CN103739426A - Method for increasing the ethylene yield in process of preparing ethylene through ethanol dehydration - Google Patents
Method for increasing the ethylene yield in process of preparing ethylene through ethanol dehydration Download PDFInfo
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- CN103739426A CN103739426A CN201210393010.7A CN201210393010A CN103739426A CN 103739426 A CN103739426 A CN 103739426A CN 201210393010 A CN201210393010 A CN 201210393010A CN 103739426 A CN103739426 A CN 103739426A
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Abstract
The invention relates to a method for increasing the ethylene yield in a process of preparing ethylene through ethanol dehydration, and mainly solves a problem, which is not involved in documents in the past, of increasing the ethylene yield in the process of preparing ethylene through ethanol dehydration, especially a problem of ethylene rectification tower bottoms treatment or great ethylene loss. According to the technical scheme of the method, the tower bottom of an ethylene rectification tower is fed to the top of a heavy-component stripping distillation tower, the tower top vapour phase of the heavy-component stripping distillation tower is fed back to the middle and lower part of the ethylene rectification tower, and the heavy components are discharged from the bottom of the heavy-component stripping distillation tower. By the technical scheme, the problem is solved well and the method can be used in industrial production of the ethylene through ethanol dehydration.
Description
Technical field
The present invention relates to improve in a kind of producing ethylene from dehydration of ethanol technique the method for yield of ethene.
Background technology
Ethene is a kind of important large organic chemical industry's basic raw material, is mainly used to produce the multiple Organic chemical products such as polyethylene, polyvinyl chloride, ethylene oxide/ethylene glycol, ethyl benzene/styrene, vinyl acetate between to for plastic.At present, ethylene production mainly adopts petroleum catalystic pyrolysis to produce both at home and abroad.In recent years the research of non-petroleum production ethene was had to new breakthrough, particularly producing ethylene by ethanol dehydration technology.This technology be the ethanol that derives from agricultural byproducts be raw material, can avoid like this dependence to petroleum resources.To oil-poor and take agricultural as main country and regional, the raw material of producing ethanol is easy to get and is guaranteed, for producing ethene, has established enough raw material bases, can solve fossil resource shortage and the serious difficult problem of environmental pollution.
Producing ethylene with ethyl alcohol, its key factor is to study the strong technique with having the market competitiveness of a kind of new economy, and main goal in research is to improve technical process, reduces ethanol unit consumption, increases device benefit.
In the processing method of producing ethylene from dehydration of ethanol, at home and abroad oneself has many methods in disclosed document or patent, and its basic technology is mainly divided into fixed-bed process and fluidized-bed process.ABB Lummu: company once proposed to carry out ethanol dehydration reaction preparing ethylene (USP4134926) by fluidization at late nineteen seventies, but this technology not yet obtains industrial applications.At present industrial application be mainly fixed-bed process, comprise isothermal fixed-bed process and insulation fix bed technique.
Initial ethanol dehydration reaction carries out in calandria type fixed bed, and reaction pressure is normal pressure, adopts direct heating or utilizes the mode of heating medium (as fused salt) indirect heating to provide reaction heat for reacting.In reaction process, temperature of reaction and material flow are key factors, if temperature is too high or material flow is too low, will cause the generation of other by products, if but increase flow velocity, the transformation efficiency of ethanol can drop to again and solve this contradiction, United States Patent (USP) (USP4232179) has proposed skill in the thermal insulation of ethanol dehydration reaction, be that ethanol dehydration reaction carries out in insulation fix bed, before reactor, to be heated to reaction temperature required entering for reaction mass, to guarantee normally carrying out of reaction.Afterwards, they have proposed again the insulation fix bed reaction process of syllogic (USP4396789), and utilize this technique to set up 60,000 tons/year of ethylene units in the early 1980s.The insulation fix bed reactor of three series connection of this process using, comes ethanol and the vapor mixing charging of each Reactor inlet of preheating with a stove, the by products such as unreacted ethanol and ether are carried out circulation.Adding of steam reduced reaction coking, extended the life-span of catalyzer, improved productive rate.Install service data and show, when reactor inlet temperatures is 450 ℃, ethanol conversion reaches 98, at least one year of catalyst regeneration cycle.In addition Halcon/SD company and tenth century the seventies developed the double mode technology of thermal insulation or isothermal fixed bed, wherein isothermal bed technology has obtained industrial applications.Device service data shows: in 318 ℃ of temperature of reaction, liquid air speed (LHSV) 0.23 hour
-1condition under, ethylene selectivity 96.8% (mole), ethanol conversion 99.1%, 8 months catalyst regeneration cycles.After, Halcon/SD company has developed again multistage insulation fixed bed reaction process: ethanol dewaters and generates ethene enters multistage insulation fixed bed reaction after water vapor dilution in, reactant gases carries out low temperature fractionation again through washing, compression, alkali cleaning with after being dried, and finally obtains polymer grade ethylene product.Examination data show: 465 ℃ of temperature of reaction, and liquid air speed (LHSV) 0. 8 hours
-1and steam: under the condition that ethanol ratio is 3:1, ethylene selectivity 99.4% (mole), ethanol conversion 99.9%, 8 months catalyst regeneration cycles.Lummus company has realized the industrialization of fixed-bed process as far back as nineteen sixties.This process using shell and tube isothermal reactor, adopts thermal oil system to provide reaction required heat.The one Al catalysts regeneration period of silicon is 3 weeks, and every regeneration once needs 3 days.Under 315 ℃ of temperature of reaction, reaction pressure 0. 16MPa condition, ethylene selectivity approximately 94% (mole), ethanol conversion 99%.
In existing document or report, in shorter mention ethene Dehydration ethene, how to improve the problem, particularly ethylene distillation tower reactor liquid of yield of ethene and process or the larger problem of ethylene loss amount.Patent (ZL200710040705.64) proposes to adopt the method for adiabatic flash, reclaims the ethene in ethylene distillation tower reactor liquid, though recyclable part ethene, organic efficiency is not high.The invention provides a kind of method that improves yield of ethene on new producing ethylene from dehydration of ethanol in skill.The method has the advantages that ethylene recovery efficiency is high, energy consumption is low.
Summary of the invention
Technical problem to be solved by this invention is in the ethene Dehydration ethene not relating in previous literature, how to improve the problem of yield of ethene, particularly ethylene distillation tower reactor liquid is processed or the larger problem of ethylene loss amount, and a kind of method that improves yield of ethene in new producing ethylene from dehydration of ethanol technique is provided.It is high that the method has in ethene Dehydration ethene yield of ethene, and particularly ethylene distillation tower reactor liquid is processed or the less advantage of ethylene loss amount.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that improves yield of ethene in producing ethylene from dehydration of ethanol, mixture and light constituent containing ethene, ethane and carbon three and above hydrocarbon thereof enter ethylene rectification tower, at tower top, isolate the ethene vapour phase containing light constituent, vapour phase refluxes through condensation rear section, part, to light constituent stripping tower, is discharged the heavy constituent containing ethene in tower reactor; The top that enters heavy constituent stripping distillation tower containing the heavy constituent of ethene, after stripping fractionation by distillation, tower top vapour phase is returned to the middle and lower part of ethylene rectification tower, and tower reactor is heavy constituent.
In technique scheme, the service temperature of ethylene rectification tower is-35～30.0 ℃, and preferable range is-25～25.0 ℃; Working pressure is 1.3～4.5MPaG, and preferable range is 1.5～3.5MPaG; Theoretical plate number is 50～140, and preferable range is 70～120.Ethylene rectification tower feed entrance point preferred version is at 40～110 theoretical tray places.The service temperature of heavy constituent stripping distillation tower is-15～800 ℃, and preferable range is-10～700 ℃; Working pressure is 1. 0～4. 0MPaG, and preferable range is 2. 0～3.5MPaG; Theoretical plate number is 2～50, and preferable range is 5～40.Heavy constituent stripping input of column location optimization scheme is at top.The feed entrance point preferred version that stripping distillation tower tower top vapour phase is returned to ethylene rectification tower is at 39～140 theoretical tray places.
In the present invention owing to adopting stripping distillation tower to carry out stripping distillation to the tower reactor heavy constituent of ethylene rectification tower, thereby allow the ethylene content in ethylene distillation tower reactor liquid greatly to increase on the one hand, ethylene rectification tower operation is more prone to; Can fully reclaim again on the other hand the ethene in ethylene distillation tower reactor liquid, the ethene amount that makes to remain in heavy constituent reduces (from 22%, being reduced to 3%) greatly.Through evidence, adopt technical scheme of the present invention, the ethylene content that stripping distillation tower bottom drains in heavy constituent out-of-bounds can be less than 5% (weight), has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that improves yield of ethene method in producing ethylene from dehydration of ethanol soil skill of the present invention
In Fig. 1,1 is the crude ethylene from ethene dehumidification system, and 2 for the heavy constituent 3 that contains finite concentration ethene is the ethene that contains light constituent, and 4 for reclaiming ethene, and 5 is heavy constituent discharging, and 1a is ethylene rectification tower, and 2a is pump, and 3a is stripping distillation tower.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Press the schematic flow sheet of Fig. 1, from the crude ethylene of ethene dehumidification system, enter ethylene rectification tower and separate, at tower top, separate the ethene that contains light constituent, in tower reactor, isolate heavy constituent.The each composition flow rate of crude ethylene is: 0.070 kg/hr of hydrogen, 0.070 kg/hr, methane, 0.557 kg/hr of carbon monoxide, 1274.518 kgs/hr of ethene, 7.060 kgs/hr, ethane, 1.555 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, 5.631 kgs/hr of ether, 33.957 kgs/hr of heavy constituents.The each composition flow rate of ethylene rectification tower tower reactor heavy constituent is: 18.585 kgs/hr of ethene, 20.751 kgs/hr, ethane, 2.070 kgs/hr, propane, 0.119 kg/hr, acetaldehyde, 5.778 kgs/hr of ether, 36.523 kgs/hr of heavy constituents.The tower top temperature of ethylene rectification tower is-25.1 ℃, and pressure is 2.15MPaG, and tower reactor temperature is 9.3 ℃, and full tower theoretical plate number is 80, and feed entrance point is in middle and lower part.Stripping distillation is carried out at the top that this tower reactor heavy constituent is delivered to stripping distillation tower through pump pressure, and the tower top temperature of stripping distillation tower is 9.5 ℃, and pressure is 2.16MPaG, and tower reactor temperature is 59 ℃, and full tower theoretical plate number is 12.After stripping distillation, tower top steams the main Matter Transfer containing ethene and enters ethylene rectification tower bottom, and each composition flow rate is: 16.90 kgs/hr of ethene, 13.699 kgs/hr, ethane, 0.514 kg/hr, propane, ether 0.146 Grams Per Hour, 2.561 kgs/hr of heavy constituents; Tower bottom is discharged main containing ethane and C
3 +mixture, the consisting of of each component: 7.051 kgs/hr, 1.685 kgs/hr of ethane of ethene, 1.556 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, ether 5.632 Grams Per Hours, 33.962 kgs/hr of heavy constituents.The thermal load of stripping distillation tower reboiler is 4.709kw.Yield of ethene is 99.03% (weight).
[embodiment 2]
With embodiment 1, only change theoretical stage and the charging version position of ethylene rectification tower: full tower theoretical plate number is 92, feed entrance point is in middle and lower part, the other the same as in Example 1.Ethylene rectification tower tower reactor heavy constituent flow is 83.801 kgs/hr, wherein ethene is 18.579 kgs/hr, through pump pressure, deliver to the top of stripping distillation tower and carry out stripping distillation, the tower top temperature of ethylene rectification tower is-25..1 ℃, pressure is 2.15MPaG, and tower reactor temperature is 9.3 ℃, and the tower top temperature of stripping distillation tower is 9.5 ℃, pressure is 2.16MPaG, and tower reactor temperature is 59 ℃.After stripping distillation, tower top steams the main Matter Transfer containing ethene and enters ethylene rectification tower bottom, and tower bottom is discharged main containing ethane and C
3 +mixture, flow is 50.0 kgs/hr, wherein containing 1.690 kgs/hr of ethene.The thermal load of stripping distillation tower reboiler is 4.711kw.Yield of ethene is 99.03% (weight).
[embodiment 3]
With embodiment 1, only change the theoretical stage of the tower of stripping distillation tower: full tower theoretical plate number is 20, the other the same as in Example 1.Ethylene rectification tower tower reactor heavy constituent flow is 82.584 kgs/hr, wherein ethene is 18.309 kgs/hr, through pump pressure, deliver to the top of stripping distillation tower and carry out stripping distillation, the tower top temperature of ethylene rectification tower is-25..1 ℃, pressure is 2.15MPaG, and tower reactor temperature is 9.7 ℃, and the tower top temperature of stripping distillation tower is 9.8 ℃, pressure is 2.16MPaG, and tower reactor temperature is 59 ℃.After stripping distillation, tower top steams the main Matter Transfer containing ethene and enters ethylene rectification tower bottom, and tower bottom is discharged main containing ethane and C
3 +mixture, flow is 50.0 kgs/hr, wherein containing 1.676 kgs/hr of ethene.The thermal load of stripping distillation tower reboiler is 4.585kw.Yield of ethene is 99.03% (weight).
[comparative example 1]
By existing technique, from the crude ethylene of ethene dehumidification system, enter ethylene rectification tower and separate, at tower top, separate the ethene that contains light constituent, in tower reactor, isolate heavy constituent.The each composition flow rate of crude ethylene is the same, and technique is without stripping distillation tower.The each composition flow rate of ethylene rectification tower tower reactor heavy constituent is: 13.765 kgs/hr of ethene, 7.060 kgs/hr, ethane, 1.555 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, 5.631 kgs/hr of ether, 33.957 kgs/hr of heavy constituents.Yield of ethene is 98.08% (weight).
[comparative example 2]
By existing technique, from the crude ethylene of ethene dehumidification system, enter ethylene rectification tower and separate, at tower top, separate the ethene that contains light constituent, in tower reactor, isolate heavy constituent.The each composition flow rate of crude ethylene is the same.Ethylene rectification tower tower reactor heavy constituent is delivered to adiabatic flash tank through pump pressure, heating.Flash drum overhead gas phase is returned to ethylene distillation tower bottom, flash tank bottom extraction liquid phase heavy constituent, each composition flow rate is: 4.415 kgs/hr of ethene, 7.068 kgs/hr, ethane, 1.555 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, 5.630 kgs/hr of ether, 33.956 kgs/hr of heavy constituents.The thermal load of well heater is 10.864kw, and yield of ethene is 98.80% (weight).
Claims (8)
1. in a producing ethylene from dehydration of ethanol, improve the method for yield of ethene, mixture and light constituent containing ethene, ethane and carbon three and above hydrocarbon thereof enter ethylene rectification tower, at tower top, isolate the ethene vapour phase containing light constituent, vapour phase refluxes through condensation rear section, part, to light constituent stripping tower, is discharged the heavy constituent containing ethene in tower reactor; The top that enters heavy constituent stripping distillation tower containing the heavy constituent of ethene, after stripping fractionation by distillation, tower top vapour phase is returned to the middle and lower part of ethylene rectification tower, and tower reactor is heavy constituent.
2. the method that improves according to claim 1 yield of ethene in producing ethylene from dehydration of ethanol, is characterized in that the service temperature of ethylene rectification tower is-35～30.0 ℃, and working pressure is 1.3～4.5MPaG, and theoretical plate number is 50～140.
3. the method that improves according to claim 2 yield of ethene in producing ethylene from dehydration of ethanol, is characterized in that the service temperature of ethylene rectification tower is-25～25.0 ℃, and working pressure is 1.5～3.5MPaG, and theoretical plate number is 70～120.
4. the method that improves according to claim 1 yield of ethene in producing ethylene from dehydration of ethanol, is characterized in that ethylene rectification tower feed entrance point is at 40～110 theoretical tray places.
5. the method that improves according to claim 1 yield of ethene in producing ethylene from dehydration of ethanol, is characterized in that the service temperature of heavy constituent stripping distillation tower is-15～800 ℃, and working pressure is 1. 0～4. 0MPaG, and theoretical plate number is 2～50.
6. the method that improves according to claim 5 yield of ethene in producing ethylene from dehydration of ethanol, is characterized in that the service temperature of heavy constituent stripping distillation tower is-10～700 ℃, and working pressure is 2. 0～3.5MPaG, and theoretical plate number is 5～40.
7. the method that improves according to claim 1 yield of ethene in producing ethylene from dehydration of ethanol, is characterized in that heavy constituent stripping input of column position is at top.
8. improve according to claim 1 the method for yield of ethene in producing ethylene from dehydration of ethanol, it is characterized in that feed entrance point that stripping distillation tower tower top vapour phase returns to ethylene rectification tower is at 39～140 theoretical tray places.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306973A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Process for recovering ethylene in process of ethylene preparation by ethanol dehydration |
| CN102372558A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing ethylene by using ethanol |
| CN103420752A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Separation refinement method for ethylene preparation through biomass ethanol dehydration |
| CN103664448A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Separating and refining method for preparing ethylene by dehydrating biomass ethanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306973A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Process for recovering ethylene in process of ethylene preparation by ethanol dehydration |
| CN102372558A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing ethylene by using ethanol |
| CN103420752A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Separation refinement method for ethylene preparation through biomass ethanol dehydration |
| CN103664448A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Separating and refining method for preparing ethylene by dehydrating biomass ethanol |
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