CN104230622B - The production method of producing ethylene from dehydration of ethanol - Google Patents
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Abstract
The present invention relates to the production method of a kind of producing ethylene from dehydration of ethanol, mainly solve the organic wastewater that in prior art, producing ethylene from dehydration of ethanol produces the most fully to be processed, to reach the purpose of recycling, though or treated, there is complex process, long flow path, problem that investment is big.The present invention is comprised the following steps by employing: a) vapour phase ethanol is contacted with catalyst dehydration and generates the reacting gas containing ethylene；B) reacting gas entrance chilling tower carries out cooling washing；C) chilling cleaning mixture entrance stripping rectifying column carries out stripping rectification, and tower top obtains containing organic logistics, and tower reactor obtains aqueous stream；D) tower reactor aqueous stream is processed by hydrotreater, and the technical scheme obtaining the fresh water (FW) that resourcebility utilizes preferably solves this problem, can be used in the commercial production of producing ethylene from dehydration of ethanol.
Description
Technical field
The present invention relates to the production method of a kind of producing ethylene from dehydration of ethanol.
Background technology
Ethylene is a kind of important large organic chemical industry's base stock, is mainly used to produce the multiple Organic chemical products such as polyethylene, polrvinyl chloride, ethylene oxide/ethylene glycol, ethyl benzene/styrene, vinyl acetate.At present, domestic and international ethylene production mainly uses petroleum catalystic pyrolysis to produce.The research that non-petroleum feedstocks produced ethylene in recent years has new breakthrough, particularly producing ethylene by ethanol dehydration technology.This technology is with the ethanol deriving from biomass as raw material, so can avoid the dependence to petroleum resources.To the 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 ethylene, it is possible to resolve the difficult problem that fossil resource shortage is serious with environmental pollution.Especially with the fast development of biotechnology, the technology of biological legal system ethanol is the most perfect, and the source of raw material is increasingly extensive, and the cost of raw material is the most more rational so that producing ethylene from dehydration of ethanol technology attention.
Producing ethylene with ethyl alcohol, it is strong and have the technique of the market competitiveness that its key factor is to study a kind of new economy, and main goal in research is to improve technological process, reduces ethanol unit consumption, increases device benefit.
In the process 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 broadly divided into fixed-bed process and fluidized-bed process.ABB Lummu company once carried out ethanol dehydration reaction preparing ethylene (US4134926) in late nineteen seventies proposition fluidization, but this technology not yet obtains industrial applications.The predominantly fixed-bed process of commercial Application at present, including isothermal fixed-bed process and insulation fix bed technique.
Initial ethanol dehydration reaction is carried out in calandria type fixed bed, and reaction pressure is normal pressure, uses and directly heats or utilize the mode adding thermal medium (such as fused salt) heating indirectly to provide reaction heat for reaction.In course of reaction, reaction temperature and material flow are key factors, if temperature is the highest or material flow is the lowest, may result in the generation of other by-products, but if increasing flow velocity, the conversion ratio of ethanol can decline again.In order to solve this contradiction, United States Patent (USP) (US4232179) proposes skill in the thermal insulation of ethanol dehydration reaction, i.e. ethanol dehydration reaction is carried out in insulation fix bed, and reaction mass is heated to react temperature required before entering the reactor, to ensure being normally carried out of reaction.Afterwards, they also been proposed the insulation fix bed reaction process of syllogic (US4396789), and utilizes this technique to set up 60,000 tons/year of ethylene units in the early 1980s.This technique uses the insulation fix bed reactors of three series connection, preheats the ethanol of each Reactor inlet and steam charging with a stove, and the by-product such as unreacted ethanol and ether is carried out and circulated.The addition of steam decreases reaction coking, extends the life-span of catalyst, improves productivity.Plant running data show, when reactor inlet temperatures is 450 DEG C, ethanol conversion reaches 98%, catalyst regeneration cycle at least a year.It addition, Halcon/SD company develops the double mode technology of thermal insulation or isothermal fixed bed in nineteen seventies, wherein isothermal bed technology has obtained industrial applications.Plant running data show: in reaction temperature 318 DEG C, liquid air speed (LHSV) 0.23 hour-1Under conditions of, 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 after steam dilution and generates ethylene, reacting gas is scrubbed, compression, alkali cleaning and carry out cryogenic rectification more after drying, finally obtains polymer grade ethylene product.Examination data show: in reaction temperature 465 DEG C, liquid air speed (LHSV) 0. 8 hours-1And steam: ethanol than under conditions of for 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 uses shell and tube isothermal reactor, uses thermal oil system to provide the heat needed for reaction.Silicon-Al catalysts regeneration period is 3 weeks, often regenerates and once needs 3 days.Under the conditions of reaction temperature 315 DEG C, reaction pressure 0. 16MPa, ethylene selectivity about 94% (mole), ethanol conversion 99%.
In existing document or report, in particular how the problem of organic wastewater treatment process in shorter mention producing ethylene from dehydration of ethanol, reduce feed ethanol consumption, the technical problem of organic wastewater resources regeneration utilization.The sewage-treatment plant that the organic wastewater of commercial plant is directly entered outside device without process at present, on the one hand it is that the Organic substance in organic wastewater, particularly ethanol do not get utilization, ethanol consumption is made to increase, on the other hand it is because organic concentration in waste water higher, the difficulty making the sewage-treatment plant outside battery limit (BL) process sewage increases, and processing cost also increases.Patent CN101376551B proposes the organic wastewater used in the disposal methods producing ethylene from dehydration of ethanol of four cell process, there is complex process, long flow path, problem that investment is big.
Summary of the invention
The technical problem to be solved is that the organic wastewater that in prior art, producing ethylene from dehydration of ethanol produces the most fully is processed, to reach the purpose of recycling, though or treated, there is complex process, long flow path, problem that investment is big, it is provided that the production method of a kind of new producing ethylene from dehydration of ethanol.The feature that the method has that technique is simple, flow process is short, small investment and organic wastewater resources regeneration utilize.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: the production method of a kind of producing ethylene from dehydration of ethanol, comprises the following steps:
A) by vapour phase ethanol and selected from γ-Al2O3, ZSM molecular sieve, molecular sieve, at least one catalyst contact in modenite, occur dehydration to generate the logistics 2 containing ethylene；
B) logistics 2 enters chilling tower bottom, and the washings counter current contacting entered with chilling top of tower carries out cooling washing, and chilling top of tower obtains vapour phase crude ethylene logistics 4, and chilling tower bottom obtains containing ethanol, ether, the liquid phase organic wastewater logistics 5 of ethylene；
C) middle and upper part of logistics 5 entrance stripping rectifying column carries out stripping rectification, and tower top obtains containing ethanol, ether, the logistics 8 of ethylene, and tower reactor obtains aqueous stream 6；
D) logistics 6 is by hydrotreater, processes through adsorbent, obtains the logistics 7 containing Organic substance≤1ppm.
In technique scheme, it is preferable that ethanol dehydration reaction produces the reactor of ethylene selected from calandria type fixed bed, multistage insulation fixed bed or single stage adiabatic fixed bed.
In technique scheme, it is preferable that it is 300～510 DEG C that ethanol dehydration reaction produces the reactor reaction temperature of ethylene, reaction pressure is calculated as 0.01～5.0MPa with gauge pressure, and reaction weight space velocity is 0.1～10 hour-1。
In technique scheme, it is preferable that chilling tower is packed tower, plate column or void tower.
In technique scheme, it is preferable that the operation temperature of chilling tower is 30～120 DEG C, operation pressure is calculated as 0.01～4.5MPa with gauge pressure, and liquid gas weight ratio is 1.2～30, and theoretical cam curve is 2～18.
In technique scheme, it is preferable that the operation temperature of stripping rectifying column is 30～210. 0 DEG C, operation pressure is calculated as 0～1.0MPa with gauge pressure, and theoretical cam curve is 2～98, and the feed entrance point of organic wastewater is at 1～85 theoretical trays.
In technique scheme, preferably, stripping rectifying column tower top Organic substance extraction is with vapour phase and/or liquid phase mode extraction, and tower reactor heat source used vapour is directly entered the bottom of tower as thermal source, or provides thermal source by the form of steam, deep fat, the reboiler of electricity or heater for stripping rectifying column.
In technique scheme, it is preferable that the adsorbent used by adsorption treatment is cation exchange resin, anthracite, activated carbon or molecular sieve.It is highly preferred that the adsorbent used by adsorption treatment is selected from anthracite or activated carbon.
Owing to using the organic wastewater produced in stripping distillation combine adsorption PROCESS FOR TREATMENT producing ethylene from dehydration of ethanol in the present invention, ethanol, ether and a small amount of ethylene, carbon three and the Organic substance of above hydrocarbon thereof in removing organic wastewater, make the Organic substance in organic wastewater, particularly ethanol get utilization, reduce the consumption of feed ethanol.After present invention process processes, the content of organics≤1ppm of technique waste water, can be used as boiler feedwater.Use the inventive method, have that technique is simple, flow process is short and the feature of small investment, device for ton, coarse ethanol 222 tons/year (concentration is about 80 weight %) in recyclable organic wastewater, in organic wastewater, organic concentration is down to trace (content of organics≤1ppm) from 0.265 weight %, achieves preferable technique effect.
Accompanying drawing explanation
Fig. 1 is the inventive method schematic flow sheet.
In Fig. 1,1 is vapour phase ethanol, 2 reacting gas generated for dehydration, 3 is the washings of chilling tower, 4 is the crude ethylene gas after chilling washing, and 5 is the organic wastewater after chilling washs, and 6 is the lean organic wastewater processed through stripping, 7 is the technique waste water through adsorption treatment, the tower top organic-rich material that 8 is stripping rectifying column, 1a is reactor, and 2a is chilling tower, 3a is stripping rectifying column, and 4a is absorption hydrotreater.
In Fig. 1, raw material vapour phase ethanol enters gas solid phase fixed bed reactor 1a, and containing γ-Al2O3, ZSM molecular sieve, at least one catalyst contact in molecular sieve or modenite, dehydration produces ethylene and other by-product.Reacting gas 2 enters gas chilled tower 2a, with washings 3 chilling washing reaction gas, obtaining crude ethylene 4 after chilling washing goes follow up device to process, organic wastewater 5 after chilling washing enters stripping rectifying column 3a, isolating the logistics 8 containing ethanol, ether and ethylene, carbon three and above hydrocarbon thereof at tower top, discharge the logistics 6 containing micro-content organism in tower reactor, logistics 6 is after hydrotreater 4a adsorption treatment, content of organics in logistics 7 technique waste water is less than 1ppm, can be used as boiler feedwater.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Technical scheme as shown in Figure 1, raw material vapour phase ethanol is in reaction temperature 345 DEG C, reaction pressure 0.06MPaG, liquid phase ethanol air speed 0.9hr-1Under conditions of, with γ-Al2O3Catalyst contact dehydration produces ethylene, reacting gas washs with washings in the chilling tower of 0.04MPaG, top temperature 40 DEG C is pressed on top, liquid phase organic wastewater after washing enters stripping rectifying column and separates, separate containing organic secondary organic wastewater at tower top, isolate the lean organic wastewater containing micro-content organism in tower reactor.The each composition flow rate of organic wastewater is: carbon dioxide 0.016 kg/hr, ethylene 0.799 kg/hr, 0.002 kg/hr of ethane, 0.001 kg/hr of propane, 0.977 kg/hr of acetaldehyde, ethanol 22.229 kgs/hr, ether 0.398 kg/hr, heavy constituent 0.07 kg/hr, 9204.193 kgs/hr of water.Separating containing organic organic-rich waste water at stripping rectifying column tower top, flow is 27.744 kgs/hr, concentration of alcohol 79.6%wt, 0.942 kg/hr of a small amount of tail gas；Isolating the lean organic wastewater containing micro-content organism in tower reactor, flow is 9200 kgs/hr, enters the hydrotreater equipped with activated carbon, and after adsorption treatment, Waste Organic substance in water is zero.The tower top temperature of stripping rectifying column is 90.8 DEG C, and pressure is 0.11MPaG, and bottom temperature is 125 DEG C, and full tower theoretical cam curve is 12, and feed entrance point, at middle part, provides thermal source with the form of reboiler for stripping rectifying column.The thermic load of stripping distillation column reboiler is 578.635kw.
[embodiment 2]
With [embodiment 1], only change the theoretical stage of stripping rectifying column: full tower theoretical cam curve is 22, and feed entrance point is in middle and upper part.Stripping rectifying column overhead extraction richness organic wastewater 27.744 kgs/hr, concentration of alcohol 79.6%wt, 0.942 kg/hr of a small amount of tail gas；The stripping lean organic wastewater of tower bottom of rectifying tower is 9200 kgs/hr, enters the hydrotreater equipped with activated carbon, and after adsorption treatment, Waste Organic substance in water is zero.The tower top temperature of stripping rectifying column is 90.8 DEG C, and pressure is 0.11MPaG, and bottom temperature is 125 DEG C.The thermic load of stripping distillation column reboiler is 557.833kw.
[embodiment 3]
With [embodiment 1], only changing the tower reactor mode of heating of stripping distillation column, the bottom being directly entered tower with steam replaces reboiler, tower top frozen-free device, and vapour phase extraction returns producing ethylene from dehydration of ethanol device.Stripping rectifying column overhead vapor phase (rich organic wastewater) flow is 240.024 kgs/hr, concentration of alcohol 9.23wt%；The stripping lean organic wastewater of tower bottom of rectifying tower is 10538.662 kgs/hr, and wherein Organic substance is 12.7ppm, enters the hydrotreater equipped with activated carbon, and after adsorption treatment, in technique waste water, content of organics is less than 1ppm.The tower top temperature of stripping rectifying column is 120.5 DEG C, and pressure is 0.11MPaG, and bottom temperature is 123.3 DEG C.The flow of stripping distillation column stripped vapor is 1550 kgs/hr.
Claims (8)
1. a production method for producing ethylene from dehydration of ethanol, comprises the following steps:
A) by vapour phase ethanol and selected from γ-Al2O3, ZSM molecular sieve, beta-molecular sieve, in modenite
The contact of at least one catalyst, occur dehydration to generate containing the logistics (2) of ethylene；
B) logistics (2) enters chilling tower bottom, and the washings counter current contacting entered with chilling top of tower is entered
Row cooling washing, chilling top of tower obtains vapour phase crude ethylene logistics (4), and chilling tower bottom obtains containing second
Alcohol, ether, liquid phase organic wastewater logistics (5) of ethylene；
C) logistics (5) enter stripping rectifying column middle and upper part carry out strip rectification, tower top obtain containing ethanol,
Ether, the logistics (8) of ethylene, tower reactor obtains aqueous stream (6)；
D) hydrotreater is passed through in logistics (6), processes through adsorbent, obtains containing Organic substance≤1ppm
Logistics (7)；
Wherein, described adsorbent is anthracite or activated carbon.
The production method of producing ethylene from dehydration of ethanol the most according to claim 1, it is characterised in that second
Dehydration of alcohols reaction produces the reactor of ethylene selected from calandria type fixed bed, multistage insulation fixed bed or single
Section is insulation fix bed.
The production method of producing ethylene from dehydration of ethanol the most according to claim 2, it is characterised in that anti-
Answering temperature is 300～510 DEG C, and reaction pressure is calculated as 0.01～5.0MPa with gauge pressure, reacts weight space velocity
It it is 0.1～10 hour-1。
The production method of producing ethylene from dehydration of ethanol the most according to claim 1, it is characterised in that anxious
Cold tower is packed tower, plate column or void tower.
The production method of producing ethylene from dehydration of ethanol the most according to claim 1, it is characterised in that anxious
The operation temperature of cold tower is 30～120 DEG C, and operation pressure is calculated as 0.01～4.5MPa with gauge pressure, liquid gas
Weight ratio is 1.2～30, and theoretical cam curve is 2～18.
The production method of producing ethylene from dehydration of ethanol the most according to claim 1, it is characterised in that vapour
The operation temperature carrying rectifying column is 30～210.0 DEG C, and operation pressure is calculated as 0～1.0MPa with gauge pressure,
Theoretical cam curve is 2～98, and the feed entrance point of organic wastewater is at 1～85 theoretical trays.
The production method of producing ethylene from dehydration of ethanol the most according to claim 1, it is characterised in that vapour
Proposing rectifying column tower top Organic substance extraction is with vapour phase and/or liquid phase mode extraction.
The production method of producing ethylene from dehydration of ethanol the most according to claim 1, it is characterised in that vapour
Carry tower bottom of rectifying tower heat source used vapour and be directly entered the bottom of tower as thermal source, or with steam,
The form of deep fat, the reboiler of electricity or heater provides thermal source for stripping rectifying column.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4134926A (en) * | 1977-04-18 | 1979-01-16 | The Lummus Company | Production of ethylene from ethanol |
| CN101134704A (en) * | 2007-10-16 | 2008-03-05 | 南京工业大学 | Process for producing ethylene by ethanol dehydration |
| 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 |
| CN101327443A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院上海有机化学研究所 | Molecular sieve catalyst, preparation method and use in preparing ethylene by dehydrating ethanol |
| CN101747136A (en) * | 2008-12-04 | 2010-06-23 | 焦作市河阳酒精实业有限公司 | Technique for producing ethylene through catalyzing and dehydrating ethanol |
| WO2013170752A1 (en) * | 2012-05-16 | 2013-11-21 | 中国石油化工股份有限公司 | Device and method for producing ethylene |
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2013
- 2013-06-17 CN CN201310236941.0A patent/CN104230622B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4134926A (en) * | 1977-04-18 | 1979-01-16 | The Lummus Company | Production of ethylene from ethanol |
| 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 |
| CN101134704A (en) * | 2007-10-16 | 2008-03-05 | 南京工业大学 | Process for producing ethylene by ethanol dehydration |
| CN101327443A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院上海有机化学研究所 | Molecular sieve catalyst, preparation method and use in preparing ethylene by dehydrating ethanol |
| CN101747136A (en) * | 2008-12-04 | 2010-06-23 | 焦作市河阳酒精实业有限公司 | Technique for producing ethylene through catalyzing and dehydrating ethanol |
| WO2013170752A1 (en) * | 2012-05-16 | 2013-11-21 | 中国石油化工股份有限公司 | Device and method for producing ethylene |
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