CN103739426B - The method of yield of ethene is improved in producing ethylene from dehydration of ethanol technique - Google Patents
The method of yield of ethene is improved in producing ethylene from dehydration of ethanol technique Download PDFInfo
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- CN103739426B CN103739426B CN201210393010.7A CN201210393010A CN103739426B CN 103739426 B CN103739426 B CN 103739426B CN 201210393010 A CN201210393010 A CN 201210393010A CN 103739426 B CN103739426 B CN 103739426B
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Abstract
The present invention relates to a kind of method improving yield of ethene in producing ethylene from dehydration of ethanol, mainly solve in previous literature the problem, the particularly process of ethylene distillation tower reactor liquid how improving yield of ethene in the ethene Dehydration ethene do not related to or the larger problem of ethylene loss amount.The technical scheme of heavy constituent is discharged at the bottom of the middle and lower part that ethylene distillation tower reactor liquid is entered a heavy constituent stripping distillation tower top by adopting by the present invention, overhead vapor phase returns ethylene rectification tower, tower, solve this problem preferably, can be used in producing ethylene from dehydration of ethanol industrial production.
Description
Technical field
The present invention relates to a kind of method improving yield of ethene in producing ethylene from dehydration of ethanol technique.
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, domestic and international ethylene production mainly adopts petroleum catalystic pyrolysis to produce.New breakthrough was had, particularly producing ethylene by ethanol dehydration technology in recent years to the research of non-petroleum feedstocks production ethene.This technology derives from the ethanol of agricultural byproducts for raw material, can avoid the dependence to petroleum resources like this.To oil-poor and country based on agricultural and area, the raw material producing ethanol is easy to get and guaranteed, has established enough raw material bases for producing ethene, 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 improving technique flow 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.ABBLummu: company once carried out ethanol dehydration reaction preparing ethylene (USP4134926) in late nineteen seventies proposition fluidization, but this technology not yet obtains industrial applications.Current 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, the generation of other by products will be caused, if but increase flow velocity, the transformation efficiency of ethanol can drop to again and solve this contradiction, skill in the thermal insulation that United States Patent (USP) (USP4232179) proposes ethanol dehydration reaction, namely ethanol dehydration reaction carries out in insulation fix bed, it is temperature required that reaction mass is heated to reaction before entering the reactor, to ensure normally carrying out of reaction.Afterwards, they also been proposed 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.This technique adopts three insulation fix bed reactors of connecting, and comes ethanol and the vapor mixing charging of each Reactor inlet of preheating with a stove, and the by products such as unreacted ethanol and ether carry out circulation.Adding of steam decreases reaction coking, extends the life-span of catalyzer, improves productive rate.Plant running data show, when reactor inlet temperatures is 450 DEG C, ethanol conversion reaches 98, catalyst regeneration cycle at least one year.In addition Halcon/SD company and tenth century the seventies develop the double mode technology of thermal insulation or isothermal fixed bed, wherein isothermal bed technology obtains industrial applications.Plant running data show: in temperature of reaction 318 DEG C, liquid air speed (LHSV) 0.23 hour
-1condition under, ethylene selectivity 96.8% (mole), ethanol conversion 99.1%, catalyst regeneration cycle 8 months.After, Halcon/SD company develops again multistage insulation fixed bed reaction process: ethanol enters dehydration in multistage insulation fixed bed reaction and generates ethene after steam dilution, reactant gases carries out low temperature fractionation again after washing, compression, alkali cleaning and drying, finally obtains polymer grade ethylene product.Examination data show: temperature of reaction 465 DEG C, liquid air speed (LHSV) 0.8 hour
-1and steam: under the condition that ethanol ratio is 3:1, ethylene selectivity 99.4% (mole), ethanol conversion 99.9%, catalyst regeneration cycle 8 months.Lummus company achieves the industrialization of fixed-bed process as far back as nineteen sixties.This technique adopts shell and tube isothermal reactor, and employing thermal oil system provides the heat needed for reaction.The silicon one Al catalysts regeneration period is 3 weeks, often regenerates and once needs 3 days.Under temperature of reaction 315 DEG C, reaction pressure 0.16MPa condition, ethylene selectivity about 94% (mole), ethanol conversion 99%.
In existing document or report, in shorter mention ethene Dehydration ethene, how to improve the problem, the particularly process of ethylene distillation tower reactor liquid of yield of ethene or the larger problem of ethylene loss amount.Patent (ZL200710040705.64) proposes the method adopting adiabatic flash, and the ethene in recovered ethylene rectifying tower bottoms, though recyclable part ethene, organic efficiency is not high.The invention provides a kind of method new producing ethylene from dehydration of ethanol improving yield of ethene 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 how to improve the problem of yield of ethene in the ethene Dehydration ethene do not related in previous literature, particularly the process of ethylene distillation tower reactor liquid or the larger problem of ethylene loss amount, provide a kind of method improving yield of ethene in new producing ethylene from dehydration of ethanol technique.It is high that the method has yield of ethene in ethene Dehydration ethene, particularly the process of ethylene distillation tower reactor liquid 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 improving yield of ethene in producing ethylene from dehydration of ethanol, ethylene rectification tower is entered containing the mixture of ethene, ethane and carbon three and above hydrocarbon thereof and light constituent, the ethene vapour phase containing light constituent is isolated at tower top, vapour phase refluxes through condensation rear section, part, to light constituent stripping tower, discharges the heavy constituent containing ethene in tower reactor; Heavy constituent containing ethene enters the top of heavy constituent stripping distillation tower, and after stripping fractionation by distillation, overhead vapor phase returns 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 DEG C, and preferable range is-25 ~ 25.0 DEG C; 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 DEG C, and preferable range is-10 ~ 700 DEG C; 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 position preferred version is at top.The feed entrance point preferred version that stripping overhead vapour phase returns ethylene rectification tower is at 39 ~ 140 theoretical tray places.
Owing to adopting the tower reactor heavy constituent of stripping distillation tower to ethylene rectification tower to carry out stripping distillation in the present invention, thus allow the ethylene content in ethylene distillation tower reactor liquid greatly to increase on the one hand, ethylene rectification tower is operated and is more prone to; On the other hand again can ethene fully in recovered ethylene rectifying tower bottoms, the ethene amount remained in heavy constituent is reduced (being reduced to 3% from 22%) greatly.Prove to adopt technical scheme of the present invention through test, the ethylene content drained into bottom stripping distillation tower in heavy constituent out-of-bounds can be less than 5% (weight), achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet improving yield of ethene method in producing ethylene from dehydration of ethanol of the present invention soil skill
In Fig. 1,1 is the crude ethylene from ethene dehumidification system, and 2 is be the ethene containing light constituent containing the heavy constituent 3 of finite concentration ethene, and 4 is recovered ethylene, 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]
By the schematic flow sheet of Fig. 1, the crude ethylene from ethene dehumidification system enters ethylene rectification tower and is separated, and separates the ethene containing light constituent, isolate heavy constituent in tower reactor at tower top.The each composition flow rate of crude ethylene is: hydrogen 0.070 kg/hr, 0.070 kg/hr, methane, carbon monoxide 0.557 kg/hr, ethene 1274.518 kgs/hr, 7.060 kgs/hr, ethane, 1.555 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, ether 5.631 kgs/hr, heavy constituent 33.957 kgs/hr.The each composition flow rate of ethylene rectification tower tower reactor heavy constituent is: ethene 18.585 kgs/hr, 20.751 kgs/hr, ethane, 2.070 kgs/hr, propane, 0.119 kg/hr, acetaldehyde, ether 5.778 kgs/hr, heavy constituent 36.523 kgs/hr.The tower top temperature of ethylene rectification tower is-25.1 DEG C, and pressure is 2.15MPaG, and bottom temperature is 9.3 DEG C, 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 delivers to stripping distillation tower through pump pressure, and the tower top temperature of stripping distillation tower is 9.5 DEG C, and pressure is 2.16MPaG, and bottom temperature is 59 DEG C, 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: ethene 16.90 kgs/hr, 13.699 kgs/hr, ethane, 0.514 kg/hr, propane, ether 0.146 Grams Per Hour, heavy constituent 2.561 kgs/hr; Tower bottom is discharged main containing ethane and C
3 +mixture, consisting of of each component: 7.051 kgs/hr, ethene 1.685 kgs/hr of ethane, 1.556 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, ether 5.632 Grams Per Hour, heavy constituent 33.962 kgs/hr.The thermal load of stripping distillation tower reboiler is 4.709kw.Yield of ethene is 99.03% (weight).
[embodiment 2]
With embodiment 1, the theoretical stage of a change ethylene rectification tower and charging version position: full tower theoretical plate number is 92, feed entrance point 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, stripping distillation is carried out at the top delivering to stripping distillation tower through pump pressure, the tower top temperature of ethylene rectification tower is-25..1 DEG C, pressure is 2.15MPaG, and bottom temperature is 9.3 DEG C, and the tower top temperature of stripping distillation tower is 9.5 DEG C, pressure is 2.16MPaG, and bottom temperature is 59 DEG C.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 ethene 1.690 kgs/hr.The thermal load of stripping distillation tower reboiler is 4.711kw.Yield of ethene is 99.03% (weight).
[embodiment 3]
With embodiment 1, the theoretical stage of the tower of a change 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, stripping distillation is carried out at the top delivering to stripping distillation tower through pump pressure, the tower top temperature of ethylene rectification tower is-25..1 DEG C, pressure is 2.15MPaG, and bottom temperature is 9.7 DEG C, and the tower top temperature of stripping distillation tower is 9.8 DEG C, pressure is 2.16MPaG, and bottom temperature is 59 DEG C.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 ethene 1.676 kgs/hr.The thermal load of stripping distillation tower reboiler is 4.585kw.Yield of ethene is 99.03% (weight).
[comparative example 1]
By existing technique, the crude ethylene from ethene dehumidification system enters ethylene rectification tower and is separated, and separates the ethene containing light constituent, isolate heavy constituent in tower reactor at tower top.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: ethene 13.765 kgs/hr, 7.060 kgs/hr, ethane, 1.555 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, ether 5.631 kgs/hr, heavy constituent 33.957 kgs/hr.Yield of ethene is 98.08% (weight).
[comparative example 2]
By existing technique, the crude ethylene from ethene dehumidification system enters ethylene rectification tower and is separated, and separates the ethene containing light constituent, isolate heavy constituent in tower reactor at tower top.The each composition flow rate of crude ethylene is the same.Ethylene rectification tower tower reactor heavy constituent delivers to adiabatic flash tank through pump pressure, heating.Flash drum overhead gas phase returns ethylene distillation tower bottom, extraction liquid phase heavy constituent bottom flash tank, each composition flow rate is: ethene 4.415 kgs/hr, 7.068 kgs/hr, ethane, 1.555 kgs/hr, propane, 0.113 kg/hr, acetaldehyde, ether 5.630 kgs/hr, heavy constituent 33.956 kgs/hr.The thermal load of well heater is 10.864kw, and yield of ethene is 98.80% (weight).
Claims (6)
1. in a producing ethylene from dehydration of ethanol, improve the method for yield of ethene, ethylene rectification tower is entered containing the mixture of ethene, ethane and carbon three and above hydrocarbon thereof and light constituent, the ethene vapour phase containing light constituent is isolated at tower top, vapour phase refluxes through condensation rear section, part, to light constituent stripping tower, discharges the heavy constituent containing ethene in tower reactor; Heavy constituent containing ethene enters the top of heavy constituent stripping distillation tower, and after stripping fractionation by distillation, overhead vapor phase returns to the middle and lower part of ethylene rectification tower, and tower reactor is heavy constituent;
Wherein, the service temperature of ethylene rectification tower is-35 ~ 30.0 DEG C, and working pressure is 1.3 ~ 4.5MPaG, and theoretical plate number is 50 ~ 140; The service temperature of heavy constituent stripping distillation tower is-15 ~ 800 DEG C, and working pressure is 1.0 ~ 4.0MPaG, and theoretical plate number is 2 ~ 50.
2. improve the method for yield of ethene according to claim 1 in producing ethylene from dehydration of ethanol, it is characterized in that the service temperature of ethylene rectification tower is-25 ~ 25.0 DEG C, working pressure is 1.5 ~ 3.5MPaG, and theoretical plate number is 70 ~ 120.
3. improve the method for yield of ethene according to claim 1 in producing ethylene from dehydration of ethanol, it is characterized in that ethylene rectification tower feed entrance point is at 40 ~ 110 theoretical tray places.
4. improve the method for yield of ethene according to claim 1 in producing ethylene from dehydration of ethanol, it is characterized in that the service temperature of heavy constituent stripping distillation tower is-10 ~ 700 DEG C, working pressure is 2.0 ~ 3.5MPaG, and theoretical plate number is 5 ~ 40.
5. improve the method for yield of ethene according to claim 1 in producing ethylene from dehydration of ethanol, it is characterized in that heavy constituent stripping input of column position is at top.
6. improve the method for yield of ethene according to claim 1 in producing ethylene from dehydration of ethanol, it is characterized in that stripping overhead vapour phase returns the feed entrance point of ethylene rectification tower at 39 ~ 140 theoretical tray places.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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