 It is a schematic diagram of a reaction kettle after the dicyclopentadiene cracking kettle residue is treated in the present invention. DETAILED DESCRIPTION

[0045] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0046] It should be noted that the heating temperature rise rate and cooling rate parameters of the cracking tower kettle in the present invention are adjusted automatically according to the temperature set by the cracking tower kettle equipment used; and parameters such as the stirring speed are not particularly limited as long as they meet industry standards.

[0047] Please refer to the following examples and comparative examples for the treatment process of dicyclopentadiene cracking kettle residue. Figure 1 .

[0048] Example 1

[0049] This embodiment provides a method for treating dicyclopentadiene cracking residue using triethylene glycol as an auxiliary agent, comprising the following steps:

[0050] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the pyrolysis tower kettle is reduced to 70°C, and triethylene glycol (500g) and residual polycyclopentadiene (125g) are added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:4;

[0051] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 153±3°C;

[0052] Step 3. After the temperature reaches 153±3°C, continue stirring and reacting for 5 hours;

[0053] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0054] As attached Figure 2 As shown, the untreated residue in the kettle is a milky white, highly viscous waxy substance that is not easy to flow and is not easy to remove.

[0055] As attached Figure 3 As shown, there is basically no residue left on the inner wall of the kettle after the auxiliary agent treatment, and the residue has good fluidity during the discharge process and is easy to discharge.

[0056] Example 2

[0057] This embodiment provides a method for treating the residue from the cracking of methylcyclopentadiene dimer using tetraethylene glycol dimethyl ether as an auxiliary agent, comprising the following steps:

[0058] Step 1. After the cracking of methylcyclopentadiene dimer is completed, the temperature of the residual methylcyclopentadiene polymer in the pyrolysis tower is reduced to 70°C, and tetraethylene glycol dimethyl ether, 650g of tetraethylene glycol dimethyl ether and 130g of residual methylcyclopentadiene polymer are added to the tower according to the equivalent ratio of residual methylcyclopentadiene to auxiliary agent = 1:5;

[0059] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 163±3°C;

[0060] Step 3. After the temperature reaches 163±3°C, continue stirring and reacting for 6 hours;

[0061] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 39±1°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0062] During the release process, the residue has good fluidity and is easy to release.

[0063] Example 3

[0064] This embodiment provides a method for treating the residue from the cracking of isopropyl cyclopentadiene dimer using triethylene glycol dimethyl ether as an auxiliary agent, comprising the following steps:

[0065] Step 1. After the cracking of isopropylcyclopentadiene dimer is completed, the temperature of the residual isopropylcyclopentadiene polymer in the cracking tower is lowered to 60°C, and triethylene glycol dimethyl ether, 672g of triethylene glycol dimethyl ether and 112g of residual isopropylcyclopentadiene polymer are added to the tower according to the equivalent ratio of residual to auxiliary agent = 1:6;

[0066] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 173±3°C;

[0067] Step 3. After the temperature reaches 173±3°C, continue stirring and reacting for 4 hours;

[0068] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 37±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0069] During the release process, the residue has good fluidity and is easy to release.

[0070] Example 4

[0071] This embodiment provides a method for treating dimethylcyclopentadiene dimer cracking reactor residue using tetraethylene glycol dimethyl ether as an auxiliary agent, comprising the following steps:

[0072] Step 1. After the cracking of dimethylcyclopentadiene dimer is completed, the temperature of the dimethylcyclopentadiene polymer residue in the cracking tower is reduced to 80°C, and tetraethylene glycol dimethyl ether, 826g of tetraethylene glycol dimethyl ether and 118g of dimethylcyclopentadiene polymer residue in the tower are added into the tower according to the equivalent ratio of the residue to the auxiliary agent = 1:7;

[0073] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 178±3°C;

[0074] Step 3. After the temperature reaches 178±3°C, continue stirring and reacting for 4 hours;

[0075] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0076] During the release process, the residue has good fluidity and is easy to release.

[0077] Example 5

[0078] This embodiment provides a method for treating dicyclopentadiene cracking reactor residue using diethylene glycol butyl ether acetate as an auxiliary agent, comprising the following steps:

[0079] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the cracking tower kettle is reduced to 60°C, and diethylene glycol butyl ether acetate, 363g of diethylene glycol butyl ether acetate, and 121g of residual polycyclopentadiene are added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:3;

[0080] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 178±3°C;

[0081] Step 3. After the temperature reaches 178±3°C, continue stirring and reacting for 4 hours;

[0082] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0083] During the release process, the residue has good fluidity and is easy to release.

[0084] Example 6

[0085] This embodiment provides a method for treating dicyclopentadiene cracking reactor residue using tetraethylene glycol dimethyl ether as an auxiliary agent, comprising the following steps:

[0086] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the cracking tower kettle is reduced to 80°C, and tetraethylene glycol dimethyl ether, 1125g of tetraethylene glycol dimethyl ether and 125g of residual polycyclopentadiene are added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:9;

[0087] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 178±3°C;

[0088] Step 3. After the temperature reaches 178±3°C, continue stirring and reacting for 4 hours;

[0089] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0090] During the release process, the residue has good fluidity and is easy to release.

[0091] Example 7

[0092] This embodiment provides a method for treating dicyclopentadiene cracking residue using ethylene glycol carbonate as an auxiliary agent, comprising the following steps:

[0093] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the pyrolysis tower kettle is reduced to 60°C, and ethylene glycol carbonate is added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:4, 516g of ethylene glycol carbonate and 129g of residual polycyclopentadiene;

[0094] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 173±3°C;

[0095] Step 3. After the temperature reaches 173±3°C, continue stirring and reacting for 5 hours;

[0096] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0097] During the release process, the residue has good fluidity and is easy to release.

[0098] Example 8

[0099] This embodiment provides a method for treating dicyclopentadiene cracking residue using N-methylpyrrolidone as an auxiliary agent, comprising the following steps:

[0100] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the pyrolysis tower kettle is reduced to 60°C, and N-methylpyrrolidone, 345g of N-methylpyrrolidone and 115g of residual polycyclopentadiene are added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:3;

[0101] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 178±3°C;

[0102] Step 3. After the temperature reaches 178±3°C, continue stirring and reacting for 4 hours;

[0103] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0104] During the release process, the residue has good fluidity and is easy to release.

[0105] Comparative Example 1

[0106] This comparative example provides a method for treating dicyclopentadiene cracking reactor residue using tetraethylene glycol dimethyl ether as an auxiliary agent, comprising the following steps:

[0107] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the pyrolysis tower kettle is reduced to 70°C, and tetraethylene glycol dimethyl ether is added as an auxiliary agent into the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:5, 625g of tetraethylene glycol dimethyl ether and 125g of residual polycyclopentadiene;

[0108] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 123±3°C;

[0109] Step 3. After the temperature reaches 123±3°C, continue stirring and reacting for 6 hours;

[0110] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0111] During the discharge process, the residue in the tower bottom has poor fluidity and is not easy to discharge.

[0112] Comparative Example 2

[0113] This comparative example provides a method for treating dicyclopentadiene cracking reactor residue using tetraethylene glycol dimethyl ether as an auxiliary agent, comprising the following steps:

[0114] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the cracking tower kettle is reduced to 60°C, and tetraethylene glycol dimethyl ether, 120g of tetraethylene glycol dimethyl ether and 120g of residual polycyclopentadiene are added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:1;

[0115] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 178±3°C;

[0116] Step 3. After the temperature reaches 178±3°C, continue stirring and reacting for 4 hours;

[0117] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 33±3°C, and the mixture residue in the tower kettle is discharged into the waste liquid barrel.

[0118] During the discharge process, the residue in the tower bottom has poor fluidity and is not easy to discharge.

[0119] Comparative Example 3

[0120] This comparative example provides a method for treating dicyclopentadiene cracking reactor residue using ethylene glycol monomethyl ether as an auxiliary agent, comprising the following steps:

[0121] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the pyrolysis tower kettle is reduced to 60°C, and ethylene glycol monomethyl ether, 625g of ethylene glycol monomethyl ether and 125g of residual polycyclopentadiene are added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:5;

[0122] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 162±3°C;

[0123] Step 3. After the temperature reaches 162±3°C, continue stirring and reacting for 6 hours;

[0124] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 39±1°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0125] During the discharge process, the residue in the bottom of the tower has poor fluidity and is not easy to discharge, and ethylene glycol monomethyl ether is detected in the polycyclopentadiene cracking receiving tank.

[0126] Comparative Example 4

[0127] This comparative example provides a method for treating dicyclopentadiene cracking reactor residue using ethylene glycol as an auxiliary agent, comprising the following steps:

[0128] Step 1. After the cracking of dicyclopentadiene is completed, the temperature of the residual polycyclopentadiene in the cracking tower kettle is reduced to 60°C, and ethylene glycol is added to the kettle according to the equivalent ratio of residual polycyclopentadiene to auxiliary agent = 1:5, 590g of ethylene glycol and 118g of residual polycyclopentadiene;

[0129] Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 162±3°C;

[0130] Step 3. After the temperature reaches 162±3°C, continue stirring and reacting for 6 hours;

[0131] Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle is lowered to 39±1°C, and the mixture residue in the kettle is discharged into the waste liquid barrel.

[0132] During the discharge process, the residue in the tower bottom has poor fluidity and is not easy to discharge, and ethylene glycol is detected in the polycyclopentadiene cracking receiving tank.

[0133] In the above-mentioned Examples 1-8 and Comparative Examples 1-4, the experimental parameters such as the type of auxiliary agent, the mass ratio of the kettle residue to the auxiliary agent, and the temperature related to the temperature control in the tower kettle are compared in Table 1.

[0134] Table 1

[0135]

[0136]

[0137] The treatment results of the treatment methods of Examples 1-8 and Comparative Examples 1-4 were tested, and the testing standard was a combination of visual inspection + calculation of the completion degree of the treatment of the inlet and outlet mass ratio and the kettle residue:

[0138] (1) Visual inspection: Observe the inner surface of the cracking tower kettle through the sight glass to see if there is any polycyclopentadiene residue (white waxy and viscous substance). Focus on and repeatedly check the dead corners. If no polycyclopentadiene residue can be seen on the surface of the cracking tower kettle with the naked eye, it is qualified.

[0139] The test results are shown in Table 2:

[0140] Table 2

[0141]

[0142] (2) The calculation formula for the completion degree of the inlet and outlet mass ratio of the kettle residue treatment is:

[0143]

[0144] The mass of the residual polycyclopentadiene in the cracking tower is calculated according to the theoretical mass, specifically the difference between the amount of dicyclopentadiene used and the yield of cyclopentadiene in the preparation of cyclopentadiene by cracking dicyclopentadiene (i.e., cyclopentadiene dimer);

[0145] The larger the value, the more completely the still residue is processed. When the result is between 99% and 100%, it can be considered that the still residue has been completely removed.

[0146] The test results are shown in Table 3:

[0147] Table 3

[0148]

[0149]

[0150] By comparing the above test results, it can be seen that by regulating the treatment temperature and dosage ratio of the dicyclopentadiene cracking still residue, the properties of polycyclopentadiene can be effectively changed and its fluidity can be improved; in addition, by limiting the structure of the auxiliary agent, the functional groups in its structure are utilized to penetrate into the chain cross-linked structure of polycyclopentadiene through intermolecular action, and further participate in the cross-linking reaction, so that the still residue polycyclopentadiene can be melted and removed, thereby improving the safety and effectiveness of the treatment of the dicyclopentadiene cracking still residue, thereby improving the production efficiency of the cyclopentadiene production system and reducing the production cost.

[0151] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0152] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for treating dicyclopentadiene cracking still residue, characterized in that: The following steps are involved: Add an auxiliary agent to the dicyclopentadiene cracking kettle residue and heat to react, wherein the auxiliary agent is selected from at least one of the following structural formulas: Formula (I): Wherein, R1 and R2 are independently selected from H, C1-5 alkyl or substituted alkyl, X is C or N, and n=1 or 2; Formula (II): Wherein, R3 and R4 are independently selected from H, C1-5 alkyl or substituted alkyl, R5 is selected from any one of H, C1-5 alkyl or substituted alkyl, -NR3R4, Y is C or P, and m is 1 or 2; Formula (III): Wherein, R6 and R7 are independently selected from C1-5 alkyl or substituted alkyl, C1-5 alkoxy or substituted alkoxy; or R6R7 form a cyclic structure. Formula (IV): Wherein, R8 and R9 are independently selected from H, C1-C10 alkyl, -OH, RCOO-, RCO-, wherein R is selected from C1-C5 alkyl or substituted alkyl, and s is an integer of 2-6.

2. A method for treating dicyclopentadiene cracking still residue according to claim 1, characterized in that: The auxiliary agent having the structure of formula (I) to formula (IV) has a boiling point of >150°C.

3. A method for treating dicyclopentadiene cracking still residue according to claim 2, characterized in that: The auxiliary agent having the structure of formula (I) to formula (IV) has a boiling point of >180°C.

4. A method for treating dicyclopentadiene cracking still residue according to claim 1, characterized in that: The dosage of the auxiliary agent is at least 3 times the mass of the dicyclopentadiene cracking kettle residue.

5. A method for treating dicyclopentadiene cracking still residue according to claim 1, characterized in that: The reaction temperature of the heating reaction is ≤200°C.

6. A method for treating dicyclopentadiene cracking still residue according to claim 1, characterized in that: The following steps are involved: Step 1. After the cracking of dicyclopentadiene is completed, the temperature in the cracking tower kettle is lowered to below 100° C., and then an auxiliary agent is added to the tower kettle; Step 2. Start stirring and heat the temperature in the cracking tower kettle to the reaction temperature of 130-200°C; Step 3. After the temperature reaches 130-200°C, continue stirring to react until complete; Step 4. After the reaction is completed, the temperature in the pyrolysis tower kettle drops below 50° C. and the mixture residue in the tower kettle is discharged.

7. A method for treating dicyclopentadiene cracking still residue according to claim 6, characterized in that: The reaction temperature in step 2 is 140-190°C.

8. A method for treating dicyclopentadiene cracking still residue according to claim 6, characterized in that: The reaction time in step 3 is 4-6h.

9. A method for treating dicyclopentadiene cracking still residue according to claim 1, characterized in that: The auxiliary agent is a substance represented by formula (III).

10. A method for treating dicyclopentadiene cracking still residue according to claim 1, characterized in that: The auxiliary agent is a substance represented by formula (IV).

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