CN101260018A - Method for synthesizing exo-tetrahydrocyclopentadiene - Google Patents
Method for synthesizing exo-tetrahydrocyclopentadiene Download PDFInfo
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- CN101260018A CN101260018A CNA2008100939584A CN200810093958A CN101260018A CN 101260018 A CN101260018 A CN 101260018A CN A2008100939584 A CNA2008100939584 A CN A2008100939584A CN 200810093958 A CN200810093958 A CN 200810093958A CN 101260018 A CN101260018 A CN 101260018A
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- dicyclopentadiene
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Abstract
The invention discloses a synthesis method of hanging type tetrahydro dicyclopentadiene, and aims to solve the problems of long operation flow and high equipment investment during synthesizing hanging type tetrahydro dicyclopentadiene. The synthesis method, which adopts bridge type tetrahydro dicyclopentadiene and hanging type tetrahydro dicyclopentadiene conglomeration as raw material, carries out isomerization reaction to synthesize hanging type tetrahydro dicyclopentadiene under the action of isomerization catalyst inside a catalytic rectification tower; moreover, a reaction section is used to carry out isomerization reaction, while a rectification section is used to remove unreacted bridge type tetrahydro dicyclopentadiene and refined hanging type tetrahydro dicyclopentadiene products; in addition, the adopted catalytic rectification tower comprises an upper tower and a lower tower which are connected in series with the lower tower consisting of the reaction section and a tower kettle and the upper tower consisting of the rectification section. The synthesis method is mainly used in the synthesis of hanging type tetrahydro dicyclopentadiene.
Description
Technical field
The present invention relates to the synthetic method of a kind of hanging type tetrahydrochysene dicyclopentadiene (exo-THDCPD).
Technical background
Hanging type tetrahydrochysene dicyclopentadiene (THDCPD) is important chemical intermediate, can be used for high-energy synthetic fuel and polymkeric substance.
Usually in the hanging type tetrahydrochysene dicyclopentadiene synthetic method, generally adopting bridge-type tetrahydro-dicyclopentadiene is raw material, carries out isomerization reaction in the presence of catalyzer, after reaction product is removed catalyzer, steaming desolventizes, and by rectifying, obtains the hanging type tetrahydrochysene dicyclopentadiene product.
Catalytic rectification process is a kind of novel technique that catalyzed reaction and product rectifying are combined and carries out simultaneously.Catalyzer is contained in the stage casing of tower, and rectifying section and stripping section can be equipped with in the tower upper and lower, also rectifying section or stripping section can only be housed.Because reactant gone out by fractionation at any time, help improving reaction conversion ratio, and will react generation heat and be directly used in rectifying, thereby conserve energy.Catalytic rectification process has been used to produce technological processs such as methyl tertiary butyl ether, C4 dimerizing olefins.
US4086284 discloses a kind of synthetic method of hanging type tetrahydrochysene dicyclopentadiene, it is raw material that this method adopts bridge-type tetrahydro-dicyclopentadiene, methylene dichloride is a reaction solvent, aluminum chloride is a catalyzer, through the isomerization reaction synthetizing wall type tetrahydro-dicyclopentadiene, after reaction finishes, obtain hanging type tetrahydrochysene dicyclopentadiene by separation aluminum trichloride catalyst, solvent recuperation, product rectifying.Isomerization reaction in this patent, solvent recuperation, product rectifying are carried out in unit independently respectively, have caused the problem that operating process is long, facility investment is high.
By retrieval, do not retrieve the data of the catalytic distillation synthetic method of hanging type tetrahydrochysene dicyclopentadiene.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that exists in the background technology, provides that a kind of operating process is short, facility investment is low, isomerization reaction, product rectification cell is concentrated on the synthetic method of the hanging type tetrahydrochysene dicyclopentadiene in the catalytic rectifying tower.
The invention provides a kind of synthetic method of hanging type tetrahydrochysene dicyclopentadiene, be characterized in: with bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture is raw material, carrying out the isomerization reaction synthetizing wall type tetrahydro-dicyclopentadiene in the presence of isomerization catalyst is to carry out in catalytic rectifying tower, conversion zone carries out isomerization reaction, rectifying section removes unreacted bridge-type tetrahydro-dicyclopentadiene and refining hanging type tetrahydrochysene dicyclopentadiene, the bridge-type tetrahydro-dicyclopentadiene that removes is back to catalytic distillation Tata still, the hanging type tetrahydrochysene dicyclopentadiene product is from the extraction of catalytic distillation column overhead, and isomerization catalyst is cerium modified USY type molecular sieve.
Catalytic rectifying tower used in the present invention is placed in-line Shang Ta and Xia Ta, following tower is made up of conversion zone and tower still, last tower is a rectifying section, carry out isomerization reaction at following tower conversion zone, remove unreacted bridge-type tetrahydro-dicyclopentadiene and refining hanging type tetrahydrochysene dicyclopentadiene at Shang Ta, the bridge-type tetrahydro-dicyclopentadiene that removes is back to catalytic distillation Tata still, the column overhead extraction from the catalytic rectifying tower of hanging type tetrahydrochysene dicyclopentadiene product.
Among the present invention, the temperature of reaction of catalytic rectifying tower conversion zone is to carry out in 150 ℃～200 ℃ scopes of bubble point temperature of bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture.
Among the present invention, can be filled with the fraction elements of heat, matter transmission in placed in-line catalytic distillation Shang Ta and the following Tata.The working pressure of tower is 0.55MPa～1.05MPa on the catalytic distillation, and the working pressure of tower is 0.60MPa～1.10MPa under the catalytic distillation.
Raw material used in the present invention is dicyclopentadiene hydrogenated product, and it is generally bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture, and wherein the weight percentage of bridge-type tetrahydro-dicyclopentadiene is 40%～90%.
Among the present invention, the conversion zone of tower is filled with isomerization catalyst under the catalytic rectifying tower, the filling of isomerization catalyst need guarantee that beds has enough freeboards, the flow passage of vapour-liquid phase is provided, to guarantee carrying out catalyzed reaction and gas-liquid mass transfer, general effective voidage is 40%～70%.The isomerization catalyst that conversion zone adopted is the solid acid with acid catalysis performance, can be cerium modified USY type molecular sieve, also metal ion-modified or unmodified Y type, MCM-22 type, USY type molecular sieve can be, the silico-aluminate of aluminum chloride, phosphoric acid modification can also be.
Among the present invention, with bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture is that raw material carries out the isomerization reaction synthetizing wall type tetrahydro-dicyclopentadiene and also can carry out in a catalytic rectifying tower, and this catalytic rectifying tower comprises rectifying section, conversion zone and stripping section.
Advantage of the present invention:
The present invention carries out isomerization reaction at the catalytic rectifying tower conversion zone, rectifying section carries out the hanging type tetrahydrochysene dicyclopentadiene product purification, make hanging type tetrahydrochysene dicyclopentadiene catalytic distillation synthetic operation flow process short, compare with the US4086284 patent, the present invention has reduced separating catalyst, solvent recovery unit equipment, facility investment is low, and isomerization reaction, product rectification cell are concentrated on catalytic rectifying tower.
Description of drawings
Accompanying drawing 1 expression cascade reaction rectification process schematic flow sheet of the present invention.
Mark meaning in the accompanying drawing 1 is as follows:
Tower under 1 catalytic distillation; Tower on 2 catalytic distillations; 6 reboilers; 10 condensers; 14 return tanks;
3,4,5,7,8,9,11,12,13 be pipeline.
Embodiment
Embodiment 1
1 couple of the present invention is described in further detail in conjunction with the accompanying drawings.
Catalytic rectifying tower is divided on the catalytic distillation tower 1 under the tower 2 and catalytic distillation, and on catalytic rectifying tower tower 2, be provided with the fraction elements that heat, matter are transmitted in the tower 1 down.Reaction raw materials is bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture, it introduces catalytic distillation Tata still through pipeline 3, reaction raw materials in the tower still enters pipeline 5, it heats after pipeline 7 enters tower 1 conversion zone under the catalytic distillation through reboiler 6, in the presence of the cerium modified USY type molecular sieve of isomerization catalyst, the bridge-type tetrahydro-dicyclopentadiene reaction generates hanging type tetrahydrochysene dicyclopentadiene, isomerization reaction is carried out at the bubble point temperature of bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture, isomerization reaction is thermopositive reaction, and reaction heat is absorbed and control reaction temperature by the hanging type tetrahydrochysene dicyclopentadiene vaporization.Flow out at the top of hanging type tetrahydrochysene dicyclopentadiene that generates in the reaction process and unreacted bridge-type tetrahydro-dicyclopentadiene tower 1 under the catalytic distillation, and enter on the catalytic rectifying tower through pipeline 4 and to separate in the tower 2.Hanging type tetrahydrochysene dicyclopentadiene tower 2 cats head from the catalytic rectifying tower flow out, enter pipeline 8 and enter return tank 14 through condenser 10, condensed liquid phase hanging type tetrahydrochysene dicyclopentadiene partly returns tower 2 on the catalytic distillation through pipeline 9, as the backflow of this tower, another part goes out device as the product hanging type tetrahydrochysene dicyclopentadiene through pipeline 11.The bridge-type tetrahydro-dicyclopentadiene that removes tower 2 from the reaction fractionating tower flow at the bottom of this Tata, is back to tower 1 tower still under the catalytic rectifying tower through pipeline 13.
Operational condition is:
Tower on the catalytic rectifying tower
Tower top pressure: 0.85MPa;
Tower bottom pressure: 0.90MPa;
Tower top temperature: 168 ℃;
Column bottom temperature: 179 ℃;
Tower under the catalytic rectifying tower
Tower top pressure: 0.88MPa;
Tower bottom pressure: 0.93MPa;
Tower top temperature: 176 ℃;
Column bottom temperature: 193 ℃;
Temperature of reaction: 179 ℃;
Catalyzer: weight percentage is 1.0% cerium modified USY type molecular sieve;
The weight percentage of bridge-type tetrahydro-dicyclopentadiene is 79.46% in the reaction raw materials, and the reaction mass feeding rate is 200g/h;
Tower extraction product on the gas chromatographic analysis catalytic rectifying tower, hanging type tetrahydrochysene dicyclopentadiene purity is 98.73%.
Basic identical with embodiment 1 operation, the operational condition of different is catalytic rectifying tower is:
Tower on the catalytic rectifying tower
Tower top pressure: 0.92MPa;
Tower bottom pressure: 0.97MPa;
Tower top temperature: 181 ℃;
Column bottom temperature: 193 ℃;
Tower under the catalytic rectifying tower
Tower top pressure: 0.95MPa;
Tower bottom pressure: 1.03MPa;
Tower top temperature: 182 ℃;
Column bottom temperature: 199 ℃;
Temperature of reaction: 184 ℃;
Catalyzer: weight percentage is 3.0% cerium modified USY type molecular sieve;
The weight percentage of bridge-type tetrahydro-dicyclopentadiene is 88.5% in the reaction raw materials, and feeding rate is 100g/h;
Tower extraction product on the gas chromatographic analysis catalytic rectifying tower, hanging type tetrahydrochysene dicyclopentadiene purity is 98.59%.
Basic identical with embodiment 1 operation, the operational condition of different is catalytic rectifying tower is:
Tower on the catalytic rectifying tower
Tower top pressure: 0.58MPa;
Tower bottom pressure: 0.66MPa;
Tower top temperature: 163 ℃;
Column bottom temperature: 172 ℃;
Tower under the catalytic rectifying tower
Tower top pressure: 0.63MPa;
Tower bottom pressure: 0.72MPa;
Tower top temperature: 168 ℃;
Column bottom temperature: 186 ℃;
Temperature of reaction: 173 ℃;
Catalyzer: weight percentage is 0.5% cerium modified USY type molecular sieve;
The weight percentage of bridge-type tetrahydro-dicyclopentadiene is 42.34% in the reaction raw materials, and feeding rate is 80g/h.
Tower extraction product on the gas chromatographic analysis catalytic rectifying tower, hanging type tetrahydrochysene dicyclopentadiene purity is 99.10%.
Embodiment 4
Basic identical with embodiment 1 operation, different is that catalyzer is that weight percentage is 5.0% cerium modified USY type molecular sieve; The weight percentage of bridge-type tetrahydro-dicyclopentadiene is 58.34% in the reaction raw materials, and feeding rate is 80g/h.
Gas chromatographic analysis catalytic distillation column overhead extraction product, hanging type tetrahydrochysene dicyclopentadiene purity is 98.79%.
Claims (4)
1. the synthetic method of a hanging type tetrahydrochysene dicyclopentadiene, it is characterized in that: with bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture is raw material, carrying out the isomerization reaction synthetizing wall type tetrahydro-dicyclopentadiene in the presence of isomerization catalyst is to carry out in catalytic rectifying tower, conversion zone carries out isomerization reaction, rectifying section removes unreacted bridge-type tetrahydro-dicyclopentadiene and refining hanging type tetrahydrochysene dicyclopentadiene, the bridge-type tetrahydro-dicyclopentadiene that removes is back to catalytic distillation Tata still, the hanging type tetrahydrochysene dicyclopentadiene product is from the extraction of catalytic distillation column overhead, and isomerization catalyst is cerium modified USY type molecular sieve.
2. the synthetic method of hanging type tetrahydrochysene dicyclopentadiene according to claim 1, it is characterized in that described catalytic rectifying tower is placed in-line Shang Ta and Xia Ta, following tower is made up of conversion zone and tower still, last tower is a rectifying section, carry out isomerization reaction at following tower conversion zone, remove unreacted bridge-type tetrahydro-dicyclopentadiene and refining hanging type tetrahydrochysene dicyclopentadiene at Shang Ta, the bridge-type tetrahydro-dicyclopentadiene that removes is back to catalytic distillation Tata still, the column overhead extraction from the catalytic rectifying tower of hanging type tetrahydrochysene dicyclopentadiene product.
3. the synthetic method of hanging type tetrahydrochysene dicyclopentadiene according to claim 2, the temperature of reaction that it is characterized in that conversion zone is to carry out in 150 ℃～200 ℃ scopes of bubble point temperature of bridge-type tetrahydro-dicyclopentadiene and hanging type tetrahydrochysene dicyclopentadiene mixture.
4. the synthetic method of hanging type tetrahydrochysene dicyclopentadiene according to claim 2 is characterized in that the working pressure of tower on the catalytic distillation is 0.55MPa～1.05MPa, and the working pressure of tower is 0.60MPa～110MPa under the catalytic distillation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106518595A (en) * | 2016-10-10 | 2017-03-22 | 天津大学 | Continuous isomerization method for tetrahydrotricyclopentadiene |
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| CN101130471A (en) * | 2007-08-24 | 2008-02-27 | 大连理工大学 | Novel method for producing hanging type tetrahydrochysene dicyclopentadiene on solid acid catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518595A (en) * | 2016-10-10 | 2017-03-22 | 天津大学 | Continuous isomerization method for tetrahydrotricyclopentadiene |
| CN106518595B (en) * | 2016-10-10 | 2019-11-12 | 天津大学 | A kind of method of the continuous isomerization of three cyclopentadiene of tetrahydro |
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