CN103102236A - Method for enhancing purity of olefin product - Google Patents
Method for enhancing purity of olefin product Download PDFInfo
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- CN103102236A CN103102236A CN2011103517213A CN201110351721A CN103102236A CN 103102236 A CN103102236 A CN 103102236A CN 2011103517213 A CN2011103517213 A CN 2011103517213A CN 201110351721 A CN201110351721 A CN 201110351721A CN 103102236 A CN103102236 A CN 103102236A
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- active metal
- halohydrocarbon
- olefin
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- alkene
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Abstract
The invention relates to a method for enhancing purity of an olefin product. The method comprises the following steps: step 1, adding active metal into olefin containing halogenated hydrocarbon under protection of nitrogen, and directly contacting the active metal with halogenated hydrocarbon for reaction; step 2: distilling the product obtained in the step 1 to obtain an olefin product. The method provided by the invention can reduce the content of halogenated hydrocarbon in the olefin to a low level; and the method adopts the active metal to directly contact with halogenated hydrocarbon, and has advantages of quick reaction, high efficiency, low cost, simple operation and easiness to implement.
Description
Technical field
The present invention relates to a kind of method that improves olefin product purity, more particularly relate to a kind of method of removing the halohydrocarbon in alkene.
Background technology
Alpha-olefin typically refers to C
4And C
4Above higher olefins is to develop a kind of Organic Chemicals rapidly over nearly 30 years.The alpha-olefin main application is as follows: (1) as comonomer, the comonomer that uses in LLDPE and HDPE production mainly contains 1-butylene, 1-hexene and 1-octene, and 40% above alpha-olefin is used as the comonomer use of PE; (2) as washing composition and detergent alcohol, the detergent alcohol synthetic by alpha-olefin has good biological degradability; (3) as ucon oil, poly-alpha olefins is the ucon oil of high-quality, and its main component is the oligopolymer of 1-decene and 1-octene; (4) as plasticizer alcohol, C
8～C
10Linear alpha-olefin is low through the plasticizer alcohol volatility that oxo process makes, and has good light stability and oxidation-resistance; (5) be used as lubricating oil additive and drilling fluid, tackiness agent, sealing agent etc.
The production method of alpha-olefin mainly contains wax destructive distillation method, ethylene oligomerization method, extraction separation method, Fatty Alcohol(C12-C14 and C12-C18) dehydriding, internal olefin isomerate process etc.Wherein, the ethylene oligomerization method has because of the alpha-olefin of its production the important method that purity is high, selectivity good, the raw material availability advantages of higher becomes alpha-olefin production.
About alpha-olefin aspect using as comonomer, the 1-hexene progressively substitutes 1-butylene and produces high performance PE product, LLDPE resin by the 1-hervene copolymer is compared with the multipolymer of 1-butylene, tensile strength, resistance to impact shock, tear strength and performance durable in use are all obviously excellent, are particularly suitable for the agricultural mulch films such as packing film and greenhouse, canopy chamber etc.
Continue John R.Briggs at J.Chem.Soc., Chem.Commun., reported in 1989,674-675 page come catalyzed ethylene trimerization selectivity to prepare the approach of 1-hexene with homogeneous phase ternary chromium-based catalysts after, 1-hexene production technology has obtained significant progress.Meanwhile, polyolefinic production technique is also maked rapid progress.Along with the exploitation of high-efficiency polymerization technique, impel people to pursue more high-quality 1-hexene product.In 1-hexene production process, in order to obtain the selectivity of catalyst activity and 1-hexene preferably, adopt the trimerization catalyst system of four components, and need in catalyst system to adopt halogenide as promotor.Halid existence has caused new impurity halohydrocarbon can occurring in 1-hexene product, and it can not be separated with product 1-hexene fully in the last handling processes such as rectifying, has affected the subsequent applications of 1-hexene.
Therefore, be necessary to provide a kind for the treatment of process to reduce the content of halogenated hydrocarbon in 1-hexene product, in order to obtain meeting the high-quality 1-hexene product that polyolefin process requires.
Summary of the invention
For existing above-mentioned technical problem in prior art, the present invention proposes a kind of method of removing halohydrocarbon in alkene, it can reduce the content of the halohydrocarbon in alkene, and simple to operate, is easy to realize.
The method according to this invention comprises the following steps:
First step: under protection of inert gas, the active metal is joined in the alkene that contains halohydrocarbon, make the active metal directly contact and react with halohydrocarbon;
Second step: the product that will obtain in first step carries out rectifying, obtains olefin product.
According to the present invention, the active metal directly contacts and reacts with halohydrocarbon, and the product boiling point that generates after reaction changes, and is conducive to and the separating of alkene.And alkene is more stable, is difficult for reacting with the active metal.The content of the halohydrocarbon after processing in alkene obviously reduces, and the purity of alkene is improved significantly.
In one embodiment of the invention, described alkene is alpha-olefin.In a preferred embodiment of the invention, described alkene is the 1-hexene.
In one embodiment of the invention, described halohydrocarbon is hydrochloric ether, hydrobromic ether or idohydrocarbon.In a preferred embodiment of the invention, described halohydrocarbon is one or more in 1,2-dichloroethene, 2-N-PROPYLE BROMIDE, trichloromethane, 1-chloro-2-methyl propane.
In one embodiment of the invention, the shielding gas that uses in described first step is nitrogen.Easily be understood that, other rare gas element such as argon gas etc. also can be used as this shielding gas.
According to one embodiment of present invention, described active metal is IA family's metal and/or IIA family metal.In a preferred embodiment of the invention, this active metal is one or more in lithium, potassium or calcium, and its form can be powdery, sheet or particulate state.
According to the present invention, add the amount of active metal to provide with the amount that can effectively reduce at least the concentration of halohydrocarbon.According to one embodiment of present invention, in the reaction in first step, the mol ratio of active metal and halohydrocarbon is 1: 1-1000: 1, be preferably 2: 1-500: 1, more preferably 3: 1-100: 1.According to another embodiment of the invention, in the reaction in described first step, the reaction times is 1 minute to 20 hours, is preferably 2-60 minute, more preferably 3-30 minute.
In an object lesson, the temperature of the reaction in first step is 60-65 ℃.
According to the present invention, by active metal and halohydrocarbons reaction with its product is carried out rectifying two steps, the content of the halohydrocarbon in final alkene can be reduced to very low level.And the present invention has adopted the active metal directly to contact with halohydrocarbon, and reaction is fast, efficient is high, expense is low, and simple to operate, implements easily.
Embodiment
By reference following examples, can further understand how to realize and use the present invention and advantage thereof, do not only limit to following content but should not understand the present invention.
Embodiment 1:
Under the condition of normal pressure, get the round-bottomed flask of 500ml drying, cleaning, get 1-hexene material 500ml under nitrogen protection, the concentration of its halohydrocarbon that contains (1,2-dichloroethene) is that (content is 3.34 * 10 to 9.6mg/Kg
-5Then add 8.35 * 10 mol),
-4The mol metallic lithium powder is taken a sample after 3 minutes in reaction under 60-65 ℃ of condition and is analyzed.Experimental result sees Table 1.
Embodiment 2:
Use experimental installation and the experiment condition identical with embodiment 1, get 1-hexene material 500ml, wherein the concentration of halohydrocarbon (2-N-PROPYLE BROMIDE) is that (content is 6.7 * 10 to 19.2mg/Kg
-5Then add 1.34 * 10 mol),
-3The mol metallic lithium powder reacts and carries out sampling analysis after 10 minutes.Experimental result sees Table 1.
Embodiment 3:
Use experimental installation and the experiment condition identical with embodiment 1, get 1-hexene material 500ml, wherein the concentration of halohydrocarbon (1,2-dichloroethene) is 57.6mg/Kg, and (content is 2.0 * 10
-4Then add 1.20 * 10 mol),
-3The mol metallic lithium powder, reacting took a sample after 10 minutes analyzes.Experimental result sees Table 1.
Embodiment 4:
Use experimental installation and the experiment condition identical with embodiment 1, get 1-hexene material 500ml, wherein the concentration of halohydrocarbon (1,2-dichloroethene) is that (content is 2.0 * 10 to 57.6mg/Kg
-4Then add 1 * 10 mol),
-2Mol potassium metal thin slice, reacting took a sample after 5 minutes analyzes.Experimental result sees attached list 1.
Embodiment 5:
Use experimental installation and the experiment condition identical with embodiment 1, get 1-hexene material 500ml, wherein the concentration of halohydrocarbon (trichloromethane) is that (content is 1.4 * 10 to 40.32mg/Kg
-4Then add 1.4 * 10 mol),
-2Mol potassium metal thin slice, reacting took a sample after 30 minutes analyzes, and experimental result sees Table 1.
Embodiment 6:
Use experimental installation and the experiment condition identical with embodiment 1, get 1-hexene material 500ml, wherein the concentration of halohydrocarbon (1-chloro-2-methyl propane) is that (content is 1.4 * 10 to 40.32mg/Kg
-4Then add 7 * 10 mol),
-3The mol granules of metal Ca, reacting took a sample after 10 minutes analyzes, and experimental result sees Table 1.
Table 1
Can see by above-described embodiment, by method of the present invention, use the seldom active metal of amount under normal temperature, normal pressure, only use 3.34 * 10 as lithium
-5Mol can significantly reduce the content of the halohydrocarbon (1,2-dichloroethene in embodiment, 2-N-PROPYLE BROMIDE, trichloromethane and 1-chloro-2-methyl propane) in alkene, and its content can be low to moderate less than 1mg/Kg, and this has greatly improved the purity of alkene.Simultaneously, method of the present invention is simple to operate, is easy to realize.
Although invention has been described with reference to preferred embodiment, without departing from the scope of the invention, can carry out various improvement to it.The present invention is not limited to disclosed specific embodiment in literary composition, but comprises all technical schemes in the scope that falls into claim.
Claims (10)
1. a method that improves the purity of olefin product, comprise the following steps,
First step: under protection of inert gas, the active metal is joined in the alkene that contains halohydrocarbon, make the active metal directly contact and react with halohydrocarbon;
Second step: the product that will obtain in first step carries out rectifying, obtains olefin product.
2. method according to claim 1, is characterized in that, described active metal is IA family's metal and/or IIA family metal.
3. method according to claim 2, is characterized in that, described active metal is one or more in lithium, potassium or calcium.
4. the described method of any one in 3 according to claim 1, is characterized in that, in the reaction in described first step, the mol ratio of described active metal and halohydrocarbon is 1: 1-1000: 1, be preferably 2: 1-500: 1, more preferably 3: 1-100: 1.
5. the described method of any one in 4 according to claim 1, is characterized in that, in the reaction in described first step, the reaction times is 1 minute to 20 hours, is preferably 2-60 minute, more preferably 3-30 minute.
6. the described method of any one in 5 according to claim 1, is characterized in that, the temperature of the reaction in described first step is 60-65 ℃.
7. method described according to any one in the claims, is characterized in that, described shielding gas is rare gas element, is preferably nitrogen.
8. method described according to any one in the claims, is characterized in that, described alkene is alpha-olefin.
9. method according to claim 8, is characterized in that, described alkene is the 1-hexene.
10. method described according to any one in the claims, is characterized in that, described halohydrocarbon is hydrochloric ether, hydrobromic ether or idohydrocarbon, is preferably one or more in 1,2-dichloroethene, 2-N-PROPYLE BROMIDE, trichloromethane, 1-chloro-2-methyl propane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272809A (en) * | 2014-07-17 | 2016-01-27 | 中国科学院上海高等研究院 | Removal method of oxygen-containing compounds in coal alpha-olefins |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124410A (en) * | 1994-05-19 | 2000-09-26 | Mitsui Chemicals, Inc. | Method for purification of alpha-olefins for polymerization use and method for production of poly-alpha-olefins |
| CN101255089A (en) * | 2008-04-03 | 2008-09-03 | 中国石油大学(北京) | Purification technique for producing propylene by refinery plant |
-
2011
- 2011-11-09 CN CN201110351721.3A patent/CN103102236B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124410A (en) * | 1994-05-19 | 2000-09-26 | Mitsui Chemicals, Inc. | Method for purification of alpha-olefins for polymerization use and method for production of poly-alpha-olefins |
| CN101255089A (en) * | 2008-04-03 | 2008-09-03 | 中国石油大学(北京) | Purification technique for producing propylene by refinery plant |
Non-Patent Citations (1)
| Title |
|---|
| 隋军龙等，: "1-己烯产品中氯化物的脱除研究", 《当代化工》, vol. 42, no. 1, January 2013 (2013-01-01), pages 35 - 38 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272809A (en) * | 2014-07-17 | 2016-01-27 | 中国科学院上海高等研究院 | Removal method of oxygen-containing compounds in coal alpha-olefins |
| CN105272809B (en) * | 2014-07-17 | 2017-04-26 | 中国科学院上海高等研究院 | Removal method of oxygen-containing compounds in coal alpha-olefins |
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