CN109651045A - A kind of refining methd of bridge-type tetrahydro-dicyclopentadiene - Google Patents
A kind of refining methd of bridge-type tetrahydro-dicyclopentadiene Download PDFInfo
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- CN109651045A CN109651045A CN201811593063.7A CN201811593063A CN109651045A CN 109651045 A CN109651045 A CN 109651045A CN 201811593063 A CN201811593063 A CN 201811593063A CN 109651045 A CN109651045 A CN 109651045A
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- bridge
- dicyclopentadiene
- type tetrahydro
- refining methd
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- 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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to technical field of chemical separation, particularly disclose a kind of refining methd of bridge-type tetrahydro-dicyclopentadiene.The refining methd of the bridge-type tetrahydro-dicyclopentadiene, using the product obtained after cycle pentadiene dimer plus hydrogen as raw material, it is characterised in that: raw material is cooled to -10 DEG C -50 DEG C, the operation of low temperature crystallization separative unit is carried out, obtains solid product；Solid product is warming up to 30 DEG C -70 DEG C, carries out the operation of high-temperature wash extraction cells, the bridge-type tetrahydro-dicyclopentadiene product of finally obtained purification.Operation of the present invention unit is simple, and product purity is high, solves the problems, such as that bridge-type tetrahydro-dicyclopentadiene purity is low in the prior art, and production cost is low, is suitable for wide popularization and application.
Description
(1) technical field
The present invention relates to technical field of chemical separation, in particular to a kind of refining methd of bridge-type tetrahydro-dicyclopentadiene.
(2) background technique
The big major product in bridge-type tetrahydro-dicyclopentadiene downstream two is adamantane and high-energy fuel.Adamantane is a kind of chemical and medicine industry
The important additives such as raw material and lubricant, resin, photosensitive material.It is different that adamantane generally passes through bridge-type tetrahydro-dicyclopentadiene
Structure and be made.The higher bridge-type tetrahydro-dicyclopentadiene of purity, then can be made the adamantane of higher yield and higher quality, this
It is very important for medical material, the yield of product can also be improved while improving product quality.High-energy fuel
It is mainly basic unit with hanging type tetrahydrochysene dicyclopentadiene, since hydrocarbon density is high, so having higher calory burning.
However high-energy fuel controls the impurity content of high-melting-point, Yi Shenghua, strict control hanging tetrahydrochysene to the more demanding of basic material
The weight content of dicyclopentadiene is not less than 90% etc..For in terms of these, the life of high-purity bridge-type tetrahydro-dicyclopentadiene
Production method is the technology of necessary and extremely important key.
Currently, dicyclopentadiene is mainly from cracking by-product light dydrocarbon and cracks by-product carbon nine, because forming and separating technology
Difference, the dicyclopentadiene obtained in the by-product light dydrocarbon, purity is generally 80% or so, and from obtaining in by-product carbon nine
Dicyclopentadiene, purity is generally 93% or more.To obtain the bridge-type tetrahydro-dicyclopentadiene of high-purity, further purify
The purity of cycle pentadiene dimer, increased costs amplitude are big.Therefore pass through the purification side of adjusting bridge-type tetrahydro-dicyclopentadiene
Method will become a kind of possible route.
Important medicine can be obtained using catalytic isomerization to bridge-type tetrahydro-dicyclopentadiene by dicyclopentadiene hydrogenated
Raw material adamantane (Roger P.Kirchen, Can.J.Chem. Vol.71,1993).Due to the production requirement of medical adamantane
It is more harsh, and the quality requirements of product are also higher, generally also have use as hydrogenating materials using 99% dicyclopentadiene
As hydrogenating materials, (Wang Nan, two steps, one round-robin method produce Buddha's warrior attendant to 85% dicyclopentadiene (the isolated dicyclopentadiene of light dydrocarbon)
Alkane new process, CN200810045391.3,2008), but its hydrogenation pressure at least will be in 10MPa or more, reaction condition is extremely
It is harsh.Some investigators, as solvent, carry out light dydrocarbon dicyclopentadiene to add hydrogen (Gu Yanlong, petroleum using ionic liquid
Work the 5th phase of volume 31 in 2002), however since the use condition of ionic liquid is harsh and expensive, therefore limit it
Application industrially.There is research institution to add hydrogen (Guo Jianwei, catalysis using supported ni catalyst progress dicyclopentadiene
Report, the 3rd phase of volume 22 in 2001), however the research is mainly to discuss that DCPD's adds hydrogen, does not consider feelings existing for various polymers
Under condition plus hydrogen effect.It is either raw material with light dydrocarbon cycle pentadiene dimer is still raw material with carbon nine, although raw material
Impurity is different, but all there is the problems such as azeotropic, Yi Juhe, depolymerization copolymerization, the bridge-type tetrahydro-dicyclopentadiene after adding hydrogen
Purity is not also high.Purification by raw material is to be difficult to further increase, however traditional rectifying separates, also face is adjacent for recrystallization separation
Problems, such as sublimation problem, structure cell packet liquid.So it is imperative to develop a kind of efficient process for refining and purifying.
(3) summary of the invention
The bridge-type tetrahydro that in order to compensate for the shortcomings of the prior art, the present invention provides a kind of operating units is simple, product purity is high
The refining methd of dicyclopentadiene.
The present invention is achieved through the following technical solutions:
A kind of refining methd of bridge-type tetrahydro-dicyclopentadiene, using the product obtained after cycle pentadiene dimer plus hydrogen as raw material,
It is characterized by: raw material is cooled to -10 DEG C -50 DEG C, the operation of low temperature crystallization separative unit is carried out, solid product is obtained；It will consolidate
Body product is warming up to 30 DEG C -70 DEG C, carries out the operation of high-temperature wash extraction cells, the bridge-type tetrahydro of finally obtained purification bicyclic penta
Diene products.
Obtained product is raw material to the present invention after adding hydrogen using cycle pentadiene dimer, successively using low temperature crystallization separation list
Atom operation, the operation of high-temperature wash extraction cells, the purity of bridge-type tetrahydro-dicyclopentadiene is significantly improved.
More excellent technical solution of the invention are as follows:
The weight content of the cycle pentadiene dimer is 10-99.9%, preferably 30-80%, more optimizedly 45-75%；It is obtained after adding hydrogen
The weight content of the bridge-type tetrahydro-dicyclopentadiene arrived is not less than 10%.
The raw material is cooled to 10 DEG C -30 DEG C, and the operation of low temperature crystallization separative unit passes through one in filtering, sedimentation, centrifugation
Kind is separated, and is preferably settled or is filtered.
The high-temperature wash extraction cells operation is to mix solid with organic extraction solvent；The organic extraction is molten
Agent is ethyl acetate, methyl acetate, toluene, benzene, hexamethylene, hexahydrotoluene, water, methanol, ethyl alcohol, acetone and glycol dinitrate
One of ether is a variety of.
The invention proposes a kind of separation methods different from existing bridge-type tetrahydro-dicyclopentadiene, pass through above-mentioned technology
Scheme may be implemented, 99.5% or more the purity of bridge-type tetrahydro-dicyclopentadiene, and the total content of metal impurities is less than 100ppm.
Present invention employs a kind of simple low temperature solid-liquid separation process, obtain a kind of bridge-type four with certain pure
Hydrogen dicyclopentadiene product；The operation of high-temperature wash extraction cells, the bridge-type tetrahydro bicyclic penta 2 after low temperature being separated by solid-liquid separation
Alkene product carries out recrystallization separation, further improves the purity of bridge-type tetrahydro-dicyclopentadiene
Operation of the present invention unit is simple, and product purity is high, and it is low to solve bridge-type tetrahydro-dicyclopentadiene purity in the prior art
Problem, production cost is low, is suitable for wide popularization and application.
(4) specific embodiment
The present invention will be further described below by way of examples, but these embodiments are not constituted the scope of the present invention
Limitation.
Embodiment 1:
By 1.0 kilograms of bridge-type tetrahydro-dicyclopentadiene products (weight content 50%), 1 hour is stood at 10 DEG C, then by product
It is filtered separation, obtains 0.40 kilogram of solid product；0..40 kilograms is washed admittedly with 0.1 kilogram of ethyl acetate in 25 DEG C
After washing, product is dried for body product.Through chromatography, the content of bridge-type tetrahydro-dicyclopentadiene is 95.5%.
Embodiment 2:
By 1.0 kilograms of bridge-type tetrahydro-dicyclopentadiene products (weight content 30%), 2 hours are stood at 0 DEG C, then by product
It is filtered separation, obtains 0.25 kilogram of solid product；It is produced in 35 DEG C with 0.1 kilogram 0.25 kilogram of solid of acetone washing
After washing, product is dried for product.Through chromatography, the content of bridge-type tetrahydro-dicyclopentadiene is 97.5%.
Embodiment 3:
By 1.0 kilograms of bridge-type tetrahydro-dicyclopentadiene products (weight content 40%), 3 hours are stood at 15 DEG C, then by product
It is filtered separation, obtains 0.35 kilogram of solid product；0.35 thousand are washed with 0.15 kilogram of glycol dimethyl ether in 35 DEG C
Gram solid product, after washing, product is dried.Through chromatography, the content of bridge-type tetrahydro-dicyclopentadiene is 98.3%.
Embodiment 4-10:
According to the terms and conditions of embodiment 1, bridge-type tetrahydro-dicyclopentadiene is refined, only the temperature of low temperature and when
Between, the temperature of high temperature it is different from solvent type, be specifically listed in the following table.
Claims (8)
1. a kind of refining methd of bridge-type tetrahydro-dicyclopentadiene is former with the product obtained after cycle pentadiene dimer plus hydrogen
Material, it is characterised in that: raw material is cooled to -10 DEG C -50 DEG C, the operation of low temperature crystallization separative unit is carried out, obtains solid product；It will
Solid product is warming up to 30 DEG C -70 DEG C, carries out the operation of high-temperature wash extraction cells, and the bridge-type tetrahydro of finally obtained purification is bicyclic
Pentadiene product.
2. the refining methd of bridge-type tetrahydro-dicyclopentadiene according to claim 1, it is characterised in that: the cyclopentadiene
The weight content of dimer is 10-99.9%, adds the weight content of the bridge-type tetrahydro-dicyclopentadiene obtained after hydrogen not less than 10%.
3. the refining methd of bridge-type tetrahydro-dicyclopentadiene according to claim 1, it is characterised in that: the raw material cooling
To 10 DEG C -30 DEG C, the operation of low temperature crystallization separative unit is separated by one of filtering, sedimentation, centrifugation.
4. the refining methd of bridge-type tetrahydro-dicyclopentadiene according to claim 1, it is characterised in that: the high-temperature wash
Extraction cells operation is to mix solid with organic extraction solvent.
5. the refining methd of bridge-type tetrahydro-dicyclopentadiene according to claim 2, it is characterised in that: the cyclopentadiene
The weight content of dimer is 30-80%.
6. the refining methd of bridge-type tetrahydro-dicyclopentadiene according to claim 3, it is characterised in that: the low temperature crystallization
Separative unit operation is separated by sedimentation or filtering.
7. the refining methd of bridge-type tetrahydro-dicyclopentadiene according to claim 4, it is characterised in that: the organic extraction
Solvent is ethyl acetate, methyl acetate, toluene, benzene, hexamethylene, hexahydrotoluene, water, methanol, ethyl alcohol, acetone and ethylene glycol two
One of methyl ether is a variety of.
8. the refining methd of bridge-type tetrahydro-dicyclopentadiene according to claim 2 or 5, it is characterised in that: the ring penta
The weight content of diene dimer is 45-75%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229990A (en) * | 2008-02-21 | 2008-07-30 | 泸州大洲化工有限公司 | Novel technique for producing adamantine by two-step-one-circulation method |
| CN105175213A (en) * | 2015-10-20 | 2015-12-23 | 山东玉皇化工有限公司 | Method for hydrogenation of C5 dicyclopentadiene |
| CN105294381A (en) * | 2015-09-10 | 2016-02-03 | 西安近代化学研究所 | Method for separating and purifying bridge type tetrahydrodicyclopentadiene |
-
2018
- 2018-12-25 CN CN201811593063.7A patent/CN109651045A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229990A (en) * | 2008-02-21 | 2008-07-30 | 泸州大洲化工有限公司 | Novel technique for producing adamantine by two-step-one-circulation method |
| CN105294381A (en) * | 2015-09-10 | 2016-02-03 | 西安近代化学研究所 | Method for separating and purifying bridge type tetrahydrodicyclopentadiene |
| CN105175213A (en) * | 2015-10-20 | 2015-12-23 | 山东玉皇化工有限公司 | Method for hydrogenation of C5 dicyclopentadiene |
Non-Patent Citations (2)
| Title |
|---|
| 司志华等: "环戊二烯二聚体加氢研究", 《科技资讯》 * |
| 张开诚主编: "《化学实验教程》", 28 February 2018, 华中科技大学出版社 * |
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Application publication date: 20190419 |