CN107216295B - The method that ethylene oxide is prepared by oxygen and ethylene - Google Patents
The method that ethylene oxide is prepared by oxygen and ethylene Download PDFInfo
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- CN107216295B CN107216295B CN201610164995.4A CN201610164995A CN107216295B CN 107216295 B CN107216295 B CN 107216295B CN 201610164995 A CN201610164995 A CN 201610164995A CN 107216295 B CN107216295 B CN 107216295B
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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
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- 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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of method for preparing ethylene oxide by oxygen and ethylene, mainly solve the problems, such as that safety is poor in the prior art.The present invention is by using a kind of method for preparing ethylene oxide by oxygen and ethylene, reaction raw materials ethylene gas enters the oxygen flow membrane tube in reactor after gas-gas heat exchanger heats, 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 arranges in shell and tube, air enters the region outside the oxygen flow membrane tube in reactor, oxygen is in oxygen permeation membrane adsorption, after desorption enter oxygen permeation membrane pipe in and contact ethylene, reaction generates the product including ethylene oxide under catalyst, affiliated product goes out from oxygen flow membrane tube outlet stream, enter downstream separation system after gas-gas heat exchanger, the technical solution that remaining nitrogen-rich air is discharged from reactor preferably solves the above problem, it can be used for preparing in ethylene oxide.
Description
Technical field
The present invention relates to a kind of methods for preparing ethylene oxide by oxygen and ethylene.
Background technique
Ethylene oxide is important Organic chemical products in ethylene industry derivative, its production technology is generally using fixation at present
Bed reactor makes oxygen and ethylene that exothermic oxidation reaction occur on silver catalyst.Ethylene and oxygen pass through before into reactor
Oxygen mixer completes mixing, and oxygen directly affects the selectivity and conversion ratio that catalysis is reacted with the mixed effect of ethylene, this straight
Connect the mixing of contact, reaction process has the great risk that reaction temperature runaway is out of control, fires.
Composite conductor oxygen-permeating film is inorganic ceramic membrane material that is a kind of while having oxonium ion and electronic conductivity, in height
Under the driving of mild oxygen concentration gradient, oxygen can be spread through film from hyperoxia pressure side to hypoxemia pressure side, and theoretically the oxygen of material seeps
Selectivity is 100% thoroughly.
Membrane reactor that is integrated with UF membrane and constituting is reacted into catalysis, can realize reaction using the specific function of film
Control input, the reinforcing of alternate transmitting and separation in situ of product of object etc. improve reaction conversion ratio, reaction choosing to reach
Selecting property and reaction rate extend the purpose of catalyst service life and reduction equipment investment.In addition, for ethylene catalytic oxidation this
Kind reaction uses oxygen permeation membrane that can be avoided ethylene excessive oxidation that combustion reaction occurs with accurately controlling oxygen content, can also be avoided oxygen
Risk of explosion caused by gas is directly largely mixed with flammable reactant.
Therefore, the present invention proposes a kind of composite conductor oxygen-permeating film to be used to mix ethylene and oxygen for the membrane reactor of medium
It closes, reaction process integration, is mixed so that oxygen reaches molecular level with ethylene, reduce the risk that fuel gas fires,
Simultaneously effectively inhibit reaction occur temperature runaway, thus realize oxygen mixed with ethylene, the reinforcing of reaction process, reach process essence pacify
Quan Hua.
Summary of the invention
The technical problem to be solved by the present invention is to the problem that safety in the prior art is poor, provide a kind of new by oxygen
The method that gas and ethylene prepare ethylene oxide.This method is used to prepare in ethylene oxide, has the advantages that safety is preferable.
To solve the above problems, The technical solution adopted by the invention is as follows: one kind prepares ethylene oxide by oxygen and ethylene
Method, reaction raw materials ethylene gas after gas-gas heat exchanger heats enter reactor in oxygen flow membrane tube, the material of oxygen flow membrane tube
Matter uses mixed conductor inorganic ceramic membrane, and the quantity of oxygen flow membrane tube is at least one or arranges in shell and tube, and air enters reaction
The region outside oxygen flow membrane tube in device, oxygen enters in oxygen permeation membrane pipe after oxygen permeation membrane adsorption, desorption and contact ethylene,
Reaction generates the product including ethylene oxide under catalyst, and affiliated product goes out from oxygen flow membrane tube outlet stream, after gas-gas heat exchanger
Into downstream separation system, remaining nitrogen-rich air is discharged from reactor.
In above-mentioned technical proposal, it is preferable that state and be equipped with catalyst bed in oxygen flow membrane tube, catalyst is silver.
In above-mentioned technical proposal, it is preferable that the operating condition of the reactor are as follows: 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 ethylene 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 the reaction raw materials ethylene gas is heated to 180~200 through gas-gas heat exchanger
Enter the oxygen flow membrane tube in reactor after DEG C.
The mixing of ethylene and oxygen, reaction process are coupled by the present invention, realize process intensification between each other, with biography
System calandria type fixed bed reactor, which is compared, can be improved conversion ratio and selectivity.Oxygen source is used air as in the present invention, it can
Equipment investment when directlying adopt oxygen is effectively reduced.It is rate-determining steps that oxygen, which enters reaction side through oxygen permeation membrane, in the present invention,
Can accurately controlling oxygen content, avoid that temperature runaway occurs in reactor, while oxygen is mixed with ethylene by fenestra and can reach point
Sub horizontal, the risk that the system of can reduce fires achieves preferable technical effect.
Detailed description of the invention
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 be ring
Oxidative ethane outlet；7 be catalyst bed；8 be oxygen flow fenestra.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
A method of ethylene oxide being prepared by oxygen and ethylene, as shown in Figure 1 or 2.Reaction raw materials ethylene gas warp
Gas-gas heat exchanger enters the oxygen flow membrane tube in reactor after being heated to 180 DEG C, the material of oxygen flow membrane tube is inorganic using mixed conductor
Ceramic membrane, the quantity of oxygen flow membrane tube are one, and air enters the region outside the oxygen flow membrane tube in reactor, and oxygen is in oxygen permeation membrane table
After the Adsorption and desorption of face enter oxygen permeation membrane pipe in and contact ethylene, under silver catalyst reaction generate include ethylene oxide product,
Affiliated product goes out from oxygen flow membrane tube outlet stream, and downstream separation system is entered after gas-gas heat exchanger, and remaining nitrogen-rich air is from anti-
It answers in device and is discharged.
The operating condition of the reactor is 180 DEG C of temperature, pressure 2.0MPaG (gauge pressure).The body of the ethylene and air
Product is than being 1:9.0.Oxygen content in the nitrogen-rich air is 16%.
The result shows that ethylene conversion per pass 12%, ethylene oxide is selectively 95%.
[embodiment 2]
According to condition described in embodiment 1 and step, only ethylene gas enters after gas-gas heat exchanger is heated to 185 DEG C
Oxygen flow membrane tube in reactor, oxygen flow membrane tube are 2, are arranged in shell and tube, and the operating condition of the reactor is temperature 185
DEG C, pressure 2.05MPaG.The volume ratio of the ethylene and air is 1:9.2.Oxygen content in the nitrogen-rich air is 15.4%.
The result shows that ethylene conversion per pass 13.6%, ethylene oxide is selectively 95.2%.
[embodiment 3]
According to condition described in embodiment 1 and step, only ethylene gas enters after gas-gas heat exchanger is heated to 192 DEG C
Oxygen flow membrane tube in reactor, oxygen flow membrane tube are 4, are arranged in shell and tube, and the operating condition of the reactor is temperature 192
DEG C, pressure 2.06MPaG.The volume ratio of the ethylene and air is 1；9.5.Oxygen content in the nitrogen-rich air is 13.6%.
The result shows that ethylene conversion per pass 14.8%, ethylene oxide is selectively 95.6%.
[embodiment 4]
According to condition described in embodiment 1 and step, only ethylene gas enters after gas-gas heat exchanger is heated to 200 DEG C
Oxygen flow membrane tube in reactor, oxygen flow membrane tube are 8, are arranged in shell and tube, and the operating condition of the reactor is temperature 200
DEG C, pressure 2.1MPaG.The volume ratio of the ethylene and air is 1:9.8.Oxygen content in the nitrogen-rich air is 12.4%.
The result shows that ethylene conversion per pass 14.1%, ethylene oxide is selectively 94.7%.
[comparative example]
The production of conventional epoxy ethane uses fixed bed reactors, ethylene conversion per pass usually only 7-8%, ethylene oxide
Selectivity 85% or so.The pure oxygen obtained using space division is as oxidant, and oxygen content is not easy accurately to control in reactor, holds
It easily forms hot spot and temperature runaway occurs.
The mixing of ethylene and oxygen, reaction process are coupled by the present invention, realize process intensification between each other, with biography
System calandria type fixed bed reactor, which is compared, can be improved conversion ratio (conversion per pass > 12%) and selectivity (selectivity > 94%).
Oxygen source is used air as in the present invention, can be effectively reduced equipment investment when directlying adopt oxygen.Oxygen is saturating in the present invention
Crossing oxygen permeation membrane to enter reaction side is rate-determining steps, can accurately controlling oxygen content, avoid that temperature runaway occurs in reactor, while oxygen
Molecular level can be reached by being mixed by fenestra with ethylene, and the risk that the system of can reduce fires achieves preferable skill
Art effect.
Claims (2)
1. a kind of method for preparing ethylene oxide by oxygen and ethylene, reaction raw materials ethylene gas heat laggard through gas-gas heat exchanger
Enter the 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
Arranged for one or in shell and tube, air enters the region outside the oxygen flow membrane tube in reactor, oxygen oxygen permeation membrane adsorption,
After desorption enter oxygen permeation membrane pipe in and contact ethylene, under catalyst reaction generate include ethylene oxide product, affiliated product
Go out from oxygen flow membrane tube outlet stream, downstream separation system is entered after gas-gas heat exchanger, remaining nitrogen-rich air is arranged from reactor
Out；Catalyst bed is equipped in the oxygen flow membrane tube, catalyst is silver；The operating condition of the reactor are as follows: reaction temperature
180-200 DEG C, react gauge pressure 2.0-2.1MPa；The volume ratio of the ethylene and air is 1:9~9.8；In the nitrogen-rich air
Oxygen content be 12-16%；The reaction raw materials ethylene gas enters reaction after gas-gas heat exchanger is heated to 180~200 DEG C
Oxygen flow membrane tube in device.
2. the method for preparing ethylene oxide by oxygen and ethylene according to claim 1, it is characterised in that in the reactor
Oxygen flow membrane tube in shell and tube arrange.
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| 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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| 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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| CN107216295A CN107216295A (en) | 2017-09-29 |
| CN107216295B true CN107216295B (en) | 2019-07-23 |
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| IN165859B (en) * | 1985-05-01 | 1990-01-27 | Halcon Sd Group Inc | |
| US6355093B1 (en) * | 1993-12-08 | 2002-03-12 | Eltron Research, Inc | 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 |
| CN103272488B (en) * | 2013-05-23 | 2015-10-28 | 南京工业大学 | Multi-layer composite ceramic oxygen permeable membrane and Synthesis and applications thereof |
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