CN101734991A - Method for improving content of 1-hexene in hexene materials - Google Patents
Method for improving content of 1-hexene in hexene materials Download PDFInfo
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- CN101734991A CN101734991A CN200810225945A CN200810225945A CN101734991A CN 101734991 A CN101734991 A CN 101734991A CN 200810225945 A CN200810225945 A CN 200810225945A CN 200810225945 A CN200810225945 A CN 200810225945A CN 101734991 A CN101734991 A CN 101734991A
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Abstract
The invention discloses a method for improving a content of 1-hexene in hexene materials. Aiming at solving the problems of long flow and high energy consumption existing in the prior art, the invention provides the method, which comprises two steps of complexation and distillation and particularly the steps of: complexing a complexing agent and hexane, and concentrating the 1-hexene; extracting the concentrated 1-hexene materials from the complexing solution by reduced pressure distillation; and repeating the steps for several times to obtain the 1-hexene products in high purity. Compared with the complexation-extraction-distillation method, the method of the invention for concentrating the 1-hexene can save energy by 26 percent; and compared with the precise distillation process, the method can save energy by at least 32.6 percent.
Description
Technical field
The present invention relates to a kind of method of carrying dense 1-hexene, more particularly, relate to a kind of method that adopts complexing, distillation procedure to carry dense 1-hexene.
Background technology
The 1-hexene is the important comonomer of linear polyethylene (low density and high-density) resin, also is to make senior softening agent, the important source material of fine chemical products such as ucon oil and lipid acid.The most of 1-hexene of China must be from external import.At present, China's linear polyethylene substantially all is to adopt 1-butylene as comonomer, and this is that still, the excellent properties that the linear polyethylene of 1-hervene copolymer has is that the linear polyethylene of 1-butylene copolymerization hardly matches because 1-butylene is cheap and easy to get.Therefore, replace 1-butylene imperative with the 1-hexene as comonomer.
At present, mainly exist three kinds of industrialized 1-hexene production technique in the world: Sasol extraction process, ethylene oligomerization technology and Philip ethylene trimerization technology.The Sasol extraction process is the by product that contains the 1-hexene that utilizes with the coal the large-scale synthol factory that is raw material; The two kinds of technologies in back are as raw material with broad-spectrum ethene.
And C
4The novel process of producing the 1-hexene from disproportionation be with 2-butylene as raw material, the separation, 1-butylene that turns to 1-butylene, 1-butylene through the 2-butylene isomery is that 3-hexene, 3-hexene isomery turn to five big units operations such as 1-hexene, the separation of 1-hexene and form from disproportionation.Wherein the hexene material of 1-hexene separating unit is made up of 1-hexene, anti--the 2-hexene, suitable-the 2-hexene, anti--the 3-hexene, suitable-3-hexene, and the separation of 1-hexene is finished by precise distillation.Because the boiling point of 1-hexene and 3-hexene is approaching, the minimum boiling-point difference of hexene material needs very high theoretical plate number and higher energy consumption, about 180 as stage number less than 4 ℃ by fractionation by distillation 1-hexene, reflux ratio 120: 1, thus the cost of the process cost of making and product is higher.
In addition, application number 200510117436.X has proposed a kind of employing complexing, extraction, three processing steps of distillation and has carried dense 1-hexene, and 1-hexene isolated method from the hexene material the most at last.Because this method introducing toluene or heptane make the technology of carrying dense 1-hexene longer as extraction agent, owing to need from extraction liquid, isolate extraction agent, cause energy consumption to increase simultaneously by distillation.
Summary of the invention
The inventor is in order to solve long flow path and the high problem of energy consumption that prior art exists, and through deep research, proposed a kind of employing complexing, two processing steps of distillation are carried dense 1-hexene, and 1-hexene isolated method from the hexene material the most at last.The present invention invents with 200510117436.X and compares, and has the separation process weak point, the advantage that energy consumption is lower.
Hexene material of the present invention comprises 1-hexene, anti--the 2-hexene, suitable-the 2-hexene, anti--3-hexene and suitable-3-hexene.
Concrete, the method for carrying dense 1-hexene from the hexene material of the present invention may further comprise the steps:
(1) described hexene material is mixed with complexing agent, stir, leave standstill, it is two-layer that mixed solution is divided into, and the upper strata is oil reservoir a, and lower floor is the complex liquid b that contains the hexene material of 1-hexene concentration raising;
(2) the complex liquid b that step (1) is obtained distills, and cat head obtains the hexene material c that 1-hexene concentration improves, and the tower still obtains complexing agent d, and its distillation pressure is 0.0067～0.3MPa, 20～90 ℃ of temperature
In order to realize purpose of the present invention, selected complexing agent should have relative stronger complexing action with the 1-hexene; Selected extraction agent must be insoluble with enveloping agent solution simultaneously, and should make hexene solubleness therein very big, and the boiling point difference of hexene and extraction agent is very big, is easy to separate.Preferably, described complexing agent is for containing Ag ionic ethylene glycol solution or Diethylene Glycol ethereal solution, and Ag ionic weight percent concentration is 1% to its saturation concentration in the described complexing agent.Described complexing agent can be the various salt of Ag, preferred AgNO
3
Described complexing agent is AgNO
3Ethylene glycol solution, wherein Ag ionic weight percent concentration is 5%～22%.
The weight ratio of the consumption of described complexing agent and hexene material inlet amount is 1～15: 1, more preferably 1～4: 1, and the complexing temperature is 10～60 ℃, complexing pressure is 0.1～1MPa.
The complexing agent d that step (2) is obtained recycles.
The hexene material c that step (2) is obtained repeats the operation of step (1) to step (2), is 40%～60% hexene material until obtaining weight percent concentration.
In described step (1), oil reservoir a is the hexene material that 1-hexene concentration reduces.Because each Substance Properties is more approaching in the hexene material, therefore, the complexing agent of selecting for use is when absorbing the 1-hexene, also absorbed the material in the hexene material, just because the complexation constant of complexing agent that the present invention selects for use and 1-hexene is far longer than the complexation constant with other hexene, most 1-hexene is absorbed by complexing agent, thereby has obtained containing the complex liquid that the 1-hexene is carried dense hexene material.
In described step (2), preferably distilling pressure is 0.013～0.053MPa, 35～60 ℃ of temperature.
Because what complexing agent of selecting for use and hexene took place is weak Complex effect, therefore in the described step (2),, contain the hexene material hardly among the complexing agent d that obtains at the bottom of the tower by underpressure distillation, therefore, preferably the complexing agent d that step (2) is obtained recycles.
The hexene material of handling through the method for carrying dense 1-hexene of the present invention, the weight content of 1-hexene wherein approximately can be enhanced about more than once, and repeatedly through several times processing, can obtain the 1-hexene of high density.
Because the concentration of complexing agent consumption and 1-hexene has certain relation, therefore, when repeating step (1)～(2), preferably suitably improves the consumption of complexing agent.
Another specific embodiments of the present invention is as follows:
The method of separating the 1-hexene from the hexene material, described hexene material comprise 1-hexene, anti--the 2-hexene, suitable-the 2-hexene, anti--3-hexene and suitable-3-hexene, it is characterized in that, may further comprise the steps:
(I) described hexene material is mixed with complexing agent, stir, leave standstill, it is two-layer that mixed solution is divided into, and the upper strata is oil reservoir a, and lower floor is the complex liquid b that contains the hexene material of 1-hexene concentration raising;
(II) the complex liquid b that step (I) is obtained distills, and obtains hexene material c and complexing agent d that 1-hexene concentration improves, and complexing agent d recycles;
(III) the hexene material c that step (II) is obtained repeats the operation of step (I) to (II), and the weight percent concentration that obtains the 1-hexene is 40～60% hexene material;
(IV) weight percent concentration of the 1-hexene that step (III) is obtained is that 40～60% hexene material carries out rectifying, obtains weight percent concentration and be the 1-hexene more than 99.5%.
Preferably, in described step (IV), the stage number of rectifying is 120～180, and reflux ratio is 0.5～10.
Be that 8% hexene material is an example with the concentration expressed in percentage by weight of handling the 1-hexene below, specify the method that obtains high purity 1-hexene of the present invention:
(1) be that 8% hexene material 10～30 grams are put into there-necked flask with the concentration expressed in percentage by weight of 1-hexene, at room temperature, add the complexing agent of 1～4 times of hexene weight of material, complexing pressure is 0.1～1Mpa; Fully stir after 10～20 minutes, leave standstill, the solution layering separates the complex liquid b of lower floor with separating funnel;
(2) the complex liquid b that step (1) is obtained carries out underpressure distillation in there-necked flask, and pressure is 0.013～0.053MPa, 35～60 ℃ of temperature, and cat head obtains carrying the hexene material c of dense 1-hexene, and the tower still obtains complexing agent d.
(3) concentration expressed in percentage by weight of the 1-hexene that step (2) is obtained be 16% hexene material c as raw material, repeating step (1) is to (2), the concentration expressed in percentage by weight that obtains the 1-hexene is 29% hexene material;
(4) concentration expressed in percentage by weight of the 1-hexene that step (3) is obtained be 29% hexene material as raw material, repeating step (1) is to (2), the concentration expressed in percentage by weight that obtains the 1-hexene is 42% hexene material;
(5) concentration expressed in percentage by weight of the 1-hexene that step (4) is obtained be 42% hexene material as raw material, repeating step (1) is to (2), the concentration expressed in percentage by weight that obtains the 1-hexene is 75% hexene material;
(6) concentration expressed in percentage by weight of the 1-hexene that step (5) is obtained be 75% hexene material as raw material, repeating step (1) is to (2), obtains concentration expressed in percentage by weight and be 98% 1-hexene product.
The advantage of method of the present invention:
The present invention compares with prior art, but not only can shortened process, but and energy efficient, reduce production costs.
Embodiment
Comparative example 1
The composition and the content thereof of used hexene material see Table 1 in the comparative example.
The composition of table 1 hexene material
| The 1-hexene | Hexene-3 | Anti-hexene-2 | Along hexene-2 | Heavy constituent | |
| Raw material wt% | ??8.12 | ??42.40 | ??32.46 | ??14.88 | Surplus |
At ambient temperature, with 500 gram AgNO
3Be dissolved in the 1000ml ethylene glycol (analytical pure), stirred ten minutes, make AgNO
3Fully dissolving is stand-by.
(1) is that 8.12% hexene material, 500 grams are put into there-necked flask with 1-hexene concentration expressed in percentage by weight, adds AgNO
3Ethylene glycol solution 1000ml; The complexing temperature is 20 ℃, and complexing pressure is 0.1Mpa; Fully stir after 15 minutes, the solution layering, the upper strata is oil reservoir a, with separating funnel the complex liquid b of lower floor is separated.The weight percent concentration 3.92% of 1-hexene among the oil reservoir a, totally 330 grams.
(2) the complex liquid b that step (1) is obtained is placed in the there-necked flask, adds heptane 500 grams again and extracts; Extraction temperature is 10-40 ℃, and pressure is 0.1Mpa; Stir after 15 minutes, solution is divided into extraction liquid c and complexing agent d, and complexing agent d can be recycled.
(3) the extraction liquid c that step (2) is obtained distill carry dense, distillation pressure 0.1MPa, the concentration expressed in percentage by weights that obtain 180 gram 1-hexenes are 16.2% hexene material c; Distilling remaining extraction agent recycles.
Calculate through Aspen Plus, the energy consumption of this process is the hexene material of 1950Kcal/kg 16.2%
Comparative example 2
By precise distillation the hexene feed separation being obtained purity is 99.5% 1-hexene product.
The composition and the content thereof of used hexene material are identical with comparative example 1.
Adopt the stage number 180 of rectifying tower, reflux ratio 112,64 ℃ of tower top temperatures, 89 ℃ of tower still temperature.The 1000 alkene materials of restraining oneself are introduced from the middle part of rectifying tower, and it is 99.4% 1-hexene product that cat head obtains 52 gram purity, and cat head obtains hexene material 940 grams that concentration is 2.9% 1-hexene.
Calculate through Aspen Plus, the energy consumption of this process is the 1-hexene of 9290Kcal/kg 99.4%.
Embodiment 1
The composition of used hexene material and content thereof are identical with comparative example 1 in the embodiments of the invention.
At ambient temperature, with 500 gram AgNO
3Be dissolved in the 1000ml ethylene glycol, stirred 10 minutes, make AgNO
3Fully dissolving is stand-by.
(1) is that 8.12% hexene material is put into there-necked flask with 500 gram 1-hexene concentration expressed in percentage by weights, adds 1000ml AgNO
3Ethylene glycol solution; The complexing temperature is 20 ℃, and complexing pressure is 0.1Mpa; Fully stir after 15 minutes, the solution layering, the upper strata is oil reservoir a, with separating funnel the complex liquid b of lower floor is separated.The weight percent concentration 3.92% of 1-hexene among the oil reservoir a, totally 300 grams.
(2) the complex liquid b that step (1) is obtained distills, and distillation pressure is 0.013-0.053MPa, and 34 ℃ of head temperature, the concentration expressed in percentage by weights that the top obtains 193 gram 1-hexenes are 16.2% hexene material c; 55 ℃ of complex liquid b temperature are distilled remaining complexing agent d and are recycled
Calculate through Aspen Plus, the energy consumption of this process is the hexene material of 1438Kcal/kg 16.2%
By the comparison of comparative example 1 and embodiment 1, complexing-distillating method of the present invention is as can be known carried dense 1-hexene and is put forward dense 1-hexene energy efficient 26% than complexing-extraction-distillating method.
Embodiment 2
It is 99.5% 1-hexene product that the hexene feed separation is obtained purity.
Particularly, repeat the step of embodiment 1:
(1) be that 16.2% hexene material c is as raw material with the 500 1-hexene concentration expressed in percentage by weights that obtain of gram embodiment 1, repeat the step of embodiment 1, obtain 317 gram 1-hexene weight percent concentration and be 8.3% oil reservoir a, 188 gram 1-hexene concentration expressed in percentage by weights are 29.3% hexene material.Calculate the hexene material of this process power consumption 1523Kcal/kg 29.3% through Aspen Plus
(2) be that 29.3% hexene material is as raw material with the 500 1-hexene concentration expressed in percentage by weights that obtain of gram steps (1), repeat the step of embodiment 1, obtain 271 gram 1-hexene weight percent concentration and be 16.5% oil reservoir a, 235 gram 1-hexene concentration expressed in percentage by weights are 42.8% hexene material.Calculate the hexene material of this process power consumption 1600Kcal/kg 29.3% through Aspen Plus
(3) step (2) being obtained 1-hexene concentration expressed in percentage by weight is that 42.8% hexene material carries out rectifying and carries densely in rectifying tower, obtains concentration expressed in percentage by weight and be 99.5% 1-hexene product; The stage number 160 of its rectifying tower, reflux ratio 2.Calculate the 1-hexene of this process power consumption 1700Kcal/kg 99.5% through Aspen Plus.
By the comparison of comparative example 2 and embodiment 2, complexing-distillation of the present invention as can be known-precise distillation method obtains the precise distillation method acquisition 99.5%1-hexene energy efficient 32.6% of 99.5%1-hexene than prior art.
Claims (8)
1. method that improves 1-hexene concentration in the hexene material, described hexene material comprise 1-hexene, anti--the 2-hexene, suitable-the 2-hexene, anti--3-hexene and suitable-3-hexene, it is characterized in that, said method comprising the steps of:
(1) described hexene material is mixed with complexing agent, stir, leave standstill, it is two-layer that mixed solution is divided into, and the upper strata is oil reservoir a, and lower floor is the complex liquid b that contains the hexene material of 1-hexene concentration raising;
(2) the complex liquid b that step (1) is obtained distills, and cat head obtains the hexene material c that 1-hexene concentration improves, and the tower still obtains complexing agent d, and its distillation pressure is 0.0067～0.3MPa, 20～90 ℃ of temperature.
2. method according to claim 1 is characterized in that described complexing agent for containing Ag ionic ethylene glycol solution or Diethylene Glycol ethereal solution, and Ag ionic weight percent concentration is 1% to its saturation concentration in the described complexing agent.
3. method according to claim 2 is characterized in that described complexing agent is AgNO
3Ethylene glycol solution, wherein Ag ionic weight percent concentration is 5%～22%.
4. method according to claim 1 is characterized in that the consumption of described complexing agent and the weight ratio of hexene material inlet amount are 1～15: 1, and the complexing temperature is 10～60 ℃, and complexing pressure is 0.1～1MPa.
5. method according to claim 1 is characterized in that the complexing agent d that step (2) obtains is recycled.
6. method according to claim 1 is characterized in that the hexene material c that step (2) is obtained repeats step (1) to the operation of step (2), is 40%～60% hexene material until obtaining weight percent concentration.
7. method of from the hexene material, separating the 1-hexene, described hexene material comprises 1-hexene, anti--the 2-hexene, suitable-the 2-hexene, anti--3-hexene and suitable-3-hexene, it is characterized in that, said method comprising the steps of:
(1) described hexene material is mixed with complexing agent, stir, leave standstill, it is two-layer that mixed solution is divided into, and the upper strata is oil reservoir a, and lower floor is the complex liquid b that contains the hexene material of 1-hexene concentration raising;
(2) the complex liquid b that step (1) is obtained distills, and obtains hexene material c and complexing agent d that 1-hexene concentration improves, and complexing agent d recycles;
(3) the hexene material c that step (2) is obtained repeats the operation of step (1) to (2), and the weight percent concentration that obtains the 1-hexene is 40～60% hexene material;
(4) weight percent concentration of the 1-hexene that step (3) is obtained is that 40～60% hexene material carries out rectifying, obtains weight percent concentration and be the 1-hexene more than 99.5%.
8. method according to claim 7 is characterized in that, in described step (4), the stage number of rectifying is 120～180, and reflux ratio is 0.5～10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819299A (en) * | 2014-02-24 | 2014-05-28 | 上海兖矿能源科技研发有限公司 | Method for separating and purifying 1-hexene in carbon hydrogen mixture |
| CN106588551A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Separation method of 1-hexylene namely ethylene oligomerization product |
-
2008
- 2008-11-07 CN CN200810225945A patent/CN101734991A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819299A (en) * | 2014-02-24 | 2014-05-28 | 上海兖矿能源科技研发有限公司 | Method for separating and purifying 1-hexene in carbon hydrogen mixture |
| CN103819299B (en) * | 2014-02-24 | 2016-09-07 | 上海兖矿能源科技研发有限公司 | A kind of method of separating-purifying 1-hexene from hydrocarbon mixture material |
| CN106588551A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Separation method of 1-hexylene namely ethylene oligomerization product |
| CN106588551B (en) * | 2015-10-19 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of separation method of the 1- hexene for ethylene oligomerization product |
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Application publication date: 20100616 |