CN102276409A - Novel dimerization temperature control process for producing dicyclopentadiene based on cyclopentadiene reaction - Google Patents
Novel dimerization temperature control process for producing dicyclopentadiene based on cyclopentadiene reaction Download PDFInfo
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- CN102276409A CN102276409A CN2011100997295A CN201110099729A CN102276409A CN 102276409 A CN102276409 A CN 102276409A CN 2011100997295 A CN2011100997295 A CN 2011100997295A CN 201110099729 A CN201110099729 A CN 201110099729A CN 102276409 A CN102276409 A CN 102276409A
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Abstract
The invention discloses a novel dimerization temperature control process for producing dicyclopentadiene based on cyclopentadiene reaction, and the method comprises the following step of: in a process for producing the dicyclopentadiene from cyclopentadiene through a thermal dimerization reaction, segmenting the cyclopentadiene at lower temperature into five shares, wherein one share enters a preheater and then enters a primary thermal polymerization reactor for reacting, and the left four shares which are not preheated respectively enter a first section and a second section of the primary thermal polymerization reactor and a first section and a second section of a secondary thermal polymerization reactor for reacting so as to be used as a reaction raw material on the one hand and used as a cooling medium replacing cooling water on the other hand, thus energy loss caused by first heating and then cooling in the original thermal dimerization reaction is greatly reduced, and a large quantity of cooling water is saved.
Description
Technical field
The present invention relates to the poly-temperature control flow process in a kind of cyclopentadiene reaction generation dicyclopentadiene process, particularly the cold of application response thing own replaces water coolant temperature required to reach reactor, the novel poly-temperature control method of energy efficient.
Background technology
Cracked C 5 fraction is the by product in petrochemical complex oil refining apparatus, catalytic cracking unit and the heavy oil cracking device cracking ethylene preparation process, is a kind of basic material with potential value, and its output is generally 10%～20% of ethylene yield.In the comprehensive utilization of C5 fraction, what have utility value most is these three kinds of alkene of isoprene, m-pentadiene and cyclopentadiene, its content accounts for 45%～55% of total content, is that raw material can be produced multiple petrochemical complex and fine chemical product with these diolefins.
Separating ring pentadiene (CPD) is the important component part of carbon five isolation technique from C5 fraction, industrially all adopts hot dimerization method.Diolefin in the C5 fraction all can take place from dimerization and codimerization and poly reaction, because cyclopentadiene than the reactive behavior height of other diolefin, just takes place under the room temperature to generate dicyclopentadiene (DCPD), thereby become main reaction from dimerization reaction.The purposes of product dicyclopentadiene maximum is to prepare hydrogenation amiantuhs resin by thermopolymerization or catalyzed polymerization, C 5 petroleum resin is acidproof, water-fast owing to having, fusing point is low, viscosity is high, can be used as sizing agent, paint additive, synthetic rubber additive etc.In addition, dicyclopentadiene can also be used to making unsaturated polyester and synthesizing adamantane.The technological process of hot dimerization reaction is that C5 fraction is heated with the temperature that is not higher than 130 ℃ in polymeric kettle earlier, makes cyclopentadiene aggregate into dicyclopentadiene, steams light constituent from cat head then.Bottoms enters the dicyclopentadiene treating tower, can obtain containing 80%～90% dicyclopentadiene after making with extra care.It is 95%～99% dicyclopentadiene that dicyclopentadiene can obtain purity through technologies such as condensation and rectifying again.Through verification experimental verification, when temperature of reaction reached 130 ℃, the depolymerization of dicyclopentadiene increased, and yield descends, and side reaction increases, so temperature of reaction generally is selected in 100～120 ℃.In the present hot dimerization reaction flow process, the lower raw material cyclopentadiene of temperature need be heated at first that certain temperature is sent into one-level hot polymerization reactor later on again and secondary hot polymerization reactor reacts through preheater, this reaction is thermopositive reaction, for making the unlikely too high depolymerization that causes the product dicyclopentadiene of temperature of reaction, in reaction process, also need to shift out partial reaction heat with water coolant, with the temperature that keeps suiting, thereby reach higher transformation efficiency.This cold process in hot earlier back has caused the certain energy loss.
Summary of the invention
In order to solve the problem that prior art exists, the invention provides a kind of novel poly-temperature control flow process, to solve the big problem of the hot dimerization reaction power loss of prior art based on cyclopentadiene reaction generation dicyclopentadiene.
The present invention is achieved through the following technical solutions:
1) temperature is lower raw material cyclopentadiene is divided into five strands, controls its flow with flow director respectively.Wherein a stock-traders' know-how preheater is preheated to about 150 ℃, sends into one-level hot polymerization reactor and secondary hot polymerization reactor again and carries out the hot polymerization reaction, generates dicyclopentadiene.
2) all the other four strands raw material cyclopentadiene without preheating are sent into a section, second-stage reaction of a section of one-level hot polymerization reactor, second-stage reaction and secondary hot polymerization reactor respectively, on the one hand as reactant, replace water coolant on the other hand, utilize self temperature to provide optimal temperature for reactor, hot dimerization reaction temperature is 100～120 ℃.The application of temperature controller is controlled the flow of four strands of cold raw materials, to reach required temperature of reaction and reaction conversion ratio.
3) if insufficient raw material is to provide reaction required cold, all the other colds are still provided by water coolant.
Novel poly-temperature control method of the present invention is primarily aimed at the old flow process of hot dimerization reaction, and the heat back is cold earlier, causes the problem of power loss to propose.The cold of the novel poly-temperature control method application of cold temperature raw material that the present invention adopts itself replaces water coolant, has both reduced the energy consumption of preheater, greatly reduces the consumption of water coolant again, has reached the effect of good saving general facilities.
Description of drawings
Fig. 1 is the prior art processes schema;
Wherein 1 is preheater, and 2 is first step hot polymerization reactor, and 3 is second stage hot polymerization reactor, and 4 is temperature regulator, and 5-10 is a pipeline, and 11 is raw material, and 12 is product; Water coolant from pipeline 5 flows out from pipeline 6 through the hot polymerization reactor.
The novel poly-temperature control schema of the present invention when Fig. 2 is raw material cold abundance;
Wherein 1 is preheater, and 2 is first step hot polymerization reactor, and 3 is second stage hot polymerization reactor, and 4 is temperature regulator, and 5-8 is divided into five strands wherein four strands of raw material, and 9 is raw material, and 10 is product.
The novel poly-temperature control schema of the present invention when Fig. 3 is raw material cold deficiency;
Wherein 1 is preheater, and 2 is first step hot polymerization reactor, and 3 is second stage hot polymerization reactor, 4 is temperature regulator, and 5-8 is divided into five strands wherein four strands of raw material, and 9-10 is a pipeline, 11 is raw material, and 12 is product, flows out from pipeline 10 through the hot polymerization reactor from the water coolant of pipeline 9.
Embodiment
Further describe details of the present invention by the following examples.Under identical reaction conditions, prove advantage of the present invention by the energy consumption difference that compares the old and new's flow process.
Adopt former technical process, with temperature is that 25 ℃ raw material cyclopentadiene 100kmol/h all sends into preheater and is preheated to 150 ℃, and then send into one-level hot polymerization reactor, behind two-stage reaction, send into secondary hot polymerization reactor again, carry out two-stage reaction equally, finally obtain the mixture of product dicyclopentadiene and unreacted cyclopentadiene.Heat unnecessary in the reaction process is all shifted out by water coolant.Wherein the temperature of reaction of one-level hot polymerization is 110 ℃, and the temperature of reaction of secondary hot polymerization is 100 ℃, and the reaction total conversion rate is 90%.
Use novel poly-temperature control method of the present invention, same temperature is that 25 ℃ raw material cyclopentadiene 100kmol/h is divided into five strands with it before entering preheater, and each thigh is 20kmol/h.Wherein a stock-traders' know-how preheater is preheated to 150 ℃, sends into one-level hot polymerization reactor again and reacts, and sends into secondary hot polymerization reactor behind two-stage reaction again, carries out two-stage reaction equally.All the other then send into one section of one-level hot polymerization reactor, second-stage reaction and one section of secondary hot polymerization reactor, second-stage reaction respectively without the cyclopentadiene of preheating, on the one hand as reaction raw materials, also provide heat-eliminating medium for shifting out unnecessary reaction heat on the other hand.Replenish by water coolant for reaching needed all the other colds of reaction optimal temperature.Wherein the temperature of reaction of one-level hot polymerization is 110 ℃, and the temperature of reaction of secondary hot polymerization is 100 ℃, and the reaction total conversion rate is 90%.
Table 1 is that the energy consumption of two kinds of flow processs of the old and new compares.
Table 1 the old and new flow process energy consumption relatively
| Project | Former flow process | Novel poly-temperature control flow process |
| Preheater energy consumption/M*KJ/h | 4.0159 | 0.8032 |
| One section energy consumption of one-level hot polymerization reactor | -1.4198 | -0.7954 |
| Two sections energy consumptions of one-level hot polymerization reactor | -1.3404 | -0.5489 |
| One section energy consumption of secondary hot polymerization reactor | -2.0378 | -0.5793 |
| Two sections energy consumptions of secondary hot polymerization reactor | -0.7597 | -0.4215 |
| Total cold energy consumption/M*KJ/h | -5.5577 | -2.3451 |
| Cooling water inflow/t/h | 132.966 | 56.106 |
Data by adopting novel poly-temperature control flow process, are saved the heat energy consumption and are reached 80.00% as can be seen from table 1, and cooling water amount also is reduced to 57.80% of former flow process, and the reduction effect of general facilities is quite obvious.
Claims (1)
1. one kind generates the novel poly-temperature control flow process of dicyclopentadiene based on cyclopentadiene reaction, and this method may further comprise the steps:
1) temperature is lower raw material cyclopentadiene is divided into five strands, controls its flow with flow director respectively, and a wherein stock-traders' know-how preheater preheating is sent into one-level hot polymerization reactor and secondary hot polymerization reactor again and carried out the hot polymerization reaction, generates dicyclopentadiene;
2) all the other four strands raw material cyclopentadiene without preheating are sent into a section, second-stage reaction of a section of one-level hot polymerization reactor, second-stage reaction and secondary hot polymerization reactor respectively, on the one hand as reactant, replace water coolant on the other hand, utilize self temperature to provide optimal temperature for reactor, hot dimerization reaction temperature is 100～120 ℃, the application of temperature controller is controlled the flow of four strands of cold raw materials, to reach required temperature of reaction and reaction conversion ratio;
3) if insufficient raw material is to provide reaction required cold, all the other colds are still provided by water coolant.
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| CN2011100997295A CN102276409A (en) | 2010-05-12 | 2011-04-20 | Novel dimerization temperature control process for producing dicyclopentadiene based on cyclopentadiene reaction |
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| CN2011100997295A CN102276409A (en) | 2010-05-12 | 2011-04-20 | Novel dimerization temperature control process for producing dicyclopentadiene based on cyclopentadiene reaction |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591948A (en) * | 2013-10-30 | 2015-05-06 | 中石化上海工程有限公司 | Method for reducing energy consumption in the process for separation of 1,3-pentadiene from petroleum cracking C5 fraction |
| US11465951B2 (en) | 2018-12-12 | 2022-10-11 | Sabic Global Technologies B.V. | Dimerization of cyclopentadiene using shell and tube heat exchanger |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292370A (en) * | 1999-09-23 | 2001-04-25 | 化学工业部上海化工研究院 | Preparation method of high-purity endocyclic type cyclopentadiene |
| CN101215224A (en) * | 2008-01-07 | 2008-07-09 | 烟台同业化工技术有限公司 | Low energy-consumption method for preparing dimethyl ether from methanol |
| CN101643382A (en) * | 2009-07-13 | 2010-02-10 | 淄博齐鲁乙烯鲁华化工有限公司 | Preparation method for endocyclic dicyclopentadiene and device thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292370A (en) * | 1999-09-23 | 2001-04-25 | 化学工业部上海化工研究院 | Preparation method of high-purity endocyclic type cyclopentadiene |
| CN101215224A (en) * | 2008-01-07 | 2008-07-09 | 烟台同业化工技术有限公司 | Low energy-consumption method for preparing dimethyl ether from methanol |
| CN101643382A (en) * | 2009-07-13 | 2010-02-10 | 淄博齐鲁乙烯鲁华化工有限公司 | Preparation method for endocyclic dicyclopentadiene and device thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵新春等: "高纯双环戊二烯的制备", 《金山油化纤》, no. 4, 31 December 1999 (1999-12-31), pages 34 - 38 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591948A (en) * | 2013-10-30 | 2015-05-06 | 中石化上海工程有限公司 | Method for reducing energy consumption in the process for separation of 1,3-pentadiene from petroleum cracking C5 fraction |
| CN104591948B (en) * | 2013-10-30 | 2018-04-24 | 中石化上海工程有限公司 | It is a kind of to reduce the method that pentadiene process energy consumption is separated from petroleum cracking C5 fractions |
| US11465951B2 (en) | 2018-12-12 | 2022-10-11 | Sabic Global Technologies B.V. | Dimerization of cyclopentadiene using shell and tube heat exchanger |
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