CN103664466A - Method for preparing high-purity cyclopentadiene - Google Patents
Method for preparing high-purity cyclopentadiene Download PDFInfo
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- CN103664466A CN103664466A CN201210363876.3A CN201210363876A CN103664466A CN 103664466 A CN103664466 A CN 103664466A CN 201210363876 A CN201210363876 A CN 201210363876A CN 103664466 A CN103664466 A CN 103664466A
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- cyclopentadiene
- dicyclopentadiene
- depolymerization
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Abstract
The invention discloses a method for preparing high-purity cyclopentadiene (CPD) from crude dicyclopentadiene (DCPD). According to the method, crude dicyclopentadiene is taken as a raw material, a diluent is added in depolymerization, dicyclopentadiene and the diluent are mixed by a mass ratio of (1-4):1 and then put into a depolymerization kettle, under the conditions of normal pressure, depolymerization temperature of 160 DEG C-200 DEG C and reflux ratio of 0.5-5, the yield of cyclopentadiene is 90%, and finally, cyclopentadiene with purity more than 99% can be obtained. The method has obvious positive effects that polymerization of crude dicyclopentadiene can be effectively reduced, and the yield of dicyclopentadiene is improved; furthermore, the diluent can guarantee impurities such as isopropenyl norbornene not to be depolymerized so as to guarantee the purity of cyclopentadiene; the method is particularly suitable for preparing high-purity cyclopentadiene from raw material crude dicyclopentadiene obtained through thermal dimerization separation in splitting C5.
Description
Technical field
The invention discloses a kind of method of preparing high-purity cyclopentadiene, particularly by thick dicyclopentadiene depolymerization, prepared the method for high-purity cyclopentadiene.By the method for adding thinner in dicyclopentadiene solution collecting process, to improve the depolymerization degree of dicyclopentadiene and the gathering of avoiding separating polymer in collecting process.
Background technology
Cyclopentadiene (CPD) in carbon five (C5) component is conjugated diene, reaction property is active, can carry out the reactions such as polymerization, hydrogenation, halogenation, addition, condensation and reduction, of many uses, become the important source material of organic synthesis industry, itself there is very high market and utilize prospect.
In prior art, highly purified cyclopentadiene is generally to obtain through the depolymerization of thick dicyclopentadiene (DCPD).Raw material is the cyclopentadiene separated thick dicyclopentadiene obtaining after polymerization in petroleum cracking ethylene by-product C5 processed fraction, owing to existing side reaction in dimerization, and the purity of dicyclopentadiene lower (85% left and right).And because boiling point and the dicyclopentadiene boiling point of by product are nearer, common rectifying mode is difficult to remove the impurity such as pseudoallyl norbornylene in dicyclopentadiene product, thereby affects the quality of cyclopentadiene.
At present, the depolymerization method of dicyclopentadiene mainly contains vapor phase process and liquid phase method, approximately 300～500 ℃ of gas phase depolymerization temperature of reaction, dicyclopentadiene residence time in reaction zone is short, speed of reaction is fast, dicyclopentadiene transformation efficiency is high, but depolymerization also occurs impurity simultaneously, and product is difficult to separated with cyclopentadiene.Liquid phase method be take high boiling solvent as thermal barrier, and feature is that reaction conditions is gentle, and can in reactive distillation column, carry out, and will separate collecting process and rectifying coupling, isolates in time the cyclopentadiene of generation, promotes that depolymerization reaction carries out.Tower top can directly obtain high-purity cyclopentadiene product, and technical process is simple, but liquid phase method shortcoming is that dicyclopentadiene depolymerization degree is limited, improves depolymerization degree, and the increase of reaction solution viscosity is difficult to discharge, and aggregates into resin, even coking.Therefore common liquid phase depolymerization yield is lower, and production equipment is also difficult to long-play.
Current disclosed dicyclopentadiene Depolymerization Technique, as: US Patent No. P5,321,177 disclose a kind of high purity dicyclo pentylene production process, adopt tubular reactor solution polydicyclopentadiene, the cracking of this mode dicyclopentadiene is more complete, but impurity cracking simultaneously, it is separated that product and cyclopentadiene are difficult to, therefore be difficult to obtain high purity dicyclo pentylene.USP3,719,718 disclose a kind of progressively method of quantitative depolymerization of dicyclopentadiene, can obtain higher dicyclopentadiene yield, but dicyclopentadiene purity are low.
Chinese patent CN1334262 discloses a kind of method and necessary specific equipment of preparing high-purity cyclopentadiene, and this method can avoid using solvent, but has the problem that depolymerization degree is low, and cyclopentadiene yield is lower.CN1781887 discloses a kind of low temperature dicyclopentadiene production technique, catalytic degradation dicyclopentadiene at a lower temperature, and this technique need to be used catalyzer, and flow process is more complicated.CN102060649A discloses a kind of method of preparing high purity dicyclo pentylene, adopts higher temperature carrier, and dicyclopentadiene is depolymerization therein, but polymer assembles therein, easily coking, and in industrial application, device cannot long-play.
Liquid phase depolymerization is because the residence time is longer, and the thick dicyclopentadiene of raw material is easily polymerization in separating collecting process, causes solution collecting process yield low, and in depolymerization still, polymer is accumulated the defects such as coking.Meanwhile, in prior art, in preparing high-purity cyclopentadiene process, cannot take into account the continuity problem of depolymerization degree, cyclopentadiene yield, cyclopentadiene purity and the production technique of dicyclopentadiene.
Summary of the invention
The invention provides a kind of method of preparing high-purity cyclopentadiene, by the method for adding thinner in thick dicyclopentadiene solution collecting process, not only can effectively improve dicyclopentadiene depolymerization degree, and then improved yield, and a large amount of minimizing understood polymer gathering in collecting process, avoids coking to conciliate equipment latch up phenomenon in collecting process.
Essence of the present invention is to add a kind of thinner in thick dicyclopentadiene solution collecting process, makes in thick dicyclopentadiene solution collecting process, and in system, the concentration of material reduces, and improves depolymerization degree, avoids the generation of polymer in reaction process and coking.Avoided the decomposition of impurity simultaneously, can obtain high-purity cyclopentadiene, be specially adapted to by the separated thick dicyclopentadiene raw material obtaining of cracking c5.
Below main technical schemes of the present invention:
A method of preparing high-purity cyclopentadiene, mainly comprises the following steps
1) in tempering tank, add a certain amount of thick dicyclopentadiene and thinner, the mass ratio of dicyclopentadiene and thinner is (1～4): 1.
2) by step 1) the dicyclopentadiene raw material of the dilution that obtains squeezes into depolymerization tower bottom of rectifying tower by volume pump; Under normal pressure, in tower reactor, there is depolymerization reaction and generate cyclopentadiene in dicyclopentadiene, depolymerization theoretical number of plates of rectifying tower is 10～40,160 ℃～200 ℃ of depolymerization temperature, reflux ratio is 0.5～5, depolymerization time 1～3h, and the cyclopentadiene that depolymerization generates is rectification and purification in rectifying tower up, tower top obtains high-purity cyclopentadiene product, and tower reactor still liquid is got rid of continuously.
Above-mentioned steps 1) described thinner is ethylene cracker by-product C9～C10 component or aromatics reformer by-product C9～C10 component.
Above-mentioned steps 1) described dicyclopentadiene: thinner mass ratio is preferably (3～4): 1
Above-mentioned steps 2) described temperature of reaction is preferably 170～190 ℃, and the depolymerization time is preferably 2～3h, and reflux ratio is preferably 1～2.
Contriver is through finding thick producing cyclopentadience by depolymerizing dicyclopentadience process study, thick dicyclopentadiene depolymerization key point is to improve the depolymerization degree and the generation of avoiding polymer of dicyclopentadiene, contriver finds to add thinner in system simultaneously, can not only improve the depolymerization degree of dicyclopentadiene, improve cyclopentadiene yield, can reduce the generation of separating polymer in collecting process, avoid coking simultaneously.This is to be mainly dicyclopentadiene and dicyclopentadiene character approaching pseudoallyl norbornylene impurity and polymer because thick dicyclopentadiene material forms, easy coking when high temperature, concentration are higher, therefore reduces and separates material concentration in collecting process and can effectively reduce the phenomenon of separating polymer coking in collecting process.Meanwhile, in separating collecting process, constantly remove cyclopentadiene, reaction is carried out to the direction that generates cyclopentadiene, thereby can effectively improve the cracking severity of dicyclopentadiene, improve the yield of cyclopentadiene.
Compared with prior art, effect of the present invention is fairly obvious, on the one hand, the mode that liquid phase depolymerization combines with reactive distillation is produced the technology comparative maturity of highly purified cyclopentadiene continuously, can avoid the pseudoallyl norbornylene that pyroreaction generates to decompose, thereby avoid generating, be difficult to separated isoprene with cyclopentadiene, tower top can directly obtain high-purity cyclopentadiene.The thick dicyclopentadiene raw material that is specially adapted to be generated by cracking c5.On the other hand, the thinner that the present invention adopts can improve dicyclopentadiene depolymerization degree, reduces poly reaction, improves tower top cyclopentadiene yield, and avoids tower reactor coking.Meanwhile, the thinner consumption that the present invention adopts is less, cheap, and there are affluent resources refinery.It is simple that the production technique of design has equipment, and reaction conditions is gentle, and constant product quality, is easy to the advantages such as industrialization; The cyclopentadiene purity obtaining is greater than 99%, and yield surpasses 90%.
Below by specific embodiment, the invention will be further described, and in an embodiment, the yield of cyclopentadiene is defined as:
Accompanying drawing explanation
Fig. 1 is the process flow sheet of preparing high-purity cyclopentadiene
embodiment
[embodiment 1～10]
Accompanying drawing is shown in embodiment 1～10 technical process, and raw material is the separating obtained thick dicyclopentadiene of the hot dimerization of cracking c5, and it forms in Table 1.
In tempering tank, add by a certain percentage thick dicyclopentadiene and thinner, the dicyclopentadiene raw material of dilution is squeezed into reactive distillation column tower reactor by volume pump; There is depolymerization reaction and generate cyclopentadiene in dicyclopentadiene, the cyclopentadiene that depolymerization generates is rectification and purification in rectifying tower up in tower reactor, and tower top obtains high-purity cyclopentadiene product, and tower reactor still liquid is got rid of continuously.The operational condition of depolymerization rectifying tower is in Table 2, adopts the methods analyst tower top of gas-chromatography to form, and the composition of tower top enrichment cyclopentadiene is in Table 3, then in conjunction with the yield of each inventory ring pentadiene, and result is with in Table 3.
Table 1
| Component | Content (wt.%) |
| Cyclopentadiene | 1.0 |
| Isoprene | 0.8 |
| M-pentadiene | 0.8 |
| Dicyclopentadiene | 86 |
| Pseudoallyl norbornylene | 5.2 |
| Surplus | 6.2 |
| Amount to | 100 |
Table 2
Table 3
| Cyclopentadiene concentration/% | Cyclopentadiene yield/% | |
| Embodiment 1 | 98 | 80 |
| Embodiment 2 | 99 | 90 |
[0030]
| Embodiment 3 | 99 | 89 |
| Embodiment 4 | 99 | 91 |
| Embodiment 5 | 98 | 88 |
| Embodiment 6 | 99 | 92 |
| Embodiment 7 | 99 | 89 |
| Embodiment 8 | 98 | 82 |
| Embodiment 9 | 99 | 92 |
| Embodiment 10 | 98 | 88 |
Claims (6)
1. a method of preparing high-purity cyclopentadiene, mainly comprises the following steps:
1) in tempering tank, add a certain amount of thick dicyclopentadiene and thinner, additional proportion is dicyclopentadiene: thinner mass ratio is (1～4): 1;
2) in steps 1) the dicyclopentadiene raw material of gained dilution is squeezed into depolymerization tower bottom of rectifying tower by volume pump, there is depolymerization reaction generation cyclopentadiene in dicyclopentadiene under normal pressure in tower reactor, depolymerization theoretical number of plates of rectifying tower is 10～40, depolymerization temperature is 160 ℃～200 ℃, reflux ratio is 0.5～5, depolymerization time 1～3h, and the cyclopentadiene that depolymerization generates is rectification and purification in rectifying tower up, tower top obtains high-purity cyclopentadiene product, and tower reactor still liquid is got rid of continuously.
2. a kind of method of preparing high-purity cyclopentadiene according to claim 1, is characterized in that dicyclopentadiene: thinner mass ratio is preferably (3～4): 1.
3. a kind of method of preparing high-purity cyclopentadiene according to claim 1, is characterized in that described thinner is ethylene cracker by-product C9～C 10 components or aromatics reformer by-product C9～C 10 components.
4. according to a kind of method of preparing high-purity cyclopentadiene described in claim 1 and 2, it is characterized in that temperature of reaction is preferably 170～190 ℃.
5. according to a kind of method of preparing high-purity cyclopentadiene described in claim 1 and 2, it is characterized in that the depolymerization time is preferably 2～3h.
6. according to a kind of method of preparing high-purity cyclopentadiene described in claim 1 and 2, it is characterized in that reflux ratio is preferably 1～2.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820025A (en) * | 2016-04-19 | 2016-08-03 | 大连理工大学 | Method for preparing high-purity cyclopentadiene |
| CN107188908A (en) * | 2017-06-26 | 2017-09-22 | 江苏南大光电材料股份有限公司 | Three（Dimethylamino）The preparation method of cyclopentadienyl group zirconium |
| CN108865259A (en) * | 2018-06-09 | 2018-11-23 | 濮阳市联众兴业化工有限公司 | A method of the cracking decoloration of carbon nine is deodorized |
| CN109704905A (en) * | 2019-01-24 | 2019-05-03 | 洋浦傲立石化有限公司 | A kind of depolymerization process of dicyclopentadiene |
| CN110563533A (en) * | 2019-09-19 | 2019-12-13 | 广东新华粤石化集团股份公司 | Method for preparing methyl cyclopentadiene dimer from cracking carbon nine fraction |
| CN112679297A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of high-purity dicyclopentadiene |
| CN114085138A (en) * | 2021-11-16 | 2022-02-25 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer and intermediate thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227534A (en) * | 1996-08-06 | 1999-09-01 | 埃克森化学专利公司 | Process for forming cyclopentane from dicyclopentadiene |
| WO2000029358A1 (en) * | 1998-11-13 | 2000-05-25 | Exxon Chemical Patents Inc. | Use of catalytic distillation to produce cyclopentane or cyclopentene |
| CN1334262A (en) * | 2000-07-13 | 2002-02-06 | 中国石油化工股份有限公司 | Process for preparing high-purity cyclopentadiene and its special equipment |
| CN1389444A (en) * | 2001-06-06 | 2003-01-08 | 中国科学院大连化学物理研究所 | Prepn. of high-purity cyclopentadiene and dicyclopentadiene |
-
2012
- 2012-09-25 CN CN201210363876.3A patent/CN103664466A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1227534A (en) * | 1996-08-06 | 1999-09-01 | 埃克森化学专利公司 | Process for forming cyclopentane from dicyclopentadiene |
| WO2000029358A1 (en) * | 1998-11-13 | 2000-05-25 | Exxon Chemical Patents Inc. | Use of catalytic distillation to produce cyclopentane or cyclopentene |
| CN1334262A (en) * | 2000-07-13 | 2002-02-06 | 中国石油化工股份有限公司 | Process for preparing high-purity cyclopentadiene and its special equipment |
| CN1389444A (en) * | 2001-06-06 | 2003-01-08 | 中国科学院大连化学物理研究所 | Prepn. of high-purity cyclopentadiene and dicyclopentadiene |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820025A (en) * | 2016-04-19 | 2016-08-03 | 大连理工大学 | Method for preparing high-purity cyclopentadiene |
| CN107188908A (en) * | 2017-06-26 | 2017-09-22 | 江苏南大光电材料股份有限公司 | Three（Dimethylamino）The preparation method of cyclopentadienyl group zirconium |
| CN108865259A (en) * | 2018-06-09 | 2018-11-23 | 濮阳市联众兴业化工有限公司 | A method of the cracking decoloration of carbon nine is deodorized |
| CN108865259B (en) * | 2018-06-09 | 2022-08-05 | 濮阳市联众兴业化工有限公司 | Method for decoloring and deodorizing cracking carbon nine |
| CN109704905A (en) * | 2019-01-24 | 2019-05-03 | 洋浦傲立石化有限公司 | A kind of depolymerization process of dicyclopentadiene |
| CN109704905B (en) * | 2019-01-24 | 2019-09-13 | 洋浦傲立石化有限公司 | A kind of depolymerization process of dicyclopentadiene |
| CN110563533A (en) * | 2019-09-19 | 2019-12-13 | 广东新华粤石化集团股份公司 | Method for preparing methyl cyclopentadiene dimer from cracking carbon nine fraction |
| CN112679297A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Preparation method of high-purity dicyclopentadiene |
| CN114085138A (en) * | 2021-11-16 | 2022-02-25 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer and intermediate thereof |
| CN114085138B (en) * | 2021-11-16 | 2023-12-29 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer and intermediate thereof |
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