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CN114656317A - Method and system for preparing olefin through oxidative coupling of methane and application of method and system - Google Patents

Method and system for preparing olefin through oxidative coupling of methane and application of method and system Download PDF

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Publication number
CN114656317A
CN114656317A CN202011534805.6A CN202011534805A CN114656317A CN 114656317 A CN114656317 A CN 114656317A CN 202011534805 A CN202011534805 A CN 202011534805A CN 114656317 A CN114656317 A CN 114656317A
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methane
gas
absorbent
inlet
mixed gas
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马守涛
孙峰
姜杰
杨哲
徐伟
朱云峰
周明川
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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    • C—CHEMISTRY; METALLURGY
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    • 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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    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract

The invention relates to the field of catalysis, and discloses a method and a system for preparing olefin by oxidative coupling of methane and application thereof, wherein the method comprises the following steps: (1) premixing methane, oxygen and inactive gas, and heating the premixed mixed gas by using water vapor; (2) contacting the heated mixed gas with a catalyst to perform catalytic reaction; (3) contacting the gas product obtained from the catalytic reaction with an absorbent to absorb methane and water vapour in the gas product, and returning the material containing methane, water vapour and absorbent to step (1) for regeneration to release methane and water vapour. The method has the advantages that the retention time of the methane in the reactor is prolonged by reducing the premixing time and prolonging the spontaneous combustion induction time of the methane, so that the explosion risk can be reduced, the reaction time of the methane is prolonged, and the conversion rate of the methane is improved.

Description

Method and system for preparing olefin through oxidative coupling of methane and application of method and system
Technical Field
The invention relates to the field of catalysis, in particular to a method and a system for preparing olefin through oxidative coupling of methane and application thereof.
Background
Methane is the main component of natural gas and rock gas, and has the advantages of high heat value, low pollution, low price and the like. With the shortage of petroleum resources, the utilization of natural gas is expected to replace petroleum resources, and can become one of the sources of new raw materials in the chemical industry.
At present, the most mature process in natural gas chemical industry is a synthesis gas process, which firstly oxidizes and converts methane into carbon monoxide and hydrogen, and then synthesizes chemical products such as methanol, ammonia, dimethyl ether, synthetic alcohol and the like from the carbon monoxide and the hydrogen. The conversion of methane to synthesis gas is mainly divided into three pathways: steam reforming, carbon dioxide reforming and partial oxidation. Because ethylene is an important chemical raw material, the demand is large, and the output value is high, the technology for preparing olefin by directly oxidizing methane is concerned by a great number of engineers. However, the methane oxidation reaction needs to be carried out at high temperature and high pressure, and the requirement on the retention time of the methane-oxygen gas mixture in the reactor is strict, the main reason is that the spontaneous combustion induction time of the methane-oxygen gas mixture at high temperature and high pressure is short, and if the retention time of the methane-oxygen gas mixture in the reactor is too long, the spontaneous combustion induction time of the gas mixture is longer than the retention time, and the possibility of explosion occurs.
In recent years, researchers have conducted extensive research on a process for producing olefins from methane, and after research, CN107108401A discloses a method for producing ethylene and synthesis gas by combining oxidative coupling of methane with dry reforming reaction of methane, wherein the specific process of the invention is to introduce a feed gas containing methane and oxygen into a methane oxidative coupling reactor, and catalytically react methane and oxygen to produce CO and CO2、H2O and C2H4And the reacted gas passes through a cooling and separating unit to separate C2H4To obtain a catalyst mainly containing CH4、CO、CO2、H2Preheating the mixed gas, introducing the preheated mixed gas into a dry reforming reactor, and introducing CO into the dry reforming reactor2And CH4Catalytically converted to synthesis gas. The method uses the heat generated by the oxidative coupling of methane for driving the endothermic dry reforming of methane reaction, but the method places the reaction process of the oxidative coupling of methane for preparing ethylene and the reaction process of methane reforming for preparing synthesis gas in the same reaction vessel, and simultaneously assists the sectional alternate distribution of catalytic materials and inert materials in the reactor, so that the reaction products are mixed together and are difficult to separate, and the change of residence time and spontaneous combustion induction time is not considered, thereby having the risk of explosion.
CN102093157A provides an integrated process for the direct conversion of methane containing feedstocks to ethylene with the production of synthesis gas. The present invention overcomes the limitations of the previous direct production of ethylene from methane targeting a single product, and allows for the further utilization of methane, i.e. high yield conversion to synthesis gas, in addition to high yield conversion of methane to ethylene. However, the invention adopts a methane wet reforming process to prepare the synthesis gas, needs to consume a large amount of water and heat, and wastes reaction heat released by methane oxidative coupling. In addition, the explosion risk of the methane gas mixture is not considered.
Because the oxidative coupling is an exothermic reaction, the methane and the oxygen are easy to explode, so that casualties are caused, but the explosion risk of the methane in the oxidative coupling reactor is not considered in the prior art.
Disclosure of Invention
The invention aims to overcome the problem of burning explosion caused by too long retention time of methane in a reactor in the prior art, and provides a method and a system for preparing olefin through methane oxidative coupling and application thereof.
The inventor of the invention unexpectedly finds in experiments that by premixing and heating methane, oxygen, water vapor and non-active gas in advance and then carrying out catalytic reaction, the water vapor can effectively prevent the methane from being released or exploded by a safety valve due to the problem of overhigh temperature or overlarge pressure after the methane is exploded in the oxidative coupling, in addition, by absorbing water and unreacted methane generated in the catalytic reaction in the oxidative coupling by using an absorbent, and then returning the material containing the methane, the water vapor and the absorbent to the premixing and heating step for regeneration so as to release the methane and the water vapor, the resource utilization of the methane and the water vapor can be realized.
In order to achieve the above object, one aspect of the present invention provides a method for preparing olefins by oxidative coupling of methane, the method comprising:
(1) premixing methane, oxygen and inactive gas, and heating the premixed mixed gas by using water vapor;
(2) contacting the heated mixed gas with a catalyst to perform catalytic reaction;
(3) contacting the gas product obtained from the catalytic reaction with an absorbent to absorb methane and water vapour in the gas product, and returning the material containing methane, water vapour and absorbent to step (1) for regeneration to release methane and water vapour.
The second aspect of the present invention provides a system for producing olefin by oxidative coupling of methane, the system comprising:
the system comprises a premixing device, a gas-liquid separator and a gas-liquid separator, wherein the premixing device is provided with a methane inlet, an oxygen inlet, an inactive gas inlet, a first absorbent outlet, a water vapor inlet and a mixed gas outlet, and can be used for premixing methane, oxygen and inactive gas introduced into the premixing device and heating the premixed mixed gas by introducing water vapor into the premixing device;
the reaction device is filled with a catalyst and is provided with a mixed gas inlet and a gas product outlet, and the mixed gas outlet is connected with the mixed gas inlet so as to send the heated mixed gas into the reaction device;
the absorption device is provided with a gas product inlet, an olefin outlet and a second absorbent outlet, the gas product outlet is connected with the gas product inlet, and the second absorbent outlet is connected with the first absorbent inlet.
The system for preparing olefin by oxidative coupling of methane comprises a premixing device, a reaction device and an absorption device, wherein methane, oxygen and inactive gas in the premixing device are premixed and heated by using water vapor and then enter the reaction device for catalytic reaction, a gas product obtained by the catalytic reaction is contacted with an absorbent in the absorption device to absorb the methane and the water vapor in the gas product, and a material containing the methane, the water vapor and the absorbent is returned to the premixing device for regeneration to release the methane and the water vapor, through the processes, the cyclic utilization of the methane and the water vapor can be realized, the safety valve is prevented from discharging or explosion due to the problem of overhigh temperature or overhigh pressure after the oxidative coupling is exploded, and the reaction time of the methane is increased by reducing the premixing time and prolonging the spontaneous combustion induction time of the methane, the conversion rate of methane is improved.
A third aspect of the invention provides the use of the above system for the production of olefins.
Drawings
FIG. 1 is a schematic diagram of a system for producing olefins by oxidative coupling of methane according to an embodiment of the present invention.
Description of the reference numerals
100 premixing device, 101 methane inlet, 102 oxygen inlet, 103 inactive gas inlet, 104 first absorbent inlet, 105 first absorbent outlet, 106 mixed gas outlet, 107 water vapor inlet, 200 reaction device, 201 mixed gas inlet, 202 gas product outlet, 203 heat exchange device, 204 catalyst, 300 absorption device, 301 gas product inlet, 302 olefin outlet, 303 second absorbent outlet, 304 second absorbent inlet, 11 circulating coolant and 12 fresh absorbent.
Detailed Description
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
One aspect of the present invention provides a method for preparing olefins by oxidative coupling of methane, comprising:
(1) premixing methane, oxygen and inactive gas, and heating the premixed mixed gas by using water vapor;
(2) contacting the heated mixed gas with a catalyst to perform catalytic reaction;
(3) contacting the gas product obtained from the catalytic reaction with an absorbent to absorb methane and water vapour in the gas product, and returning the material containing methane, water vapour and absorbent to step (1) for regeneration to release methane and water vapour.
In some embodiments of the present invention, to achieve energy recycling and thus reduce energy consumption, the method may further include: and conveying the heat generated by the catalytic reaction to the heating step by taking water vapor as a heat carrier so as to heat the mixed gas.
In the present invention, the kind of the catalyst is not limited, and a catalyst in which the active components are oxides of sodium tungstate and manganese and the carrier is silica is preferable. For example, a wt% Na may be used2WO4B% by weight Mn/SiO2Wherein a is the weight percentage of sodium tungstate calculated by W and ranges from 1 to 10, and b is the weight percentage of manganese oxide calculated by MnAnd the range is 1-10.
According to a preferred embodiment of the invention, catalyst Na2WO4-Mn/SiO2The preparation method of (2) is as follows:
preparation of Na by sol-gel method2WO4-Mn/SiO2Calculating different dosage according to the composition of the catalyst, adding Na under stirring at 50-70 deg.C2WO4Mixing the manganese precursor and the silicon source, adding a solvent (for example, the volume ratio of ethanol to water is 1-2: 1) and concentrated nitric acid, reacting for 0.5-5h, continuing aging for 10-12h, drying at 110-120 ℃ for 10-12h, roasting at 500-550 ℃ for 3-4h, and roasting at 800-850 ℃ for 3-4 h. The manganese precursor can be a water-soluble manganese salt, and preferably, the manganese precursor is manganese nitrate. The kind of the silicon source is not limited, and preferably, the silicon source is tetraethoxysilane.
In some embodiments of the invention, to achieve recycling of the absorbent, the method further comprises: the regenerated absorbent is used in step (3) to contact with the gaseous product to absorb methane and water vapor in the gaseous product.
In some embodiments of the invention, to reduce the residence time of methane in the reactor, deflagration is prevented. Preferably, the heating condition is such that the temperature of the heated mixed gas is 100-350 ℃ lower than the temperature of the catalytic reaction, and more preferably, the heating condition is such that the temperature of the heated mixed gas is 450-500 ℃.
In some embodiments of the present invention, the inert gas may be any gas or gas mixture that does not react with the raw material and the product, and may be at least one of a group-zero element gas and nitrogen, for example.
In some embodiments of the present invention, the absorbent has the advantages of low saturated vapor pressure, low volatility and methane absorption, and is preferably an ionic liquid, the anion of which is represented by formula i, and the cation of which is represented by formula ii or iii:
Figure BDA0002853001000000061
wherein in the formula II, R1And R2Identical or different and each independently selected from hydrogen or an aliphatic radical of C1-C12, which may be, for example, methyl, ethyl, n-propyl or n-butyl.
In the formula III, R1、R2、R3And R4Identical or different and each independently selected from hydrogen or an aliphatic radical of C1-C12, which may be, for example, methyl, ethyl, n-propyl or n-butyl.
In some embodiments of the invention, the absorbent is preferably at least one of 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt, methyltributylphosphine bis (trifluoromethanesulfonyl) imide salt and 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt.
In some embodiments of the invention, the volumetric flow ratio of methane to oxygen is preferably 1: 0.25-4. The volume flow ratio of the water vapor to the inactive gas is preferably 1-5: 1. after the water vapor is introduced into the mixed gas, the volume percentage of the methane is preferably 20 to 80 volume percent. In some embodiments of the invention, the conditions of the catalytic reaction include: the catalytic reaction temperature is preferably 600-850 ℃. The catalytic reaction pressure is preferably 0.5 to 5 MPa. The hourly space velocity of the reaction gas in terms of methane and oxygen is preferably 100-200 mL/(g.h). The catalytic reaction time is preferably 80 to 100 ms.
In some embodiments of the invention, the conditions of absorption comprise: the temperature of the absorption is preferably 50 to 100 deg.C, more preferably 55 to 80 deg.C. The pressure of the absorption is preferably 1 to 5MPa, more preferably 1 to 2 MPa.
In the present invention, the residence time means the time that the fluid micro-element passes from the inlet to the outlet of the reactor.
In the present invention, the autoignition induction time is a time period after the combustible gas is mixed with oxygen and the mixture is not immediately combusted even if the temperature exceeds the autoignition point, but is combusted after a certain time period, which is called as autoignition induction time and is one of important parameters of the fuel.
The second aspect of the present invention provides a system for producing olefin by oxidative coupling of methane, the system comprising:
the system comprises a premixing device, a gas-liquid separator and a gas-liquid separator, wherein the premixing device is provided with a methane inlet, an oxygen inlet, an inactive gas inlet, a first absorbent outlet, a water vapor inlet and a mixed gas outlet, and can be used for premixing methane, oxygen and inactive gas introduced into the premixing device and heating the premixed mixed gas by introducing water vapor into the premixing device;
the reaction device is filled with a catalyst and is provided with a mixed gas inlet and a gas product outlet, and the mixed gas outlet is connected with the mixed gas inlet so as to send the heated mixed gas into the reaction device;
the absorption device is provided with a gas product inlet, an olefin outlet and a second absorbent outlet, the gas product outlet is connected with the gas product inlet, and the second absorbent outlet is connected with the first absorbent inlet.
In some embodiments of the present invention, in order to achieve recycling of energy and thus achieve an effect of reducing energy consumption, the reaction apparatus is further provided with a heat exchange device, and the heat exchange device is capable of transporting heat generated in the reaction apparatus to the premixing apparatus by using water vapor as a heat carrier.
In the invention, the specific structure of the heat exchange equipment is not limited, and the heat exchange equipment can be a coil pipe or a coil pipe and the like arranged along the inner wall of the reaction device in a surrounding manner, as long as the heat in the reaction device can be conveyed to the premixing device by taking water vapor as a heat carrier.
In some embodiments of the present invention, in order to recycle the absorbent, the absorption device is further provided with a second absorbent inlet, wherein the second absorbent inlet is connected with the first absorbent outlet.
In the present invention, the second absorbent inlet may be used for feeding fresh absorbent into the absorption apparatus or absorbent circulated back from the premixing apparatus.
In some embodiments of the invention, the inert gas is preferably at least one of a group zero element gas and nitrogen.
In some embodiments of the present invention, the method for producing olefins by oxidative coupling of methane is performed in the above-described system.
According to a preferred embodiment of the present invention, according to fig. 1, methane, oxygen and inert gas are introduced into the premixing device 100 through a methane inlet 101, an oxygen inlet 102 and an inert gas inlet 103, respectively, for premixing, water vapor is discharged from the heat exchange device 203 and introduced into the premixing device 100 through a water vapor inlet 107 to heat the mixed gas, the heated mixed gas is discharged from a mixed gas outlet 106, and then enters the reaction device 200 through a mixed gas inlet 201, and contacts with a catalyst 204 for catalytic reaction, a gas product obtained from the catalytic reaction enters the absorption device 300 through a gas product inlet 301, contacts with an absorbent to absorb methane and water vapor in the gas product, an olefin product obtained by separation exits the absorption device 300 through an olefin outlet 302, and a material containing methane, water vapor and the absorbent exits the absorption device 300 through a second absorbent outlet 303, returns to the premixing device 100 through the first absorbent inlet 104 for regeneration to release methane and water vapor. In addition, the reaction device 200 is also provided with a heat exchange device 203, high-pressure steam (the temperature is 400-; the absorber 300 is further provided with a second absorbent inlet 304, and the methane and water vapor released absorbent exits the premixing device 100 through the second absorbent inlet 304 and is circulated to the absorber 300 through the second absorbent inlet 304. Wherein either fresh absorbent 12 or absorbent 11 recycled from the premixing device may be introduced into the absorption device 300 through the second absorbent inlet 304.
In the invention, the inactive gas has the function of prolonging the spontaneous combustion induction time of methane-oxygen, and the safety valve can be prevented from discharging or exploding due to the problem of overhigh temperature or overlarge pressure after the methane is subjected to oxidative coupling and exploding after water vapor is introduced. After the spontaneous combustion induction time is prolonged, the residence time of methane in the catalyst bed layer can be properly increased, so that the reaction time of methane is further increased, and the conversion rate of methane is improved.
In the invention, the height of the catalyst bed layer can be set according to the feeding rate, the reaction temperature and pressure and the residence time, and the setting principle is that the residence time of the methane-oxygen mixed gas is less than the spontaneous combustion induction time under the temperature and pressure.
A third aspect of the invention provides the use of the above system for the production of olefins.
In the present invention, the unit "mL/(g.h)" is the amount (mL) of the total gas of methane and oxygen used at a time of 1 hour, relative to 1g of the catalyst by mass.
In the present invention, the pressure means gauge pressure.
In the present invention, C2 means at least one of ethylene, ethane and acetylene.
The present invention will be described in detail below by way of examples. In the examples and comparative examples, the reagents used were all commercially available analytical reagents.
Preparation example 1
Catalyst 5 wt% Na2WO42% by weight Mn/SiO2Preparation of
100mL of tetraethoxysilane was measured, heated to 60 ℃ with stirring in an oil bath, and then 5g of Na was added2WO4And 2g of Mn (NO)3)2Respectively adding into the ethyl orthosilicate, adding 20mL of ethanol (the volume ratio of ethanol to water is 2: 1) and 10mL of 20 (volume)% concentrated nitric acid, reacting for 2h, aging for 12h, drying at 120 deg.C for 12h, calcining at 550 deg.C for 4h, and calcining at 850 deg.C for 4 h.
Example 1
Methane, oxygen and an inactive gas are respectively introduced into the buffer tank 100 through a methane inlet 101, an oxygen inlet 102 and an inactive gas inlet 103 for premixing, wherein the feed flow rate of the methane is 100L/h, the feed flow rate of the oxygen is 50L/h, the feed flow rate of the inactive gas is 150L/h, water vapor is discharged from the coil 203 and introduced into the premixing device 100 through a water vapor inlet 107 for heating the mixed gas, the feed flow rate of the water vapor is 200L/h, and the volume percentage of the methane is 20 volume percent. The temperature of the heated mixed gas is 500 ℃, the heated mixed gas is discharged from the mixed gas outlet 106, and then enters the reaction device 200 through the mixed gas inlet 201 to contact with the catalyst 204 for catalytic reaction, the catalyst is the catalyst obtained in the preparation example 1, the loading amount of the catalyst is 10g, the loading height is 0.5m, and the temperature of the catalytic reaction is 750 ℃. The pressure is 0.5MPa, the hourly space velocity of reaction gas calculated by methane and oxygen is 150 mL/(g.h), the reaction time is 80ms, the residence time of premixed gas in a bed layer of the catalyst is 100ms, a gas product obtained by catalytic reaction enters an absorption device 300 through a gas product inlet 301 and contacts with an absorbent 1-butyl-3-methylimidazole bistrifluoromethanesulfonylimide salt to absorb methane and water vapor in the gas product, the absorption temperature is 40 ℃, and the pressure is 1 MPa. The separated olefin product exits the absorber apparatus 300 through the olefin outlet 302 and the feed containing methane, water vapor and absorbent exits the absorber apparatus 300 through the second absorbent outlet 303 and is returned to the premixing apparatus 100 through the first absorbent inlet 104 for regeneration to release methane and water vapor. In addition, high-pressure steam (the temperature is 500 ℃ and the pressure is 14.5MPa) is introduced into the heat exchange equipment 203, the high-pressure steam can heat the reaction device and can transmit heat generated in the reaction device 200 to the high-pressure steam in the heat exchange equipment, the steam is discharged from the heat exchange equipment 203 and then is transmitted to the premixing device 100 through the steam inlet 107, and therefore mixed gas in the premixing device 100 is heated; the absorber 300 is further provided with a second absorbent inlet 304, and the methane and water vapor released absorbent exits the premixing device 100 through the second absorbent inlet 304 and is circulated to the absorber 300 through the second absorbent inlet 304. After the reaction was completed, the reaction product discharged from the olefin outlet 302 was collected.
Example 2
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the absorbent was methyltributylphosphine bis (trifluoromethanesulfonyl) imide salt.
Example 3
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the absorbent was 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide salt.
Example 4
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the feed rate of methane was 150L/h and the feed rate of oxygen was 50L/h.
Example 5
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the feed rate of methane was 200L/h and the feed rate of oxygen was 50L/h.
Example 6
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the temperature of the heated mixed gas was 450 ℃.
Example 7
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the temperature of the heated mixed gas was 475 ℃.
Example 8
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the temperature of the catalytic reaction was 800 ℃ and the pressure was 3.5 MPa.
Example 9
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the temperature of the catalytic reaction was 850 ℃ and the pressure was 5 MPa.
Example 10
The reaction for the oxidative coupling of methane to olefins was carried out as in example 1, except that the absorbent was an imidazole-based ionic liquid, i.e., 1-ethyl, 3-methylimidazole hydrochloride.
Example 11
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that the temperature of the heated mixed gas was 300 ℃.
Comparative example 1
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that no premixing apparatus was provided for the premixing, and that the residence time (600ms) of the reaction mixture gas in the reactor was longer than the spontaneous combustion induction time (500 ms), and that the explosion occurred.
Comparative example 2
The reaction for producing olefins by oxidative coupling of methane was carried out in the same manner as in example 1, except that N was not added2。
Test example 1
The reaction product components obtained in the examples and comparative examples were measured on a gas chromatograph available from Agilent under the model number 7890A. The product is measured by a double detection channel triple valve four-column system, wherein the FID detector is connected with an alumina column and is used for analyzing CH4、C2H6、C2H4、C3H8、C3H6、C4H10、C4H8、CnHmEqual-component TCD detector mainly used for detecting CO and CO2、N2、O2、CH4。
The methane conversion and the like are calculated as follows:
methane conversion ═ amount of methane consumed by the reaction/initial amount of methane × 100%
C2 selectivity-the amount of methane consumed by C2 produced/total consumption of methane × 100%
Ethylene yield-methane conversion x ethylene selectivity x 100%
TABLE 1
Figure BDA0002853001000000131
Figure BDA0002853001000000141
Note: "-" indicates that the explosion occurred in comparative example 1, and no corresponding data was obtained.
As can be seen from the results in Table 1, examples 1-11, which have high methane conversion, C2 selectivity and ethylene yield and no explosion phenomenon, were prepared by oxidative coupling of methane using the method of the present invention, while comparative example 1, which does not have a premixing apparatus and has a residence time longer than the spontaneous combustion induction time, has an explosion phenomenon in the reaction system, and comparative example 2, which does not add N2The conversion rate of methane, the selectivity of C2 and the yield of ethylene obtained by the reaction are all low.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. A method for preparing olefin by oxidative coupling of methane is characterized by comprising the following steps:
(1) premixing methane, oxygen and inactive gas, and heating the premixed mixed gas by using water vapor;
(2) contacting the heated mixed gas with a catalyst to perform catalytic reaction;
(3) contacting the gas product obtained from the catalytic reaction with an absorbent to absorb methane and water vapour in the gas product, and returning the material containing methane, water vapour and absorbent to step (1) for regeneration to release methane and water vapour.
2. The method of claim 1, wherein the method further comprises: conveying heat generated by the catalytic reaction to the heating step to heat the mixed gas;
and/or, the method further comprises: the regenerated absorbent is used in step (3) to contact with the gaseous product to absorb methane and water vapor in the gaseous product.
3. The method according to claim 1 or 2, wherein the heating conditions are such that the temperature of the heated mixed gas is 100-350 ℃ lower than the temperature of the catalytic reaction, preferably the heating conditions are such that the temperature of the heated mixed gas is 450-500 ℃.
4. The method of any of claims 1-3, wherein the non-reactive gas is at least one of a group zero element gas and nitrogen.
5. A process according to any one of claims 1 to 4 wherein the absorbent is an ionic liquid, the anion of which is of formula I and the cation is of formula II or III:
Figure FDA0002853000990000021
wherein in the formula II, R1And R2Are the same or different and are each independently selected from hydrogen or an aliphatic radical of C1-C12;
in the formula III, R1、R2、R3And R4Are the same or different and are each independently selected from hydrogen or C1-C12 aliphatic radicals.
6. The method of any one of claims 1-5, wherein the absorbent is at least one of 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt, methyltributylphosphine bis (trifluoromethanesulfonyl) imide salt, and 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt.
7. The method of any one of claims 1-6, wherein the volumetric flow ratio of methane to oxygen is 1: 0.25-4;
preferably, the volume percentage of the methane is 20-80% after the water vapor is introduced into the mixed gas.
8. The method of any one of claims 1-7, wherein the conditions of the catalytic reaction comprise: the temperature is 600-;
and/or, the conditions of absorption include: the temperature is 50-100 deg.C, preferably 55-80 deg.C, and the pressure is 1-5MPa, preferably 1-2 MPa.
9. A system for preparing olefin by oxidative coupling of methane is characterized by comprising:
the system comprises a premixing device, a gas-liquid separator and a gas-liquid separator, wherein the premixing device is provided with a methane inlet, an oxygen inlet, an inactive gas inlet, a first absorbent outlet, a water vapor inlet and a mixed gas outlet, and can be used for premixing methane, oxygen and inactive gas introduced into the premixing device and heating the premixed mixed gas by introducing water vapor into the premixing device;
the reaction device is filled with a catalyst and is provided with a mixed gas inlet and a gas product outlet, and the mixed gas outlet is connected with the mixed gas inlet so as to send the heated mixed gas into the reaction device;
the absorption device is provided with a gas product inlet, an olefin outlet and a second absorbent outlet, the gas product outlet is connected with the gas product inlet, and the second absorbent outlet is connected with the first absorbent inlet.
10. The system of claim 9, wherein the reaction device is further provided with a heat exchange device capable of transferring heat generated in the reaction device to the premixing device by using steam as a heat carrier;
and/or the absorption device is also provided with a second absorbent inlet, wherein the second absorbent inlet is connected with the first absorbent outlet.
11. The method according to claim 1, wherein the method is performed in a system according to any one of claims 9-10.
12. Use of the system of any one of claims 9-10 for the production of olefins.
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