CN1334262A - Process for preparing high-purity cyclopentadiene and its special equipment - Google Patents
Process for preparing high-purity cyclopentadiene and its special equipment Download PDFInfo
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- CN1334262A CN1334262A CN 00120769 CN00120769A CN1334262A CN 1334262 A CN1334262 A CN 1334262A CN 00120769 CN00120769 CN 00120769 CN 00120769 A CN00120769 A CN 00120769A CN 1334262 A CN1334262 A CN 1334262A
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Abstract
A process for preparing high-purity cyclopentadiene from raw bicyclopentadiene through preheating, ordinary-pressure depolymerizing at 200-300 deg.C in depolymerizing rectification tower, and rectification. Its advantages are high purity (98%) and cyclic use of heat carrier for continuous production.
Description
The present invention relates to a kind of method and specific equipment thereof for preparing cyclopentadiene, specifically, the present invention relates to a kind of method and specific equipment thereof for preparing cyclopentadiene by the dicyclopentadiene depolymerization.
Cyclopentadiene has another name called luxuriant (being called for short CPD), and its structure is five carbocyclic ring conjugated dieness, is important organic chemical industry and fine chemical material.Active hydrogen has stronger response capacity on conjugated double bond and the methylene radical owing to having in the cyclopentadiene molecules, therefore chemical reactions such as it can reduce with multiple compound, oxidation, addition, copolymerization, condensation are widely used in fields such as synthetic pesticide, plastics, rubber, spices, medicine, fire retardant, unsaturated polyester.
At present, the main source of cyclopentadiene has two, and the first is separated from coal tar benzene over-head distillate, and it two is to separate from the C5 fraction of petroleum fractions thermo-cracking system ethylene unit by-product.The former originates limited, and latter's raw material abundance is the main source of current and expected future.Also comprise other component isoprene and m-pentadiene etc. in the C5 fraction.Isolate cyclopentadiene and will utilize the cyclopentadiene dimerization reaction from C5 fraction, this reaction is the heat release reversible reaction.And dimerization reactions such as cyclopentadiene and isoprene and cyclopentadiene and m-pentadiene major part can be ignored in normal range for irreversible reaction or its reversed reaction.Therefore, can at first the cyclopentadiene dimerization be become dicyclopentadiene, obtain thick dicyclopentadiene after isolating other C5 fractions by rectificating method then at 80-130 ℃.This thick dicyclopentadiene at high temperature 180-500 ℃ depolymerize to cyclopentadiene, so just can more conveniently obtain cyclopentadiene monomers.
Easy dimerization becomes dicyclopentadiene (being called for short DCPD) under the cyclopentadiene room temperature, so the commodity cyclopentadiene just is cyclopentadiene with its depolymerization all with the form sale of dicyclopentadiene when using.
The method of dicyclopentadiene depolymerization commonly used has liquid phase depolymerization and gas phase depolymerization at present.Adopt the liquid phase depolymerization of solvent to be characterized in that temperature condition relaxes, equipment is simple, but, make dicyclopentadiene in the tower still, can generate relatively large polymer, reduced the yield of product cyclopentadiene through long-time heating owing in separating collecting process, used solvent; The bad recovery of its tower still solvent simultaneously.And the gas phase depolymerization is reacted under comparatively high temps, and short in the reaction zone residence time, the dicyclopentadiene transformation efficiency is higher, but its technology is comparatively complicated.
Lower by its purity of dicyclopentadiene that obtains by the dimerization reaction separation in the C5 fraction of petroleum fractions thermo-cracking system ethylene unit by-product, greatly about about 85%.If the method with conventional liquid phase depolymerization is a cyclopentadiene with its depolymerization, then the lower large-scale industrial application that makes of yield owing to dicyclopentadiene is subjected to certain restriction, and this just needs to adopt special depolymerization method to prepare highly purified cyclopentadiene.
For obtaining highly purified dicyclopentadiene or cyclopentadiene, people have carried out more research.More early stage technology adopts high-temperature steam, paraffinic hydrocarbon, aromatic hydrocarbons mixing wet goods as thermal barrier, at high temperature mixes with dicyclopentadiene, makes dicyclopentadiene be decomposed into cyclopentadiene.For example U.S. Pat 2831954, Japanese Patent are clear 50227537, European patent EP 0509445, russian patent SU1328343 etc. all are to adopt high temperature heat-carrying logistics and thick dicyclopentadiene to mix, under normal pressure and hot conditions, carry out the decomposition reaction of gas phase or the liquid phase of moment, make the dicyclopentadiene depolymerization.The characteristics of these class methods are that the yield of dicyclopentadiene is higher, and its shortcoming is a severe reaction conditions to the having relatively high expectations of equipment, owing to need a large amount of thinners is discharged continuously the reaction process more complicated.In addition, the high temperature in the reaction process makes reactor existence coking in various degree, and the life-span of reactor also is subjected to bigger influence.
Chinese patent CN1150942A discloses a kind of method for preparing high-purity cyclopentadiene, and this patent is to adopt the high temperature heat medium oil to carry out moment with raw material in reactor contact, and the method that gas-phase decomposition is reacted takes place; Specific practice is that the material dicyclopentadiene directly is added in the still, contacts with thermal barrier in the still and is vaporized depolymerization, and collect heavy constituent under the rectifying tower internal reflux by liquid trap.But use this patented technology also to have more problem: one is because the high temperature heat medium oil directly contacts with raw material in reactor, makes the polymer and the heat medium oil combination that generate in the depolymerization, makes heat medium oil be difficult to recirculation and uses; Its two owing to rest in the reactor, just must regularly in reactor, inject fresh heat medium oil and the discharging regularly heat medium oil that gives up through the heat medium oil after the heat exchange, make the serialization production of whole device be subjected to certain restriction; Also need extra equipment to heat to heat medium oil in addition.
In order to overcome above-mentioned problems of the prior art, the inventor works out through long-term experiment and a kind ofly prepares the method for high-purity cyclopentadiene and produce the specific equipment that described high-purity cyclopentadiene institute must use.
One of purpose of the present invention is to provide a kind of method for preparing high-purity cyclopentadiene, this method can effectively overcome in the prior art through generating relatively large polymer or high temperature heating medium in the long-time heating tower still and directly contacts the thermophore that is brought with raw material be difficult to problems such as recirculation use in reactor, using preparation method of the present invention can obtain final purity is 98% cyclopentadiene, and can be on industrial equipments continuous production.
Two of purpose of the present invention is to provide the described high-purity cyclopentadiene of preparation necessary specific equipment.
To introduce technical scheme of the present invention in detail below.
The method for preparing high-purity cyclopentadiene of the present invention comprises:
(1) thick dicyclopentadiene enters the tower still of depolymerization rectifying tower after metering, preheating;
(2) thick dicyclopentadiene normal pressure depolymerization in the tower still, the depolymerization temperature is 200-300 ℃, preferred depolymerization temperature is 240 ℃-260 ℃;
(3) rectifying of the cyclopentadiene after the depolymerization;
With the thick dicyclopentadiene of raw material by test tank through volume pump, again through entering the tower still of depolymerization rectifying tower after the preheater preheating, depolymerization after the heating vaporization in the tower still, and enter the pinching section by gas passage, cyclopentadiene after the depolymerization is further purified by rectifying section, and the product cyclopentadiene after the purification enters the product jar through condenser.
Tower still of the present invention comprises the kettle and the chuck of dicyclopentadiene feed-pipe, pyramidal structure.
On the internal surface of the kettle of described pyramidal structure, be distributed with spiral helicine groove.The dicyclopentadiene feed-pipe is communicated with described groove.The mode that is communicated with can be for directly being communicated with or adopting the spray orifice mode that material is imported groove.
The degree of depth of wherein said groove is 0.5mm-10.0mm; When described tower still height was 150mm, the degree of depth of preferred groove was 1-2mm; The width of wherein said groove is 3mm-20mm; When described tower still height is 150mm, be preferably 5mm; The number of turns of described groove is the 5-15 circle, is preferably 11 or 12 circles, when being every 100mm in described tower still height.Fluted body passage of the present invention constantly is vaporized and depolymerization dicyclopentadiene along the groove forward impelling time, thereby can improve the yield of cyclopentadiene depolymerization.
The degree of depth of groove of the present invention, width can increase with the increase of tower still diameter, and the diameter of tower still is big more, and the flow of the raw material in the tower still is also just big more, and the degree of depth of groove, width also need corresponding increase.
The number of turns of groove of the present invention and described tower still height are proportional.
Groove of the present invention makes the thick dicyclopentadiene liquid of the raw material that enters sequential advancement, increased the residence time of raw material, dicyclopentadiene successive in propelling is vaporized, thereby avoided dicyclopentadiene liquid to flow under directly from the top of still at the bottom of the still and form and be difficult for being vaporized polymer; The dicyclopentadiene polymer of Sheng Chenging can be discharged by the leakage fluid dram of tower still bottom simultaneously, is beneficial to its further processing recovery.
Because described tower still has the effect that thermal material makes its vaporization that adds in this technical process, therefore enough heating-surface areas to be arranged; Method of the present invention changes heating-surface area by the method that increases the kettle height under the tower diameter condition of determining, thereby the heating-surface area and the dicyclopentadiene that can guarantee needs are vaporized the needed residence time.
Because kettle of the present invention is a pyramidal structure, the hot face of its taper is corresponding with tower section, has therefore guaranteed the uniform distribution of rising gas in the tower; Simultaneously, under the tower diameter condition of determining, the heating-surface area of taper still can change by the height that increases cone, thereby the heating-surface area and the dicyclopentadiene that have guaranteed needs are vaporized the needed residence time.
Wherein said chuck is the heating jacket of hollow, and the medium in the heating jacket can be thermal oil; Thermal oil forms the uniform heating face in the interlayer of chuck, heat the kettle of described pyramidal structure.The temperature of the thermal oil in the chuck is 200-300 ℃, is preferably 240-260 ℃.
Wherein said pinching section comprises gas passage and side line discharge port; Contain two kinds of dimers that cyclopentadiene and isoprene and cyclopentadiene and m-pentadiene form in the raw material dicyclopentadiene, the percentage composition of these two kinds of dimers in the raw material gross weight is 6-10%, because it is less that these two kinds of dimers are separated in the collecting process depolymerization rate in vaporization, thereby be condensed at rectifying section, and from the side line discharge port to be obtained carrying dense by the mode of extraction, the about 12-18% of its concentration, by weight percentage, thus for further utilizing these two kinds of dimers to obtain the source of material.
Processes such as metering of the present invention, preheating, condensation all can adopt the existing conventional technology.
Rectifying tower in rectifying section of the present invention and the conventional tripping device relatively, its structure and effect are basic identical, in whole process of preparation, play the effect of rectification and purification, in preparation method of the present invention, cyclopentadiene after the depolymerization is further purified cyclopentadiene at rectifying section by refinery distillation, obtains highly purified product from cat head.
The necessary specific equipment of preparation high-purity cyclopentadiene of the present invention is meant tower still of the present invention.
Described tower still comprises the kettle and the chuck of dicyclopentadiene feed-pipe, pyramidal structure.
On the internal surface of the kettle of described pyramidal structure, be distributed with spiral helicine groove.The dicyclopentadiene feed-pipe is communicated with described groove.The mode that is communicated with can be for directly being communicated with or adopting the spray orifice mode that material is imported groove.
The degree of depth of wherein said groove is 0.5mm-10.0mm; When described tower still height was 150mm, the degree of depth of preferred groove was 1-2mm; The width of wherein said groove is 3mm-20mm; When described tower still height is 150mm, be preferably 5mm; The number of turns of described groove is the 5-15 circle, is preferably 11 or 12 circles, when being every 100mm in described tower still height.Wherein said chuck is the heating jacket of hollow, and the medium in the heating jacket can be thermal oil, and thermal oil forms the uniform heating face in the interlayer of chuck, heats the kettle of described pyramidal structure.
Further describe technical scheme of the present invention below in conjunction with accompanying drawing.
Fig. 1 is the schematic flow sheet of the depolymerization rectifying tower of preparation cyclopentadiene method of the present invention.
Fig. 2 is the longitudinal section synoptic diagram of preparation cyclopentadiene specific equipment tower still of the present invention.
With the thick dicyclopentadiene of raw material by measuring tank 1 through measuring pump 2, it is laggard to pass through feed preheater 3 preheatings again Enter tower reactor 4, in the interior depolymerization after the heating vaporization of tower reactor 4, and enter pinching section 5, depolymerization by gas passage 14 After cyclopentadiene further purified by rectifying section 6, the product cyclopentadiene after the purification is through cryogenic condensation Device 7 enters products pot 8. The dimer that generates in the course of reaction is plucked out of from side line discharge 9.
Compared with prior art, the present invention has following beneficial effect: 1. method of the present invention does not exist material and the direct of high-temperature heat carrier to contact, thereby has avoided heat carrier Pollute and loss, also avoided the loss of material simultaneously. 2. be distributed with spiral helicine groove on the inner surface of kettle in the method for the present invention, guaranteed dicyclopentadiene Can not produce directly flow to still from the top of still at the bottom of, simultaneously since dicyclopentadiene when the Baltimore groove forward impelling not Disconnected is heated, vaporizes, thereby can improve the vaporization depolymerization rate of dicyclopentadiene. In the method for the present invention since kettle be pyramidal structure, the heating surface of its taper is corresponding with tower section, Thereby guaranteed that the gas that is heated vaporization can be evenly distributed in the tower, can solve like this in the engineering amplification needs The problem that distributes of gas uniform. 4. method employing lateral line discharging of the present invention can be concentrated in carbon five hydrocarbon and be difficult for by the dimer of depolymerization, makes them No longer be back to tower reactor, and directly from the side line discharge extraction, thereby reduced the generation of polymer, simultaneously can Ceaselessly concentrate and discharge this being difficult for by the dimer of depolymerization, for serialization production provides condition. 5. use special equipment of the present invention, can make vaporization, depolymerization, rectification process integrator, simplify behaviour Do to be fit to very much again serialization production. Produce cyclopentadiene by method of the present invention, once through yield can reach 85%, Cyclopentadiene purity reaches 98%.
Describe the present invention further below by embodiment, the present invention is more in depth understood with promotion.But the present invention is not subjected to the restriction of these embodiment.Those skilled in the art can make amendment or improve under the guide of spirit of the present invention the present invention, all belong to apparent.Protection scope of the present invention proposes in claims.
Embodiment
Embodiment 1
With concentration is that 90% dicyclopentadiene is a raw material, and dicyclopentadiene, is advanced downwards along groove by the dicyclopentadiene feed-pipe continuously by entering the tower still by volume pump.The degree of depth of its further groove is 1mm, and the width of groove is 5mm, and tower still height is 150mm; The number of turns of inner surface recesses is 15 circles.Oily temperature control outside the still is at 284 ℃, and tower top temperature is 44 ℃.Cat head obtains the cyclopentadiene product, and purity is 98%, and the yield of cyclopentadiene is 85%.
With concentration is that 83.9% dicyclopentadiene is a raw material, and the dimer concentration 7-8% in the raw material enters the tower still continuously, and the degree of depth of its further groove is 1mm, and the width of groove is 5mm, and tower still height is 150mm; The number of turns of inner surface recesses is 15 circles.289 ℃ of the outer thermal oil temperature of still, 40 ℃ of tower top temperatures obtain the cyclopentadiene product, and purity is 96%, the yield 70% of cyclopentadiene.Dimer concentration is 16.32% from the material of side line extraction.
Claims (10)
1. a method for preparing cyclopentadiene is a raw material with thick dicyclopentadiene, comprises the steps:
(1) thick dicyclopentadiene enters the tower still [4] of depolymerization rectifying tower after metering, preheating;
(2) thick dicyclopentadiene normal pressure depolymerization in tower still [4], the depolymerization temperature is 200-300 ℃;
(3) rectifying of the cyclopentadiene after the depolymerization;
Wherein said tower still [4] comprises the kettle [11] and the chuck [12] of dicyclopentadiene feed-pipe [10], pyramidal structure;
On the internal surface of the kettle [11] of described pyramidal structure, be distributed with spiral helicine groove [13]; Dicyclopentadiene feed-pipe [10] is communicated with described groove [13].
2. method according to claim 1 is characterized in that, the degree of depth of described groove [13] is 0.5mm-10.0mm, and the width of groove [13] is 3mm-20mm; The number of turns of groove [13] is 5 one 15 circles, when highly being every 100mm in described tower still [4].
3. method according to claim 1 is characterized in that, the degree of depth of described groove [13] is 1-2mm.
4. method according to claim 1 is characterized in that, the width of described groove [13] is 5mm.
5. method according to claim 1 is characterized in that, the number of turns of described groove [13] is 11 or 12 circles, when highly being every 100mm in described tower still [4].
6. method according to claim 1 is characterized in that, described depolymerization temperature is 240 ℃-260 ℃.
7. an equipment for preparing high-purity cyclopentadiene is characterized in that, described equipment is tower still [4], and described tower still [4] comprises the kettle [11] and the chuck [12] of dicyclopentadiene feed-pipe [10], pyramidal structure;
On the internal surface of the kettle [11] of described pyramidal structure, be distributed with spiral helicine groove [13]; Dicyclopentadiene feed-pipe [10] is communicated with described groove [13];
The degree of depth of wherein said groove [13] is 0.5mm-10.0mm, and the width of groove [13] is 3mm-20mm; The number of turns of groove [13] is the 5-15 circle, when highly being every 100mm in described tower still [4].
8. equipment according to claim 7 is characterized in that, the degree of depth of described groove [13] is 1-2mm.
9. equipment according to claim 7 is characterized in that, the width of described groove [13] is 5mm.
10. equipment according to claim 7 is characterized in that, the number of turns of described groove [13] is 11 or 12 circles, when highly being every 100mm in described tower still [4].
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001207695A CN1163459C (en) | 2000-07-13 | 2000-07-13 | Process for preparing high-purity cyclopentadiene and its special equipment |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001207695A CN1163459C (en) | 2000-07-13 | 2000-07-13 | Process for preparing high-purity cyclopentadiene and its special equipment |
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| CN1334262A true CN1334262A (en) | 2002-02-06 |
| CN1163459C CN1163459C (en) | 2004-08-25 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664466A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing high-purity cyclopentadiene |
| US9988324B2 (en) | 2015-11-04 | 2018-06-05 | Exxonmobil Chemical Patents Inc. | Process and system for making cyclopentadiene and/or dicyclopentadiene |
-
2000
- 2000-07-13 CN CNB001207695A patent/CN1163459C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664466A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing high-purity cyclopentadiene |
| US9988324B2 (en) | 2015-11-04 | 2018-06-05 | Exxonmobil Chemical Patents Inc. | Process and system for making cyclopentadiene and/or dicyclopentadiene |
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| Publication number | Publication date |
|---|---|
| CN1163459C (en) | 2004-08-25 |
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