CN107216295A - The method that oxirane is prepared by oxygen and ethene - Google Patents
The method that oxirane is prepared by oxygen and ethene Download PDFInfo
- Publication number
- CN107216295A CN107216295A CN201610164995.4A CN201610164995A CN107216295A CN 107216295 A CN107216295 A CN 107216295A CN 201610164995 A CN201610164995 A CN 201610164995A CN 107216295 A CN107216295 A CN 107216295A
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- Prior art keywords
- oxygen
- oxirane
- reactor
- gas
- ethene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of method that oxirane is prepared by oxygen and ethene, the problem of security is poor in the prior art is mainly solved.The present invention is by using a kind of method that oxirane is prepared by oxygen and ethene, the oxygen flow membrane tube that reaction raw materials ethylene gas enters in reactor after being heated through gas-gas heat exchanger, the material of oxygen flow membrane tube uses mixed conductor inorganic ceramic membrane, the quantity of oxygen flow membrane tube is at least one or arranged in shell and tube, the region that air enters outside the oxygen flow membrane tube in reactor, oxygen is in oxygen permeation membrane adsorption, enter after desorption in oxygen permeation membrane pipe and contact ethylene, reaction generation includes the product of oxirane under catalyst, affiliated product is exported from oxygen flow membrane tube to flow out, enter downstream separation system after gas-gas heat exchanger, the technical scheme that remaining nitrogen-rich air is discharged from reactor preferably solves above mentioned problem, available for preparing in oxirane.
Description
Technical field
The present invention relates to a kind of method that oxirane is prepared by oxygen and ethene.
Background technology
Oxirane is important Organic chemical products in ethylene industry derivative, and its current production technology is typically anti-using fixed bed
Device is answered to make oxygen and ethene that exothermic oxidation reaction occur on silver catalyst.Ethene and oxygen are mixed by oxygen before into reactor
Clutch completes to mix, and the mixed effect of oxygen and ethene directly affects the selectivity and conversion ratio of catalytic reaction, this directly to connect
There is the great risk that reaction temperature runaway is out of control, fire in the mixing of touch, course of reaction.
Composite conductor oxygen-permeating film has the inorganic ceramic membrane material of oxonium ion and electronic conductivity when being one similar, in high temperature and
Under the driving of oxygen concentration gradient, oxygen can be spread through film from hyperoxia pressure side to hypoxemia pressure side, in theory the Oxygen permeation choosing of material
Selecting property is 100%.
By the membrane reactor that catalytic reaction is integrated with UF membrane and constitutes, reactant can be realized using the specific function of film
Control input, the reinforcing of alternate transmission and separation in situ of product etc., so as to reach raising reaction conversion ratio, reaction selectivity
With reaction rate, extension catalyst service life and the reduction purpose such as equipment investment.In addition, this for ethylene catalytic oxidation
Reaction, uses oxygen permeation membrane can be with accurately controlling oxygen content, it is to avoid combustion reaction occurs for ethene over oxidation, can also avoid oxygen
Risk of explosion caused by gas is directly largely mixed with flammable reactant.
Therefore, the present invention proposes a kind of to use membrane reactor that composite conductor oxygen-permeating film is medium by ethene and oxygen mix, instead
Answer process integration so that oxygen reaches that molecular level is mixed with ethene, the risk that reduction fuel gas is fired, simultaneously
Effectively suppress reaction and occur temperature runaway, thus realize oxygen mixed with ethene, the reinforcing of course of reaction, reach that process nature is safe
Change.
The content of the invention
The technical problems to be solved by the invention be the problem of security is poor in the prior art there is provided it is a kind of it is new by oxygen and
The method that ethene prepares oxirane.This method is used to prepare in oxirane, with the preferable advantage of security.
To solve the above problems, the technical solution adopted by the present invention is as follows：A kind of side that oxirane is prepared by oxygen and ethene
Method, the oxygen flow membrane tube that reaction raw materials ethylene gas enters in reactor after being heated through gas-gas heat exchanger, the material of oxygen flow membrane tube is adopted
Mixed conductor inorganic ceramic membrane is used, the quantity of oxygen flow membrane tube is at least one or arranged in shell and tube, air enters in reactor
Oxygen flow membrane tube outside region, oxygen oxygen permeation membrane adsorption, desorption after enter oxygen permeation membrane pipe in and contact ethylene, urging
Reaction generation includes the product of oxirane under agent, and affiliated product is exported from oxygen flow membrane tube to flow out, laggard through gas-gas heat exchanger
Enter downstream separation system, remaining nitrogen-rich air is discharged from reactor.
In above-mentioned technical proposal, it is preferable that state and beds are provided with oxygen flow membrane tube, catalyst is silver.
In above-mentioned technical proposal, it is preferable that the operating condition of the reactor is：180-200 DEG C of reaction temperature, reaction table
Press 2.0-2.1MPa.
In above-mentioned technical proposal, it is preferable that the volume ratio of the ethene and air is 1:9~9.8.
In above-mentioned technical proposal, it is preferable that the oxygen content in the nitrogen-rich air is 12-16%.
In above-mentioned technical proposal, it is preferable that the oxygen flow membrane tube in the reactor is arranged in shell and tube.
In above-mentioned technical proposal, it is preferable that after the reaction raw materials ethylene gas is heated to 180~200 DEG C through gas-gas heat exchanger
Into the oxygen flow membrane tube in reactor.
The mixing of ethene and oxygen, course of reaction are coupled by the present invention, and implementation process is strengthened each other, with tradition
Calandria type fixed bed reactor, which is compared, can improve conversion ratio and selectivity.Oxygen source, Neng Gouyou are used air as in the present invention
Effect reduction is directly using equipment investment during oxygen.It is rate-determining steps, energy that oxygen enters reaction side through oxygen permeation membrane in the present invention
Enough accurately controlling oxygen contents, it is to avoid temperature runaway occurs in reactor, while oxygen is mixed by fenestra with ethene can reach molecule
Level, the risk that the system that can reduce is fired achieves preferable technique effect.
Brief description of the drawings
Fig. 1 is the structure of reactor figure of single oxygen flow membrane tube；
Fig. 2 is shell and tube membrane reactor schematic diagram.
1 is ethylene gas entrance；2 be gas-gas heat exchanger；3 be reactor；4 be air intake；5 be air outlet slit；6
Exported for oxirane；7 be beds；8 be oxygen flow fenestra.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
A kind of method that oxirane is prepared by oxygen and ethene, as shown in Figure 1 or 2.Reaction raw materials ethylene gas is through gas
Gas heat exchanger is heated to the oxygen flow membrane tube entered after 180 DEG C in reactor, and the material of oxygen flow membrane tube uses the inorganic pottery of mixed conductor
Porcelain film, the quantity of oxygen flow membrane tube is one, the region that air enters outside the oxygen flow membrane tube in reactor, and oxygen is in oxygen permeation membrane table
Enter after the Adsorption and desorption of face in oxygen permeation membrane pipe and contact ethylene, reaction generation includes the product of oxirane under silver catalyst,
Affiliated product is exported from oxygen flow membrane tube to flow out, and downstream separation system is entered after gas-gas heat exchanger, remaining nitrogen-rich air is from anti-
Answer in device and discharge.
The operating condition of the reactor is 180 DEG C of temperature, pressure 2.0MPaG (gauge pressure).The body of the ethene and air
Product is than being 1:9.0.Oxygen content in the nitrogen-rich air is 16%.
As a result show, ethylene conversion per pass is 12%, oxirane is selectively 95%.
【Embodiment 2】
Enter anti-according to the condition and step described in embodiment 1, after simply ethylene gas is heated to 185 DEG C through gas-gas heat exchanger
The oxygen flow membrane tube in device is answered, oxygen flow membrane tube is 2, is arranged in shell and tube, the operating condition of the reactor is 185 DEG C of temperature,
Pressure 2.05MPaG.The volume ratio of the ethene and air is 1:9.2.Oxygen content in the nitrogen-rich air is 15.4%.
As a result show, ethylene conversion per pass is 13.6%, oxirane is selectively 95.2%.
【Embodiment 3】
Enter anti-according to the condition and step described in embodiment 1, after simply ethylene gas is heated to 192 DEG C through gas-gas heat exchanger
The oxygen flow membrane tube in device is answered, oxygen flow membrane tube is 4, is arranged in shell and tube, the operating condition of the reactor is 192 DEG C of temperature,
Pressure 2.06MPaG.The volume ratio of the ethene and air is 1；9.5.Oxygen content in the nitrogen-rich air is 13.6%.
As a result show, ethylene conversion per pass is 14.8%, oxirane is selectively 95.6%.
【Embodiment 4】
Enter anti-according to the condition and step described in embodiment 1, after simply ethylene gas is heated to 200 DEG C through gas-gas heat exchanger
The oxygen flow membrane tube in device is answered, oxygen flow membrane tube is 8, is arranged in shell and tube, the operating condition of the reactor is 200 DEG C of temperature,
Pressure 2.1MPaG.The volume ratio of the ethene and air is 1:9.8.Oxygen content in the nitrogen-rich air is 12.4%.Knot
Fruit shows that ethylene conversion per pass is 14.1%, and oxirane is selectively 94.7%.
【Comparative example】
The production of conventional epoxy ethane uses fixed bed reactors, and ethylene conversion per pass generally only has 7-8%, the choosing of oxirane
Selecting property is 85% or so.The pure oxygen obtained using space division is as oxidant, and oxygen content is difficult accurate control in reactor, easily
Form focus and occur temperature runaway.
The mixing of ethene and oxygen, course of reaction are coupled by the present invention, and implementation process is strengthened each other, with tradition
Calandria type fixed bed reactor, which is compared, can improve conversion ratio (conversion per pass>12%) it is and selective (selective>94%).
Oxygen source is used air as in the present invention, can effectively be reduced directly using equipment investment during oxygen.Oxygen is saturating in the present invention
It is rate-determining steps to cross oxygen permeation membrane to enter reaction side, being capable of accurately controlling oxygen content, it is to avoid temperature runaway occurs in reactor, while oxygen
Gas is mixed by fenestra with ethene can reach molecular level, the risk that the system that can reduce is fired, and achieve preferably
Technique effect.
Claims (7)
1. a kind of method that oxirane is prepared by oxygen and ethene, reaction raw materials ethylene gas enters after being heated through gas-gas heat exchanger
Oxygen flow membrane tube in reactor, the material of oxygen flow membrane tube uses mixed conductor inorganic ceramic membrane, and the quantity of oxygen flow membrane tube is at least
One or arranged in shell and tube, the region that air enters outside the oxygen flow membrane tube in reactor, oxygen oxygen permeation membrane adsorption,
Enter after desorption in oxygen permeation membrane pipe and contact ethylene, reaction generation includes the product of oxirane, affiliated product under catalyst
Export and flow out from oxygen flow membrane tube, downstream separation system is entered after gas-gas heat exchanger, remaining nitrogen-rich air is arranged from reactor
Go out.
2. the method for oxirane is prepared by oxygen and ethene according to claim 1, it is characterised in that in the oxygen flow membrane tube
Provided with beds, catalyst is silver.
3. the method for oxirane is prepared by oxygen and ethene according to claim 1, it is characterised in that the behaviour of the reactor
It is as condition：180-200 DEG C of reaction temperature, reaction gauge pressure 2.0-2.1MPa.
4. the method for oxirane is prepared by oxygen and ethene according to claim 1, it is characterised in that the ethene and air
Volume ratio be 1:9~9.8.
5. the method for oxirane is prepared by oxygen and ethene according to claim 1, it is characterised in that in the nitrogen-rich air
Oxygen content be 12-16%.
6. the method for oxirane is prepared by oxygen and ethene according to claim 1, it is characterised in that in the reactor
Oxygen flow membrane tube is arranged in shell and tube.
7. the method for oxirane is prepared by oxygen and ethene according to claim 1, it is characterised in that the reaction raw materials second
The oxygen flow membrane tube that alkene gas enters in reactor after being heated to 180~200 DEG C through gas-gas heat exchanger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610164995.4A CN107216295B (en) | 2016-03-22 | 2016-03-22 | The method that ethylene oxide is prepared by oxygen and ethylene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610164995.4A CN107216295B (en) | 2016-03-22 | 2016-03-22 | The method that ethylene oxide is prepared by oxygen and ethylene |
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| Publication Number | Publication Date |
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| CN107216295A true CN107216295A (en) | 2017-09-29 |
| CN107216295B CN107216295B (en) | 2019-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610164995.4A Active CN107216295B (en) | 2016-03-22 | 2016-03-22 | The method that ethylene oxide is prepared by oxygen and ethylene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110871049A (en) * | 2018-09-03 | 2020-03-10 | 中国石油化工股份有限公司 | High-efficiency heat exchange reaction tube |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904807A (en) * | 1985-05-01 | 1990-02-27 | Scientific Design Company, Inc. | Selective extraction of argon from ethylene oxide recycle stream |
| CN1280521A (en) * | 1997-10-29 | 2001-01-17 | 埃尔特朗研究股份有限公司 | Catalytic membrane reactor with two component three dimensional catalysis |
| CN202605992U (en) * | 2012-03-20 | 2012-12-19 | 南京工业大学 | Integrated tubular ceramic oxygen permeation membrane separation reactor |
| CN103272488A (en) * | 2013-05-23 | 2013-09-04 | 南京工业大学 | Multi-layer composite ceramic oxygen permeation film as well as preparation and application thereof |
-
2016
- 2016-03-22 CN CN201610164995.4A patent/CN107216295B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904807A (en) * | 1985-05-01 | 1990-02-27 | Scientific Design Company, Inc. | Selective extraction of argon from ethylene oxide recycle stream |
| CN1280521A (en) * | 1997-10-29 | 2001-01-17 | 埃尔特朗研究股份有限公司 | Catalytic membrane reactor with two component three dimensional catalysis |
| CN202605992U (en) * | 2012-03-20 | 2012-12-19 | 南京工业大学 | Integrated tubular ceramic oxygen permeation membrane separation reactor |
| CN103272488A (en) * | 2013-05-23 | 2013-09-04 | 南京工业大学 | Multi-layer composite ceramic oxygen permeation film as well as preparation and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110871049A (en) * | 2018-09-03 | 2020-03-10 | 中国石油化工股份有限公司 | High-efficiency heat exchange reaction tube |
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| CN107216295B (en) | 2019-07-23 |
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