CN103121900A - Method for preparing ethylene by dehydrating ethanol - Google Patents
Method for preparing ethylene by dehydrating ethanol Download PDFInfo
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- CN103121900A CN103121900A CN2011103669288A CN201110366928A CN103121900A CN 103121900 A CN103121900 A CN 103121900A CN 2011103669288 A CN2011103669288 A CN 2011103669288A CN 201110366928 A CN201110366928 A CN 201110366928A CN 103121900 A CN103121900 A CN 103121900A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for preparing ethylene by dehydrating ethanol and mainly solves the problem of low catalyst stability in the prior art. The problem is solved by adopting the technical scheme that ethanol which is used as a reaction raw material and a catalyst contact under the conditions that the reaction temperature is 300 to 550 DEG C, and the hourly space velocity relative to ethanol is 0.1 to 25 hours<-1> to react so as to generate ethylene, wherein the used catalyst is alumina of which the specific surface area is 150 to 250 m<2>/g and the total pore volumes are 0.5 to 1.0 cm<3>/g, and the pore volumes of pore diameters of less than 10 nanometers is 50 to 90 percent of the total pore volumes, and the pore volumes of pore diameters of more than 10 nanometers is 10 to 50 percent of the total pore volumes. The method can be used for industrial production of preparing the ethylene by dehydrating ethanol.
Description
Technical field
The present invention relates to a kind of method of producing ethylene from dehydration of ethanol.
Background technology
Ethene, molecular formula C
2H
4, be very important petrochemical material.Producing ethylene from dehydration of ethanol was once the route of a widely used acquisition ethene, and the history of more than 200 year has been arranged, and was once main ethylene production route at 19th-century.Flourish due to the twentieth century petrochemical complex, cracking ethylene preparation is more economical, and this route is eliminated gradually.But in some occasion, as the ethanol wide material sources, under the situation such as the ethene consumption is less, ethanol dehydration is still being used.
More and more face exhausted danger along with a large amount of uses of petroleum resources, oil price day by day soaring, the competitive edge of cracking legal system ethene route is more and more less.On the other hand, the develop rapidly of biochemical technology makes the production cost decrease of biomass-making ethanol, provides possibility for developing large-scale producing ethylene from dehydration of ethanol technology and device.At present, bio-ethanol is fermentation raw material except adopting farm crop corn, cassava etc., and the cellulose raw materials such as crop material, bagasse, wood chip also can be produced ethanol as fermentation raw material, and the producing ethylene from dehydration of ethanol route becomes again competitive technological line.
The producing ethylene from dehydration of ethanol reaction is stronger thermo-negative reaction, producing ethylene from dehydration of ethanol is industrial hotbed and two kinds of techniques of adiabatic reactor such as at present, the isothermal bed reaction technique generally adopts shell and tube reactor, and catalyst loading is in tubulation, and between pipe, medium provides reaction needed heat.Adiabatic reactor technique adopts the multi-stage type reactor, the mode of intersegmental heat supply.On hotbed and adiabatic reactor reaction process, its characteristics are arranged respectively, isothermal bed process energy consumption is relatively low, but yield generally is used for the small-scale device a little less than adiabatic reactor technique; Adiabatic reactor reaction process temperature of reaction is high, and working pressure 0.2～0.8MPa is high to the catalyzer requirement, is fit to fairly large device.
The catalyzer that can be used for producing ethylene from dehydration of ethanol have aluminum oxide, load phosphoric acid, pure aluminium silicate etc., and what the research report was arranged has molecular sieve, heteropolyacid etc., an industrial aluminium oxide catalyst that mainly still adopts.
The ethanol dehydration catalyst deactivation mechanisms is the carbon distribution inactivation, be the extending catalyst life cycle, propose to prepare the aluminium oxide catalyst with double-pore structure and be used for producing ethylene from dehydration of ethanol, macropore can improve the carbon ability of holding, extending catalyst life cycle, aperture satisfy the catalyst activity performance requriements.
Lummus company (Winter Olaf, Erg Meng-Teck, Hydrocarbon Process, Tnt.Ed; : 1976,55 (11): 125) with special γ-Al
2O
3Be catalyzer, 315～390 ℃ of scopes, ethylene selectivity 96%, but need regeneration in 4 weeks.
In sum, there is the shortcoming of poor catalyst stability in the aluminium oxide catalyst that adopts in conventional art.
Summary of the invention
Technical problem to be solved by this invention is the problem that has poor catalyst stability in conventional art, and a kind of method of new producing ethylene from dehydration of ethanol is provided.The method has the characteristics of good stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing ethylene from dehydration of ethanol, it is characterized in that adopting take ethanol as raw material, and be 300～550 ℃ in temperature of reaction, be 0.1～25 hour with respect to the volume space velocity of ethanol
-1Under condition, reaction raw materials contacts with catalyzer, and reaction generates ethene, and specific surface area of catalyst is 150～250 meters
2/ gram, total pore volume is 0.5～1.0 centimetre
3/ gram, the pore volume of bore dia＜10 nanometers accounts for 50～90% of total pore volume, and the pore volume of bore dia＞10 nanometers accounts for 10～50% aluminum oxide of total pore volume.
In technique scheme, the specific surface area of catalyst preferable range is 190～230 meters
2/ gram; The total pore volume preferable range of catalyzer is 0.6～0.8 centimetre
3/ gram.The pore volume preferable range of bore dia＜10 nanometers is to account for 65～85% of total pore volume, and the pore volume preferable range of bore dia＞10 nanometers is to account for 15～35% of total pore volume.The temperature of reaction preferable range is 350～500 ℃, is 0.5～15 hour with respect to the volume space velocity preferable range of ethanol
-1The weight percent concentration of ethanol is 5～100%.
In the present invention, the preparation method of catalyzer is: then aluminium oxide catalyst was obtained 400～800 ℃ of lower roastings by aluminum oxide and expanding agent mixing, extruded moulding, drying in 1～10 hour.Aluminum oxide is at least a for being selected among hibbsite, boehmite, pseudo-boehmite or amorphous hydroted alumina, expanding agent is at least a for being selected among polyoxyethylene glycol, starch, urea or ammonium hydrogencarbonate, and wherein the weight ratio of aluminum oxide and expanding agent is 1: 0.1～0.5.
In the present invention, one of life-span basis for estimation of catalyzer is through after same time reaction, obtains the carbon distribution total amount of catalyzer by differential thermal analysis, thereby obtains the carbon distribution percentage of unit time catalyzer, be i.e. carbon distribution speed (unit: %/hour).This carbon distribution speed is larger, and the deactivation rate that catalyzer is corresponding is just faster, and the life cycle of catalyzer is just shorter.
In the present invention, two of the life-span basis for estimation of catalyzer is through accelerating weathering test, carrying out on fixed-bed tube reactor (25 * 500 millimeters stainless steels of Φ).Reaction conditions: 400 ℃ of temperature of reaction, reaction pressure 0.95MPa, volume space velocity 0.8h
-1The activity that represents catalyzer with ethanol conversion, the transformation efficiency fall off rate is larger, and the life cycle of catalyzer is just shorter.
The present invention adopts aluminum oxide and the expanding agent technical scheme in required ratio mixing, extrusion, moulding, make the catalyzer that makes have structure of double peak holes, macropore can improve the appearance carbon ability of catalyzer, the extending catalyst life-span, aperture satisfies the catalyst activity performance requriements, this catalyzer is used for producing ethylene from dehydration of ethanol technique, has the characteristics of the good and good stability of reactivity worth.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Weighing pseudo-boehmite 250 grams, starch 30 grams, sesbania powder 12.5 grams were mediated in kneader 30 minutes, added 225 milliliters of 5% salpeter solutions, then mediated 20 minutes, then extruded moulding, 110 ℃ of dryings 10 hours, then put 650 ℃ of activation of retort furnace 8 hours, obtain catalyst A.The physical properties of catalyzer sees Table 1.
[embodiment 2]
Weighing aluminium hydroxide 300 grams, polyoxyethylene glycol 80 grams, sesbania powder 15 grams were mediated in kneader 30 minutes, added 185 milliliters of 5% salpeter solutions, then mediated 15 minutes, then extruded moulding, 120 ℃ of dryings 10 hours, then put 600 ℃ of activation of retort furnace 8 hours, obtain catalyst B.The physical properties of catalyzer sees Table 1.
[embodiment 3]
Weighing boehmite 200 grams, urea 100 grams, sesbania powder 15 grams were mediated in kneader 30 minutes, added 250 milliliters of 5% salpeter solutions, then mediated 25 minutes, then extruded moulding, 110 ℃ of dryings 15 hours, then put 500 ℃ of activation of retort furnace 6 hours, obtain catalyzer C.The physical properties of catalyzer sees Table 1.
[embodiment 4]
Weighing hibbsite 250 grams, ammonium hydrogencarbonate 100 grams, sesbania powder 12 grams were mediated in kneader 30 minutes, added 210 milliliters of 5% salpeter solutions, mediated again extruded moulding then, 120 ℃ of dryings 15 hours 20 minutes, put again 550 ℃ of activation of retort furnace 6 hours, obtain catalyzer D.The physical properties of catalyzer sees Table 1.
[embodiment 5]
Weighing pseudo-boehmite 250 grams, polyoxyethylene glycol 80 grams, sesbania powder 12.5 grams were mediated in kneader 30 minutes, added 180 milliliters of 5% salpeter solutions, then mediated 15 minutes, then extruded moulding, 100 ℃ of dryings 10 hours, then put 600 ℃ of activation of retort furnace 6 hours, obtain catalyzer E.The physical properties of catalyzer sees Table 1.
[embodiment 6]
Weighing aluminium hydroxide 250 grams, starch 15 grams, sesbania powder 12.5 grams were mediated in kneader 30 minutes, added 170 milliliters of 5% salpeter solutions, then mediated 15 minutes, then extruded moulding, 120 ℃ of dryings 10 hours, then put 650 ℃ of activation of retort furnace 4 hours, obtain catalyzer F.The physical properties of catalyzer sees Table 1.
[embodiment 7]
Weighing pseudo-boehmite 250 grams, urea 110 grams, sesbania powder 15 grams were mediated in kneader 30 minutes, added 200 milliliters of 5% salpeter solutions, then mediated 15 minutes, then extruded moulding, 120 ℃ of dryings 10 hours, then put 650 ℃ of activation of retort furnace 5 hours, obtain catalyzer G.The physical properties of catalyzer sees Table 1.
[embodiment 8]
Weighing boehmite 200 grams, ammonium hydrogencarbonate 50 grams, sesbania powder 10 grams were mediated in kneader 30 minutes, added 120 milliliters of 5% salpeter solutions, then mediated 25 minutes, then extruded moulding, 120 ℃ of dryings 15 hours, then put 550 ℃ of activation of retort furnace 6 hours, obtain catalyzer H.The physical properties of catalyzer sees Table 1.
[embodiment 9] accelerate weathering test
Catalyzer is accelerated weathering test and is carried out on fixed-bed tube reactor (25 * 500 millimeters stainless steels of Φ), the catalyzer that catalyzer makes for [embodiment 5], and the catalyst loading amount is 10 milliliters.Reaction product is analyzed respectively after gas-liquid separation, and gas phase adopts HP6890 gas-chromatography (3398 workstation), Al
2O
3Pillar, hydrogen flame detector; Liquid phase adopts HP4890, Plot Q kapillary pillar.Reaction conditions: ethanol weight percent concentration 93%, 400 ℃ of temperature of reaction, reaction pressure 0.95MPa, volume space velocity 0.8h
-1, reaction times 600hr.Reaction result sees Table 2.
[embodiment 10～12]
By each step of [embodiment 9], just catalyzer adopts [embodiment 6]～[embodiment 8], and reaction result sees Table 2.
[Comparative Examples 1]
Weighing pseudo-boehmite 300 grams, sesbania powder 15 grams were mediated in kneader 20 minutes, added 200 milliliters of 5% salpeter solutions, then mediated 25 minutes, extruded moulding then, and 120 ℃ of dryings 12 hours, 550 ℃ of roastings 10 hours obtain catalyst I.The physical properties of catalyzer sees Table 1.
[Comparative Examples 2]
By each step of [embodiment 9], just catalyzer adopts [Comparative Examples 1], and reaction result sees Table 2.
[embodiment 13～16]
Catalytic performance test
The performance evaluation of catalyzer is carried out on fixed-bed reactor, and the employing internal diameter is the stainless steel reactor of 10 millimeters, and catalyzer is the catalyzer that [embodiment 1]～[embodiment 4] make, and loadings is 10 milliliters, and experiment condition and reaction result see Table 3.
[Comparative Examples 3]
By each Step By Condition of [embodiment 16], just catalyzer adopts [Comparative Examples 1], and experiment condition and reaction result see Table 3.
Table 1
Table 2
Table 3
Claims (4)
1. the method for a producing ethylene from dehydration of ethanol, take ethanol as raw material, be 300～550 ℃ in temperature of reaction, is 0.1～25 hour with respect to the volume space velocity of ethanol
-1Under condition, reaction raw materials contacts with catalyzer, and reaction generates ethene, and wherein catalyzer used is 150～250 meters of specific surface areas
2/ gram, total pore volume is 0.5～1.0 centimetre
3/ gram, the pore volume of bore dia＜10 nanometers accounts for 50～90% of total pore volume, and the pore volume of bore dia＞10 nanometers accounts for 10～50% aluminum oxide of total pore volume.
2. the method for producing ethylene from dehydration of ethanol according to claim 1, is characterized in that specific surface area of catalyst is 190～230 meters
2/ gram; Total pore volume is 0.6～0.8 centimetre
3/ gram; The pore volume of bore dia＜10 nanometers accounts for 65～85% of total pore volume; The pore volume of bore dia＞10 nanometers accounts for 15～35% of total pore volume.
3. the method for producing ethylene from dehydration of ethanol according to claim 1, is characterized in that temperature of reaction is 350～500 ℃, is 0.5～15 hour with respect to the volume space velocity of ethanol
-1
4. the method for producing ethylene from dehydration of ethanol according to claim 1, the weight percent concentration that it is characterized in that ethanol is 5～100%.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11260367B2 (en) | 2018-12-12 | 2022-03-01 | Instituto Nacional De Tecnologia | Catalytic system and process for the production of light olefins from ethanol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1689703A (en) * | 2004-04-29 | 2005-11-02 | 中国石油化工股份有限公司 | Alumina support with dual apertures and preparation method thereof |
| CN101486479A (en) * | 2009-02-24 | 2009-07-22 | 中国石油化工集团公司 | Method for simply synthesizing gamma-Al2O3 and use thereof in ethanol dehydration |
| CN101890382A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and application thereof |
-
2011
- 2011-11-18 CN CN201110366928.8A patent/CN103121900B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1689703A (en) * | 2004-04-29 | 2005-11-02 | 中国石油化工股份有限公司 | Alumina support with dual apertures and preparation method thereof |
| CN101486479A (en) * | 2009-02-24 | 2009-07-22 | 中国石油化工集团公司 | Method for simply synthesizing gamma-Al2O3 and use thereof in ethanol dehydration |
| CN101890382A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11260367B2 (en) | 2018-12-12 | 2022-03-01 | Instituto Nacional De Tecnologia | Catalytic system and process for the production of light olefins from ethanol |
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