CN101265242B - Method for directly preparing epoxy ethane by ethane one-step oxidation - Google Patents
Method for directly preparing epoxy ethane by ethane one-step oxidation Download PDFInfo
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- CN101265242B CN101265242B CN2008100606675A CN200810060667A CN101265242B CN 101265242 B CN101265242 B CN 101265242B CN 2008100606675 A CN2008100606675 A CN 2008100606675A CN 200810060667 A CN200810060667 A CN 200810060667A CN 101265242 B CN101265242 B CN 101265242B
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- ethane
- tubular reactor
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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 epoxy ethane from ethane, in particular to a method for directly preparing epoxy ethane by one-step oxidizing ethane. The invention aims at the disadvantages in the prior epoxy ethane production process such as inconvenient operation, excessive technological processes, high reaction temperature and high energy consumption, and provides a method for directly preparing epoxy ethane by one-step oxidizing ethane, which has the advantages of convenient operation, less technological processes, low reaction temperature and low energy consumption. The method for directly preparing epoxy ethane by one-step oxidizing ethane includes employing a tubular reactor for preparing epoxy ethane, disposing silver nickel oxide composite catalyst in the tubular reactor, and allowing ethane and air at a certain ratio to pass through the tubular reactor while controlling the temperature of the tubular reactor at 250 DEG C-390 DEG C to obtain epoxy ethane. The silver nickel oxide composite catalyst is made from silver salt, nickel salt and urea.
Description
Technical field
The present invention relates to the method for the method that a kind of ethane prepares oxyethane, particularly a kind of directly preparing epoxy ethane by ethane one-step oxidation.
Background technology
Oxyethane is the important organic chemical industry's product that is only second to polyethylene and polyvinyl chloride in the ethylene industry derivative.As a kind of very important Elementary Chemical Industry raw material and organic chemical industry's intermediate, it is widely used in and produces ethylene glycol and other polyvalent alcohols.Also be used for the production of ethoxylate, thanomin, solvent and the glycol ether of detergent industry.In addition, oxyethane also can be used for sterilizing agent of producing fumigant and medicine etc.Along with development of modern industry, the demand to oxyethane grows with each passing day both at home and abroad.
Early stage ethylene oxide production adopts chlorohydrination technology, and the process of chlorohydrination reaction is: (1) ethanol dehydration, time chlorination of (2) ethene, (3) alkalization.Because produce a large amount of Halogen waste water in the chlorohydrination production process, environmental pollution is serious, so method is inactive substantially at present.At present, oxirane production technology generally adopts the direct oxidation of ethylene to method both at home and abroad, and wherein comparatively sophisticated production technique is in calandria type fixed bed reactor, uses silver as catalyzer, adopts pure oxygen and ethene to produce oxyethane for the raw material direct oxidation.
Present industrial oxidation of ethylene prepares the temperature of reaction of oxyethane generally between 200 ℃～300 ℃, ethane oxidation prepares the temperature of ethene then usually more than 900 ℃, both temperature are mutually far short of what is expected, and be used for the silver as catalyzer that oxidation of ethylene prepares oxyethane and at high temperature easily make reaction that deep oxidation takes place, therefore yet there are no the report that directly prepares oxyethane with ethane and air one-step oxidation.In the present oxirane production technology, must make ethene by ethane earlier, again by the oxidation of ethylene epoxy ethane, so present oxirane production technology exists the weak point that operation is inconvenient, technological process is many, temperature of reaction is high, energy consumption is big.
Summary of the invention
The objective of the invention is to exist operation inconvenience, technological process is many, temperature of reaction is high, energy consumption is high weak point, a kind of method of easy and simple to handle, technological process is few, temperature of reaction is low, energy consumption is low directly preparing epoxy ethane by ethane one-step oxidation is provided at existing oxirane production technology.
The present invention finishes by following technical scheme: a kind of method of directly preparing epoxy ethane by ethane one-step oxidation, the reactor of preparation oxyethane adopts tubular reactor, in tubular reactor, be provided with silver-colored nickel oxygen composite catalyst, preparation is controlled at 250 ℃～390 ℃ with the temperature of tubular reactor during oxyethane, and ethane and air can obtain oxyethane after by this tubular reactor.
In the preparation method of above-mentioned oxyethane, the proportioning between ethane and the air is 1: 3～6.
In the preparation method of above-mentioned oxyethane, silver nickel oxygen composite catalyst adopts silver salt, nickel salt and urea are that raw material is made, its preparation method is: the silver salt that will take by weighing according to a certain ratio, nickel salt and urea are put into container, in container, add deionized water, with after the container sealing at 65～95 ℃ of lower magnetic force stirring reactions after 4～12 hours, the shrend quenching, again gained precipitate with deionized water and ethanol are respectively washed 2～4 times, dried by the fire 6～12 hours down in 100～110 ℃, and then place retort furnace, after beginning to warm to 380～400 ℃ with the temperature rise rate of 1～4 ℃/min from 100 ℃, roasting 2～4 hours promptly gets required catalyzer.Wherein, the ratio of the amount of substance between silver salt, nickel salt and the urea is 1～3: 1: 1.8～4.
In the preparation method of above-mentioned silver-colored nickel oxygen composite catalyst, in the raw material of preparation catalyzer, can add auxiliary agent, auxiliary agent is one or more among Na, K, Rb, Cs, Ca, Ba, Re, the Cl, and the consumption of auxiliary agent is 0.005～0.015% of a nickel salt amount of substance
The present invention compares with existing oxirane production technology, have easy and simple to handle, technological process is few, temperature of reaction is low, characteristic of low energy consumption.
Embodiment
Below in conjunction with embodiment the present invention is made further and to specify, but the present invention is not limited to these embodiment.
Embodiment 1
Take by weighing AgNO
36.7948g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
23.6036g, put into round-bottomed flask, add the 20ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 85 ℃ of lower magnetic forces, react after 7 hours, the shrend quenching is respectively washed three times with deionized water and ethanol, dries by the fire 8 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, be warmed up to 390 ℃ with 2 ℃/min, roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 320 ℃, and air and ethane flow are controlled at 25ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 2
Take by weighing AgNO
36.7948g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
23.6036g, put into round-bottomed flask, add the 30ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 90 ℃ of lower magnetic forces.React after 5 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 8 hours down at 100 ℃, place retort furnace again, from 100 ℃ of beginnings, 2 ℃/min is warmed up to 380 ℃, and roasting promptly got catalyzer in 4 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 250 ℃, and air and ethane flow are controlled at 30ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 3
Take by weighing AgNO
33.3974g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
22.1622g, put into round-bottomed flask, add the 20ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 95 ℃ of lower magnetic forces.React after 8 hours, the shrend quenching is with deionized water and each washed twice of ethanol.Dried by the fire 10 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 3 ℃/min is warmed up to 390 ℃, and roasting promptly got catalyzer in 4 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 350 ℃, and air and ethane flow are controlled at 15ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 4
Take by weighing AgNO
310.1922g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
24.8048g, put into round-bottomed flask, add the 40ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 65 ℃ of lower magnetic forces.React after 10 hours, the shrend quenching is respectively washed four times with deionized water and ethanol.Dried by the fire 12 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 2 ℃/min is warmed up to 390 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 330 ℃, and air and ethane flow are controlled at 20ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 5
Take by weighing AgNO
36.7948g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
23.6036g, put into round-bottomed flask, add the 20ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 80 ℃ of lower magnetic forces.React after 9 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 8 hours down at 100 ℃, place retort furnace again, from 100 ℃ of beginnings, 2 ℃/min is warmed up to 400 ℃, and roasting promptly got catalyzer in 2 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 390 ℃, and air and ethane flow are controlled at 25ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 6
Take by weighing AgNO
33.3974g, Ni (NO
3)
26H
2O 2.9081g, CO (NH
2)
22.4024g, put into round-bottomed flask, add the 20ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 90 ℃ of lower magnetic forces.React after 8 hours, the shrend quenching is with deionized water and each washed twice of ethanol.Dried by the fire 8 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 1 ℃/min is warmed up to 400 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 330 ℃, and air and ethane flow are controlled at 20ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 7
Take by weighing AgNO
33.3974g, Ni (NO
3)
26H
2O 2.9081g, CO (NH
2)
22.4024g, put into round-bottomed flask, add the 10ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 80 ℃ of lower magnetic forces.React after 8 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 12 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 2 ℃/min is warmed up to 390 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 320 ℃, and air and ethane flow are controlled at 28ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 8
Take by weighing AgNO
36.7948g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
23.6036g, put into round-bottomed flask, add the 20ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 65 ℃ of lower magnetic forces.React after 12 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 6 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 4 ℃/min is warmed up to 390 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 320 ℃, and air and ethane flow are controlled at 25ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 9
Take by weighing AgNO
36.7948g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
23.6036g, put into round-bottomed flask, add the 20ml deionized water, add 0.001g Repone K again and make auxiliary agent, put into little magneton after the dissolving, cover glass stopper, stir in 85 ℃ of lower magnetic forces.React after 7 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 10 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 5 ℃/min is warmed up to 380 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 350 ℃, and air and ethane flow are controlled at 25ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 10
Take by weighing AgNO
35.0961g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
23.0030g, put into round-bottomed flask, add the 20ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 85 ℃ of lower magnetic forces.React after 12 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 8 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 2 ℃/min is warmed up to 390 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 310 ℃, and air and ethane flow are controlled at 25ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 11
Take by weighing AgNO
38.4935g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
24.2042g, put into round-bottomed flask, add the 10ml deionized water, put into little magneton after the dissolving, cover glass stopper, stir in 85 ℃ of lower magnetic forces.React after 8 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 8 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 2 ℃/min is warmed up to 390 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 330 ℃, and air and ethane flow are controlled at 25ml/min and 5ml/min.Analytical results sees Table 1.
Embodiment 12
Take by weighing AgNO
36.7948g, Ni (NO
3)
26H
2O 5.8162g, CO (NH
2)
23.6036g, put into round-bottomed flask, add the 0.002g cesium carbonate again and make auxiliary agent, add the 20ml deionized water then, put into little magneton after the dissolving, cover glass stopper, stir in 85 ℃ of lower magnetic forces.React after 7 hours, the shrend quenching is respectively washed three times with deionized water and ethanol.Dried by the fire 8 hours down at 110 ℃, place retort furnace again, from 100 ℃ of beginnings, 2 ℃/min is warmed up to 390 ℃, and roasting promptly got catalyzer in 3 hours.The catalyzer that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed-bed reactor of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 330 ℃, and air and ethane flow are controlled at 25m1/min and 5ml/min.Analytical results sees Table 1.
Table 1 catalyst performance evaluation experiment analysis results
| Embodiment | The transformation efficiency of ethane (%) | The selectivity of oxyethane (%) | The productive rate of oxyethane (%) |
| Embodiment 1 | 27.8 | 11.5 | 3.2 |
| Embodiment 2 | 14.2 | 17.0 | 2.4 |
| Embodiment 3 | 24.8 | 9.4 | 2.3 |
| Embodiment 4 | 24.4 | 10.5 | 2.6 |
| Embodiment 5 | 29.4 | 8.2 | 2.4 |
| Embodiment 6 | 25.8 | 10.5 | 2.7 |
| Embodiment 7 | 26.4 | 10.0 | 2.6 |
| Embodiment 8 | 24.7 | 11.0 | 2.7 |
| Embodiment 9 | 26.4 | 11.6 | 3.1 |
| Embodiment 10 | 25.0 | 9.9 | 2.5 |
| Embodiment 11 | 24.8 | 11.1 | 2.8 |
| Embodiment 12 | 25.8 | 13.2 | 3.4 |
Claims (2)
1. the method for a directly preparing epoxy ethane by ethane one-step oxidation, it is characterized in that the reactor for preparing oxyethane adopts tubular reactor, in tubular reactor, be provided with silver-colored nickel oxygen composite catalyst, preparation is controlled at 250 ℃～390 ℃ with the temperature of tubular reactor during oxyethane, and ethane and air can obtain oxyethane after by this tubular reactor; Wherein, ethane and the proportioning between the air by tubular reactor is 1: 3～6; Silver nickel oxygen composite catalyst adopts silver salt, nickel salt and urea are that raw material is made, its preparation method is: the silver salt that will take by weighing according to a certain ratio, nickel salt and urea are put into container, in container, add deionized water, with after the container sealing at 65～95 ℃ of lower magnetic force stirring reactions after 4～12 hours, the shrend quenching, again gained precipitate with deionized water and ethanol are respectively washed 2～4 times, dried by the fire 6～12 hours down in 100～110 ℃, and then place retort furnace, after beginning to warm to 380～400 ℃ with the temperature rise rate of 1～4 ℃/min from 100 ℃, roasting 2～4 hours, promptly get required catalyzer, wherein, silver salt, the ratio of the amount of substance between nickel salt and the urea is 1～3: 1: 1.8～4.
2. the method for directly preparing epoxy ethane by ethane one-step oxidation according to claim 1, it is characterized in that in the raw material of preparation catalyzer, adding auxiliary agent, auxiliary agent is more than one in Na, K, Rb, Cs, Ca, Ba, Re, the Cl element, and the consumption of auxiliary agent is 0.005～0.015% of a nickel salt amount of substance.
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|---|---|---|---|
| CN2008100606675A CN101265242B (en) | 2008-04-16 | 2008-04-16 | Method for directly preparing epoxy ethane by ethane one-step oxidation |
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|---|---|---|---|
| CN2008100606675A CN101265242B (en) | 2008-04-16 | 2008-04-16 | Method for directly preparing epoxy ethane by ethane one-step oxidation |
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| Publication Number | Publication Date |
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| CN101265242A CN101265242A (en) | 2008-09-17 |
| CN101265242B true CN101265242B (en) | 2011-07-20 |
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| CN102626637B (en) * | 2012-03-20 | 2013-11-06 | 浙江师范大学 | Catalyst for one-step preparation of epoxyethane from ethane, and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226782A (en) * | 1977-05-23 | 1980-10-07 | Imperial Chemical Industries Limited | Production of alkylene oxides and catalysts thereof |
| US5008412A (en) * | 1988-07-06 | 1991-04-16 | The Boc Group, Inc. | Process for the production of oxides |
| EP0850936A1 (en) * | 1996-12-25 | 1998-07-01 | Agency Of Industrial Science And Technology | Method of manufacturing epoxide and catalyst for use therein |
| US20020161249A1 (en) * | 2001-02-22 | 2002-10-31 | Guido Mul | Preparation of epoxides from alkanes using lanthanide-promoted silver catalysts |
-
2008
- 2008-04-16 CN CN2008100606675A patent/CN101265242B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226782A (en) * | 1977-05-23 | 1980-10-07 | Imperial Chemical Industries Limited | Production of alkylene oxides and catalysts thereof |
| US5008412A (en) * | 1988-07-06 | 1991-04-16 | The Boc Group, Inc. | Process for the production of oxides |
| EP0850936A1 (en) * | 1996-12-25 | 1998-07-01 | Agency Of Industrial Science And Technology | Method of manufacturing epoxide and catalyst for use therein |
| US20020161249A1 (en) * | 2001-02-22 | 2002-10-31 | Guido Mul | Preparation of epoxides from alkanes using lanthanide-promoted silver catalysts |
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Assignee: Jiaxing Yongming Petrochemical Co., Ltd. Assignor: Zhejiang Normal University Contract record no.: 2012330000172 Denomination of invention: Method for directly preparing epoxy ethane by ethane one-step oxidation Granted publication date: 20110720 License type: Exclusive License Open date: 20080917 Record date: 20120413 |
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