CN102850171A - Method for chemically removing trace amount of cyclopentadiene in isoprene - Google Patents
Method for chemically removing trace amount of cyclopentadiene in isoprene Download PDFInfo
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- CN102850171A CN102850171A CN2012103676252A CN201210367625A CN102850171A CN 102850171 A CN102850171 A CN 102850171A CN 2012103676252 A CN2012103676252 A CN 2012103676252A CN 201210367625 A CN201210367625 A CN 201210367625A CN 102850171 A CN102850171 A CN 102850171A
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- isoprene
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Abstract
The invention provides a method for chemically removing a trace amount of cyclopentadiene in isoprene. The method comprises the following steps of: mixing a remover with a solvent, and then mixing the mixture with the isoprene containing a trace amount of cyclopentadiene; feeding the mixed material into a reactor loaded with a solid alkali molecular sieve catalyst so as to perform removal reaction; and carrying out distillation separation on the reacted material to obtain high-purity isoprene and simultaneously separating out a mixed liquor containing the remover, the solvent and fulvene compounds and water, wherein the remover is ketone, the solvent is an organic solvent, and the content of the cyclopentadiene in the isoprene containing a trace amount of cyclopentadiene is not less than 10ppm. By utilizing the method provided by the invention, the trace amount of cyclopentadiene in the isoprene can be effectively removed, and the content of cyclopentadiene in refined isoprene is less than 1ppm; and the method is favorable in selectivity, can be used for improving the isoprene quality and simultaneously improving the quality of isoprene downstream polymerization products.
Description
Technical field
The present invention relates to a kind of process for purification of isoprene, relate in particular to the chemical removal method of micro-cyclopentadiene in the isoprene.
Background technology
The comprehensive utilization of petroleum cracking C 5 fraction resource becomes one of important technology of chemical industry day by day, in pyrolysis C 5, content at most and most worthy be isoprene, the diolefins such as m-pentadiene and cyclopentadiene (CPD), wherein the value of isoprene is particularly outstanding, can be for the synthesis of polyisoprene rubber etc.
Separating isoprene from the C5 raw material, poor little and have a reason such as azeotropic owing to boiling, except alkynes, it is very large that cyclopentadiene in the isoprene removes difficulty, process by industrial rectifying is difficult to cyclopentadiene is removed fully, simultaneously also can cause the reflux ratio of device very large, energy consumption is sharply increased.In the production processes of polyalcohol take isoprene as raw material, even there is other cyclopentadiene of ppm level, still can exert an influence to polymerization product character, so micro-cyclopentadiene need to thoroughly be removed.For other cyclopentadiene of ppm level that contains in the isoprene, present removal methods mainly contains the methods such as extracting rectifying, super rectifying, and these methods or cost are higher, or complex process, or higher to equipment requirements.
Summary of the invention
The invention provides the chemical removal method of micro-cyclopentadiene in a kind of isoprene, the defects that exists to overcome prior art.
The present invention realizes by the following technical solutions:
The chemical removal method of micro-cyclopentadiene comprises the steps: in a kind of isoprene
To remove agent and solvent, then mix with the isoprene that contains micro-cyclopentadiene;
The said mixture material is passed in the reactor that solid alkali zeolite catalyst is housed, remove reaction;
Reacting rear material obtains high-purity isoprene by rectifying separation, isolates simultaneously to contain the mixed solution that removes agent, solvent, fulvene compounds and water;
It is described that to remove agent be ketone; Described solvent is organic solvent;
In the described isoprene that contains micro-cyclopentadiene, the content of cyclopentadiene is not less than 10ppm.
The content of cyclopentadiene is less than 1ppm in the high-purity isoprene that obtains.
As preferred version, described solid alkali zeolite catalyst for loading type inoganic solids alkali or organic solid alkaline catalysts, loads on the molecular sieve; Wherein alkali can be selected from organic amine, alkaline carbonate, alkali metal hydrogen saline oxide etc., such as quadrol, yellow soda ash, salt of wormwood, potassium hydroxide etc.; Molecular sieve can be selected from one or both mixing of silicon-dioxide and aluminium sesquioxide;
Remove the optional self-saturation aliphatic ketone of agent, saturated fat cyclic ketones or aromatic ketone, preferred butanone, propione, pimelinketone, methyl phenyl ketone or benzophenone;
Solvent can be selected conventional organic solvent, such as ethanol, butanols, tetrahydrofuran (THF), sherwood oil, hexanaphthene, pentamethylene, normal heptane etc., preferred alcohol, tetrahydrofuran (THF) or normal heptane;
As further preferred version, in the hybrid reaction material, isoprene is 30～300:1 with the ratio that removes the molar mass of agent; Solvent is 2～3:2 with the ratio that removes the molar mass of agent;
Remove temperature in the reactor described in the reaction and be controlled at 0～25 ℃ and get final product, remove the time of reaction, namely the hybrid reaction material pass through catalyzer time at 5～40 minutes, preferably at 10～30 minutes, fully contact, react completely in order to make between reactant;
Described rectifying separation step is undertaken by rectifying tower, and the working pressure of described rectifying tower is 10～50kPa, 50～120 ℃ of tower reactor temperature, and 40～60 ℃ of tower top temperatures, reflux ratio are 1～5.
Rectifying separation obtains contains the mixed solution that removes agent, solvent, fulvene compounds and water, isolates solvent and unreacted ketone recycle through solvent recuperation, and the by product fulvene compound has industrial value.
Raw material used in the present invention all adopts conventional commercially available prod.
The inventor passes through lot of experiments, the unexpected discovery adds above-mentioned agent and the solvent of removing in a large amount of isoprene that exist and other C5 active ingredients of trace, and under the katalysis of solid alkali zeolite catalyst, the orientable wherein cyclopentadiene of trace that removes, selectivity is very good.Its principle is that the cyclopentadiene that removes in agent ketone and the isoprene issues biochemical reaction generation fulvene compounds and water at catalyst action, and this compounds is easy to separate with isoprene, and the cyclopentadiene in the isoprene is removed.
Certainly this chemical method removes the method for micro-cyclopentadiene in the isoprene, is not limited to removing of ppm rank cyclopentadiene, also can be applicable to removing of a small amount of or a large amount of cyclopentadiene.
The chemical removal method of micro-cyclopentadiene in the isoprene provided by the invention, can carry out effective elimination to the cyclopentadiene that reaches the ppm level in the isoprene, cyclopentadiene content is less than 1ppm in the isoprene after refining, has preferably selectivity, improve the quality of isoprene, improved simultaneously the quality product of isoprene downstream polymerization product.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
Wherein: V1 is the isoprene tank, and V2 is for removing agent and solvent tank, and P1, P2, P3 are fresh feed pump, and G1 is static mixer, and R1 is that cyclopentadiene removes reactor, and T1 is rectifying tower;
Material A is the isoprene material that contains micro-cyclopentadiene, material B is for removing agent and solvent material, material C is for removing reacted mixture, and material D is high-purity isoprene material, and material E is solvent, remove the mixtures such as agent, fulvene compounds, water.
Embodiment
Provide preferred embodiment of the present invention below in conjunction with accompanying drawing, to describe technical scheme of the present invention in detail.
As shown in Figure 1, the isoprene material (not containing stopper) of V1 tank and V2 tank removed agent (ketone) and solvent material, mix through static mixer G1, enter the cyclopentadiene that solid alkali zeolite catalyst is housed and remove reactor R1, the chemical reaction of ketone and cyclopentadiene occurs in hybrid reaction material at a certain temperature through the filler catalyzer, reacted mixture enters rectifying tower T1, with isoprene from overhead extraction; Tower reactor extraction material has solvent, ketone, and fulvene compounds and water are isolated solvent and unreacted ketone recycle through solvent recuperation, and the by product fulvene compound has industrial value.
Embodiment 1
The isoprene material A of V1 tank (is not contained stopper, the cyclopentadiene that contains 20ppm) and remove agent and the solvent of V2 tank (remove agent and select propione, solvent is selected ethanol) mixture B, mix through static mixer G1, enter solid alkali zeolite catalyst (KOH load Al is housed
2O
3Molecular sieve) cyclopentadiene removes reactor R1, wherein isoprene: propione: the ratio of the molar mass of ethanol is 300:2:1; At the lower chemical reactions that ketone and cyclopentadiene occur of 5 ℃ of temperature, the reaction times is controlled at 10 minutes through catalyst filling for hybrid reaction material A, B, and reacted mixture C enters rectifying tower T1, with isoprene D from overhead extraction; Tower reactor extraction material E has solvent, ketone, and fulvene compounds and water are isolated solvent and unreacted ketone recycle through solvent recuperation.Rectifying tower T1 column overhead material cyclopentadiene content is less than 1ppm, and cyclopentadiene obtains effective elimination.
Embodiment 2
The isoprene material A of V1 tank (is not contained stopper, the cyclopentadiene that contains 100ppm) and remove agent and the solvent of V2 tank (remove agent and select pimelinketone, solvent is selected normal heptane) mixture B, mix through static mixer G1, enter solid alkali zeolite catalyst (K is housed
2CO
3Load Al
2O
3Molecular sieve) cyclopentadiene removes reactor R1, wherein isoprene: pimelinketone: the ratio of the molar mass of normal heptane is 200:2:3; At the lower chemical reactions that ketone and cyclopentadiene occur of 10 ℃ of temperature, the reaction times is controlled at 20 minutes through catalyst filling for hybrid reaction material A, B, and reacted mixture C enters rectifying tower T1, with isoprene D from overhead extraction; Tower reactor extraction material E has solvent, ketone, and fulvene compounds and water are isolated solvent and unreacted ketone recycle through solvent recuperation.Rectifying tower T1 column overhead material cyclopentadiene content is less than 1ppm, and cyclopentadiene obtains effective elimination.
Embodiment 3
The isoprene material A of V1 tank (is not contained stopper, the cyclopentadiene that contains 500ppm) and remove agent and the solvent of V2 tank (remove agent and select the benzene hexanone, solvent is selected tetrahydrofuran (THF)) mixture B, mix through static mixer G1, enter solid alkali zeolite catalyst (ethamine load SiO is housed
2Molecular sieve) cyclopentadiene removes reactor R1, wherein isoprene: the benzene hexanone: the ratio of the molar mass of tetrahydrofuran (THF) is 90:2:2; At the lower chemical reactions that ketone and cyclopentadiene occur of 20 ℃ of temperature, the reaction times is controlled at 30 minutes through catalyst filling for hybrid reaction material A, B, and reacted mixture C enters rectifying tower T1, with isoprene D from overhead extraction; Tower reactor extraction material E has solvent, ketone, and fulvene compounds and water are isolated solvent and unreacted ketone recycle through solvent recuperation.Rectifying tower T1 column overhead material cyclopentadiene content is less than 1ppm, and cyclopentadiene obtains effective elimination.
Claims (9)
1. the chemical removal method of micro-cyclopentadiene in the isoprene is characterized in that, comprises the steps:
To remove agent and solvent, then mix with the isoprene that contains micro-cyclopentadiene;
The said mixture material is passed in the reactor that solid alkali zeolite catalyst is housed, remove reaction;
Reacting rear material obtains high-purity isoprene by rectifying separation, isolates simultaneously to contain the mixed solution that removes agent, solvent, fulvene compounds and water;
It is described that to remove agent be ketone; Described solvent is organic solvent;
In the described isoprene that contains micro-cyclopentadiene, the content of cyclopentadiene is not less than 10ppm.
2. the method for claim 1, it is characterized in that, described solid alkali zeolite catalyst, be loading type inoganic solids alkali or organic solid alkaline catalysts, load on the molecular sieve, wherein alkali is selected from organic amine, alkaline carbonate, alkali metal hydrogen saline oxide, and molecular screening is from one or both mixing of silicon-dioxide and aluminium sesquioxide.
3. method as claimed in claim 2 is characterized in that, described alkali is ethamine, salt of wormwood or potassium hydroxide.
4. the method for claim 1 is characterized in that, describedly removes agent and is selected from saturated fatty ketone, saturated fat cyclic ketones or aromatic ketone.
5. method as claimed in claim 4 is characterized in that, described to remove agent be butanone, propione, pimelinketone, methyl phenyl ketone or benzophenone.
6. the method for claim 1 is characterized in that, described solvent is selected from ethanol, tetrahydrofuran (THF) or normal heptane.
7. such as each described method of claim 1～6, it is characterized in that in the hybrid reaction material, isoprene is 30～300:1 with the ratio that removes the molar mass of agent; Solvent is 2～3:2 with the ratio that removes the molar mass of agent.
8. method as claimed in claim 7 is characterized in that, the temperature that removes in the reactor described in the reaction is controlled at 0～25 ℃, removes the time of reaction at 5～40 minutes.
9. method as claimed in claim 7 is characterized in that, described rectifying separation step is undertaken by rectifying tower, and the working pressure of described rectifying tower is 10～50kPa, 50～120 ℃ of tower reactor temperature, and 40～60 ℃ of tower top temperatures, reflux ratio are 1～5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725182A (en) * | 2015-02-04 | 2015-06-24 | 新疆独山子天利实业总公司 | Purification method of m-pentadiene crude product separated from byproduct C5 in ethylene preparation process by petroleum cracking |
| CN107840777A (en) * | 2016-09-21 | 2018-03-27 | 中国石油天然气股份有限公司 | The method of micro cyclopentadiene in chemical method removing pentadiene |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3538179A (en) * | 1968-11-20 | 1970-11-03 | Phillips Petroleum Co | Purification of isoprene |
| US3804911A (en) * | 1971-07-09 | 1974-04-16 | A Liakumovich | Method of decontaminating hydrocarbons used as solvents and monomers in production of synthetic rubber |
| US3832416A (en) * | 1972-07-17 | 1974-08-27 | Shell Oil Co | Process for the removal of cyclopentadiene from hydrocarbon mixtures |
| SU819077A1 (en) * | 1977-11-09 | 1981-04-07 | Предприятие П/Я В-8705 | Method of continuous separation of normal hydrocarbons from oil fractions |
| US4392004A (en) * | 1982-02-22 | 1983-07-05 | The Goodyear Tire & Rubber Company | Reduction of cyclopentadiene from isoprene streams |
| US4438289A (en) * | 1982-02-22 | 1984-03-20 | The Goodyear Tire & Rubber Company | Reduction of cyclopentadiene from isoprene streams |
-
2012
- 2012-09-27 CN CN2012103676252A patent/CN102850171A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3538179A (en) * | 1968-11-20 | 1970-11-03 | Phillips Petroleum Co | Purification of isoprene |
| US3804911A (en) * | 1971-07-09 | 1974-04-16 | A Liakumovich | Method of decontaminating hydrocarbons used as solvents and monomers in production of synthetic rubber |
| US3832416A (en) * | 1972-07-17 | 1974-08-27 | Shell Oil Co | Process for the removal of cyclopentadiene from hydrocarbon mixtures |
| SU819077A1 (en) * | 1977-11-09 | 1981-04-07 | Предприятие П/Я В-8705 | Method of continuous separation of normal hydrocarbons from oil fractions |
| US4392004A (en) * | 1982-02-22 | 1983-07-05 | The Goodyear Tire & Rubber Company | Reduction of cyclopentadiene from isoprene streams |
| US4438289A (en) * | 1982-02-22 | 1984-03-20 | The Goodyear Tire & Rubber Company | Reduction of cyclopentadiene from isoprene streams |
Non-Patent Citations (1)
| Title |
|---|
| 无: "异戊二烯的生产", 《合成橡胶工业》, no. 1, 31 December 1978 (1978-12-31), pages 19 - 38 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725182A (en) * | 2015-02-04 | 2015-06-24 | 新疆独山子天利实业总公司 | Purification method of m-pentadiene crude product separated from byproduct C5 in ethylene preparation process by petroleum cracking |
| CN107840777A (en) * | 2016-09-21 | 2018-03-27 | 中国石油天然气股份有限公司 | The method of micro cyclopentadiene in chemical method removing pentadiene |
| CN107840777B (en) * | 2016-09-21 | 2021-01-29 | 中国石油天然气股份有限公司 | Method for removing trace cyclopentadiene from m-pentadiene by chemical method |
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Application publication date: 20130102 |