RU2540322C1 - Method of producing dicyclopentadiene - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing dicyclopentadiene, which comprises monomerisation of a dicyclopentadiene-containing fraction in the presence of an inert high-boiling solvent and a polymerisation inhibitor to obtain cyclopentadiene, dimerisation of the cyclopentadiene and fractionation of the concentrated dicyclopentadiene. The initial dicyclopentadiene-containing fraction with total concentration of dicyclopentadiene and cyclopentadiene of 80-98 wt % is mixed with a recycle stream to achieve total concentration of dicyclopentadiene and cyclopentadiene of 50-97 wt %; monomerisation is carried out in the presence of dodecane, which is added in weight ratio of dicyclopentadiene: solvent of 40:60 to 90:10, and alkylphenol which is added in concentration of 0.01-0.5 wt % to achieve dicyclopentadiene conversion of 99.4%. The method includes regenerating the high-boiling solvent, separating unreacted dicyclopentadiene at 115-180°C and pressure of 4-12 kPa and subsequent recycling thereof.

EFFECT: use of the invention increases concentration of dicyclopentadiene in the end product, increases conversion of dicyclopentadiene at the monomerisation step with high total output of dicyclopentadiene and improves technological effectiveness of the process.

2 cl, 2 dwg, 2 tbl, 6 ex

Description

The invention relates to petrochemistry, and specifically to a method for producing dicyclopentadiene from a dicyclopentadiene-containing fraction, including impurities of cyclopentadiene co-dimers with diene hydrocarbons. High-purity dicyclopentadiene is used to produce polydicyclopentadiene, ethylene propylene diene rubbers, petroleum resin, adamantane, ethylidene norbornene and other valuable petrochemical synthesis products.

A known method of producing dicyclopentadiene of high purity from technical dicyclopentadiene with a basic substance content of 80-85 wt.% Or concentrated dicyclopentadiene with a basic substance content of about 90 wt.% Obtained by dimerization of a C ₅ fraction of gasoline pyrolysis followed by fractionation. The raw material, a dicyclopentadiene-containing fraction, is subjected to monomerization at a temperature of from 140 to 250 ° C, mainly 180-190 ° C, and the residence time of the contact solution in the reactor is 0.1-6 hours, mainly 1-3 hours. Cyclopentadiene with a basic substance content of 99, 4 wt.% Is separated by distillation and sent to dimerization at a temperature of from 50 to 150 ° C and a residence time of 0.1-50 hours. The resulting dimerizate is further purified by steam distillation. To remove trimers and cyclopentadiene oligomers, the target product is additionally passed through aluminosilicate, silica, mainly bentonite, or activated carbon. According to this method, the concentration of dicyclopentadiene in the target product of 97.6-99.55 wt.% Is achieved. The yield of dicyclopentadiene in this case is 68-79%. CS 276654, C07C 13/15, 05.20.1992.

The disadvantages of this technology are energy intensity and multi-stage. So, the monomerization process and separation of the obtained monomerizate is carried out in various devices, which leads to a long contact time of the obtained cyclopentadiene with dicyclopentadiene in the reaction mass at high temperature, which, in turn, causes increased gum formation, decreased selectivity and yield of cyclopentadiene and, as a consequence yield of dicyclopentadiene.

A known method for producing high-purity dicyclopentadiene from a C ₅ pyrolysis fraction, which consists in dimerizing a C ₅ pyrolysis fraction at 30-80 ° C, followed by fractionation and isolation of a dicyclopentadiene concentrate. A dicyclopentadiene concentrate with a basic substance content of 89.9 wt.% Is monomerised in the presence of alkyl substituted phenols (2,6-ditretbutylphenol, 2,4-ditretbutylphenol, 2,4,6-tritretbutylphenol) at 165-180 ° C. The resulting cyclopentadiene is subjected to repeated dimerization at 40-60 ° C followed by monomerization of the product. The stage of repeated monomerization is characterized by a selectivity of 94% and a yield of cyclopentadiene of 92% with a concentration of the main substance of 99.31 mass%. The known method allows to obtain dicyclopentadiene with a concentration of the main substance of 98.62 wt.%, The total yield of the target product is 81%. RU 2289564 C2, C07C 2/42, C07C 13/61, 12.20.2006.

The disadvantages of this method are the low selectivity of the monomerization stage 94-96% and the total yield of dicyclopentadiene 80-81%, the need for additional energy consumption at the melting stage of a mixture of tert-butyl substituted phenols, which are crystalline substances.

A known method of producing dicyclopentadiene of high purity from cyclopentadiene-containing fractions of hydrocarbons. The method consists in dimerizing a cyclopentadiene-containing fraction of hydrocarbons with a content of at least 15 wt.% Cyclopentadiene at 80-110 ° C, followed by fractionation in the presence of methanol. The obtained dicyclopentadiene-containing fraction (the content of the basic substance is 83.4-95.7 wt.%) Monomerize at a temperature of 165-185 ° C in the presence of alkyl- and aryl-substituted phenols in a mass ratio (50-70) :( 50-30), respectively, introduced in an amount of 10-20 wt.% to dicyclopentadiene-containing fraction. As alkyl substituted phenols use Agidol-21 (TU 2425-452-05742686-2003), which is a mixture of mono - and dialkylphenols. As aryl substituted phenols use Agidol-20 (TU 38103160-91), which is a mixture of methylbenzylphenols. The phenol mixture is preheated in a recuperative heat exchanger with the bottom products of the monomerization column. Then cyclopentadiene is re-dimerized at a temperature of 60-80 ° C. RU 2463284 C1, C07C 13/61, C07C 7/20, C07C 2/42, C07C 2/50, 10/10/2012.

This method allows to obtain dicyclopentadiene with a basic substance content of at least 98.5 wt.%. However, the known method is not effective enough due to the low selectivity of 85.8-96.6% of the monomerization stage, which is the reason for the low total yield of the target dicyclopentadiene 90%.

The closest in technical essence is a method for producing dicyclopentadiene from a C ₅ fraction of hydrocarbon pyrolysis, including dimerization of a C ₅ fraction of pyrolysis at a temperature of 50-110 ° C, followed by fractionation. The obtained dicyclopentadiene-containing fraction (the content of the main substance is 83-88 wt.%) Is subjected to the monomerization process in the presence of a high boiling solvent and a polymerization inhibitor at 180-210 ° C. Heptadecane is used as a high boiling solvent, and ditolylmethane can also be used. Hydroquinone is used as a polymerization inhibitor, and benzoquinone can also be used. Then the obtained cyclopentadiene is dimerized at a temperature of 50-60 ° C and fractionation is carried out. The obtained dicyclopentadiene has a concentration of 100 wt.%. RU 2186051 C1, C07C 13/61, 07.27.2002.

The disadvantages of this method are the low efficiency at the stage of repeated monomerization of the dicyclopentadiene-containing fraction at a concentration of dicyclopentadiene less than 84.0 wt.% (Low conversion of dicyclopentadiene (88.0-90.0%) and the purity of the resulting cyclopentadiene 86.44 wt.%), Leading to lower yield of the target product, and high toxicity of ditolylmethane.

An object of the present invention is to develop a method for producing dicyclopentadiene from a dicyclopentadiene-containing fraction, including impurities of cyclopentadiene co-dimers with diene hydrocarbons, in the presence of an inert high-boiling solvent and a polymerization inhibitor with recirculation of unreacted dicyclopentadiene and regenerated solvent streams.

The technical result from the implementation of the invention consists in increasing the purity of cyclopentadiene to a concentration of 99.90 wt.% And increasing the conversion of dicyclopentadiene to 99.4% at the stage of monomerization, increasing the total yield of dicyclopentadiene in the target stream to 97.8% with a concentration of the main substance to 99 , 98 wt.%. Recycling the flows of unreacted dicyclopentadiene and an inert high boiling solvent can reduce the possible environmental impact, as well as improve the processability.

The method is illustrated by the following diagram presented in figure 1.

Dicyclopentadiene monomerization is carried out in a facility consisting of a monomerization reactor (P-1), which is a distillation column with an increased volume of bottoms, as well as a distillation column for the inert high-boiling solvent regeneration and separation of unreacted dicyclopentadiene (K-1). The initial raw material dicyclopentadiene-containing fraction (1) with a total concentration of dicyclopentadiene and cyclopentadiene in the range from 80 to 98 wt.% Is mixed with the recycle stream (12). The resulting feed stream (2) with a total concentration of dicyclopentadiene and cyclopentadiene in the range from 50 to 97 wt.% Is fed to the reactor (P-1), where dicyclopentadiene is monomerized at a temperature of 180-210 ° C. An inert high-boiling solvent is introduced into the lower section of the reactor (P-1) together with a polymerization inhibitor (3) to control the temperature of the monomerization process, reduce gum formation and prevent the process of dicyclopentadiene oligomerization. The mass ratio of dicyclopentadiene: solvent is from 40:60 to 90:10. The polymerization inhibitor is supplied in a concentration of from 0.01 to 0.5 wt.%. The average residence time of the contact solution in the reaction zone is 4-5 hours. The cyclopentadiene obtained from the lower part of the reactor (P-1) passes through mass transfer devices to separate it from heavy boiling impurities and solvent, after which high-purity cyclopentadiene (4) is removed from the upper part of the reactor (P -1) and sent to a dimerization reactor (P-2) operating at a temperature of 40-110 ° C, preferably 50-90 ° C, and a pressure of 0.3-1 MPa, preferably 0.4-0.8 MPa. The average residence time in the dimerization reactor (P-2) is 3-6 hours. The resulting dimerizate (5) is sent to a distillation column (K-2). From the top of the column (K-2) stream (6) containing unreacted cyclopentadiene and light impurities is withdrawn for further processing. The bottoms product (7) of the distillation column (K-2) is sent to the column (K-3) to separate heavy boiling impurities and dicyclopentadiene oligomers (9). The distillate (8) of the distillation column (K-3) is dicyclopentadiene with a basic substance content in the target stream of 98.5-100 wt.%. Fraction (10), consisting mainly of a high boiling solvent, impurities and unreacted dicyclopentadiene, is taken from the bottom of the monomerization reactor (P-1) and sent to the solvent regeneration and separation of unreacted dicyclopentadiene to a distillation column (K-1). The distillation column (K-1) operates at a pressure of 4-12 kPa and a bottom temperature of 115-180 ° C. From the top of the column (K-1), fraction (11) containing dicyclopentadiene was selected. A portion of the obtained fraction (11) in an amount of 50-95 wt.% Is returned by recycle (12) to the inlet of the reactor (P-1), the remaining part (13) is removed from the system for disposal. From the middle part of the distillation column (K-1), a high-boiling solvent (14) with a basic substance content of 90.0-99.9 wt.% Is selected and returned to the inlet of the reactor (P-1). The bottoms product (15) of the distillation column (K-1) contains heavy impurities.

The invention is illustrated by the following examples of specific performance.

Example 1. The initial raw material dicyclopentadiene-containing fraction (1) with a total concentration of dicyclopentadiene and cyclopentadiene of 95.8 wt.% Is mixed with the recycle stream (12) until the total concentration of dicyclopentadiene and cyclopentadiene is 82.4 wt.% And sent to the monomerization reactor (P- one). A polymerization inhibitor and an inert high boiling solvent (3) mixed with a recycled solvent recycling stream (14) are also fed there. The mass ratio of dicyclopentadiene: solvent is 70:30. The concentration of the polymerization inhibitor in the contact solution is maintained at 0.1 wt.%. As a high-boiling solvent dodecane with a concentration of the main substance of 99 wt.% Is used. As a polymerization inhibitor, para-tert-butylcatechol with a basic substance concentration of 99% by weight is used. In the reactor (P-1) at a temperature of 195 ° C and an average residence time of the contact solution in the reactor for 4 hours, dicyclopentadiene monomerizes. The resulting cyclopentadiene (4) after separation of heavy impurities on the mass transfer devices is discharged through the upper section of the reactor (P-1). The concentration of cyclopentadiene (4) is 99.90 wt.% With a yield of 98.8%. The bottom stream (10) from the monomerization reactor (P-1) is sent to a distillation column (K-1) to regenerate the solvent and separate the unreacted dicyclopentadiene. The distillation column (K-1) operates at a pressure of 4 kPa and a bottom temperature of the column of 115 ° C. From the top of the column (K-1), fraction (11) containing unreacted dicyclopentadiene is taken, part of which in the amount of 80 wt.% Is returned by recycle (12) to the inlet of the reactor (P-1), and the remaining part (13) is removed from the system to recycling. From the middle part of the column (K-1), dodecane (14) with a basic substance content of 99% by weight is taken and returned to the inlet of the reactor (P-1). A heavy residue (15), consisting mainly of dicyclopentadiene oligomers, is taken from the column cube (K-1) and sent for disposal. The cyclopentadiene (4) obtained at the monomerization stage is sent to the reactor (P-2), where at a temperature of 70 ° C, a pressure of 0.6 MPa and an average residence time of the contact solution in the reactor for 5 hours, dimerizate to form dicyclopentadiene (5). After purification from unreacted cyclopentadiene and light impurities (6) in the distillation column (K-2) and the formed dicyclopentadiene oligomers (9) in the column (K-3), high-purity dicyclopentadiene (8) with a basic substance concentration of 99.98 wt% is obtained. The output of dicyclopentadiene at the dimerization stage is 99.0%, selectivity 99.7%. The total yield of dicyclopentadiene is 97.82%.

Example 2. The raw material and high boiling solvent for the monomerization of dicyclopentadiene are similar to example 1.

The initial dicyclopentadiene-containing feed fraction (1) is mixed with the recycle stream (12) until the total concentration of dicyclopentadiene and cyclopentadiene reaches 82.6 wt.% And is sent to the monomerization reactor (P-1). A polymerization inhibitor and an inert high boiling solvent (3) mixed with a recycled solvent recycling stream (14) are also fed there. The mass ratio of dicyclopentadiene: solvent is 80:20. The concentration of the polymerization inhibitor in the contact solution is maintained at 0.1 wt.%. As a polymerization inhibitor, di-tert-butylphenol is used. In the reactor (P-1) at a temperature of 190 ° C and an average residence time of the contact solution in the reactor for 5 hours, dicyclopentadiene monomerizes. The resulting cyclopentadiene (4) after separation of heavy impurities on the mass transfer devices is discharged through the upper section of the reactor (P-1). The concentration of cyclopentadiene (4) is 99.83 wt.% With a yield of 98.5%. The bottom stream (10) from the monomerization reactor (P-1) is sent to a distillation column (K-1) to regenerate the solvent and separate the unreacted dicyclopentadiene. The distillation column (K-1) operates at a pressure of 8 kPa and a bottom temperature of 150 ° C. From the top of the column (K-1), fraction (11) containing unreacted dicyclopentadiene is taken, part of which in the amount of 80 wt.% Is returned by recycle (12) to the inlet of the reactor (P-1), and the remaining part (13) is removed from the system to recycling. From the middle part of the column (K-1), dodecane (14) with a basic substance content of 99% by weight is taken and returned to the inlet of the reactor (P-1). A heavy residue (15), consisting mainly of dicyclopentadiene oligomers, is taken from the column cube (K-1) and sent for disposal. The cyclopentadiene (4) obtained at the monomerization stage is sent to the reactor (P-2), where at a temperature of 50 ° C, a pressure of 0.4 MPa and an average residence time of the contact solution in the reactor for 6 hours, dimerizate to form dicyclopentadiene (5). After purification from unreacted cyclopentadiene and light impurities (6) in the distillation column (K-2) and the formed dicyclopentadiene oligomers (9) in the column (K-3), high-purity dicyclopentadiene (8) with a basic substance concentration of 99.99 wt% is obtained. The output of dicyclopentadiene at the dimerization stage is 99.0%, selectivity 99.5%. The total yield of dicyclopentadiene is 97.54%.

Example 3. A high boiling solvent and a polymerization inhibitor for dicyclopentadiene monomerization are similar to Example 1.

The initial raw material dicyclopentadiene-containing fraction (1) with a total concentration of dicyclopentadiene and cyclopentadiene of 94.1 wt.% Is mixed with the recycle stream (12) until the total concentration of dicyclopentadiene and cyclopentadiene is 76.9 wt.% And sent to the monomerization reactor (P-1). A polymerization inhibitor and an inert high boiling solvent (3) mixed with a recycled solvent recycling stream (14) are also fed there. The mass ratio of dicyclopentadiene: solvent is 70:30. The concentration of the polymerization inhibitor in the contact solution is maintained at 0.02 wt.%. In the reactor (P-1) at a temperature of 191 ° C and an average residence time of the contact solution in the reactor for 2 hours, dicyclopentadiene monomerizes. The resulting cyclopentadiene (4) after separation of heavy impurities on the mass transfer devices is discharged through the upper section of the reactor (P-1). The concentration of cyclopentadiene is 99.80 wt.% With a yield of 98.5%. The bottom stream (10) from the monomerization reactor (P-1) is sent to a distillation column (K-1) to regenerate the solvent and separate the unreacted dicyclopentadiene. The distillation column (K-1) operates at a pressure of 10 kPa and a bottom temperature of the column of 160 ° C. From the top of the column (K-1), fraction (11) containing unreacted dicyclopentadiene is taken, part of which in the amount of 80 wt.% Is returned by recycle (12) to the inlet of the reactor (P-1), and the remaining part (13) is removed from the system to recycling. From the middle part of the column (K-1), dodecane (14) with a basic substance content of 99% by weight is taken and returned to the inlet of the reactor (P-1). A heavy residue (15), consisting mainly of dicyclopentadiene oligomers, is taken from the column cube (K-1) and sent for disposal. The cyclopentadiene (4) obtained at the monomerization stage is sent to the reactor (P-2), where at a temperature of 80 ° C, a pressure of 0.7 MPa and an average residence time of the contact solution in the reactor for 4 hours, dimerizate to form dicyclopentadiene (5). After purification from unreacted cyclopentadiene and light impurities (6) in the distillation column (K-2) and the formed dicyclopentadiene oligomers (9) in the column (K-3), high-purity dicyclopentadiene (8) with a basic substance concentration of 99.97 wt.% Is obtained. The output of dicyclopentadiene at the dimerization stage is 98.0%, selectivity 99.5%. The total yield of dicyclopentadiene is 96.5%.

Example 4. A high boiling solvent for the monomerization of dicyclopentadiene is similar to example 1.

The initial raw material dicyclopentadiene-containing fraction (1) with a total concentration of dicyclopentadiene and cyclopentadiene of 83.4 wt.% Is mixed with the recycle stream (12) to achieve a total concentration of dicyclopentadiene and cyclopentadiene of 50.6 wt.% And sent to the monomerization reactor (P-1). A polymerization inhibitor and an inert high boiling solvent (3) mixed with a recycled solvent recycling stream (14) are also fed there. The mass ratio of dicyclopentadiene: solvent is 70:30. The concentration of the polymerization inhibitor in the contact solution is maintained at 0.1 wt.%. As a polymerization inhibitor, di-tert-butyl methylphenol is used. In the reactor (P-1) at a temperature of 192 ° C and an average residence time of the contact solution in the reactor for 4 hours, dicyclopentadiene monomerizes. The resulting cyclopentadiene (4) after separation of heavy impurities on the mass transfer devices is discharged through the upper section of the reactor (P-1). The concentration of cyclopentadiene (4) is 99.85 wt.% With a yield of 98.9%. The bottom stream (10) from the monomerization reactor (P-1) is sent to a distillation column (K-1) to regenerate the solvent and separate the unreacted dicyclopentadiene. The distillation column (K-1) operates at a pressure of 12 kPa and a bottom temperature of 180 ° C. From the top of the column (K-1), fraction (11) containing unreacted dicyclopentadiene is taken, part of which in the amount of 80 wt.% Is returned by recycle (12) to the inlet of the reactor (P-1), and the remaining part (13) is removed from the system to recycling. From the middle part of the column (K-1), dodecane (14) with a basic substance content of 99% by weight is taken and returned to the inlet of the reactor (P-1). A heavy residue (15), consisting mainly of dicyclopentadiene oligomers, is taken from the column cube (K-1), which is sent for recycling. The cyclopentadiene (4) obtained at the monomerization stage is sent to the reactor (P-2), where at a temperature of 90 ° C, a pressure of 0.8 MPa and an average residence time of the contact solution in the reactor for 3 hours, dimerizate to form dicyclopentadiene (5). After purification from unreacted cyclopentadiene and light impurities (6) in the distillation column (K-2) and the formed dicyclopentadiene oligomers (9) in the column (K-3), highly pure dicyclopentadiene (8) with a basic substance concentration of 99.97 wt% is obtained. The output of dicyclopentadiene at the dimerization stage is 98.5%, selectivity 99.5%. The total yield of dicyclopentadiene is 97.41%.

Example 5 (prototype). The raw materials and conditions for dicyclopentadiene monomerization are similar to Example 4. The monomerization process is carried out without solvent regeneration and separation of unreacted dicyclopentadiene in accordance with the traditional process scheme shown in FIG. 2. The concentration of the resulting cyclopentadiene (4) is 99.85 wt.% With a yield of 96.6%. The cyclopentadiene (4) obtained at the monomerization stage is sent to the reactor (P-2), where at a temperature of 50 ° C, a pressure of 0.4 MPa and an average residence time of the contact solution in the reactor for 6 hours, dimerizate to form dicyclopentadiene (5). After purification from unreacted cyclopentadiene and light impurities (6) in the distillation column (K-2) and the formed dicyclopentadiene oligomers (9) in the column (K-3), high-purity dicyclopentadiene (8) with a basic substance concentration of 99.97 wt.% Is obtained. The output of dicyclopentadiene at the dimerization stage is 98.5%, selectivity 99.5%. The total yield of dicyclopentadiene is 95.15%.

Example 6 (prototype). The raw materials and conditions for dicyclopentadiene monomerization are similar to Example 1. The monomerization process is carried out without solvent regeneration and separation of unreacted dicyclopentadiene in accordance with the traditional process scheme shown in FIG. 2. The concentration of the resulting cyclopentadiene (4) is 99.90 wt.% With a yield of 96.2%. The cyclopentadiene (4) obtained at the monomerization stage is sent to the reactor (P-2), where at a temperature of 50 ° C, a pressure of 0.4 MPa and an average residence time of the contact solution in the reactor for 6 hours, dimerizate to form dicyclopentadiene (5). After purification from unreacted cyclopentadiene and light impurities (6) in the distillation column (K-2) and the formed dicyclopentadiene oligomers (9) in the column (K-3), high-purity dicyclopentadiene (8) with a basic substance concentration of 99.98 wt% is obtained. The output of dicyclopentadiene at the dimerization stage is 99.0%, selectivity 99.5%. The total yield of dicyclopentadiene is 95.24%.

From examples 1-4 it is seen that the process of obtaining dicyclopentadiene according to the scheme, including the regeneration of a high-boiling solvent and separation of unreacted dicyclopentadiene at the stage of monomerization followed by their recycling, allows to increase at a stage of dicyclopentadiene 50.6-82.6 wt. monomerization conversion of dicyclopentadiene to 99.0-99.4% with a selectivity of 99.5%, which corresponds to a total yield of dicyclopentadiene of 96.5-97.8%. The concentration of dicyclopentadiene in the target product is 99.97-99.99 wt.%.

As can be seen from examples of specific performance 5 and 6, the process of obtaining dicyclopentadiene without regeneration at the stage of monomerization of an inert high boiling solvent and separating unreacted dicyclopentadiene does not provide a high yield of the target product, since at the stage of monomerization of dicyclopentadiene with a selectivity of 99.5%, the conversion of dicyclopentadiene is 96, 7%. The total yield of dicyclopentadiene in example 5 is 95.15%, in example 6 it is 95.24%, which is lower than in the process involving the regeneration of a high boiling agent and separation of unreacted dicyclopentadiene by 2.67% and 2.54%, respectively.

The combination of features of the claimed object allows to obtain from a dicyclopentadiene-containing fraction with a concentration of 50.6-82.6 wt.% Dicyclopentadiene with a concentration of 99.98 wt.%, Which is used to obtain polydicyclopentadiene, ethylene propylene diene rubbers, petroleum resins, adamantane, ethylidene norbornene and other valuable products petrochemical synthesis. The inventive method allows to increase the total yield of dicyclopentadiene in the target stream to 97.8% by increasing the purity of cyclopentadiene to a concentration of 99.9 wt.% And the conversion of dicyclopentadiene to 99.4% at the stage of monomerization.

Table 1 The parameters of the process of obtaining dicyclopentadiene Example No. The concentration of DCPD and CPD in the initial fraction (1), wt.% The concentration of DCPD and CPD in raw materials (2) at the inlet to the reactor R-1, wt.% Mass ratio of DCPD: solvent at the inlet to the reactor R-1 The concentration of the inhibitor at the entrance to the reactor R-1, wt.% Temperature in the lower section of the R-1 reactor, ° C The average residence time in the reactor R-1, h The temperature of the bottom of the column K-1, ° C The pressure in the column K-1, kPa The output of the CPU,% one 95.8 82,4 70:30 0.1 195 four 115 four 98.8 2 95.8 82.6 80:20 0.1 190 5 150 8 98.5 3 94.1 76.9 70:30 0.02 191 2 160 10 98.5 four 83,4 50.6 70:30 0.1 192 four 180 12 98.9 5 83,4 - 70:30 0.1 192 four - - 96.6 6 95.8 - 70:30 0.1 194 four - - 96.2 Example No. Selectivity at the stage of monomerization,% The conversion at the stage of monomerization,% The pressure in the reactor R-2, MPa The temperature in the reactor R-2, ° C The average residence time in the reactor R-2, h The output of DCPD in the process of dimerization,% Selectivity at the stage of dimerization,% The conversion at the stage of dimerization,% The output of the DCPD for the process,% one 99.5 99.3 0.6 70 5 99.0 99.7 99.3 97.82 2 99.5 99 0.4 fifty 6 99.0 99.5 99.5 97.54 3 99.5 99 0.7 80 four 98.0 99.5 98.5 96.50 four 99.5 99,4 0.8 90 3 98.5 99.5 99.0 97.41 5 99.5 97.1 0.4 fifty 6 98.5 99.5 99.0 95.15 6 99.5 96.7 0.4 fifty 6 99.0 99.5 99.5 95.24

table 2  The compositions of the incoming, outgoing and intermediate streams of the process of obtaining dicyclopentadiene Example No. The composition of the incoming flows, wt.% one 3 DCPD + CPD isoprene + piperylene co-dimers oligomers solvent impurities one 95.80 0.00 4.20 0.00 99.00 1.00 2 95.80 0.00 4.20 0.00 99.00 1.00 3 94.10 0.00 5.90 0.00 99.00 1.00 four 83.40 0.00 16.60 0.00 99.00 1.00 5 83.40 0.00 16.60 0.00 99.00 1.00 6 95.80 0.00 4.20 0.00 99.00 1.00 Example No. The compositions of the outgoing and intermediate flows, wt.% four 5 6 8 JRC isoprene + piperylene JRC DCPD co-dimers oligomers JRC isoprene + piperylene DCPD co-dimers one 99.90 0.10 0.74 98.90 0.02 0.25 88.93 11.07 99.98 0.02 2 99.83 0.17 0.49 98.83 0.01 0.50 75.12 24.88 99,99 0.01 3 99.80 0.20 1.48 97.80 0,03 0.50 88.94 11.06 99.97 0,03 four 99.85 0.15 0.99 98.35 0,03 0.50 87.81 12.19 99.97 0,03 5 99.85 0.15 0.99 98.35 0,03 0.50 87.83 12.17 99.97 0,03 6 99.90 0.10 0.49 98.90 0.02 0.50 84.22 15.78 99.98 0.02 Example No. The compositions of the outgoing and intermediate flows, wt.% 10 fifteen DCPD co-dimers solvent oligomers DCPD co-dimers solvent oligomers one 4.30 27.60 67.40 0.60 0.00 0.00 4.90 95.10 2 8.10 37.40 53.60 0.90 0.00 0.00 2.90 97.10 3 5.30 52.50 61.10 0.50 0.00 0.00 5.30 94.70 four 1,60 52.50 45.60 0.30 0.00 0.00 7.80 92.20 5 3.90 26.70 68.70 0.70 - - - - 6 6.20 8.30 84.50 0.90 - - - -

Claims (2)

1. A method for producing dicyclopentadiene, comprising monomerizing a dicyclopentadiene-containing fraction in the presence of an inert high-boiling solvent and a polymerization inhibitor to obtain cyclopentadiene, dimerization of cyclopentadiene and rectification of concentrated dicyclopentadiene, characterized in that the starting raw material dicyclopentadiene-containing dicyclopentadiene-containing 90% mass fraction. with the recycle stream until the total concentration of dicyclopentadiene and iclopentadiene 50-97 wt.%, monomerization is carried out in the presence of dodecane, introduced in a mass ratio of dicyclopentadiene: solvent from 40:60 to 90:10, and alkylphenol, introduced in a concentration of 0.01-0.5 wt.%, until conversion is achieved dicyclopentadiene 99.4%, carry out the regeneration of a high-boiling solvent, separating unreacted dicyclopentadiene at a temperature of 115-180 ° C and a pressure of 4-12 kPa and their subsequent recycling. 2. The method according to claim 1, characterized in that para-tert-butylcatechol, di-tert-butylphenol or di-tert-butyl methylphenol is used as alkylphenol.

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