CN102992939A - High-yield preparation method for high-purity cyclopentadiene - Google Patents
High-yield preparation method for high-purity cyclopentadiene Download PDFInfo
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- CN102992939A CN102992939A CN2012105218460A CN201210521846A CN102992939A CN 102992939 A CN102992939 A CN 102992939A CN 2012105218460 A CN2012105218460 A CN 2012105218460A CN 201210521846 A CN201210521846 A CN 201210521846A CN 102992939 A CN102992939 A CN 102992939A
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Abstract
The invention discloses a high-yield preparation method for high-purity cyclopentadiene, which is mainly used for purifying cyclopentadiene via a section of a fractional column. The high-yield preparation method comprises the following steps of: by taking cyclopentadiene as a raw material, dripping cyclopentadiene in a cracking reactor containing high-temperature heat-conducting oil to crack, and purifying the generated gaseous-phase product via the fractional column to obtain a fraction, and condensing the obtained fraction to obtain the high-purity cyclopentadiene. The purity of the cyclopentadiene obtained via the method is up to more than 96%, and the product yield is up to more than 96%; and moreover, the preparation process is simple in process flow, the device is simple and easy, and the process is easy to control.
Description
Technical field
The present invention relates to the synthetic of organic intermediate, be specifically related to a kind of preparation method of high yield high-purity cyclopentadiene.
Background technology
Cyclopentadiene (being called for short CPD), molecular formula C
5H
6, fusing point-97.542 ℃, 40 ℃ of boiling points, because it contains two two keys and a methylene radical, chemical property is very active, is important chemical intermediate, and is of many uses, is the raw material of synthetic pesticide, plastics, rubber etc.
Cyclopentadiene namely can be grouped to dimer dicyclopentadiene (being called for short DCPD) at normal temperatures, and industrial goods also are dicyclopentadiene.31.5 ℃ at dicyclopentadiene zero pour, 170 ℃ of boiling points (decomposition), it is heated and then becomes cyclopentadiene.The characteristics of the easy dimerization of cyclopentadiene are used to it from cracking of ethylene by product C
5, the coal tar process the benzene front-end volatiles in separate, obtain cyclopentadiene and isolated dicyclopentadiene can be carried out heating pyrolyze and get final product.
Dicyclopentadiene thermal depolymerization method is mainly adopted in the at present preparation of cyclopentadiene.Chinese patent (CN1292369A) mixes thick dicyclopentadiene with batching gas (water vapor or nitrogen or toluene), carry out decomposition reaction after preheating, purify by separation column, the method device is more, operation inconvenience, the existence of batching gas makes subsequent purification technique be tending towards complicated.Chinese patent (CN101913977A) adopts deep fat cracking dicyclopentadiene, in rectifying mechanism, be added with the hot water prolong, product after the purification namely obtains cyclopentadiene through after the condensation, the existence of hot water prolong increases the flow process energy consumption in the method, and need to carry out temperature control to it, flow operations is comparatively complicated, and product yield is not high.Chinese patent (CN102442875A) adds a kind of salts substances in cracking process, be used for reducing cracking temperature, avoids the generation of charing phenomenon, but cracking temperature reduces and is not obvious, owing to add salts substances, reaction mass increases, and the technique subsequent disposal is comparatively various.Dicyclopentadiene is after the preheater preheating in the United States Patent (USP) (US5877366), contact with heat-conducting fluid and to carry out thermo-cracking, the cyclopentadiene that obtains is by the first condenser and mist eliminator, again by the second condenser condenses, finally obtain product, comprise preheater in this method, contain the reactor of electrical heating element, two condensers and mist eliminator, technical process is all comparatively complicated with device, and the temperature parameter of control is also more.Therefore, develop the cyclopentadiene preparation method that a kind of technical process is simple, device is simple and easy, process is easily controlled, yield is high, purity is high and seem particularly important.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high yield high-purity cyclopentadiene, yield and the purity of raising cyclopentadiene, and reaction unit is simple and easy, and simple to operate.
Preparation method of the present invention is according to as follows: take dicyclopentadiene as raw material, it is dripped cracking in containing the cracking reactor of high temperature heat conductive oil, after the gas-phase product that generates was purified through fractional column, the gained cut namely obtained highly purified cyclopentadiene by condenser condenses.
Described preparation method comprises the steps:
A) dicyclopentadiene is dripped cracking generation cyclopentadiene in containing the cracking reactor of high temperature heat conductive oil;
B) gas-phase product that generates is purified through fractional column;
C) purification gained cut namely obtains highly purified cyclopentadiene after by condenser condenses.
The below does above-mentioned preparation method and specifies.
In the step a), thermal conductance oil temperature of the present invention is recommended between 200-290 ℃.
In the step b), packed height is recommended between 1-5 the height equivalent to one theoretical plate (HETP) in the fractional column of the present invention.
In the step b), purification gained cut temperature of the present invention is recommended between 30-45 ℃.
In the step b), the lower end gained liquid phase mixture of fractional column of the present invention is recommended to return cracking reactor as reaction raw materials.
In the step c), preferred 0 ℃ or following of condensing temperature of the present invention.
The present invention compares its advantage applies with existing technique and exists:
1, in present method, dicyclopentadiene enters the decomposition reaction of namely gasifying of cracking reactor and high temperature heat conductive oil Contact, because duration of contact is extremely short, the chance that generates polymer reduces greatly.
2, in present method, the fractional column of use plays the purification effect, and unconventional rectifier unit, and is simple to operate, noenergy consumption.
3, in present method, after the vapor-phase thermal cracking product is purified by fractional column, fractional column lower end gained liquid phase mixture, the liquid that mostly is unreacted dicyclopentadiene and carries secretly, it is back in the cracking reactor as raw material continuation reaction, when guarantee obtaining the high-purity cyclopentadiene product, again Effective Raise the yield of product.
4, the technical process of using in present method is simple, installs simple and easyly, and process is easily controlled, and is fit to periodical operation and serialization production.
Adopt preparation method of the present invention, the cyclopentadiene purity that production obtains is more than 96%, and yield can reach more than 96%.
Description of drawings
Fig. 1 is preparation method's of the present invention process flow sheet.
Attached number in the figure explanation
1 is the raw material dicyclopentadiene; 2 is the vapor-phase thermal cracking product; 3 is fractional column lower end gained liquid phase mixture; 4 is cut between 30-45 ℃ of the fractional column upper end gained; 5 is highly purified cyclopentadiene product.
Embodiment
The 200ml thermal oil adds in the cracking reactor, be warming up between 200-290 ℃, dicyclopentadiene 200g is added drop-wise in the cracking reactor, the rapid cracking of dicyclopentadiene, gas-phase product is purified through filling Packed fractional column, packed height is between 1-5 height equivalent to one theoretical plate (HETP), cut between collecting 30-45 ℃, the liquid phase mixture of fractional column lower end returns and continues reaction in the cracking reactor, and the cut that fractional column is collected passes through condensing tube condensation, and condensing temperature remains on 0 ℃ or following, after dicyclopentadiene drips and finishes, the heavy 193.2g of the cyclopentadiene product of collecting, purity 97.5%, yield 96.6%.
Embodiment 2
The 200ml thermal oil adds in the cracking reactor, be warming up between 200-290 ℃, dicyclopentadiene 300g is added drop-wise in the cracking reactor, the rapid cracking of dicyclopentadiene, gas-phase product is purified through filling Packed fractional column, packed height is between 1-5 height equivalent to one theoretical plate (HETP), cut between collecting 30-45 ℃, the liquid phase mixture of fractional column lower end returns and continues reaction in the cracking reactor, and the cut that fractional column is collected passes through condensing tube condensation, and condensing temperature remains on 0 ℃ or following, after dicyclopentadiene drips and finishes, the heavy 291.3g of the cyclopentadiene product of collecting, purity 96.9%, yield 97.1%.
Claims (7)
1. the preparation method of a high yield high-purity cyclopentadiene, described preparation method is as follows: take dicyclopentadiene as raw material, it is dripped cracking in containing the cracking reactor of high temperature heat conductive oil, after the gas-phase product that generates was purified through fractional column, the gained cut namely obtained highly purified cyclopentadiene by condenser condenses.
2. one kind requires the preparation method of described high yield high-purity cyclopentadiene such as right 1, and described preparation method comprises the steps:
A) dicyclopentadiene is dripped cracking generation cyclopentadiene in containing the cracking reactor of high temperature heat conductive oil;
B) gas-phase product that generates is purified through fractional column;
C) purification gained cut namely obtains highly purified cyclopentadiene after by condenser condenses.
3. the preparation method of high yield high-purity cyclopentadiene as claimed in claim 2 is characterized in that the thermal oil temperature is between 200-290 ℃ in the described cracking reactor of step a).
4. the preparation method of high yield high-purity cyclopentadiene as claimed in claim 2 is characterized in that packed height is between 1-5 height equivalent to one theoretical plate (HETP) in the described fractional column of step b).
5. the preparation method of high yield high-purity cyclopentadiene as claimed in claim 2 is characterized in that the described purification gained of step b) cut temperature is between 30-45 ℃.
6. the preparation method of high yield high-purity cyclopentadiene as claimed in claim 2 is characterized in that the lower end gained liquid phase mixture of the described fractional column of step b) can returning cracking reactor as reaction raw materials.
7. the preparation method of high yield high-purity cyclopentadiene as claimed in claim 2 is characterized in that the described condenser condenses temperature of step c) is at 0 ℃ or following.
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| CN2012105218460A CN102992939A (en) | 2012-12-07 | 2012-12-07 | High-yield preparation method for high-purity cyclopentadiene |
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| CN2012105218460A CN102992939A (en) | 2012-12-07 | 2012-12-07 | High-yield preparation method for high-purity cyclopentadiene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111036A (en) * | 2015-09-22 | 2015-12-02 | 天津天大天海化工新技术有限公司 | Novel method for separating cyclopentadiene and methyl cyclopentadiene from ethylene by-product C9 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070262A (en) * | 2007-06-06 | 2007-11-14 | 江苏克胜集团股份有限公司 | Dicyclopentadiene continuous cracking novel process |
| CN101913977A (en) * | 2010-08-26 | 2010-12-15 | 上海立科药物化学有限公司 | Method for preparing high-purity cyclopentadiene with high yield |
| CN102060649A (en) * | 2009-11-17 | 2011-05-18 | 中国石油天然气股份有限公司 | Method for preparing high-purity cyclopentadiene |
-
2012
- 2012-12-07 CN CN2012105218460A patent/CN102992939A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070262A (en) * | 2007-06-06 | 2007-11-14 | 江苏克胜集团股份有限公司 | Dicyclopentadiene continuous cracking novel process |
| CN102060649A (en) * | 2009-11-17 | 2011-05-18 | 中国石油天然气股份有限公司 | Method for preparing high-purity cyclopentadiene |
| CN101913977A (en) * | 2010-08-26 | 2010-12-15 | 上海立科药物化学有限公司 | Method for preparing high-purity cyclopentadiene with high yield |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111036A (en) * | 2015-09-22 | 2015-12-02 | 天津天大天海化工新技术有限公司 | Novel method for separating cyclopentadiene and methyl cyclopentadiene from ethylene by-product C9 |
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Application publication date: 20130327 |