CN102875309B - Method for preparing propylene from ethanol - Google Patents

Method for preparing propylene from ethanol Download PDF

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CN102875309B
CN102875309B CN201110193493.1A CN201110193493A CN102875309B CN 102875309 B CN102875309 B CN 102875309B CN 201110193493 A CN201110193493 A CN 201110193493A CN 102875309 B CN102875309 B CN 102875309B
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reaction
ethanol
propylene
carbon
ethene
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CN102875309A (en
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宣东
王仰东
刘苏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method for preparing propylene from ethanol, mainly solving the problem of low propylene selectivity in the prior art. The method adopts ethanol and etherified C4 as raw materials, and comprises the following steps: (1)reacting ethanol under the effect of a dehydration catalyst to generate an ethene-containing flow I; (2) contacting the flow I with etherified C4 under the effect of an isomerization catalyst to generate a flow II; (3) contacting the flow II with a disproportionation catalyst to generate a reaction product flow III containing ethene, propylene, butylene and trace C5; (4) separating the follow III through a deethylenizer to obtain ethene at the top and a flow IV containing propylene, butylene and trace C5 at the bottom; and (5) separating the flow IV through a depropenizer to obtain propylene at the top and butylene and trace C5 at the bottom. The method disclosed herein well solves the problems and can be applied in the industrial production of preparing propylene from ethanol.

Description

Ethanol is prepared the method for propylene
Technical field
The present invention relates to a kind of ethanol and prepare the method for propylene.
Background technology
In recent years, along with the development of global economy, market will constantly increase the demand of light olefin (comprising ethene, propylene etc.).Propylene is scale inferior to one of most important basic organic of ethene, and its maximum purposes is to produce polypropylene (accounting for the half of its total amount), is secondly to produce vinyl cyanide, propylene oxide, Virahol, isopropyl benzene, oxo-alcohols, vinylformic acid, oligomerization of propene thing.
US4302357 relates in the method by ethanol dehydration reaction ethene processed and adopts aluminium oxide catalyst.In specification sheets, the LHSV of ethanol is 0.25～5h -1, be preferably 0.5～3h -1. 370 DEG C of examples of implementation, 10kg/cm 2pressure and 1h -1lHSV under carry out, the selectivity of ethene is 99.3%.
WO2007083241A2 has described the preparation method of propylene, and described method is to make in ethanol successive reaction on catalyzer and is propylene by ethanol conversion.Used catalyst is solid acid catalyst.
CN101939276A has introduced a kind of method of being manufactured alkene by ethanol, relating to ethanol conversion is ethene, propylene and the mixture compared with heavy olefins, described method comprises: in the first cryogenic reaction zone, dewater, oligomeric-type catalyzer under the first reaction conditions by ethanol conversion for substantially containing ethene, propylene and the mixture compared with heavy olefins.Then, effectively absorb propylene, optionally extract water and remaining unconverted oxygenate, make compared with heavy olefins and the logistics that contacts to obtain having high propylene content in vinyl acetate the second high temperature reaction zone with olefin cracking catalyzer.
When for ethanol propylene reaction processed, all there is the problem that target product selectivity is low in the method in above document.
Summary of the invention
Technical problem to be solved by this invention is the low problem of target product Propylene Selectivity existing in prior art, provides a kind of new ethanol to prepare the method for propylene.When the method is prepared propylene reaction for ethanol, have advantages of that target product Propylene Selectivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of ethanol propylene processed, taking carbon four after ethanol and ether as raw material, comprise successively step: (1) ethanol generates containing ethylene streams I under the effect of dehydration catalyst; (2) stream I contacts production logistics II with carbon after ether four through isomerization catalyst; (3) stream I I and disproportionation catalyst contact reacts generate the reaction product stream III containing ethene, propylene, butylene and trace carbon five components; (4) stream I II separates through de-ethylene column, and tower top obtains ethene, and tower reactor obtains stream I V and comprises propylene, butylene and trace carbon five; (5) stream I V separates through depropenizer, and tower top obtains propylene, and tower reactor obtains butylene and trace carbon five.
In technique scheme, the preferred version of ethanol dehydration catalyzer is γ-Al 2o 3; The optimum condition of ethanol dehydration reaction is 420～480 DEG C of temperature of reaction, reaction pressure 0.01～1.0MPa, and reaction mass air speed is 0.2～0.8 hour -1; After ethanol and ether, the preferred molar ratio of carbon four is 1～5; The preferred version of isomerization catalyst is that specific surface area is for being greater than 200 meters 2/ gram magnesium oxide, the preferred version of disproportionation catalyst is WO 3/ SiO 2, the preferred weight ratio of disproportionation catalyst and isomerization catalyst is 1: 4～1: 6; The preferred version of disproportionation reaction operational condition is: 250～350 DEG C of temperature of reaction, reaction pressure 0.1～1MPa, the mass space velocity of carbon 4 1～10 hour -1; The preferred version of de-ethylene column operational condition is: 50～60 of column plates, tower top: 2.2～2.6MPa ,-15～-25 DEG C; The preferred version of the operational condition of depropenizer is: 70～80 of column plates, tower top: 1.7～1.9MPa, 40～50 DEG C; Preferred version is to separate the unreacted ethene and the butylene that obtain to return as disproportionation reaction feedstock recycle.
After the present invention passes through to adopt ether, carbon four is as reaction raw materials, due to iso-butylene and butene-1 reaction generation ethene and 2-methyl-2-amylene, iso-butylene and butene-2 reaction generate propylene and 2-methyl-2-butene, after ether, in carbon four, the content of iso-butylene is less, therefore disproportionation reaction produces less by product, target product propylene has better selectivity, simultaneously by adopting γ-Al 2o 3as the catalyzer of ethanol dehydration reaction, WO 3/ SiO 2with magnesia with high specific surface be disproportionation and isomerization catalyst, improve after ether the isomerized reactive behavior of 1-butylene in carbon four, the selectivity of target product propylene also improves thereupon.The selectivity of target product propylene can reach 97%, and prior art selectivity has improved 10% relatively, has obtained good technique effect.
Brief description of the drawings
Fig. 1 be alcohol production propylene the schema of the technology of the present invention system.
In Fig. 1,1 is ethanol feed stream, 2 is ethylene streams, 3 is carbon four logistics after ether, 4 is the mixing raw material of carbon four and ethene, 5 is the effluent after disproportionation reaction, 6 ethylene streams that obtain for taking off ethylene column, 7 is propylene product, 8 is the above hydrocarbon of carbon five, 9 is that carbon four and carbon five logistics are emptying, 10 for containing n-butene, the logistics of normal butane and a small amount of carbon five above hydrocarbon, , 11 is cyclic carbon four logistics, 21 is disproportionation reaction step, 22 is de-ethene step, 23 is de-propylene step, 24 is carbon four fractionating steps, 31 is ethanol dehydration reaction device, 32 is disproportionation reactor, 33 is de-ethylene column, 34 is depropenizer, 35 is carbon four separation columns.
With reference to Fig. 1, method of the present invention is briefly expressed in schema.
As shown in Figure 1, fresh ethanol thing 1 enters ethanol dehydration reaction device 31, after reaction product ethylene feed 2 and fresh ether, carbon 43 is mixed to form material 4, mixture 4 enters and in reactor 32, carries out disproportionation reaction, reaction product 5 comprises C 4 materials after unreacted ethene and ether, also has target product propylene and the above hydrocarbon of small portion carbon five very; Above-mentioned material, successively by de-ethylene column 33 and depropenizer 34, is fractionated out to unreacted ethene and reaction product propylene 7, and wherein ethene 6 is circulated to ethylene feed 2 mixed as reaction raw materials at least partly; The material of depropenizer after out comprises after unreacted ether carbon four and the above hydrocarbon of byproduct of reaction carbon five of small portion very, when above-mentioned material process debutanizing tower 35, be separated into the above hydrocarbon 8 of carbon five and carbon four logistics 10, wherein carbon four logistics 11 recirculation continue reaction as reaction raw materials.
Ethanol dehydration reaction is to be 420～480 DEG C in temperature of reaction, and reaction pressure is that 0.01～1.0MPa reaction mass air speed is 0.2～0.8 hour -1.Catalyzer is γ-Al 2o 3.
The catalyzer of disproportionation reaction is WO 3/ SiO 2, isomerization catalyst is that specific surface area is for being greater than 200 meters 2/ gram magnesium oxide, the weight ratio of disproportionation catalyst and isomerization catalyst is 1: 4～1: 6; Operational condition is: 250～350 DEG C of temperature of reaction, reaction pressure 0.1～1MPa, the mass space velocity of carbon 4 1～10 hour -1.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The ethanol material 1 of 95% (weight content) is sent into ethanol dehydration reaction device 31, and ethanol is at γ-Al 2o 3under the effect of catalyzer, at 420 DEG C, reaction mass air speed is 0.5 hour -1; Reaction pressure be under 0.05MPa condition reaction obtain weight ethylene content be 98% containing ethylene feed 2, to be mixed to form material 4 containing carbon 43 after ethylene feed 2 and fresh ether, mixture 4 enters in reactor 32 and carries out disproportionation reaction, and after ethene and ether, carbon four is at 8%WO 3/ SiO 2under magnesium oxide effect, at 300 DEG C, reaction pressure 0.5MPa, the mass space velocity of carbon 46 hours -1under condition, obtain containing propylene material 5, material 5, successively by de-ethylene column 33 and depropenizer 34, is fractionated out to unreacted ethene and reaction product propylene 7, wherein ethene 6 is circulated to ethylene feed 2 mixed as reaction raw materials at least partly; The material of depropenizer after out comprises after unreacted ether carbon four and the above hydrocarbon of byproduct of reaction carbon five of small portion very, when above-mentioned material process debutanizing tower 35, be separated into the above hydrocarbon 8 of carbon five and carbon four logistics 10, wherein carbon four logistics 11 recirculation continue reaction as reaction raw materials, to improve the output of propylene.The propylene product selectivity that this technique obtains can reach 97%.
[embodiment 2]
The ethanol material 1 of 95% (weight content) is sent into ethanol dehydration reaction device 31, and ethanol is at γ-Al 2o 3under the effect of catalyzer, at 450 DEG C, reaction mass air speed is 0.7 hour -1; Reaction pressure be under 0.02MPa condition reaction obtain weight ethylene content be 97% containing ethylene feed 2, to be mixed to form material 4 containing carbon 43 after ethylene feed 2 and fresh ether, mixture 4 enters in reactor 32 and carries out disproportionation reaction, and after ethene and ether, carbon four is at 8%WO 3/ SiO 2under magnesium oxide effect, at 320 DEG C, reaction pressure 0.3MPa, the mass space velocity of carbon 44 hours -1under condition, obtain containing propylene material 5, material 5, successively by de-ethylene column 33 and depropenizer 34, is fractionated out to unreacted ethene and reaction product propylene 7, wherein ethene 6 is circulated to ethylene feed 2 mixed as reaction raw materials at least partly; The material of depropenizer after out comprises after unreacted ether carbon four and the above hydrocarbon of byproduct of reaction carbon five of small portion very, when above-mentioned material process debutanizing tower 35, be separated into the above hydrocarbon 8 of carbon five and carbon four logistics 10, wherein carbon four logistics 11 recirculation continue reaction as reaction raw materials, to improve the output of propylene.The propylene product selectivity that this technique obtains can reach 96%.
[embodiment 3]
The ethanol material 1 of 95% (weight content) is sent into ethanol dehydration reaction device 31, and ethanol is at γ-Al 2o 3under the effect of catalyzer, at 470 DEG C, reaction mass air speed is 0.2 hour -1; Reaction pressure be under 0.8MPa condition reaction obtain weight ethylene content be 97.5% containing ethylene feed 2, to be mixed to form material 4 containing carbon 43 after ethylene feed 2 and fresh ether, mixture 4 enters in reactor 32 and carries out disproportionation reaction, and after ethene and ether, carbon four is at 8%WO 3/ SiO 2under magnesium oxide effect, at 275 DEG C, reaction pressure O.1MPa, the mass space velocity of carbon 48 hours -1under condition, obtain containing propylene material 5, material 5, successively by de-ethylene column 33 and depropenizer 34, is fractionated out to unreacted ethene and reaction product propylene 7, wherein ethene 6 is circulated to ethylene feed 2 mixed as reaction raw materials at least partly; The material of depropenizer after out comprises after unreacted ether carbon four and the above hydrocarbon of byproduct of reaction carbon five of small portion very, when above-mentioned material process debutanizing tower 35, be separated into the above hydrocarbon 8 of carbon five and carbon four logistics 10, wherein carbon four logistics 11 recirculation continue reaction as reaction raw materials, to improve the output of propylene.The propylene product selectivity that this technique obtains can reach 96.5%.
[comparative example 1]
The ethanol material 1 of 95% (weight content) is sent into ethanol dehydration reaction device 31, and ethanol is under the effect of ZSM-5 molecular sieve catalyzer, and at 420 DEG C, reaction mass air speed is 0.5 hour -1; Reaction pressure be under 0.05MPa condition reaction obtain weight ethylene content be 95% containing ethylene feed 2, will be mixed to form material 4 containing ethylene feed 2 and fresh carbon 43, mixture 4 enters in reactor 32 and carries out disproportionation reaction, after ethene and ether, carbon four is at 8%MoO 3/ Al 2o 3under calcium oxide effect, at 300 DEG C, reaction pressure 0.5MPa, the mass space velocity of carbon 46 hours -1under condition, obtain containing propylene material 5, material 5, successively by de-ethylene column 33 and depropenizer 34, is fractionated out to unreacted ethene and reaction product propylene 7, wherein ethene 6 is circulated to ethylene feed 2 mixed as reaction raw materials at least partly; The material of depropenizer after out comprises after unreacted ether carbon four and the above hydrocarbon of byproduct of reaction carbon five of small portion very, when above-mentioned material process debutanizing tower 35, be separated into the above hydrocarbon 8 of carbon five and carbon four logistics 10, wherein carbon four logistics 11 recirculation continue reaction as reaction raw materials, to improve the output of propylene.The propylene product selectivity that this technique obtains can reach 85%.

Claims (4)

1. a method for ethanol propylene processed,, comprises the following steps as raw material successively taking carbon four after ethanol and ether:
(1) ethanol generates containing ethylene streams I under the effect of dehydration catalyst;
(2) logistics I contacts and generates logistics II through isomerization catalyst with carbon after ether four;
(3) logistics II and disproportionation catalyst contact reacts generate the reaction product stream III containing ethene, propylene, butylene and trace carbon five components;
(4) logistics III separates through de-ethylene column, and tower top obtains ethene, and tower reactor obtains logistics IV and comprises propylene, butylene and trace carbon five;
(5) logistics IV separates through depropenizer, and tower top obtains propylene, and tower reactor obtains butylene and trace carbon five;
Described disproportionation catalyst is WO3/SiO2, and isomerization catalyst is that specific surface area is to be greater than the magnesium oxide of 200 meters 2/ gram, and the weight ratio of disproportionation catalyst and isomerization catalyst is 1:4～1:6; Operational condition is: 250～350 DEG C of temperature of reaction, reaction pressure 0.1～1MPa, the mass space velocity of carbon 4 1～10 hour-1;
Described ethanol dehydration catalyzer is γ-Al2O3; Ethanol dehydration reaction condition is 420～480 DEG C of temperature of reaction, reaction pressure 0.01～1.0MPa, reaction mass air speed 0.2～0.8 hour-1.
2. the method for a kind of ethanol according to claim 1 propylene processed, is characterized in that the mol ratio of carbon four is 1～5 after ethanol and ether.
3. the method for a kind of ethanol according to claim 1 propylene processed, is characterized in that the operational condition of de-ethylene column is: 50～60 of column plates, tower top: 2.2～2.6MPa ,-15～-25 DEG C; The operational condition of depropenizer is: 70～80 of column plates, tower top: 1.7～1.9MPa, 40～50 DEG C.
4. the method for a kind of ethanol according to claim 1 propylene processed, is characterized in that separating the unreacted ethene and the butylene that obtain and returns as disproportionation reaction feedstock recycle.
CN201110193493.1A 2011-07-12 2011-07-12 Method for preparing propylene from ethanol Active CN102875309B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6586649B1 (en) * 1998-09-04 2003-07-01 Sasol Technology (Proprietary) Limited Production of propylene
CN101121625A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for preparing ethylene by ethanol dehydration
CN101679146A (en) * 2007-06-14 2010-03-24 利安德化学技术有限公司 Propylene production
CN101486479B (en) * 2009-02-24 2011-04-27 中国石油化工集团公司 Method for simply synthesizing gamma-Al2O3 and use thereof in ethanol dehydration

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110077444A1 (en) * 2009-09-29 2011-03-31 Fina Technology, Inc. Metathesis Catalyst for Olefin Production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6586649B1 (en) * 1998-09-04 2003-07-01 Sasol Technology (Proprietary) Limited Production of propylene
CN101121625A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for preparing ethylene by ethanol dehydration
CN101679146A (en) * 2007-06-14 2010-03-24 利安德化学技术有限公司 Propylene production
CN101486479B (en) * 2009-02-24 2011-04-27 中国石油化工集团公司 Method for simply synthesizing gamma-Al2O3 and use thereof in ethanol dehydration

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