CN103304361A - Production method of high purity cyclopentene - Google Patents
Production method of high purity cyclopentene Download PDFInfo
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- CN103304361A CN103304361A CN2012100669647A CN201210066964A CN103304361A CN 103304361 A CN103304361 A CN 103304361A CN 2012100669647 A CN2012100669647 A CN 2012100669647A CN 201210066964 A CN201210066964 A CN 201210066964A CN 103304361 A CN103304361 A CN 103304361A
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Abstract
The invention relates to the technical field of production of chemical products, and in particular relates to a production method of high purity cyclopentene. The method comprises the following steps of: feeding part of a hydrogenated c5 fraction to a rectifying tower A; separating a coarse isoamylene fraction from the top; obtaining a tower bottom liquid comprising cyclopentene and cyclopentane fractions from the kettle; feeding the tower bottom liquid after dimerization reaction to a rectifying tower B for rectification; and extracting cyclopentene from the top. The method provided by the invention has the advantages that when the part of hydrogenated c5 fraction is separated to produce cyclopentene, 2-methyl-2-butene which is very approximate to cyclopentene in boiling point is converted into a heavy component with higher boiling point through the dimerization reaction on a catalyst bed layer, so that cyclopentene is easily separated from 2-methyl-2-butene, so that not only is the energy consumption remarkably reduced, but also cyclopentene with purity over 99% can be produced.
Description
Technical field
The present invention relates to the Chemicals production technical field, particularly a kind of production method of separation of high-purity Cyclopentene.
Background technology
Cyclopentenes is a kind of intermediate of fine chemical product, and it can be used as high added value medicine intermediates such as producing cyclopentanol, bromocyclopentane, chlorocyclopentane, chaulmoogric acid, and separation of high-purity Cyclopentene is still gathered one of main raw material of cycloolefin high molecular polymer.Be cyclopentenes most important applications field with the cyclopentenes for the raw material production cyclopentanone wherein.Cyclopentanone is the intermediate of spices and medicine industry, can be used for producing novel spices methyl dihydrojasmonate and fine chemical products such as white orchid ketone and anxiolytic buspirone, also can be used for the synthetic of agricultural chemicals such as sterilant and weedicide, in addition, because cyclopentanone has good solubility property, is used widely as solvent in electron trade.
The a considerable amount of C5 fractions of by-product in the process of industrial preparing ethylene by steam cracking.This C5 fraction can be divided into two classes according to complete processing and composition.One class is the C5 fraction that obtains by the method that cracked C 5 fraction is directly separated, contain 40～60% the diolefins such as isoprene, cyclopentadiene and m-pentadiene of having an appointment in this class C5 fraction, these diolefin chemical property are active, be the important source material of a lot of fine chemical products, the means that can adopt traditional rectifying separation and technologies such as extracting rectifying separates to combine are carried out the separation of C5 fraction and are purified; Second class is the C5～C9 cut that will obtain in the preparing ethylene by steam cracking process, earlier at Pd/Al
2O
3On carry out selective hydrogenation and make wherein diolefin and alkynes be converted into monoolefine, the C5 fraction that obtains through rectifying separation again, this part material can be described as the partial hydrogenation C5 fraction.The partial hydrogenation C5 fraction can obtain cyclopentenes through rectifying separation.
It is raw material with the partial hydrogenation pyrolysis gasoline that US Patent No. P6153804 has introduced a kind of, by rectifying separation produce pentamethylene or (with) method of cyclopentenes.Elder generation is from the lower boiling C5 fraction of cat head extraction of first rectifying tower, the tower reactor extraction contains six carbon and above heavy constituent, contain pentamethylene and cyclopentenes from the side line extraction and be at least 40% cut, this cut is sent into hydrogenator, making conversion of olefines is alkane, hydrogenation products is sent into second rectifying tower again, tells Skellysolve A and iso-pentane mixture from cat head, and tower bottoms is sent into the 3rd rectifying tower and obtained pentamethylene.Perhaps will contain pentamethylene and cyclopentenes is at least 40% cut and directly carries out rectifying separation and obtain cyclopentenes and pentamethylene.
US Patent No. P6264799 proposed a kind of production pentamethylene or (with) method of cyclopentenes.The partial hydrogenation C5 fraction is carried out rectifying at first rectifying tower, and lower boiling C5 fraction separates from cat head, the tower reactor cut is sent into second rectifying tower carry out rectifying again, tells cyclopentenes from cat head.
Aforesaid method mainly is to obtain cyclopentenes by rectifying separation technology, but owing to relate to separating of monoolefine 2-methyl-2-butene that boiling point and cyclopentenes approach very much, energy consumption is higher, and the cyclopentenes content that obtains only has an appointment 90%, has influenced the chemical utilization in its downstream.
Summary of the invention
The invention provides a kind of production method of separation of high-purity Cyclopentene, technical problem to be solved is that the cyclopentenes purity of producing in the prior art is not high, the more high weak point of production process energy consumption.
Below be the concrete technical scheme of the present invention:
A kind of production method of separation of high-purity Cyclopentene, this method may further comprise the steps:
1) rectifying tower A is sent in the partial hydrogenation C5 fraction, tell the coarse isoamylene cut from cat head, obtain containing the tower bottoms of cyclopentenes, pentamethylene cut from tower reactor;
2) tower bottoms that rectifying tower A is contained cyclopentenes, pentamethylene cut carries out dimerization reaction, produces dimerization reaction liquid;
3) dimerization reaction liquid is sent into rectifying tower B and carry out rectifying, tell cyclopentenes from cat head.
Further, described rectifying tower A is packing tower, and its theoretical plate number is 70～110, and the tower reactor temperature is 70～100 ℃, and tower top temperature is 40～68 ℃, and working pressure is 0.1～0.3MPa, and reflux ratio is 6～15.
Further, the catalyzer of described dimerization reaction is the sulfonic group Zeo-karb, and reaction bed is fixed bed.
Further, the particle diameter of described sulfonic group Zeo-karb is 0.1～3mm, and the mass exchange capacity is 3～5.5mmol/g.
Further, the particle diameter of described sulfonic group Zeo-karb is 0.40～1.25mm, is shaped as sphere, and the mass exchange capacity is 4～5.5mmol/g.
Further, described rectifying tower B is packing tower, and its theoretical plate number is 70～120, and the tower reactor temperature is 60～100 ℃, and tower top temperature is 40～70 ℃, and working pressure is 0.1～0.3MPa, and reflux ratio is 6～10.
Further, the mass percent of each component is in the described partial hydrogenation C5 fraction: carbon 4 2～5%, pentane 30～50%, 2-methyl-1-butene alkene 3～5%, 2-methyl-2-butene 10～20%, cyclopentenes 10～18%, pentamethylene 8～15%, other C 5 monoolefin 8～15%, carbon six and above component 2～5%, sulphur content≤1ppm.
Compared with prior art, the invention has the advantages that when the partial hydrogenation C5 fraction carried out the separation of produced cyclopentenes, by making wherein the 2-methyl-2-butene that approaches very much with the cyclopentenes boiling point change into the higher heavy constituent of boiling point at beds by dimerization reaction, make cyclopentenes be easy to separate with the 2-methyl-2-butene, not only can significantly cut down the consumption of energy, and can production purity reach cyclopentenes more than 99%.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is process flow sheet of the present invention.
Among the figure: A, B are rectifying tower A, B.
Embodiment
The following stated only is preferred embodiment of the present invention, does not therefore limit protection scope of the present invention.
Embodiment, see shown in Figure 1:
With form as the partial hydrogenation C5 fraction of table 1 as described in rectifying tower A carry out rectifying.Described rectifying tower A is packing tower, and its theoretical plate number is 90～110.The partial hydrogenation C5 fraction is when being preheating to 45～55 ℃, the 50 plate charging from rectifying tower A, the tower working pressure is 0.18～0.20MPa, the tower reactor temperature is 70～80 ℃, tower top temperature is 45～55 ℃, reflux ratio is 8～15, and cat head extraction mass percent is 71% low boiler cut, and tower reactor discharges that to contain mass percent be 21% cyclic hydrocarbon cut.This step is told the light constituent that boiling point is lower than 38.57 ℃ (2-methyl-2-butene boiling points) from the cat head of described rectifying tower A, and boiling point is higher than the cut of 44.24 ℃ (cyclopentenes boiling points) from the tower reactor discharging.Because when rectifying, Rectification Column's Theoretical Plate Number can not be too high, reflux ratio can not be excessive, otherwise energy consumption is excessive.Therefore, though after adopting rectifying tower A of the present invention to carry out rectifying separation, the content of 2-methyl-2-butene still reaches 2～3% in the tower reactor cut.Therefore only adopt the method for rectifying separation to be difficult to obtain highly purified cyclopentenes, and wherein contained 2-methyl-2-butene will badly influence the downstream application of cyclopentenes.Certainly, described rectifying tower A also can use bubble-plate column, tiltedly spray the tower of other types such as tower, sieve-tray tower.
The 2-methyl-2-butene of described rectifying tower A tower reactor material is carried out the catalytic dimerization reaction.Dimerization catalyst be particle diameter at the spherical sulfonic group Zeo-karb of 0.40～1.25mm, the mass exchange capacity of resin is 3～5.5mmol/g, mass space velocity is 1～35hr
-1, temperature of reaction is 18～45 ℃, reaction pressure is 0.1～0.5MPa.Dimerization transformation efficiency 〉=99% of 2-methyl-2-butene.Certainly, can also use the sulfonic group Zeo-karb of other shape or have other catalyzer of identical catalytic effect.Theoretically, acidic resins all have the catalytic dimerization effect for alkene, but because the difference that 2-methyl-2-butene and cyclopentenes structurally exist, the 2-methyl-2-butene is easy to generate dipolymer at catalyst surface generation dimerization reaction, and cyclopentenes does not participate in reaction substantially, the dipolymer boiling point significantly raises, and makes cyclopentenes and separating of dipolymer are become very simple, thereby reaches the purpose that cyclopentenes is separated with the 2-methyl-2-butene.After dimerization reaction liquid was further made with extra care, the remaining 2-methyl-2-butene that does not carry out dimerization reaction can be removed basically fully.
Above-mentioned dimerization reaction liquid is carried out rectifying in described rectifying tower B.Described rectifying tower B is packing tower, and its theoretical plate number is 100～120, and opening for feed is positioned at the 50 block of plate.Working pressure is 0.10～0.15MPa, and the tower reactor temperature is 60～70 ℃, and tower top temperature is 46～55 ℃, and reflux ratio is 8～10.Obtaining content from cat head is 99.38% cyclopentenes.Certainly, described rectifying tower B also can use bubble-plate column, tiltedly spray the tower of other types such as tower, sieve-tray tower.The tower bottoms of discharging from tower reactor can be by hydrogenation and rectifying production high purity pentamethylene again, in the heavy constituent of rectifying and the dimerization generation use that can act as a fuel, belongs to environmentally friendly technology.
The above only is preferred embodiments of the present invention, so all equivalences of making according to the described technological principle of patent claim of the present invention change or revise, is included in the patent claim of the present invention.
Table 1. partial hydrogenation C5 fraction raw material is formed
| Composition | Massfraction/% |
| Carbon four (in normal butane) | 3.66 |
| Iso-pentane | 13.16 |
| The 1-amylene | 1.17 |
| 2-methyl-1-butene alkene | 4.04 |
| Skellysolve A | 20.76 |
| Trans 2-amylene | 9.11 |
| Cis 2-amylene | 3.34 |
| The 2-methyl-2-butene | 15.19 |
| Cyclopentenes | 13.76 |
| Pentamethylene | 10.45 |
| Other carbon five | 0.45 |
| More than carbon six reaches | 4.63 |
| Sulphur content | ≤1ppm |
Claims (7)
1. the production method of a separation of high-purity Cyclopentene is characterized in that, this method may further comprise the steps:
1) rectifying tower A is sent in the partial hydrogenation C5 fraction, tell the coarse isoamylene cut from cat head, obtain containing the tower bottoms of cyclopentenes, pentamethylene cut from tower reactor;
2) tower bottoms that rectifying tower A is contained cyclopentenes, pentamethylene cut carries out dimerization reaction, produces dimerization reaction liquid;
3) dimerization reaction liquid is sent into rectifying tower B and carry out rectifying, tell cyclopentenes from cat head.
2. the production method of separation of high-purity Cyclopentene according to claim 1, it is characterized in that: described rectifying tower A is packing tower, its theoretical plate number is 70～110, the tower reactor temperature is 70～100 ℃, tower top temperature is 40～68 ℃, and working pressure is 0.1～0.3MPa, and reflux ratio is 6～15.
3. the production method of separation of high-purity Cyclopentene according to claim 1, it is characterized in that: the catalyzer of described dimerization reaction is the sulfonic group Zeo-karb, reaction bed is fixed bed.
4. the production method of separation of high-purity Cyclopentene according to claim 3, it is characterized in that: the particle diameter of described sulfonic group Zeo-karb is 0.1～3mm, the mass exchange capacity is 3～5.5mmol/g.
5. the production method of separation of high-purity Cyclopentene according to claim 3, it is characterized in that: the particle diameter of described sulfonic group Zeo-karb is 0.40～1.25mm, is shaped as sphere, the mass exchange capacity is 4～5.5mmol/g.
6. the production method of separation of high-purity Cyclopentene according to claim 1, it is characterized in that: described rectifying tower B is packing tower, its theoretical plate number is 70～120, the tower reactor temperature is 60～100 ℃, tower top temperature is 40～70 ℃, and working pressure is 0.1～0.3MPa, and reflux ratio is 6～10.
7. the production method of separation of high-purity Cyclopentene according to claim 1, it is characterized in that: the mass percent of each component is in the described partial hydrogenation C5 fraction: carbon 4 2～5%, pentane 30～50%, 2-methyl-1-butene alkene 3～5%, 2-methyl-2-butene 10～20%, cyclopentenes 10～18%, pentamethylene 8～15%, other C 5 monoolefin 8～15%, carbon six and above component 2～5%, sulphur content≤1ppm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668924A (en) * | 2019-08-28 | 2020-01-10 | 派尔科化工材料（启东）有限公司 | Combined process for comprehensive utilization of partial hydrogenation carbon five-fraction |
| CN110698318A (en) * | 2019-08-28 | 2020-01-17 | 派尔科化工材料（启东）有限公司 | Production method of high-purity cyclopentene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793381A (en) * | 1971-06-26 | 1974-02-19 | Erdoelchemie Gmbh | Process for purifying cyclopentene |
| US20010020580A1 (en) * | 1998-03-05 | 2001-09-13 | Ec Erdolchemic Gmbh, Corporation Of Germany | Process for isolating cyclopentane and/or cyclopentene |
| CN1789221A (en) * | 2005-12-26 | 2006-06-21 | 山东玉皇化工有限公司 | Method for producing high-purity cyclopentadiene and cyclopentane by coarse piperyene |
| CN101544534A (en) * | 2009-04-16 | 2009-09-30 | 中国石油兰州石油化工公司 | Method for directly separating and purifying cyclopentene from C5 raw material adopting extraction and distillation technology |
-
2012
- 2012-03-13 CN CN2012100669647A patent/CN103304361A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793381A (en) * | 1971-06-26 | 1974-02-19 | Erdoelchemie Gmbh | Process for purifying cyclopentene |
| US20010020580A1 (en) * | 1998-03-05 | 2001-09-13 | Ec Erdolchemic Gmbh, Corporation Of Germany | Process for isolating cyclopentane and/or cyclopentene |
| CN1789221A (en) * | 2005-12-26 | 2006-06-21 | 山东玉皇化工有限公司 | Method for producing high-purity cyclopentadiene and cyclopentane by coarse piperyene |
| CN101544534A (en) * | 2009-04-16 | 2009-09-30 | 中国石油兰州石油化工公司 | Method for directly separating and purifying cyclopentene from C5 raw material adopting extraction and distillation technology |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110668924A (en) * | 2019-08-28 | 2020-01-10 | 派尔科化工材料（启东）有限公司 | Combined process for comprehensive utilization of partial hydrogenation carbon five-fraction |
| CN110698318A (en) * | 2019-08-28 | 2020-01-17 | 派尔科化工材料（启东）有限公司 | Production method of high-purity cyclopentene |
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Application publication date: 20130918 |