CN111747811B - Process for oxidative coupling of methane - Google Patents
Process for oxidative coupling of methane Download PDFInfo
- Publication number
- CN111747811B CN111747811B CN201910240047.8A CN201910240047A CN111747811B CN 111747811 B CN111747811 B CN 111747811B CN 201910240047 A CN201910240047 A CN 201910240047A CN 111747811 B CN111747811 B CN 111747811B
- Authority
- CN
- China
- Prior art keywords
- methane
- heat
- reaction
- oxidative coupling
- unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
-
- 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
-
- 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 belongs to the field of petrochemical industry, and relates to a process for oxidative coupling of methane. Mixing the methane-rich gas and the oxygen-rich gas in an alkane-oxygen mixer to obtain a mixed gas, feeding the mixed gas reaching the temperature required by the reaction into a constant-temperature reactor filled with a catalyst for methane oxidation coupling reaction, wherein a plurality of groups of reaction units and a plurality of groups of heat taking units which are arranged at intervals and a heat insulation structure are arranged in the constant-temperature reactor, the catalyst is filled in the reaction units, and a heat taking medium flows in the heat taking units and absorbs heat emitted by the reaction units; the heat insulation structure is arranged between the reaction unit and the heat taking unit, the temperature of the contact surface of the heat insulation structure and the reaction unit is higher than the initial temperature of the methane oxidative coupling reaction, and the temperature difference between the contact surface of the heat insulation structure and the heat taking unit and the heat taking medium in the heat taking unit is 5-50 ℃. The method of the invention ensures that each section of catalyst bed layer is basically constant, and the reaction is carried out at the optimal temperature.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a process for oxidative coupling of methane.
Background
Ethylene is one of the chemical products with the largest yield in the world, the ethylene industry is the core of the petrochemical industry, and the ethylene product accounts for more than 75 percent of petrochemical products and occupies an important position in national economy. Ethylene production has been used worldwide as one of the important indicators for the development of petrochemical in one country.
With the great fluctuation of the international crude oil price and the technical progress, in order to change the condition that the ethylene production raw material excessively depends on petroleum resources, the ethylene production raw material is changed, and the technology for producing ethylene by taking methanol as the raw material is developed and becomes a technology with wide industrial application in the novel coal chemical industry technology.
The technology for preparing ethylene by Oxidative Coupling of Methane (OCM) is an important technology for producing ethylene, takes natural gas as a raw material, can prepare ethylene by only one-step reaction process, and has high theoretical value and economic value. After more than 30 years of research, the research on the ethylene preparation by the methane one-step method has made a breakthrough, and the industrial demonstration device for preparing ethylene by methane coupling is successfully put into production, which is the way to the beginning of industrialization. The method has great significance for breaking the bottleneck of raw material sources in the ethylene industry, reducing the production cost and enhancing the competitiveness of the ethylene industry and downstream industries.
Research and development at home and abroad are most typical of Siluria technology company in the United states, and the Siluria develops an industrially feasible methane direct ethylene catalyst by precisely synthesizing a nanowire catalyst by using a biological template. The catalyst can efficiently catalyze methane to be converted into ethylene under the condition of 200-300 ℃ lower than the operation temperature of the traditional steam cracking method and under the pressure of 5-10 atmospheric pressures. The technology prolongs the service life of the catalyst, greatly reduces the operation temperature, but has no substantial breakthrough on the conversion rate of methane and the yield of ethylene.
The reactor types used in the reaction process of preparing ethylene by oxidative coupling of methane include fluidized bed reactor, fixed bed reactor, membrane reactor, etc., but the industrial application of these reactors is yet to be further developed.
Disclosure of Invention
The invention aims to provide a process for oxidative coupling of methane. The technological process of the present invention makes the catalyst bed basically constant, so that the reaction is performed at optimal temperature and the stable bed temperature is favorable to the stability of the catalyst performance.
In order to achieve the purpose, the invention provides a process for methane oxidative coupling, wherein methane-rich gas and oxygen-rich gas are mixed in an alkane-oxygen mixer to obtain mixed gas, the mixed gas reaching the temperature required by reaction enters a constant-temperature reactor filled with a catalyst to perform methane oxidative coupling reaction, a plurality of groups of reaction units and a plurality of groups of heat-taking units which are arranged at intervals and a heat-insulating structure are arranged in the constant-temperature reactor, the catalyst is filled in the reaction units, and a heat-taking medium flows in the heat-taking units and absorbs heat emitted by the reaction units; the heat insulation structure is arranged between the reaction unit and the heat taking unit, the temperature of the contact surface of the heat insulation structure and the reaction unit is higher than the initial temperature of the methane oxidative coupling reaction, and the temperature difference between the contact surface of the heat insulation structure and the heat taking unit and the heat taking medium in the heat taking unit is 5-50 ℃.
The material and arrangement of the heat insulation structure are not particularly limited in the present invention, as long as the above requirements are satisfied. Various insulation structures in the art may be employed, for example, the insulation structure may use refractory materials as the primary construction material, with the refractory materials being selected such as corundum firebrick and the like.
The arrangement of the reaction unit and the heat extraction unit is not particularly limited in the present invention, and the arrangement of the reaction unit and the heat extraction unit may be such that the mixed gas and the heat extraction medium flow in parallel, in countercurrent or in cross current, preferably in countercurrent.
According to the present invention, preferably, the heat-taking medium is selected from at least one of molten salt, water, steam, hot oil, and methane-rich gas.
Further, the heat-taking medium after absorbing the heat is recovered in the heat recovery device.
According to the invention, the temperature required for the reaction is preferably 450 to 950 ℃, and more preferably 600 to 950 ℃; the heat-taking medium is preferably water and steam; and secondly molten salt.
According to the invention, the temperature required by the reaction can be achieved by heating the mixed gas, or by preheating the methane-rich gas separately and mixing the preheated methane-rich gas with the oxygen-rich gas.
According to a preferred embodiment of the present invention, the product gas after the oxidative coupling reaction of methane enters the cracking unit, and provides heat for the hydrocarbons fed into the cracking unit to perform the cracking reaction, and simultaneously the product gas is further cooled. The cracking unit can be independently arranged and is arranged at the downstream of the constant temperature reactor; or can be arranged in the constant temperature reactor and is arranged at the downstream of the reaction unit and the heat extraction unit.
Further, the hydrocarbons fed to the cracking unit include at least one of ethane, propane, LPG, and naphtha. The cracking unit is preferably provided with a gas distributor to uniformly distribute the hydrocarbons fed into the cracking unit.
According to the invention, the reactor outlet material is preferably passed into a quench system to be cooled. In particular, the quench medium used in the quench system is selected from the group consisting of water, steam, nitrogen and CO 2 At least one of (1). The quenching system can adopt dividing wall heat exchange cooling or direct contact cooling.
According to the present invention, preferably the methane-rich gas has a methane content of >50% by volume, preferably >90% by volume, preferably the methane-rich gas is natural gas and/or shale gas; the volume content of oxygen in the oxygen-enriched gas is 12-100%.
The invention has the beneficial effects that: (1) the reaction temperature of the bed layer is constant and can be controlled at the optimal reaction temperature; (2) because the bed layer basically has no temperature rise, the performance of the catalyst is kept stable; (3) the reaction is carried out under stable conditions, and the service life of the catalyst can be prolonged.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 shows a schematic of an oxidative coupling reaction in combination with a cleavage process according to the present invention.
FIG. 2 shows a schematic of another oxidative coupling reaction in combination with a cleavage process of the present invention.
Description of the reference numerals
1-methane rich gas; 2-oxygen; 3-mixed gas; 4-discharging after reaction; 5-reaction discharging after quenching; 6. feeding water to the boiler; 7. steam; 8. cracking the feedstock hydrocarbons.
11-an alkyl oxygen mixer; 12-a heater; 13-a heat removal unit; 14-a reaction unit; 15-a cleavage unit; 16-quench heat exchanger; 17-distributor.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
As shown in figure 1, the methane-rich gas and the oxygen-rich gas enter an alkane-oxygen mixer 11, the methane-rich gas and the oxygen-rich gas are uniformly mixed in the alkane-oxygen mixer 11, the obtained mixed gas enters a heater 12, and the materials are heated to the temperature required by the reaction in the heater 12. The heated material enters a reaction unit 14 (which may be a plurality, only one of which is shown) containing a catalyst, and the methane and oxygen undergo an oxidative coupling reaction in the reaction unit 14. The heat released by the reaction is taken out by the heat-taking medium in the heat-taking unit 13 (there may be a plurality, only one of which is shown in the figure). The oxidation coupling reaction discharging material leaving the reaction unit 14 enters a cracking unit 15, and in the cracking unit 15, the cracking raw material is heated by the high-temperature oxidation coupling reaction discharging material and is heated, and cracking reaction occurs; the discharge of the oxidative coupling reaction is cooled by the cracking unit 15 and then enters a quenching system for further cooling.
The present invention is illustrated in more detail by the following examples.
Example 1
As shown in fig. 2, a preheated methane-rich gas 1 (natural gas, the methane content is 96 mol%) and oxygen 2 are in an alkane-oxygen mixer 11 to obtain a mixed gas 3, the mixed gas 3 is heated to 810 ℃ by a heater 12 (electric heater), and enters a constant temperature reactor filled with a catalyst to perform methane oxidation coupling reaction, a plurality of groups of reaction units 14 and heat extraction units 13 which are arranged at intervals are arranged in the constant temperature reactor, the reaction units 14 are filled with the catalyst, and methane and oxygen react under the action of the catalyst; the heat-taking medium is boiler feed water 6, and high-pressure (pressure 12 MPa) water is used for gasification and heat taking. The mixed gas 3 and the heat taking medium are in counter flow, and the reaction heat is absorbed by the heat taking medium so as to keep the reaction temperature of the process side at the temperature required by the reaction; the generated steam 7 is heated and then sent out. A heat insulation structure is arranged in the constant temperature reactor, the heat insulation structure is arranged between the reaction unit 14 and the heat taking unit 13 (not shown), the temperature of the contact surface of the heat insulation structure and the reaction unit 14 is higher than the initial temperature of the methane oxidation coupling reaction, and the temperature difference between the contact surface of the heat insulation structure and the heat taking unit 13 and the heat taking medium in the heat taking unit 13 is 10 ℃.
The downstream of the reaction unit is provided with a cracking unit 15, the product after the methane oxidative coupling reaction enters the cracking unit 15, and the cracking raw material hydrocarbon 8 (ethane) enters the cracking unit 15 and is uniformly distributed by a distributor 17. The product gas after the methane oxidative coupling reaction provides heat for the hydrocarbons sent into the cracking unit 15 to carry out cracking reaction, and meanwhile, the product gas is further cooled. The material after the cracking reaction and the product gas after the oxidative coupling reaction, namely the reaction discharge 4, are sent into a quenching heat exchanger 16 together to be cooled to about 350 ℃ so as to inhibit side reaction, the quenching medium is boiler feed water 6, and the reaction discharge 5 after quenching is obtained.
Through the arrangement, the reactor realizes constant temperature and constant bed layer temperature, and the service life of the catalyst is prolonged.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A process for methane oxidative coupling is characterized in that methane-rich gas and oxygen-rich gas are mixed in an alkane-oxygen mixer to obtain mixed gas, the mixed gas reaching the temperature required by reaction enters a constant-temperature reactor filled with a catalyst to perform methane oxidative coupling reaction, a plurality of groups of reaction units and a plurality of groups of heat-taking units which are arranged at intervals and a heat-insulating structure are arranged in the constant-temperature reactor, the catalyst is filled in the reaction units, and a heat-taking medium flows in the heat-taking units and absorbs heat emitted by the reaction units; the heat insulation structure is arranged between the reaction unit and the heat taking unit, the temperature of the contact surface of the heat insulation structure and the reaction unit is higher than the initial temperature of the methane oxidative coupling reaction, and the temperature difference between the contact surface of the heat insulation structure and the heat taking unit and a heat taking medium in the heat taking unit is 5-50 ℃;
the reaction unit and the heat extraction unit are arranged in a way that the mixed gas and the heat extraction medium flow in a counter-current way.
2. The process for oxidative coupling of methane according to claim 1, wherein the heat-withdrawing medium is selected from at least one of molten salts, water, steam, hot oils, and methane-rich gases.
3. The process for oxidative coupling of methane according to claim 1, wherein the heat-extracting medium after absorption of heat is recovered in a heat recovery unit.
4. The process for the oxidative coupling of methane according to claim 1, wherein the temperature required for the reaction is 450 to 950 ℃; the required temperature for reaction is achieved by heating the mixed gas, or by preheating the methane-rich gas separately and mixing the preheated methane-rich gas with the oxygen-rich gas.
5. The process for oxidative coupling of methane according to claim 1, wherein the product gas after the oxidative coupling of methane enters the cracking unit, heat is provided for the hydrocarbons fed into the cracking unit to carry out cracking reaction, and the product gas is further cooled; the hydrocarbons fed to the cracking unit include at least one of ethane, propane, LPG and naphtha.
6. The process for oxidative coupling of methane according to claim 1, wherein the reactor outlet material enters a quench system to be cooled.
7. The process for oxidative coupling of methane according to claim 6, wherein the quench medium used by the quench system is selected from the group consisting of water, steam, nitrogen and CO 2 At least one of (1).
8. The process for oxidative coupling of methane according to claim 6, wherein the quench system employs a dividing wall heat exchange or direct contact temperature reduction.
9. The process for the oxidative coupling of methane according to claim 1, wherein the methane-rich gas has a methane content >50% by volume; the volume content of oxygen in the oxygen-enriched gas is 12-100%.
10. The process for oxidative coupling of methane according to claim 9, wherein the methane-rich gas has a methane content of >90% by volume, and wherein the methane-rich gas is natural gas and/or shale gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910240047.8A CN111747811B (en) | 2019-03-27 | 2019-03-27 | Process for oxidative coupling of methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910240047.8A CN111747811B (en) | 2019-03-27 | 2019-03-27 | Process for oxidative coupling of methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111747811A CN111747811A (en) | 2020-10-09 |
| CN111747811B true CN111747811B (en) | 2023-04-07 |
Family
ID=72671559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910240047.8A Active CN111747811B (en) | 2019-03-27 | 2019-03-27 | Process for oxidative coupling of methane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111747811B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3237079A1 (en) * | 1982-10-07 | 1984-04-12 | Manfred Prof. Dr. 4630 Bochum Baerns | METHOD FOR THE PRODUCTION OF ETHANE AND OR OR ETHYLENE FROM METHANE |
| US5118898A (en) * | 1989-06-30 | 1992-06-02 | The Broken Hill Proprietary Company Limited | Process for the production of olefins by combined methane oxidative coupling/hydrocarbon pyrolysis |
| CN1146373A (en) * | 1995-09-27 | 1997-04-02 | 中国科学院大连化学物理研究所 | Multi-stage fixed-bed reaction technology and device for methane oxidation coupling reaction |
| CN102365250A (en) * | 2009-03-31 | 2012-02-29 | 弗纳技术股份有限公司 | Oxidative coupling of hydrocarbons as heat source |
| US9334204B1 (en) * | 2015-03-17 | 2016-05-10 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
| CN106732201A (en) * | 2017-01-05 | 2017-05-31 | 中石化上海工程有限公司 | Catalyst for Oxidative Coupling of Methane reactor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10377682B2 (en) * | 2014-01-09 | 2019-08-13 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
-
2019
- 2019-03-27 CN CN201910240047.8A patent/CN111747811B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3237079A1 (en) * | 1982-10-07 | 1984-04-12 | Manfred Prof. Dr. 4630 Bochum Baerns | METHOD FOR THE PRODUCTION OF ETHANE AND OR OR ETHYLENE FROM METHANE |
| US5118898A (en) * | 1989-06-30 | 1992-06-02 | The Broken Hill Proprietary Company Limited | Process for the production of olefins by combined methane oxidative coupling/hydrocarbon pyrolysis |
| CN1146373A (en) * | 1995-09-27 | 1997-04-02 | 中国科学院大连化学物理研究所 | Multi-stage fixed-bed reaction technology and device for methane oxidation coupling reaction |
| CN102365250A (en) * | 2009-03-31 | 2012-02-29 | 弗纳技术股份有限公司 | Oxidative coupling of hydrocarbons as heat source |
| US9334204B1 (en) * | 2015-03-17 | 2016-05-10 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
| CN106732201A (en) * | 2017-01-05 | 2017-05-31 | 中石化上海工程有限公司 | Catalyst for Oxidative Coupling of Methane reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111747811A (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4232179A (en) | Process for preparing ethene | |
| CN101244969B (en) | Continuous aromatization and catalyst regeneration device and method thereof | |
| CA2352243C (en) | Method for converting natural gas to liquid hydrocarbons | |
| AU597362B2 (en) | Process and apparatus for the production of synthesis gas | |
| CN101928194B (en) | Tropsch synthesis method of fixed bed | |
| EP3230239A1 (en) | Methods of producing ethylene and synthesis gas by combining the oxidative coupling of methane and dry reforming of methane reactions | |
| CN210065595U (en) | Device for oxidative coupling of methane | |
| CN101293804B (en) | Fluidizer and method for preparing ethylene with ethanol dehydration | |
| CN210058196U (en) | Fixed bed reactor for producing hydrocarbons | |
| JP2010051960A (en) | Method for chemical conversion of raw material through endothermic reaction using reactor | |
| CN111747811B (en) | Process for oxidative coupling of methane | |
| CN210065594U (en) | Fluidized bed reaction device for methane oxidative coupling reaction | |
| CN111747821B (en) | Process for preparing olefin by oxidative coupling of methane | |
| SU434660A3 (en) | METHOD OF CATALYTIC GASIFICATION OF HYDROCARBONS | |
| CN111747820B (en) | Method for producing hydrocarbons | |
| CN214457791U (en) | Heavy oil processing system | |
| CN103420767B (en) | The preparation method of iso-butylene | |
| CN101343568A (en) | Method for preparing gasoline with petroleum cracking of dry gas | |
| CN104525057B (en) | A kind of synthesis gas two-step method prepares the device and technique of gasoline | |
| CN105037070B (en) | Reaction device and method for manufacturing propene by utilizing catalytic dehydration of methanol | |
| RU115780U1 (en) | INSTALLATION FOR PRODUCING HIGH-OCTANE GASOLINE COMPONENTS BY THE METHOD OF CATALYTIC REFORMING USING A TUBULAR REACTOR | |
| CN105368514B (en) | Produce the method and device of synthetic natural gas | |
| CN108017482B (en) | Method for preparing aromatic hydrocarbon by converting raw material containing oxygen-containing compound | |
| CN101870629B (en) | Low carbon olefin preparation method by utilizing hydrogen catalytic combustion to heat | |
| CN111747808B (en) | Method for producing hydrocarbon by using fluidization technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |