CN113651670A - Method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization - Google Patents
Method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization Download PDFInfo
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- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
Abstract
The invention discloses a method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization, which belongs to the technical field of synthesis of tetrahydrodicyclopentadiene and comprises the following steps: hydrogenation: uses dicyclopentadiene as raw material, adopts two-stage fixed bed reactor and one-stage hydrogenation catalyst Ni/Al2O3A catalyst; two-stage hydrogenation catalyst Mo/Al2O3A catalyst; and (3) rectifying a hydrogenation product: firstly, the materials pass through a heavy component removal tower, the materials at the top of the heavy component removal tower enter a light component removal tower, and high-purity bridge type tetrahydrodicyclopentadiene is extracted from the tower kettle of the light component removal tower; and (3) isomerization reaction: by usingBridge type tetrahydro dicyclopentadiene as raw material and anhydrous AlCl3Dichloroethane is used as a catalyst and is used as a solvent, and an isomerization reaction is carried out in a stirring kettle. The invention adopts a plurality of raw materials for hydrogenation, adopts a sulfur-resistant and nitrogen-resistant two-stage catalyst to replace a conventional hydrogenation catalyst, optimizes reaction conditions, finally improves the primary conversion rate to more than 98.5 percent and the selectivity to more than 99.4 percent, realizes industrialized large-scale production, reduces production cost and simplifies process routes.
Description
Technical Field
The invention relates to the technical field of synthesis of tetrahydrodicyclopentadiene, in particular to a method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization.
Background
As a key component of liquid propellant or fuel, the high-density fuel has great significance for aircrafts, missiles, rockets and other aerospace vehicles with limited volume. The novel high-density hydrocarbon fuel hanging type tetrahydrodicyclopentadiene has excellent comprehensive performance, has the advantages of high energy, high density, low freezing point and the like, and becomes an ideal high-density hydrocarbon fuel for rockets, high-speed aircrafts and cruise missiles. Generally, exo-tetrahydrodicyclopentadiene is accomplished via both hydrogenation and isomerization. Firstly, dicyclopentadiene is hydrogenated and converted into bridge type tetrahydro dicyclopentadiene, and then bridge type tetrahydro dicyclo is used as a raw material to generate hanging type tetrahydro dicyclopentadiene through isomerization in the presence of a catalyst; after the reaction, the catalyst is removed, and the high-purity hanging type tetrahydrodicyclopentadiene is obtained by rectification.
In the prior art, most of raw materials for hydrogenation reaction adopt single high-purity dicyclopentadiene as the raw material, because the content of nitrogen and sulfur in the crude dicyclopentadiene is higher, the hydrogenation catalyst is deactivated, and impurities in the crude dicyclopentadiene influence the subsequent isomerization reaction. At the present stage, no large-scale device for industrially and continuously producing the bridge type tetrahydrochysene dicyclopentadiene exists, and the main reason is that the bridge type tetrahydrochysene dicyclopentadiene is solid at normal temperature, and a reactor, a pipeline and a rectifying tower are easy to block. The kettle type reactor is adopted in the current-stage industrial production, and the method has the characteristics of low reaction efficiency, low safety coefficient, unstable conversion rate, complex subsequent process after the reaction is finished and the like. The isomerization reaction is carried out at a temperature of over 75 ℃ without adding a solvent, which is determined by the melting point of the bridged tetrahydrodicyclopentadiene, and the selectivity of the isomerization reaction is reduced due to the over-high temperature. The primary conversion rate and selectivity of the existing large-scale isomerization reaction bridge type tetrahydrodicyclopentadiene are respectively below 98 percent and 98 percent.
The patent with the publication number of CN102924216B discloses a method for synthesizing exo-tetrahydrodicyclopentadiene. The method comprises the following steps: (1) after the hydrogenation catalyst is subjected to reduction activation treatment, catalyzing dicyclopentadiene to perform primary hydrogenation reaction in a hydrogen atmosphere to obtain a primary hydrogenation product; (2) under the hydrogen atmosphere, carrying out a secondary hydrogenation reaction on the primary hydrogenation product under the catalysis of the hydrogenation catalyst subjected to the reduction activation treatment to obtain a secondary hydrogenation product; (3) and (3) carrying out isomerization reaction on the secondary hydrogenation product under the catalysis of anhydrous AlCl3 to obtain the exo-tetrahydrodicyclopentadiene. The primary hydrogenation temperature of the process needs to be above 120 ℃, and the secondary hydrogenation temperature needs to be above 190 ℃, so that higher yield can be obtained.
The patent with the publication number of CN101215218B discloses a preparation method of exo-tetrahydrodicyclopentadiene, which aims to solve the problem that hydrogenation catalyst in the prior art is difficult to recover. The invention takes dicyclopentadiene and hydrogen as raw materials, and comprises the following steps: A. in the presence of an alcohol solvent and a hydrogenation catalyst, dicyclopentadiene and hydrogen are subjected to hydrogenation reaction in a high-pressure reaction kettle to generate bridge type tetrahydro dicyclopentadiene; B. adding the hanging type tetrahydro dicyclopentadiene into the reaction product obtained in the step A, and filtering and separating the hydrogenation catalyst; C. b, carrying out reduced pressure rectification on the filtrate obtained in the step B, wherein the tower top component is an alcohol solvent, and the tower bottom component is a mixture of hanging type tetrahydrodicyclopentadiene and bridge type tetrahydrodicyclopentadiene; D. c, reacting the kettle component obtained in the step C in the presence of an isomerization catalyst to generate hanging type tetrahydro dicyclopentadiene; E. and D, carrying out reduced pressure rectification on the isomerization reaction product obtained in the step D to obtain a hanging type tetrahydro dicyclopentadiene product. The method has complex process and the obtained yield is only about 90 percent.
Disclosure of Invention
Aiming at the problems, the inventor obtains the method for preparing the exo-tetrahydrodicyclopentadiene through hydrogenation and isomerization by repeated experiments, wherein the hydrogenation comprises two parts, namely hydrogenation and isomerization, dicyclopentadiene is used as a raw material, dicyclopentadiene is converted into bridge-type tetrahydrodicyclopentadiene through two-stage hydrogenation reaction, and the exo-type tetrahydrodicyclopentadiene is isomerized from the bridge-type tetrahydrodicyclopentadiene into the exo-type tetrahydrodicyclopentadiene through aluminum trichloride.
A method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization comprises the following steps:
s1: hydrogenation: uses dicyclopentadiene as raw material, adopts two-stage fixed bed reactor for hydrogenation, and uses one-stage hydrogenation catalyst Ni/Al2O3A catalyst; two-stage hydrogenation catalyst Mo/Al2O3A catalyst;
s2: and (3) rectifying a hydrogenation product: after two-stage hydrogenation reaction, firstly passing through a heavy component removal tower, feeding the material at the top of the heavy component removal tower into a light component removal tower, and extracting high-purity bridge type tetrahydrodicyclopentadiene at the bottom of the light component removal tower;
s3: and (3) isomerization reaction: the bridge type tetrahydro dicyclopentadiene after hydrogenation rectification is adopted as a raw material, and anhydrous AlCl is adopted3Dichloroethane is used as a catalyst and is used as a solvent, and an isomerization reaction is carried out in a stirring kettle.
Further, in the step S1, the first-stage hydrogenation is carried out, the inlet temperature is 60-90 ℃, the bed temperature is 70-90 ℃, and the space velocity is 0.4-0.65 hr-1The hydrogen-oil ratio is 700-1000.
Further, in the step S1, the two-stage hydrogenation is carried out, wherein the inlet temperature is 150-170 ℃, the bed temperature rise is 160-180 ℃, and the space velocity is 0.7-0.9 hr-1The hydrogen-oil ratio is 400 to 600.
Further, in step S2, the de-heavy column: the pressure is 0.1 +/-0.05 Mpa, the temperature at the top of the tower is 184 +/-2 ℃, the reflux ratio is 1-1.2, the yield of the tower kettle is 100-200 kg/h, the temperature of the tower kettle is 222 +/-2 ℃, the yield at the top of the tower is 1300-1400 kg/h, the number of tower plates is 35, and the feeding temperature is 150-155 ℃.
Further, in step S2, the de-heavy column: the pressure is 0.1 +/-0.05 Mpa, the temperature at the top of the tower is 143 +/-2 ℃, the reflux ratio is 1.5-2.5, the yield of the tower kettle is 900-1000 kg/h, the temperature of the tower kettle is 210 +/-2 ℃, the yield at the top of the tower is 500-600 kg/h, the number of tower plates is 30, and the feeding temperature is 110-120 ℃.
Further, in the step S3, the mass ratio of each component is, bridge tetrahydrodicyclopentadiene: ethylene dichloride: AlCl3=100:10:0.8～1。
Further, in the step S3, the temperature is 15-40 ℃, the pressure is normal, the reaction time is 20-45 min, and the stirring speed is 400-700 rpm.
Furthermore, the dicyclopentadiene is two or more of industrial crude dicyclopentadiene, industrial refined dicyclopentadiene, dicyclopentadiene produced by cracking carbon nine and dicyclopentadiene produced by cracking gasoline.
The synthesis of the hanging type tetrahydro dicyclopentadiene takes dicyclopentadiene as a raw material and is obtained by hydrogenation, isomerization, separation and purification. In order to search for a catalyst with high hydrogenation rate, high efficiency and long service life, researchers continuously explore and make great development. The efficiency is improved, the cost is saved, and the research and optimization work of the hydrogenation process is also carried out all the time. For example, the synthesis and application progress of yellow phoenix and hanging tetrahydrodicyclopentadiene [ J ] chemical and medical engineering, 2018(01):19-22, and the research progress of dicyclopentadiene hydrogenation catalysts and tetrahydrodicyclopentadiene isomerization catalysts is intensively analyzed. Therefore, researchers generally believe that in order to improve conversion and reduce costs, a continuous hydrogenation process is possible by selecting a catalyst with high catalytic efficiency and long service life. The patent with the publication number of CN107417485B discloses a method for directly preparing exo-tetrahydrodicyclopentadiene from dicyclopentadiene, belonging to the technical field of aviation fuel preparation. The main component dicyclopentadiene of petroleum processing by-product C5 is used as raw material, and the bifunctional catalyst composed of layered double hydroxide and inorganic solid acid is used to realize the coupling of dicyclopentadiene hydrogenation reaction and isomerization reaction, and the hanging tetrahydrodicyclopentadiene is continuously prepared by one-step method, but the conversion rate is not too high. Therefore, in order to reduce the cost, researchers are keen to research catalysts for improving the catalytic efficiency and simplifying the process, but neglect the influence of the raw materials on the cost. It is generally considered that the higher the purity of the raw material, the higher the yield obtained, but the more expensive the raw material with the higher purity. Therefore, it is required to develop a method capable of obtaining exo-tetrahydrodicyclopentadiene in high yield by reducing the cost of raw materials.
The invention has the beneficial effects that:
first, this application has adopted sulphur-tolerant, two-stage catalyst of nitrogen to replace conventional hydrogenation catalyst, because the load catalyst is sulphur-tolerant, nitrogen, and the activity is difficult to reduce, so can adopt multiple raw materials to carry out the hydrogenation reaction, increased the pluralism of raw materials.
The method adopts various raw materials for hydrogenation, and has components except the bridge type tetrahydrodicyclopentadiene in the reaction and subsequent rectification processes, so that the bridge type tetrahydropentadiene is dissolved in the bridge type tetrahydrodicyclopentadiene, the blockage condition in the process can not be caused, the industrial large-scale production is realized, the production cost is reduced, the safety risk is reduced, the process route is simplified, and the conversion rate stability is improved.
And thirdly, dichloroethane is used as a solvent in the isomerization reaction, so that the contact area of the catalyst and the bridge type tetrahydro dicyclopentadiene is increased, the reaction temperature is reduced, and the conversion rate is increased.
Fourthly, reaction condition optimization: the proportion of catalyst, hydrogenation product and solvent, reaction pressure, reaction temperature and reaction time are screened by a controlled variable method, so that the reaction conversion rate and selectivity are greatly improved, the one-time conversion rate is improved to more than 98.5%, and the selectivity is improved to more than 99.4%.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
A method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization comprises the following steps:
s1: hydrogenation: uses dicyclopentadiene as raw material, adopts two-stage fixed bed reactor for hydrogenation, and uses one-stage hydrogenation catalyst Ni/Al2O3Catalyst, inlet temperature60-90 ℃, the temperature rise of the bed layer is 70-90 ℃, and the space velocity is 0.4-0.65 hr-1The hydrogen-oil ratio is 700-1000; two-stage hydrogenation catalyst Mo/Al2O3The catalyst has an inlet temperature of 150-170 ℃, a bed temperature rise of 160-180 ℃ and a space velocity of 0.7-0.9 hr-1The hydrogen-oil ratio is 400-600; the hydrogenation raw material adopts two or more of industrial crude dicyclopentadiene, industrial refined dicyclopentadiene, dicyclopentadiene produced by cracking carbon nine and dicyclopentadiene produced by cracking gasoline;
s2: and (3) rectifying a hydrogenation product: rectifying the second-stage reaction product to purify the bridge type tetrahydrodicyclopentadiene, wherein the second-stage reaction product firstly passes through a heavy component removal tower, the material at the top of the heavy component removal tower enters a light component removal tower, and high-purity bridge type tetrahydrodicyclopentadiene is extracted from the tower kettle of the light component removal tower; the rectification column operating parameters are shown in table 1 below;
TABLE 1
S3: and (3) isomerization reaction: the bridge type tetrahydro dicyclopentadiene after hydrogenation rectification is adopted as a raw material, and anhydrous AlCl is adopted3As catalyst, dichloroethane as solvent, carrying out isomerization reaction in a stirred tank; the mass ratio of each component is as follows: ethylene dichloride: AlCl3=100:10: 0.8-1; the temperature is 15-40 ℃, the pressure is normal, the reaction time is 20-45 min, and the stirring speed is 400-700 rpm.
Examples 1 to 20
In embodiments 1 to 4, the hydrogenation raw material adopts industrial crude dicyclopentadiene and industrial refined dicyclopentadiene, and the mass ratio of the industrial crude dicyclopentadiene to the industrial refined dicyclopentadiene is as follows: industrial crude dicyclopentadiene: industrial refined dicyclopentadiene =2: 1; in embodiments 5 to 8, the hydrogenation raw material employs industrial refined dicyclopentadiene and dicyclopentadiene produced by cracking carbon nine, and the mass ratio of the industrial refined dicyclopentadiene to the dicyclopentadiene is as follows: industrial refined dicyclopentadiene: dicyclopentadiene produced by cracking carbon nine =1: 3; in examples 9 to 12, the hydrogenation raw material used was industrial raw dicyclopentadiene and dicyclopentadiene produced from pyrolysis gasoline, and the mass ratio of the industrial raw dicyclopentadiene to the dicyclopentadiene produced from pyrolysis gasoline was: industrial crude dicyclopentadiene: dicyclopentadiene produced from pyrolysis gasoline =1: 2; in examples 13 to 16, the hydrogenation raw material used was industrial refined dicyclopentadiene, industrial crude dicyclopentadiene, and dicyclopentadiene produced from pyrolysis gasoline, and the mass ratio of the industrial refined dicyclopentadiene to the industrial crude dicyclopentadiene was: industrial crude dicyclopentadiene: dicyclopentadiene produced from pyrolysis gasoline =1:1.5: 2. In examples 17 to 20, the hydrogenation raw material used was industrial raw dicyclopentadiene, dicyclopentadiene produced by cracking carbon nine, and dicyclopentadiene produced by cracking gasoline, and the mass ratio of the industrial raw dicyclopentadiene to the dicyclopentadiene produced by cracking gasoline was: cracking dicyclopentadiene produced from carbon nine: dicyclopentadiene produced from pyrolysis gasoline =1:2: 3.
The hydrogenation stage, each parameter is shown in table 2, the isomerization reaction stage, each component content and parameter is shown in table 3, the detection result is shown in table 4, wherein the first conversion rate is the conversion rate of the high-purity bridge type tetrahydrodicyclopentadiene, and the selectivity is the yield of the obtained exo type tetrahydrodicyclopentadiene.
TABLE 2
TABLE 3
| Examples | Bridged tetrahydrodicyclopentadiene: ethylene dichloride: AlCl3 | Temperature (. degree.C.) | Reaction time (min) | Stirring Rate (rpm) |
| 1 | 100:10:0.8 | 15 | 20 | 700 |
| 2 | 100:10:0.9 | 15 | 25 | 650 |
| 3 | 100:10:1 | 18 | 30 | 600 |
| 4 | 100:10:0.8 | 18 | 35 | 550 |
| 5 | 100:10:0.9 | 20 | 40 | 500 |
| 6 | 100:10:1 | 20 | 20 | 650 |
| 7 | 100:10:0.8 | 25 | 25 | 550 |
| 8 | 100:10:0.9 | 25 | 30 | 500 |
| 9 | 100:10:1 | 28 | 35 | 450 |
| 10 | 100:10:0.8 | 28 | 40 | 400 |
| 11 | 100:10:0.9 | 30 | 20 | 700 |
| 12 | 100:10:1 | 30 | 25 | 650 |
| 13 | 100:10:0.9 | 32 | 30 | 600 |
| 14 | 100:10:0.8 | 32 | 35 | 550 |
| 15 | 100:10:0.9 | 35 | 40 | 400 |
| 16 | 100:10:1 | 35 | 20 | 650 |
| 17 | 100:10:1 | 38 | 25 | 650 |
| 18 | 100:10:0.9 | 38 | 30 | 600 |
| 19 | 100:10:0.8 | 40 | 35 | 600 |
| 20 | 100:10:0.9 | 40 | 40 | 550 |
TABLE 4
| Examples | First conversion (%) | Selectivity (%) |
| 1 | 98.8 | 99.4 |
| 2 | 98.8 | 99.4 |
| 3 | 98.9 | 99.5 |
| 4 | 98.8 | 99.4 |
| 5 | 98.8 | 99.4 |
| 6 | 98.8 | 99.5 |
| 7 | 98.9 | 99.5 |
| 8 | 98.9 | 99.6 |
| 9 | 98.5 | 99.7 |
| 10 | 98.6 | 99.6 |
| 11 | 98.6 | 99.7 |
| 12 | 98.6 | 99.8 |
| 13 | 98.7 | 99.7 |
| 14 | 98.8 | 99.7 |
| 15 | 98.7 | 99.6 |
| 16 | 98.7 | 99.6 |
| 17 | 98.6 | 99.5 |
| 18 | 98.6 | 99.6 |
| 19 | 98.7 | 99.4 |
| 20 | 98.6 | 99.5 |
Example 21
A method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization comprises the following steps:
s1: hydrogenation: uses dicyclopentadiene as raw material, adopts two-stage fixed bed reactor for hydrogenation, and uses one-stage hydrogenation catalyst Ni/Al2O3The catalyst has inlet temperature of 70 deg.C, bed temperature rise of 70 deg.C, and space velocity of 0.5hr-1The hydrogen-oil ratio is 800; two-stage hydrogenation catalyst Mo/Al2O3The catalyst inlet temperature is 160 deg.C, bed temperature rise is 160 deg.C, and space velocity is 0.8hr-1The hydrogen-oil ratio is 500; the hydrogenation raw materials adopt industrial crude dicyclopentadiene, industrial fine dicyclopentadiene, dicyclopentadiene produced by cracking carbon nine and dicyclopentadiene produced by cracking gasoline, and the mass ratio of the industrial crude dicyclopentadiene to the industrial fine dicyclopentadiene is as follows: industrial refined dicyclopentadiene: cracking dicyclopentadiene produced from carbon nine: dicyclopentadiene produced from pyrolysis gasoline =1:0.3:3: 2;
s2: and (3) rectifying a hydrogenation product: rectifying and purifying the bridge type tetrahydrodicyclopentadiene by using a second-stage reaction product, wherein the second-stage reaction product firstly passes through a heavy component removal tower, materials at the top of the heavy component removal tower enter a light component removal tower, high-purity bridge type tetrahydrodicyclopentadiene is extracted from the tower kettle of the light component removal tower, and the operating parameters of the rectifying tower are shown in table 1; the primary conversion rate was found to be 98.8%;
s3: and (3) isomerization reaction: the bridge type tetrahydro dicyclopentadiene after hydrogenation rectification is adopted as a raw material, and anhydrous AlCl is adopted3As catalyst, dichloroethane as solvent, carrying out isomerization reaction in a stirred tank; the mass ratio of each component is as follows: ethylene dichloride: AlCl3=100:10: 1; the temperature was 30 ℃, the pressure was normal, the reaction time was 30min, the stirring rate was 500rpm, and the selectivity was found to be 99.6%.
Example 22
The present embodiment is technically different from embodiment 21 in that: in the embodiment, the hydrogenation raw material adopts industrial crude dicyclopentadiene, industrial fine dicyclopentadiene, dicyclopentadiene produced by cracking carbon nine and dicyclopentadiene produced by cracking gasoline, and the mass ratio of the industrial crude dicyclopentadiene to the industrial fine dicyclopentadiene is as follows: industrial refined dicyclopentadiene: cracking dicyclopentadiene produced from carbon nine: the pyrolysis gasoline produced dicyclopentadiene =1:0.3:2:2, with a primary conversion of 98.7% and a selectivity of 99.6% being measured.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A method for preparing exo-tetrahydrodicyclopentadiene through dicyclopentadiene hydrogenation isomerization is characterized in that: comprises the following steps:
s1: hydrogenation: uses dicyclopentadiene as raw material, adopts two-stage fixed bed reactor for hydrogenation, and uses one-stage hydrogenation catalyst Ni/Al2O3A catalyst; two-stage hydrogenation catalyst Mo/Al2O3A catalyst;
s2: and (3) rectifying a hydrogenation product: after two-stage hydrogenation reaction, firstly passing through a heavy component removal tower, feeding the material at the top of the heavy component removal tower into a light component removal tower, and extracting high-purity bridge type tetrahydrodicyclopentadiene at the bottom of the light component removal tower;
s3: and (3) isomerization reaction: the bridge type tetrahydro dicyclopentadiene after hydrogenation rectification is adopted as a raw material, and anhydrous AlCl is adopted3Dichloroethane is used as a catalyst and is used as a solvent, and an isomerization reaction is carried out in a stirring kettle.
2. The method for isomerizing exo-tetrahydrodicyclopentadiene by dicyclopentadiene hydrogenation as claimed in claim 1, wherein: in the step S1, the first-stage hydrogenation is carried out, the inlet temperature is 60-90 ℃, the bed temperature rise is 70-90 ℃, and the space velocity is 0.4-0.65 hr-1The hydrogen-oil ratio is 700-1000.
3. The method for isomerizing exo-tetrahydrodicyclopentadiene by dicyclopentadiene hydrogenation as claimed in claim 2, wherein: in the step S1, the two-stage hydrogenation is carried out, the inlet temperature is 150-170 ℃, the bed temperature rise is 160-180 ℃, and the space velocity is 0.7-0.9 hr-1The hydrogen-oil ratio is 400 to 600.
4. The method for isomerizing exo-tetrahydrodicyclopentadiene by dicyclopentadiene hydrogenation as claimed in claim 3, wherein: in step S2, the de-heavy column: the pressure is 0.1 +/-0.05 Mpa, the temperature at the top of the tower is 184 +/-2 ℃, the reflux ratio is 1-1.2, the yield of the tower kettle is 100-200 kg/h, the temperature of the tower kettle is 222 +/-2 ℃, the yield at the top of the tower is 1300-1400 kg/h, the number of tower plates is 35, and the feeding temperature is 150-155 ℃.
5. The method for isomerizing exo-tetrahydrodicyclopentadiene by dicyclopentadiene hydrogenation as claimed in claim 4, wherein: in step S2, the de-heavy column: the pressure is 0.1 +/-0.05 Mpa, the temperature at the top of the tower is 143 +/-2 ℃, the reflux ratio is 1.5-2.5, the yield of the tower kettle is 900-1000 kg/h, the temperature of the tower kettle is 210 +/-2 ℃, the yield at the top of the tower is 500-600 kg/h, the number of tower plates is 30, and the feeding temperature is 110-120 ℃.
6. Such as rightThe method for preparing exo-tetrahydrodicyclopentadiene by dicyclopentadiene hydrogenation isomerization, which is characterized in that: in the step S3, the mass ratio of each component is, bridge tetrahydrodicyclopentadiene: ethylene dichloride: AlCl3=100:10:0.8～1。
7. The method for isomerizing exo-tetrahydrodicyclopentadiene by dicyclopentadiene hydrogenation as claimed in claim 6, wherein: in the step S3, the temperature is 15-40 ℃, the pressure is normal, the reaction time is 20-45 min, and the stirring speed is 400-700 rpm.
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| CN114805008A (en) * | 2022-05-14 | 2022-07-29 | 濮阳市联众兴业化工有限公司 | Method for preparing bridge type tetrahydro dicyclopentadiene by low-temperature hydrogenation of cracking carbon nine |
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