CN111747821B - Process for preparing olefin by oxidative coupling of methane - Google Patents
Process for preparing olefin by oxidative coupling of methane Download PDFInfo
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- CN111747821B CN111747821B CN201910240040.6A CN201910240040A CN111747821B CN 111747821 B CN111747821 B CN 111747821B CN 201910240040 A CN201910240040 A CN 201910240040A CN 111747821 B CN111747821 B CN 111747821B
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- 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
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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
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Abstract
The invention belongs to the field of petrochemical industry, and particularly relates to a process for preparing olefin by oxidative coupling of methane, which comprises the following steps: mixing the methane-rich gas and the oxygen-rich gas to form a raw material gas, and performing oxidative coupling reaction in a fixed bed reactor under the action of a catalyst to obtain a mixture at least containing CO and CO 2 Reaction gases of ethylene, ethane, carbon three and above components; a plurality of sections of catalyst bed layers connected in series are arranged in the fixed bed reactor; the height of each catalyst bed is 100-500mm, the reaction pressure is 0.1-1.5 MPaG, and the volume space velocity is 2000-10000h ‑1 The temperature rise range of the reaction temperature is 150-300 ℃; the lower part of each section of catalyst bed layer is a heat taking section, and reaction gas enters the next section of catalyst bed layer after heat exchange. The method can effectively control the reaction temperature rise, reduce side reactions and be beneficial to improving the yield of olefin, and can ensure that the conversion rate of methane reaches 34 percent and the selectivity of C2 reaches 58.7 percent.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a process for preparing olefin by 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 is an important technology for producing ethylene, and the ethylene can be prepared by only one-step reaction process by taking natural gas as a raw material, so that the method 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.
Disclosure of Invention
The invention aims to provide a process for preparing olefin by oxidative coupling of methane, so that the characteristic of strong heat release of the reaction for preparing olefin by oxidative coupling of methane is met, the reaction temperature rise can be effectively controlled by taking heat from the middle after segmentation, and the purposes of reducing side reactions and improving the yield of olefin are achieved by combining the control on the reaction process conditions.
In order to achieve the purpose, the invention provides a method for preparing alkene by oxidative coupling of methaneThe hydrocarbon process comprises mixing methane-rich gas and oxygen-rich gas to form raw material gas, performing oxidative coupling reaction in a fixed bed reactor under the action of catalyst to obtain a mixture containing at least CO and CO 2 Reaction gas of ethylene, ethane and carbon three or more components; a plurality of sections of catalyst bed layers connected in series are arranged in the fixed bed reactor; the height of each catalyst bed is more than 100mm and less than or equal to 500mm, preferably 150-500 mm, the reaction pressure is 0.1-1.5 MPaG, preferably 0.5-1.0 MPaG, and the volume space velocity is 2000-10000h -1 The reaction temperature is 150-300 ℃; the lower part of each section of catalyst bed layer is a heat taking section, and reaction gas enters the next section of catalyst bed layer after heat exchange. Namely, the first stage reaction bed is a heat-insulating bed, the upper part of each other stage bed is a heat-taking section, and the heat-taking section adopts a coil pipe for taking heat and then enters the next stage reaction bed.
The number of stages of the catalyst bed in the present invention is not particularly limited, and preferably, the number of stages of the catalyst bed is 2 to 6.
According to the invention, the operating temperature of the oxidative coupling reaction is preferably between 700 and 900 ℃.
According to the invention, the volume ratio of methane to oxygen at the inlet of each section of catalyst bed is preferably 0.1:1 to 80:1.
according to the invention, preferably, an injection opening and a gas distributor are arranged in the upper part of the catalyst bed, close to the catalyst bed, the injection material being selected from the group consisting of oxygen-rich gas and methane-rich gas, and optionally water vapor and/or inert substances. The injection ports and the gas distributors can be arranged in a plurality of ways, the injection port at the upper part of the first section of catalyst bed layer can be an inlet of the reactor, and the injection ports and the gas distributors are arranged at the upper parts of other sections of catalyst bed layers except the first section of catalyst bed layer. By arranging the injection port and the gas distributor, oxygen and natural gas can be introduced into the upper part of the reaction bed layer, and the oxygen and the natural gas are added into each section of the reaction bed layer so as to adjust the alkoxy ratio of each section within the range and control the temperature rise of the catalyst bed layer and the reaction; the temperature rise of the reaction can be controlled by adding water vapor as a diluent gas.
The inventor finds that the specific arrangement position of the injection port has a large influence on the reaction, and compared with the mode of arranging the injection port at the inlet of the reactor, the injection port close to the catalyst bed layer can better realize the control of the process condition, thereby improving the methane conversion rate and the ethylene selectivity. Specifically, the residence time of the oxygen-rich gas injected through the injection port from the injection to the bed is preferably not more than 100ms, and more preferably not more than 50ms. By controlling the residence time, the raw material loss caused by methane combustion can be reduced, the reaction process is accelerated, and the process safety is improved.
According to the present invention, preferably the methane-rich gas has a methane content of >50% by volume, preferably >90% by volume, further preferably the methane-rich gas is preferably natural gas and/or shale gas.
According to the invention, the oxygen content of the oxygen-enriched gas is preferably 12 to 100% by volume.
According to the invention, the heat extraction section can adopt coiled pipes or linear sleeves, preferably one or more groups of coiled pipes, and adopts a coiled pipe heat exchanger with a simple structure, so that the problem of thermal expansion of pipelines is solved, and the equipment cost is reduced.
According to the present invention, preferably, a heat insulation structure is provided inside the fixed bed reactor; the thermal insulation structure is used for separating a high-temperature area from a low-temperature area. The heat insulation structure can use refractory materials as main construction materials, the refractory materials can be selected from corundum refractory bricks and the like, and a high-temperature area in the reactor is separated from a low-temperature area such as an outer wall, a heat extraction structure and a pipeline. For example, the inner walls of the reactor are provided with a refractory lining.
The invention has the beneficial effects that: through sectional feeding, intermediate heat extraction and specific process condition control, the reaction temperature rise can be effectively controlled, side reactions are reduced, the olefin yield is improved, and the method can ensure that the methane conversion rate reaches 34% and the C2 selectivity reaches 58.7%.
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 specific process for preparing olefin by oxidative coupling of methane.
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.
Example 1
As shown in figure 1, the process for preparing olefin by oxidative coupling of methane comprises mixing natural gas (with methane content of 98%) and oxygen to form a feed gas, and performing oxidative coupling reaction in a fixed bed reactor under the action of a catalyst to generate a product at least containing CO and CO 2 Reaction gases of ethylene, ethane, carbon three and above components; the fixed bed reactor is provided with a refractory lining, the reactor is internally provided with 3 sections of catalyst bed layers (the third section is not shown) which are connected in series, the height of each section of catalyst bed layer is 150mm, the upper part of the catalyst bed layer, which is close to the catalyst bed layer, is provided with an injection port and a gas distributor, raw material gas respectively enters each section of catalyst bed layer, and the residence time from the injection of oxygen in the raw material gas injected from the injection port to the arrival of the raw material gas at the bed layer is 40ms; the operation temperature of the oxidative coupling reaction is 750 ℃, the pressure is 0.5MPaG, and the volume space velocity is 10000h -1 The reaction temperature rose to 200 ℃. The volume ratio of methane to oxygen at the inlet of each section of catalyst bed is 3:1. the lower part of each section of catalyst bed layer is a heat taking section which adopts two groups of coiled pipes, and reaction gas enters the next section of catalyst bed layer after heat exchange.
In the above process, the methane conversion was 34% and the C2 selectivity was 58.7%.
Example 2
The process for producing olefins by oxidative coupling of methane was carried out in accordance with the method of example 1, except that the residence time of oxygen in the feed gas injected from the injection port from the injection to the bed was 80ms. In the above process, the methane conversion was 30% and the C2 selectivity was 54%.
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 (11)
1. A process for preparing olefin by oxidative coupling of methane is characterized in that methane-rich gas and oxygen-rich gas are mixed to form a feed gas, and an oxidative coupling reaction is carried out in a fixed bed reactor under the action of a catalyst to obtain a product at least containing CO and CO 2 Reaction gas of ethylene, ethane and carbon three or more components; a plurality of sections of catalyst bed layers connected in series are arranged in the fixed bed reactor; the height of each catalyst bed is more than 100mm and less than or equal to 500mm, the reaction pressure is 0.1-1.5 MPaG, and the volume space velocity is 2000-10000h -1 The reaction temperature is raised to 150-300 ℃; the lower part of each section of catalyst bed layer is a heat taking section, and reaction gas enters the next section of catalyst bed layer after heat exchange;
an injection port and a gas distributor are arranged on the upper part of the catalyst bed layer near the catalyst bed layer, the injected material is at least one of oxygen-enriched gas, methane-enriched gas and optional steam and/or inert substances, and the residence time from the injection of the oxygen-enriched gas into the catalyst bed layer to the arrival of the oxygen-enriched gas in the injection port is not more than 100ms.
2. The process for preparing olefin by oxidative coupling of methane according to claim 1, wherein the number of stages of the catalyst bed is 2 to 6.
3. The process for preparing olefin by oxidative coupling of methane as claimed in claim 1, wherein the height of each catalyst bed is 150-500 mm; the reaction pressure is 0.5-1.0 MPaG;
the operation temperature of the oxidative coupling reaction is 700-900 ℃, and the operation pressure is 0.5-1.0 MPaG.
4. The process for preparing olefin through oxidative coupling of methane as claimed in claim 1, wherein the residence time of the oxygen-rich gas injected from the injection port to the catalyst bed is not more than 50ms.
5. The process for preparing olefin by oxidative coupling of methane according to claim 1, wherein the volume ratio of methane to oxygen at the inlet of each catalyst bed is 0.1:1 to 80:1.
6. the process for preparing olefin by oxidative coupling of methane as claimed in claim 1, wherein the methane-rich gas has a methane content of >50% by volume.
7. The process for preparing olefin by oxidative coupling of methane according to claim 6, wherein the methane-rich gas has a methane content of >90% by volume.
8. The process for preparing olefin by oxidative coupling of methane according to claim 7, wherein the methane-rich gas is natural gas and/or shale gas.
9. The process for preparing olefin by oxidative coupling of methane as claimed in claim 1, wherein the oxygen-enriched gas contains 12-100% by volume of oxygen.
10. The process for preparing olefin by oxidative coupling of methane according to claim 1, wherein the heat-extracting section employs a coiled pipe or a linear casing pipe.
11. The process for preparing olefin by oxidative coupling of methane according to claim 1, wherein a heat insulation structure is arranged in the fixed bed reactor and used for separating a high-temperature region from a low-temperature region.
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| CN114656316A (en) * | 2020-12-22 | 2022-06-24 | 中国石油化工股份有限公司 | System and method for preparing olefin through oxidative coupling of methane and application of system and method |
| CN115703075A (en) * | 2021-08-16 | 2023-02-17 | 中国石油化工股份有限公司 | Methane oxidative coupling catalyst, preparation method and application thereof, and method for preparing carbo-dylic hydrocarbon |
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