CN102671689A - Catalyst for preparing ethylene from ethanol in different concentrations by dehydration and preparation method and application of catalyst - Google Patents
Catalyst for preparing ethylene from ethanol in different concentrations by dehydration and preparation method and application of catalyst Download PDFInfo
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- CN102671689A CN102671689A CN2012100694850A CN201210069485A CN102671689A CN 102671689 A CN102671689 A CN 102671689A CN 2012100694850 A CN2012100694850 A CN 2012100694850A CN 201210069485 A CN201210069485 A CN 201210069485A CN 102671689 A CN102671689 A CN 102671689A
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- molecular sieve
- dehydration
- usy molecular
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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 catalyst for preparing ethylene from ethanol in different concentrations by dehydration and a preparation method and application of the catalyst, and the application of the catalyst belongs to the technical field of catalyst for preparing the ethylene from the ethanol by dehydration. The catalyst can adapt to preparation of the ethylene from the ethanol in diffident concentrations by dehydration at a high airspeed, and is high in reactivity and composed of transition metal oxide and a modified USY molecular sieve. The technical scheme includes that the catalyst for preparing the ethylene from the ethanol in different concentrations by dehydration comprises an active component and a carrier, wherein the active component is the transition metal oxide, the carrier is the USY molecular sieve, loading of the active component is 0.1wt%-10wt%, and the balance is the USY molecular sieve. The catalyst prepared by the method is high in reactivity, low in catalytic reaction temperature and suitable for catalyzing the ethanol different in concentration to dehydrate to be prepared into the ethylene at a high airspeed, and has high stability.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for different concentration ethanol dehydration system ethene, its application belongs to the catalyst for ethanol delydration to ethylene technical field.
Background technology
Ethene is a kind of crucial Organic Chemicals, and its output size is to weigh the sign of a national petrochemical industry development level.Traditional ethene mainly through hydrocarbon cracking production, depends critically upon petroleum resources.Along with the day of international energy situation is becoming tight; Petroleum resources are exhausted day by day; And through recyclable organism ethanol preparation ethene have green, sustainable, reaction condition is gentle and many-sided advantage such as product ethene purity height; Therefore study biological producing ethylene from dehydration of ethanol, have great economic worth and strategic importance.
Catalytic dehydration of ethanol prepares ethene and has a long history, and present stage is studied ethanol dehydration catalyst efficiently, and development biological ethane industry is significant.The producing ethylene with ethyl alcohol catalyst mainly contains metal oxide Al
2O
3With molecular sieve two big System Catalyst.It mainly is metal oxide catalyst that industry is at present gone up employed, all needs 380 ℃～400 ℃ reaction temperature like aluminium oxide, manganese oxide etc., and the little (0.4～0.6h of ethanol air speed
-1), the space time yield of ethene is low.Utilize the Zeolite molecular sieve catalysis producing ethylene from dehydration of ethanol, though reaction temperature is low, the hydrothermal stability of selectivity and catalyst is poor.Molecular sieve catalyst exists the demanding shortcoming of concentration of alcohol simultaneously.Therefore, seek the focus that more excellent, practical ethanol dehydration catalyst is numerous researchers' research always.
The 1950's, Asia and South America are set up a large amount of producing ethylene from dehydration of ethanol factory, mainly make catalyst with carclazyte and aluminium oxide, but the ethene purity of gained lower (about 96%～97%).S.B.Rho adopts the fixed-bed catalytic producing ethylene from dehydration of ethanol, with γ-Al
2O
3As catalyst, feed ethanol concentration is 97.3%.When temperature is 375 ℃, air speed is 0.134 h
-1The time, the conversion ratio of reaction is higher, and selectivity of ethylene is also higher, and the content that is lower than 375 ℃ of ether raises with temperature and increases.Marwil was with γ-Al in 1980
2O
3Be used for the alcohols dehydration reaction of carbon two to carbon 20, at 300～450 ℃ of reaction temperatures, mass space velocity (WSHV) 0.5～2.0 h
-1The time, the selectivity of alkene is 97.7%.From before result of study find out that the temperature required height of oxide catalysis ethanol dehydration, energy consumption are big, conversion ratio is lower, and used material concentration is high.
The U.S. breathes out Kanggong department and develops the Syndol catalyst eighties, and its main component is Al
2O
3～MgO/SiO
2The said firm had built up the producing ethylene from dehydration of ethanol device of producing 730000 tons per year in Brazil in 1981, and product purity reaches 98%; The said firm built up in Pakistan again and produced 640000 tons of devices per year the same year, and ethene purity can reach 99.9%.Kochar has studied the situation of ethanol dehydration on Syndol; Find that ethylene selectivity increases with the temperature rising; When temperature rises to 450 ℃ by 335 ℃; Selectivity of ethylene is increased to 98.9% from 94.5%, and he thinks when main cause is that temperature raises that ethanol conversion increases and other big molecule accessory substances reduce.The Syndol catalyst has that stability is high, reproducibility is good, product purity is than advantages such as height.Shortcoming is that catalytic activity is low, shows that reaction temperature is high, and air speed is low (to be no more than 0.13 h
-1), so energy consumption is very big.
The CN86101615 in 1986 of Nankai University successfully develops the zeolite catalyst of NKC-03A, and this catalyst is that main component is the solid acid catalyst of ZSM-5 and aluminium hydroxide.This Preparation of catalysts is after adopting hydrochloric acid (or ammonium chloride) that ZSM-5 is carried out ion-exchange; Mix with the aluminium salt (or aluminium hydroxide) of inorganic acid and carry out co-precipitation with ammoniacal liquor; Or do mixed with ZSM-5 molecular sieve after the exchange and aluminium hydroxide; Form through oven dry and roasting, the range of reaction temperature of this catalyst can be at 250 ℃～390 ℃ again, and best air speed is 1～2h
-1
Summary of the invention
In order to overcome the prior art deficiency, the purpose of this invention is to provide a kind of Different concentrations of alcohol dehydration system ethene, USY molecular sieve catalyst of the transition metal oxide modification that reactivity is high of under big air speed, adapting to.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is: a kind of catalyst that is used for different concentration ethanol dehydration system ethene; Be made up of active component and carrier, active component is a transition metal oxide, and carrier is the USY molecular sieve; Said activity component load quantity is 0.1wt%～10wt%, and all the other are the USY molecular sieve.
Said transition metal oxide is one or both of oxide of iron, cobalt, nickel, copper and zinc.
A kind of Preparation of catalysts method that is used for different concentration ethanol dehydration system ethene; Carry out according to following steps: with said USY molecular sieve at 400～600 ℃ of roasting 2～3h; Nitrate or chlorate aqueous solution with said active component carries out incipient impregnation to the USY molecular sieve through roasting again; 120 ℃ of oven dry, temperature is 400 ℃～600 ℃ roasting 4～6h, obtains finished catalyst then.
A kind of Application of Catalyst that is used for different concentration ethanol dehydration system ethene is reacted in fixed bed reactors, and the ethanol volume fraction is 10%～90%, and reaction temperature is 280 ℃～350 ℃, and the ethanol air speed is 2.0～5.0h
-1Condition under react, the reaction result ethanol conversion is greater than 98%, ethylene selectivity is greater than 95%, and catalyst has good stable property.
The beneficial effect that the present invention compared with prior art has is: the catalyst reaction of the present invention's preparation is active high, makes that the catalytic reaction temperature is low, is suitable for catalysis Different concentrations of alcohol dehydration system ethene under big air speed; In ethanol volume fraction 10%～90%, 280～350 ℃ of reaction temperatures, reaction mass air speed are 2.0～5.0h
-1The time, ethanol conversion is greater than 98%, and ethylene selectivity is greater than 95%, and has good stable property.
Description of drawings
Fig. 1 is the influence figure of concentration of alcohol to the Co/USY catalytic perfomance.
Fig. 2 is a Co/USY life of catalyst curve map.
The specific embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention does not receive the restriction of these embodiment.
The catalyst activity appreciation condition:
Reaction unit is fixed bed reactors.20～40 purpose catalyst samples are seated in stainless steel reaction pipe middle part, and fill with the quartz sand of same particle size top and the bottom.Different concentrations of alcohol solution is done material liquid, delivers to the fixed bed reactors top through liquid phase pump constant current amount, with flow velocity be the N of 100～200 mL/min
2Mix back entering reactor and react, reacted product is regularly opened stop valve and is collected liquid product through the condenser refrigerated separation in the course of reaction.Gas-phase product is collected and is analyzed after the wet gas flow meter metering.Catalyst activation: the flow velocity with 100～200 mL/min feeds N
2,, can get rid of the air in the reactor simultaneously at normal pressure, 500 ℃ of following activation 2～3 h.
The reaction gas liquid product is all analyzed through gas chromatograph, N
2Be carrier gas.
Catalyst particle size: 0.38 ~ 0.83mm
Reaction temperature: 280 ~ 350 ℃
Feed ethanol volumetric concentration: 10% ~ 95%
WHSV (calculating): 2.0 ~ 5.0h with ethanol
-1
Embodiment 1
Get the 30gUSY molecular sieve powder,, place beaker subsequent use at 500 ℃ of following roasting 2.5h.Get 3.48g Co (NO
3)
26H
2O pours in the 50ml volumetric flask, drips distilled water and makes Co (NO
3)
26H
2O dissolves fully, drips distilled water again to graduation mark, is mixed with the Co (NO of 50ml
3)
2Solution for standby.The drips of solution that configures is added in the USY molecular sieve powder of getting ready, stir, until all powder complete wetting while add; The adding surplus solution also stirs, and is placed on and stirs 12h on the magnetic stirring apparatus, through 120 ℃ of oven dry; 550 ℃ of roasting 5h prepare the ethanol dehydration catalyst, are designated as 1#.Through the catalytically active assessment experiment, 280 ℃ of control reaction temperatures, ethanol air speed 2.37 h
-1, react under the different concentration ethanol condition.Fig. 1 is the reaction result of this catalyst Different concentrations of alcohol, when Fig. 2 is 10% ethanol dehydration reaction, and this life of catalyst curve.
Embodiment 2
Get the 30gUSY molecular sieve powder,, place beaker subsequent use at 480 ℃ of following roasting 2.5h.Get 1.16Ni (NO
3)
26H
2O pours in the 50ml volumetric flask, drips distilled water and makes Ni (NO
3)
26H
2O dissolves fully, drips distilled water again to graduation mark, is mixed with the Ni (NO of 50ml
3)
2Solution for standby.The drips of solution that configures is added in the USY molecular sieve powder of getting ready, stir, until all powder complete wetting while add; The adding surplus solution also stirs, and is placed on and stirs 12h on the magnetic stirring apparatus, through 120 ℃ of oven dry; 500 ℃ of roasting 4h prepare the ethanol dehydration catalyst, are designated as 2#.Through catalytically active assessment experiment, 10% ethanol dehydration reaction, 280 ℃ of reaction temperatures, ethanol air speed 2.37 h
-1, ethanol conversion reaches 99.3%, and ethylene selectivity reaches 98.8%.
Embodiment 3
Get the 30gUSY molecular sieve powder,, place beaker subsequent use at 500 ℃ of following roasting 2.5h.Get 6.82g Fe (NO
3)
39H
2O pours in the 50ml volumetric flask, drips distilled water and makes Fe (NO
3)
3Dissolving drips distilled water again to graduation mark fully, is mixed with the Fe (NO of 50ml
3)
3Solution for standby.The drips of solution that configures is added in the USY molecular sieve powder of getting ready, stir, until all powder complete wetting while add; The adding surplus solution also stirs; Be placed on and stir 12 h on the magnetic stirring apparatus, through 120 ℃ of oven dry, 550 ℃ of roasting 5 h; Prepare the ethanol dehydration catalyst, be designated as 3#.Through catalytically active assessment experiment, 10% ethanol dehydration reaction, 280 ℃ of reaction temperatures, ethanol air speed 2.37 h
-1, ethanol conversion reaches 99.3%, and ethylene selectivity reaches 98.8%.
Embodiment 4
Get 30g USY molecular sieve powder,, place beaker subsequent use at 500 ℃ of following roasting 2.5h.Get 2.73g Cu (NO
3)
23H
2O pours in the 50ml volumetric flask, drips distilled water and makes Cu (NO
3)
23H
2O dissolves fully, drips distilled water again to graduation mark, is mixed with the Cu (NO of 50ml
3)
2Solution for standby.The drips of solution that configures is added in the USY molecular sieve powder of getting ready, stir, until all powder complete wetting while add; The adding surplus solution also stirs; Be placed on and stir 12 h on the magnetic stirring apparatus, through 120 ℃ of oven dry, 550 ℃ of roasting 5 h; Prepare the ethanol dehydration catalyst, be designated as 4#.Through catalytically active assessment experiment, 10% ethanol dehydration reaction, 280 ℃ of reaction temperatures, ethanol air speed 3.56 h
-1, ethanol conversion reaches 99.1%, and ethylene selectivity reaches 98.9%.
Embodiment 5
Get 30g USY molecular sieve powder,, place beaker subsequent use at 500 ℃ of following roasting 2.5 h.Get 5.48g Zn (NO
3)
26H
2O pours in the 50ml volumetric flask, drips distilled water and makes Zn (NO
3)
26H
2O dissolves fully, drips distilled water again to graduation mark, is mixed with the Zn (NO of 50ml
3)
2Solution for standby.The drips of solution that configures is added in the USY molecular sieve powder of getting ready, stir, until all powder complete wetting while add; The adding surplus solution also stirs; Be placed on and stir 12 h on the magnetic stirring apparatus, through 120 ℃ of oven dry, 550 ℃ of roasting 5 h; Prepare the ethanol dehydration catalyst, be designated as 5#.Through catalytically active assessment experiment, 10% ethanol dehydration reaction, 280 ℃ of reaction temperatures, ethanol air speed 3.56 h
-1, ethanol conversion reaches 99.3%, and ethylene selectivity reaches 98.8%.
Embodiment 6
Get 30g USY molecular sieve powder,, place beaker subsequent use at 500 ℃ of following roasting 2.5 h.Accurately take by weighing and get 1.10g Zn (NO
3)
26H
2O, 3.41 g Fe (NO
3)
39H
2O pours in the 50ml volumetric flask, drips distilled water medicine is dissolved fully, drips distilled water again to graduation mark, and the mixed solution that is mixed with 50ml is subsequent use.The drips of solution that configures is added in the USY molecular sieve powder of getting ready, stir, until all powder complete wetting while add; The adding surplus solution also stirs; Be placed on and stir 12 h on the magnetic stirring apparatus, through 120 ℃ of oven dry, 500 ℃ of roasting 5.5 h; Prepare the ethanol dehydration catalyst, be designated as 6#.Through catalytically active assessment experiment, 10% ethanol dehydration reaction, 300 ℃ of reaction temperatures, ethanol air speed 4.74 h
-1, ethanol conversion reaches 98.3%, and ethylene selectivity reaches 99.2%.
Claims (4)
1. one kind is used for the catalyst that ethene is made in the different concentration ethanol dehydration; Be made up of active component and carrier, it is characterized in that: active component is a transition metal oxide, and carrier is the USY molecular sieve; Said activity component load quantity is 0.1wt%～10wt%, and all the other are the USY molecular sieve.
2. a kind of catalyst that is used for different concentration ethanol dehydration system ethene according to claim 1 is characterized in that said transition metal oxide is one or both of oxide of iron, cobalt, nickel, copper and zinc.
3. the described Preparation of catalysts method that is used for different concentration ethanol dehydration system ethene of a claim 1; It is characterized in that carrying out according to following steps: with said USY molecular sieve at 400～600 ℃ of roasting 2～3h; Nitrate or chlorate aqueous solution with said active component carries out incipient impregnation to the USY molecular sieve through roasting again; 120 ℃ of oven dry, temperature is 400 ℃～600 ℃ roasting 4～6h, obtains finished catalyst then.
4. the described Application of Catalyst that is used for different concentration ethanol dehydration system ethene of a claim 1; It is characterized in that: in fixed bed reactors, react; The ethanol volume fraction is 10%～90%, and reaction temperature is 280 ℃～350 ℃, and the ethanol air speed is 2.0～5.0h
-1Condition under react, the reaction result ethanol conversion is greater than 98%, ethylene selectivity is greater than 95%, and catalyst has good stable property.
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Cited By (5)
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| CN107824222A (en) * | 2017-11-13 | 2018-03-23 | 江苏师范大学 | A kind of preparation method of Nanowire d type producing ethylene with ethyl alcohol catalyst |
| CN111250150A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Preparation method and application of modified ZSM-5 molecular sieve catalyst, and method for preparing ethylene from coal-based ethanol |
| CN113198521A (en) * | 2021-04-30 | 2021-08-03 | 江苏常青树新材料科技股份有限公司 | Preparation method of USY molecular sieve catalyst and application of catalyst in preparation of divinylbenzene |
| US11260367B2 (en) | 2018-12-12 | 2022-03-01 | Instituto Nacional De Tecnologia | Catalytic system and process for the production of light olefins from ethanol |
| CN115368375A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Method for preparing oxa-norbornene |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107824222A (en) * | 2017-11-13 | 2018-03-23 | 江苏师范大学 | A kind of preparation method of Nanowire d type producing ethylene with ethyl alcohol catalyst |
| CN111250150A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Preparation method and application of modified ZSM-5 molecular sieve catalyst, and method for preparing ethylene from coal-based ethanol |
| CN111250150B (en) * | 2018-11-30 | 2023-06-20 | 中国科学院大连化学物理研究所 | Preparation method and application of modified ZSM-5 molecular sieve catalyst and method for preparing ethylene from coal-based ethanol |
| US11260367B2 (en) | 2018-12-12 | 2022-03-01 | Instituto Nacional De Tecnologia | Catalytic system and process for the production of light olefins from ethanol |
| CN113198521A (en) * | 2021-04-30 | 2021-08-03 | 江苏常青树新材料科技股份有限公司 | Preparation method of USY molecular sieve catalyst and application of catalyst in preparation of divinylbenzene |
| CN113198521B (en) * | 2021-04-30 | 2023-04-07 | 江苏常青树新材料科技股份有限公司 | Preparation method of USY molecular sieve catalyst and application of catalyst in preparation of divinylbenzene |
| CN115368375A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Method for preparing oxa-norbornene |
| CN115368375B (en) * | 2021-05-19 | 2024-01-26 | 中国石油化工股份有限公司 | Method for preparing oxa-norbornene |
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Application publication date: 20120919 |