CN114772551A - Method and system for efficiently utilizing methane-rich gas - Google Patents
Method and system for efficiently utilizing methane-rich gas Download PDFInfo
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Abstract
The invention provides a method and a system for efficiently utilizing methane-rich gas. The invention uses natural gas of oil field and main component methane CH in associated gas4For producing carbon dioxide CO2The raw materials of (2) can solve the problems of CO of carbon dioxide capture, oil displacement and sequestration and the enhanced oil recovery technology CCS-EOR nearby2Source problem, and reduction of CO in the system by using membrane reactor and flameless combustion technology2Difficulty of trapping and trapping cost. Use of membrane reactor for enhanced CH in steam reforming of methane4The conversion rate of (3) is improved2The yield of (2). In addition, nitrogen N generated during air separation2Through an ammonia synthesis process with H2Synthesis of ammonia NH3Product, ammonia NH3The product can be used as chemical raw material, and can also be liquefied into liquid ammonia for long-distance transportation. Liquid ammonia as H2Chemical carrier during long-distance transportation (more than or equal to 200 km) and further solves the problem of H2Long distance (more than or equal to 2)00 km) transportation difficulty.
Description
Technical Field
The invention belongs to the field of energy utilization, and particularly relates to a method and a system for efficiently utilizing methane-rich gas.
Background
The CCS-EOR technology for capturing, displacing and burying carbon dioxide and improving the recovery ratio refers to a technology that carbon dioxide is captured from an industrial or energy production gas source, transported to a proper oil field in a pipeline, a tank truck and the like, and injected into an underground reservoir as an oil displacement medium to improve the recovery ratio, and simultaneously, the carbon dioxide is sealed in the underground. The carbon dioxide has high solubility in crude oil, and when the carbon dioxide is dissolved in the crude oil in a large amount, the volume of the crude oil can be expanded, the viscosity is reduced by 30-80%, and the interfacial tension between oil and water is reduced. The above changes advantageously increase oil recovery speed, improve wash efficiency and collect residual oil. Compared with the traditional steam flooding technology, the carbon dioxide flooding technology has the advantages of wide application range, low flooding cost, obvious recovery ratio improvement and the like.
As one of the technical means for effectively improving the recovery efficiency of crude oil, the EOR technology can generally improve the recovery efficiency of crude oil by 10-15% and prolong the production life of an oil well by 15-20 years. Therefore, the method has higher economic value and has been widely applied at home and abroad. But lack of relatively concentrated CO around the field2The source, if carbon dioxide from coal power, cement, steel and coal chemical industry enterprises is used, the long-distance transportation cost of the carbon dioxide offsets the benefits generated by the technology, which hinders the popularization and application of CCS-EOR.
Chinese invention patent CN 104709876B: the technological process of preparing synthetic gas with zero or negative carbon exhaust system is one methane-rich gas reforming reaction process. The synthesizer generated in the system is mainly directly used for methanol synthesis or Fischer-Tropsch process, so that CO generated in methane steam reforming is used2As raw material gas, with methane CH4Reacting to produce carbon monoxide CO and hydrogen H2. However, this patent fails to provide the CO required for EOR2。
Publication No. CN 113818842 a: an integrated method for high-efficiency exploitation, low-temperature hydrogen production and waste gas utilization of shale gas provides the use of the main component CH of the shale gas4Is subjected to steam reforming to produce H2And CO2. Preparation H2And the reaction by-product CO is removed2And the shale gas is reinjected to the stratum, so that the efficient development of the shale gas is realized. However, no combustion method for combusting shale gas to heat the methane reforming reactor is explicitly proposed in this system. Because the system is not provided with a pure oxygen preparation device, if air is used as a combustion improver, the problem of exhaust gas pollution caused by incomplete combustion of CO and NOx can occur, and in addition, N is mixed2CO capture in tail gas with other inert gases2Greatly increasing the system operating cost.
Disclosure of Invention
Aiming at the problem that the CCS-EOR technology of carbon dioxide trapping, oil displacement, burial and enhanced recovery ratio technology is difficult to popularize due to lack of carbon dioxide gas sources near an oil-gas field, the method adopts a methane autothermal steam reforming and flameless combustion mode to solve the problem of the carbon dioxide sources of the CCS-EOR technology, and simultaneously prepares hydrogen and takes ammonia as a chemical carrier to realize long-distance economic transportation of hydrogen energy. (1) Firstly, separating main components of methane from natural gas and associated gas generated in oil exploitation of an oil-gas field, and catalyzing methane and steam to perform a methane steam reforming reaction by using a nickel-based catalyst at 400-550 ℃ and 0.5-2 MPa to generate carbon dioxide and hydrogen. And (3) using a membrane reactor based on a hydrogen separation membrane to separate high-purity hydrogen in situ while carrying out methane steam reforming reaction, and introducing the residual gas into a carbon dioxide separation system to separate carbon dioxide required by oil displacement. (2) The heat source required by the system is provided by flameless combustion of methane, and high-purity oxygen (more than or equal to 99 percent) used in the flameless combustion process is generated by air cryogenic separation technology or pressure swing adsorption technology. After flameless combustion, only carbon dioxide and water are generated, and high-purity carbon dioxide can be obtained after water is condensed and recovered. (3) The nitrogen generated by air cryogenic separation technology or pressure swing adsorption technology can be combined with the hydrogen generated by methane steam reforming reaction to synthesize ammonia. The ammonia gas as a chemical carrier for hydrogen storage is easy to compress into liquid ammonia and is convenient to transport for a long distance (more than or equal to 200 km).
The technical scheme of the invention is as follows:
the invention firstly provides a method for efficiently utilizing methane-rich gas, which comprises the following steps:
1) the methane is pretreated and then fully mixed with steam to form mixed gas, and the mixed gas enters a methane steam reforming reactor after being preheated to react to generate carbon dioxide, carbon monoxide and hydrogen; the steam methane reforming reactor uses CH4Supplying heat by flameless combustion, wherein a hydrogen separation pipe is arranged in the methane steam reforming reactor, and a hydrogen separation membrane is arranged on the hydrogen separation pipe and is used for separating high-purity hydrogen in situ while carrying out methane steam reforming reaction; hydrogen obtained by separation enters a hydrogen purification and storage process to prepare H2Producing a product;
2) separation of H in a steam methane reforming reactor2The residual carbon dioxide-rich tail gas exchanges heat with liquid water and then enters CO2Purification/liquefaction/storage process; in CO2CO in the purification/liquefaction/storage process2Is separated, purified and liquefied to produce CO2Producing a product;
3）CH4in the flameless combustion process, methane is pretreated and comes from CO2Part of CO of purification/liquefaction/storage process2Premixing, preheating the mixed gas by heat exchange with combustion tail gas generated by flameless combustion, and preheating the preheated mixed gas and O by a nozzle of a combustion chamber2Spraying into a flameless combustion chamber, CH4Producing combustion tail gas CO by flameless combustion2And H2O；CH4The heat generated by the flameless combustion is provided to the methane steam reforming reactor;
4）CH4CO produced in flameless combustion processes2And H2Cooling the mixed gas of O, and then, H2Condensing and recovering O; CO 22Then enter CO2Purification/liquefaction/storage procedures.
As a preferred embodiment of the present invention, said CH4O required for flameless combustion2Is provided by an air cryogenic separation process or an air pressure swing adsorption technology; production of O by air cryogenic separation technology or air pressure swing adsorption technology2In addition, high purity N is produced2，O2And N2The molar ratio of (A) to (B) is 1: 2-2.5; o is2As combustion improver into CH4A flameless combustion process; n is a radical of hydrogen2H separated from hydrogen separation tube2Preparation of ammonia gas NH by ammonia synthesis3Product, remainder N2For purging the apparatus; ammonia gas NH3The product can be used as chemical raw material or H2Chemical carrier when delivered over long distance.
As a preferred embodiment of the present invention, the pretreatment of methane from natural gas produced in oil production from oil and gas fields and methane separated from associated gas includes separation and desulfurization.
As a preferable scheme of the invention, the methane steam reforming reaction adopts a nickel-based catalyst, and the nickel-based catalyst catalyzes methane and steam to generate the methane steam reforming reaction so as to generate carbon dioxide and hydrogen; the reforming reaction temperature of the methane steam is controlled to be 550-600 ℃, and the reaction pressure is 0.5-2 MPa.
As a preferable embodiment of the present invention, CH is contained in a mixed gas of methane and steam4And H2The molar ratio of O is =1: 3-5.
As a preferred embodiment of the present invention, H obtained in the hydrogen purification and storage step2The storage mode of the product can be a high-pressure hydrogen form of 20-70 MPa or a liquid hydrogen form or an ammonia synthesis process to prepare an ammonia product, wherein the ammonia product is used as H2Chemical carrier when transported over a long distance of over 200 km.
As a preferred embodiment of the present invention, said CO2The product is used as carbon dioxide for CCS-EOR.
As a preferable scheme of the invention, in the premixing process in the step 3), CO is controlled2Of the amount of premixing of (A) to cause O in the flameless combustion chamber2The volume percentage concentration of the methane is controlled to be 9-12%, and the volume percentage concentration of the methane is controlled to be 50-60%.
The invention also discloses a system for efficiently utilizing the methane-rich gas by implementing the method, which comprises the following steps:
a first mixing preheater for mixing and preheating of methane and steam; the heat of preheating comes from CH4Heat generated by flameless combustion；
The methane steam reforming reactor is connected with the first mixing preheater and is used for carrying out methane steam reforming reaction, and the methane steam reforming reactor is a tubular reactor and is uniformly distributed on CH4In the flameless combustion chamber, a nickel-based catalyst is filled in the methane steam reforming reactor, and a plurality of hydrogen separation pipes are arranged in the methane steam reforming reactor; the heat of the methane steam reforming reaction is totally from CH4CH of flameless combustion chamber4Heat generated by flameless combustion; the high-purity hydrogen is separated out by the hydrogen separation tube in situ while the methane steam reforming reaction is carried out;
a hydrogen separation device for purifying the hydrogen separated by the hydrogen separation tube in the methane steam reforming reactor to obtain H2Producing a product;
the liquid water heat exchanger is used for recovering the heat of the carbon dioxide-rich tail gas obtained by the methane steam reforming reactor and preparing steam to supply to the first mixing preheater; feeding the cooled tail gas rich in carbon dioxide into CO2A separation device;
CO2separation apparatus for purifying CO2To obtain CO2A product;
a second mixing preheater for mixing and preheating methane and carbon dioxide;
CH4a flameless combustion chamber which uses high-purity oxygen as combustion improver and is used for mixing the mixed gas from the second mixing preheater and the mixed gas from the CO2The separated tail gas of the separation device is subjected to flameless combustion, and the heat generated by the combustion is supplied to a mixing preheater and a methane steam reforming reactor which is uniformly arranged in CH4A flameless combustion chamber; and
cooler for separating CH4CO produced by flameless combustion chamber2And H2O, wherein H is separated off by condensation2O is supplied to the liquid water heat exchanger; CO obtained by separation2Feeding in the CO2And (4) separating equipment.
As a preferable aspect of the present invention, the system further includes: a methane pretreatment device for purifying methane gas and performing desulfurization treatment, the pretreated methane being supplied to the first mixing preheater and the second mixing preheater;
cryogenic air separation or pressure swing air adsorption systems for producing high purity oxygen and high purity nitrogen, wherein the high purity oxygen is used to supply CH4A flameless combustion chamber; the purity of the high-purity oxygen is more than 99 percent, and the purity of the high-purity nitrogen is more than 99 percent.
As a preferable aspect of the present invention, the system further includes: ammonia synthesis system for separating H from hydrogen2The product reacts with high-purity nitrogen obtained by an air cryogenic separation system or an air pressure swing adsorption system to obtain ammonia gas, and the ammonia gas is used as a chemical carrier for long-distance hydrogen transportation.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention uses the main component methane CH in natural gas/associated gas of an oil-gas field4As production of carbon dioxide CO2Raw materials. Nearby ensure CO2CO required for oil displacement2Source of, simultaneously reducing CO2Storage costs and long distance transportation costs.
2) Membrane reactor steam reforming CH4Compared with the traditional methane steam reforming mode, the method can separate high-purity hydrogen H in situ2Not only reduce the subsequent H2Pressure of separation/purification, and increase of CH4The conversion of (2). The mixed gas (containing CO) after hydrogen separation (the separation rate is more than or equal to 90 percent)2，CH4，H2Water vapor) cooling to remove water vapor, wherein CO is contained2The content can reach 70.4%, and the energy consumption and the cost of trapping are low.
3) The heat source required by the system is CH4Flameless combustion is provided, with only CO being produced after flameless combustion2And H2O, condensing and recovering H2Obtaining high-purity CO after O2. Due to no nitrogen N2And other inert gases exist, the combustion temperature is high, and the heat and mass transfer efficiency is high. In addition, the uniform heating characteristic of flameless combustion ensures the efficiency of methane steam reforming and the yield of hydrogen in the tubular membrane reactor.
4. Oxygen O used in methane flameless combustion process2The (more than or equal to 99 percent) is generated by air cryogenic separation technology or pressure swing adsorption technology to produce O2While obtaining high purity N2。N2H produced by reforming methane steam2Synthesis of ammonia NH3。NH3The chemical carrier used as hydrogen storage is easy to compress into liquid ammonia and is convenient for long-distance transportation (more than or equal to 200 km).
Drawings
FIG. 1 is a process flow diagram of the method for efficient utilization of methane-rich gas according to the present invention.
FIG. 2 is a flow chart of the steam methane reforming reaction process of the present invention.
FIG. 3 is a schematic of a flameless combustion chamber of an internal tubular membrane reactor.
FIG. 4 is a schematic of a tubular membrane reactor for steam reforming of methane.
Fig. 5 is a schematic structural view of a methane-rich gas efficient utilization system.
In the figure, a 1-methane steam reforming reactor; 2-a combustor nozzle; 3-hydrogen separation tube.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments. The described embodiments are merely exemplary of the disclosure and are not intended to limit the scope thereof. The technical characteristics of the embodiments of the invention can be correspondingly combined without mutual conflict.
The invention is based on the mode of methane autothermal steam reforming and flameless combustion, and tries to solve the problems of carbon dioxide CO of the CCS-EOR technology of carbon dioxide capture oil displacement and sequestration and the enhanced recovery ratio technology2Problem of origin, simultaneous production of hydrogen H2And with ammonia NH3The hydrogen is used as a chemical carrier of hydrogen to realize long-distance transportation (more than or equal to 200 km).
The technology for producing hydrogen by Steam Reforming of Methane (SMR) is mainly based on the following three reactions. Reaction 1 is a methane steam reforming reaction, reaction 2 is a water-vapor conversion reaction, and reaction 3 integrates reaction 1 and reaction 2. Conventionally, SMR reaction is carried out with nickel fixed thereonCatalyst (e.g. Ni/Si)3N4，Ni/Al2O3，Ni/SiO2，Ni-Co/SiO2Etc.) in a multi-tubular reactor. The reaction temperature is increased to 800-850 ℃, the pressure is controlled to be 1.6-4.1 MPa, and the molar ratio of water to carbon is CH4 : H2O =1: 2-4. Since both reactions 1 and 2 are reversible reactions, limited by the thermodynamic equilibrium, usually CH4The conversion of (A) is only about 78%.
Reaction 1: CH (CH)4 + H2O ⇌ CO + 3H2 ∆H298K = 206 kJ/mol
Reaction 2: CO + H2O ⇌ CO2 + H2 ∆H298K = -41 kJ/mol
Reaction 3: CH (CH)4 + 2H2O ⇌ CO2 + 4H2 ∆H298K = 165 kJ/mol
The present invention relates to a tubular membrane reactor using a hydrogen separation membrane (e.g., carbon membrane, silica membrane, palladium-based composite membrane) for increasing CH4Thereby increasing the conversion of CO2And H2The yield of (2). Because the hydrogen separation membrane has selective permeability to hydrogen, the hydrogen separation membrane can realize the H generated by the reaction2Carrying out in-situ separation to promote the reaction 1 and the reaction 2 to generate H continuously2The reaction is carried out in the direction of (1). Thus greatly improving CH4The transformation of (3).
The present invention provides a heat source using flameless combustion technology. Compared with the traditional air combustion process, the combustion improver is oxygen O2Rather than air. Due to the absence of nitrogen N in the air2And no excess air is introduced. Therefore, the following advantages are provided:
(1) the methane has high combustion efficiency, can be completely combusted, and the CO generated by incomplete combustion is less than 1 ppm. So that combustion as shown in reaction 4 produces only carbon dioxide CO2And water H2And O. At this time, CO2The concentration is high, and the trapping cost is low;
reaction 4: CH (CH)4 + 2O2 → CO2 +2 H2O ∆H298K = -891 kJ/mol。
(2) The flameless combustion can ensure that the temperature of each part in the combustion chamber is consistent, and the tubular membrane reactor in the combustion chamber is heated uniformly, so that the reaction temperature in the tubular membrane reactor is ensured to be uniform. Since the methane steam reforming reaction is a strongly endothermic reaction, the reaction temperature directly affects the reaction rate. The hydrogen can be stably generated only if the reaction temperature is kept uniform. Meanwhile, the hydrogen generation quantity influences the separation speed of the hydrogen separation membrane in the tubular membrane reactor, and when the hydrogen generation quantity is sufficient, the hydrogen partial pressure difference between two sides of the hydrogen separation membrane is maximum, so that the membrane separation efficiency is highest. The uniform heating characteristic of flameless combustion ensures the efficiency of methane steam reforming and the yield of hydrogen in the tubular membrane reactor.
(3) The gas quantity after burning is little, and the temperature is high, and heat transfer efficiency is high. Therefore, the technology not only reduces CO2Trapping cost and reducing system heating fuel CH4In an amount of, i.e. CH4For the total consumption of steam reforming, CH4Increase and further generate more H2。
The heat source required by the system is CH4Flameless combustion provides high purity O for use in flameless combustion processes2The (99 percent or more) is generated by air cryogenic separation technology or pressure swing adsorption technology. In the separation of high purity O2While separating out N2H produced by reforming methane steam2Synthesis of ammonia NH3。NH3As a chemical carrier for storing hydrogen, the existing mature synthesis technology and the mature technology are compressed into liquid ammonia, and the long-distance transportation cost (more than or equal to 200 km) of the liquid ammonia is far lower than that of H2。
As shown in fig. 1 and 2, the embodiment of the present invention provides a method for efficient utilization of methane-rich gas, which includes the following steps as an exemplary but non-limiting alternative implementation method:
(1) methane CH4After pretreatment such as separation/desulfurization, the mixed gas enters a mixer to be fully mixed with water vapor to form mixed gas with the water-carbon molar ratio CH4 : H2O =1: 3-5. And (3) feeding the mixed gas into a preheater, heating to about 550-600 ℃, and feeding the mixed gas into a methane steam reforming reactor. Catalysis in nickel-based catalystsThe reaction temperature is controlled to be 600-750 ℃ and the reaction pressure is 0.5-2 MPa. The mixed gas undergoes a reforming reaction to form carbon dioxide CO2CO and H2。
（2）CH4After pretreatment such as separation/desulfurization, the mixture is firstly mixed with CO2The gases are premixed. The mixed gas and the flue gas generated by flameless combustion carry out heat exchange, and the temperature reaches 500-550 ℃. Combustor nozzle CH4Mixed gas and oxygen O2Into a flameless combustion chamber, in which case O is present in the combustion chamber2The concentration of (2) is controlled to be 9-12%. CH (CH)4After complete combustion, CO is produced2And H2O。CH4The heat generated by the flameless combustion provides the steam reforming reaction of methane. CH (CH)4CO required for flameless combustion premixing2From CO in the system2Separation and purification apparatus, desired O2Is provided by an air cryogenic separation process or an air pressure swing adsorption technology.
(3) H produced by reaction in a steam methane reforming reactor2Separated out through a hydrogen separation pipe in the reactor and enters H2Purification and storage procedure to prepare H2And (5) producing the product. H2The storage mode can be a high-pressure hydrogen form of 20-70 MPa or a liquid hydrogen form.
(4) Separation of H from steam methane reforming reactor2The remaining carbon dioxide-rich CO2The tail gas is subjected to heat exchange with liquid water to be changed into steam of 100-200 ℃, and then enters CO2Purification/liquefaction/storage procedures. CO 22Is separated, purified and liquefied to produce CO2And (5) producing the product. The remaining gas (including CH)4，CO，H2) Into CH4A flameless combustion process, which is completely oxidized to generate CO2And H2O。
（5）CH4CO produced by flameless combustion chamber2/H2The O mixed gas is firstly mixed with CH to be fed into the flameless combustion chamber4/CO2The mixed gas exchanges heat and is then cooled to recover liquid water H2And O. The recovered liquid water can be heated to supplement the steam required for steam reforming of methane. CO 22Then enter into CO2Purification/liquefaction/storage process, CO2Is purified and liquefied to produce CO2And (5) producing the product.
Production of high-purity oxygen O by air cryogenic separation technology or air pressure swing adsorption technology2And high purity nitrogen N2，O2And N2The molar ratio of (A) to (B) is 1: 2 to 2.5. O is2As combustion improver into CH4And (4) a flameless combustion process. N is a radical of2And H2Preparation of ammonia gas NH by ammonia synthesis3，NH3Can be used as chemical raw material and H2Chemical carrier when transporting over long distance (more than or equal to 200 km).
In an alternative embodiment of the present invention, the above process may be used to separate methane from natural gas or oil field associated gas by using pressure swing adsorption separation techniques. Air separation plants use cryogenic air separation technology or pressure swing adsorption separation technology. Selected according to the amount of oxygen or nitrogen used, one of which is more than 3000Nm3H, using cryogenic air separation technology. If both are used in an amount of less than 3000Nm3And/h, using pressure swing adsorption separation technology to reduce cost. The purification and separation of the carbon dioxide uses a cryogenic separation technology or a pressure swing adsorption separation technology. The purification and separation of the hydrogen uses a pressure swing adsorption separation technology. The synthesis of ammonia and the liquefaction of ammonia adopt the traditional mature technology.
As shown in fig. 1-5, in one embodiment of the present invention, a methane-rich gas efficient utilization system is illustrated, comprising: a first mixing preheater, a methane steam reforming reactor 1, a hydrogen separation device, a liquid water heat exchanger, and CO2Separation device, second hybrid preheater, CH4A flameless combustion chamber, a cooler, a methane pretreatment device, an air cryogenic separation system or an air pressure swing adsorption system and an ammonia synthesis system. The following describes the components:
a first mixing preheater for mixing and preheating of methane and steam; the heat of preheating comes from CH4Heat generated by flameless combustion;
a steam methane reforming reactor connected with the first mixing preheater for performingA methane steam reforming reaction, wherein the methane steam reforming reactor is a tubular reactor which is uniformly distributed in CH4In the flameless combustion chamber, in order to make the combustion more uniform, the methane steam reforming reactor 1 and the combustion chamber nozzle 2 are alternately and uniformly arranged (as shown in fig. 3), the methane steam reforming reactor is filled with a nickel-based catalyst, and a plurality of hydrogen separation pipes 3 are arranged in the methane steam reforming reactor; the heat of the methane steam reforming reaction is totally from CH4CH of flameless combustion chamber4Heat generated by flameless combustion; high-purity hydrogen H is separated out in situ by the hydrogen separation tube while the methane steam reforming reaction is carried out2；
A hydrogen separation device for separating hydrogen H obtained by the separation of the hydrogen separation tube in the methane steam reforming reactor2Purifying to obtain H2Producing a product;
the liquid water heat exchanger is used for recovering the heat of the carbon dioxide-rich tail gas obtained by the methane steam reforming reactor and preparing steam to supply to the first mixing preheater; feeding the cooled tail gas rich in carbon dioxide into CO2A separation device;
CO2separation apparatus for purifying CO2To obtain CO2A product;
a second mixing preheater for mixing and preheating methane and carbon dioxide;
wherein the second mixing preheater is premixed with CO2The purpose of (1) includes:
1) will CH4Oxygen O in flameless combustion chamber2The volume percentage concentration of the (C) is controlled to be 9-12%, and the requirement of flameless combustion on low-oxygen reaction (generally lower than 15%) is met.
2) Due to CO2Inert gases not participating in combustion reaction, CO2Homogeneous dilution of CH4And O2And the combustion temperature of each part in the flameless combustion chamber is ensured to be consistent.
3) Using CO2Controlling CH in a combustion chamber4The combustion rate of (2). Prevent the hydrogen separation membrane from being damaged by overhigh temperature.
The purpose of preheating is in order to improve methane flameless combustion's heat utilization efficiency, reduces the consumption of methane when burning.
CH4A flameless combustion chamber which uses high-purity oxygen as combustion improver and is used for mixing the mixed gas from the second mixing preheater and the mixed gas from the CO2The separated tail gas of the separation device is subjected to flameless combustion, and the heat generated by the combustion is supplied to a mixing preheater and a methane steam reforming reactor which is uniformly arranged in CH4A flameless combustion chamber; and
cooler for separating CH4CO produced by flameless combustion chamber2And H2O, wherein H is separated off by condensation2O is supplied to the liquid water heat exchanger; CO obtained by separation2Feeding in the CO2And (4) separating equipment.
A methane pretreatment device for purifying methane gas and performing desulfurization treatment, the pretreated methane being supplied to the first mixing preheater and the second mixing preheater;
cryogenic air separation or pressure swing air adsorption systems for producing high purity oxygen and high purity nitrogen, wherein the high purity oxygen is used to supply CH4A flameless combustion chamber; the purity of the high-purity oxygen is more than 99 percent, and the purity of the high-purity nitrogen is more than 99 percent.
Ammonia synthesis system for separating H from hydrogen2The product reacts with high-purity nitrogen obtained by an air cryogenic separation system or an air pressure swing adsorption system to obtain ammonia gas, and the ammonia gas is used as a chemical carrier for long-distance hydrogen transportation.
The present invention will be further described with reference to the following embodiments.
When the system is in steady operation, methane CH is consumed per hour4449.9 kg in total, 400.0 kg of CH4Reacting with 1350.0 kg of water vapor (not less than 150 ℃) in a steam reforming membrane reactor at the reaction temperature of 500 ℃ and the pressure of 0.5 MPa. CH (CH)4Has a conversion of 98.1%, i.e. 392.0 kg CH4Conversion to carbon dioxide CO2Carbon monoxide CO and hydrogen H2. Hydrogen is selected from the reactor of separating of palladium-based composite membrane in the membrane reactor of steam reformingSeparating out H with purity higher than 99.99%2 175.6 kg，H2The separation rate was 90%. Unseparated H2With rich CO2The tail gas exchanges heat with liquid water to prepare steam at the temperature of 100-200 ℃, and then the steam enters CO2And (4) separating equipment. 1036.4 kg of CO were separated off2Then, the residual gas (including CO and H)2 & CH4) Entering a flameless combustion process and mixing with 49.9 kg of CH4And sufficient pure oxygen to recover CO after complete combustion2And H2O, the heat generated provides for the use of steam reforming of methane. CO produced by flameless combustion2And H2The O is cooled by heat exchange, and 305.9 kg of H is recovered2O, 176.2 kg of CO remaining2Into CO2And (4) separating the devices. Pure oxygen O for flameless combustion2Is provided by air pressure swing adsorption separation equipment, and at the same time, the equipment also provides pure nitrogen N2Generation of O2/N2The molar ratio is 1: 2.5. n is a radical of2And H2The reaction may produce about 994.9 kg of ammonia NH3. To sum up, CH is added every hour after the system is stably operated4The consumption of (2) was 449.9 kg, and 1212.6 kg of CO was trapped2And 994.9 kg of NH were produced3And the comprehensive heat efficiency is about 75 percent.
When the system is operating steadily, methane CH is consumed per hour41442.3 kg in total, of which 1280.0 kg of CH4Reacting with 3850.0 kg of water vapor (not less than 150 ℃) in a steam reforming membrane reactor at the reaction temperature of 500 ℃ and the pressure of 0.5 MPa. CH (CH)4Has a conversion of 98.9%, i.e. 1254.4 kg CH4Conversion to carbon dioxide CO2Carbon monoxide CO and hydrogen H2. Hydrogen is selectively separated out of the reactor by a palladium-based composite membrane in a steam reforming membrane reactor, and H with the purity higher than 99.99 percent is separated out2 562.9 kg，H2The separation rate was 90%. Unseparated H2With rich CO2The tail gas exchanges heat with liquid water to prepare steam with the temperature of 100-200 ℃, and then the steam enters CO2And (4) separating equipment. 3377.6 kg of CO were separated off2Then, the residual gas (including CO and H)2 & CH4) Entering a flameless combustion process and mixing 179.0 kg of CH4And sufficient pure oxygen to recover CO after complete combustion2And H2O, the heat generated provides for the steam reforming of methane. CO produced by flameless combustion2And H2The O is cooled by heat exchange, and 978.9 kg of H is recovered2O, remainder 524.8 kg CO2Into CO2And (4) separating the devices. Pure oxygen O for flameless combustion2Is provided by air pressure swing adsorption separation equipment, and at the same time, the equipment also provides pure nitrogen N2Generation of O2/N2The molar ratio is 1: 2.5. n is a radical of2And H2About 3189.9 kg of ammonia NH can be prepared by the reaction3. In summary, CH is added every hour after the system is stably operated4The consumption of (2) was 1442.3 kg, and 3902.4 kg of CO was trapped2And 3189.9 kg of NH were produced3The comprehensive thermal efficiency is about 77%.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit of the invention, and these are within the scope of the invention.
Claims (10)
1. A method for efficiently utilizing methane-rich gas is characterized by comprising the following steps:
1) the methane is pretreated and then fully mixed with steam to form mixed gas, and the mixed gas enters a methane steam reforming reactor after being preheated to react to generate carbon dioxide, carbon monoxide and hydrogen; the steam methane reforming reactor uses CH4Supplying heat by flameless combustion, wherein a hydrogen separation pipe is arranged in the methane steam reforming reactor, and a hydrogen separation membrane is arranged on the hydrogen separation pipe and is used for separating high-purity hydrogen in situ during the methane steam reforming reaction; the hydrogen obtained by separation enters a hydrogen purification and storage process to prepare H2A product;
2) separation of H from steam methane reforming reactor2The residual carbon dioxide-rich tail gas exchanges heat with liquid water and then enters CO2Purification ofA liquefaction/storage procedure; in CO2CO in the purification/liquefaction/storage process2Is separated, purified and liquefied to produce CO2Producing a product;
3）CH4in the flameless combustion process, the methane is pretreated and comes from CO2CO part of purification/liquefaction/storage process2Premixing, preheating the mixed gas by heat exchange with combustion tail gas generated by flameless combustion, and preheating the preheated mixed gas and O by a nozzle of a combustion chamber2Spraying into a flameless combustion chamber, CH4Flameless combustion to produce combustion tail gas CO2And H2O；CH4The heat generated by the flameless combustion is provided to the methane steam reforming reactor;
4）CH4CO produced by flameless combustion processes2And H2Cooling the mixed gas of O, and then obtaining H2Condensing and recovering O; CO 22Then enter CO2Purification/liquefaction/storage procedures.
2. The method for efficient utilization of methane-rich gas as recited in claim 1 wherein said CH4O required for flameless combustion2Is provided by an air cryogenic separation process or an air pressure swing adsorption technology; production of O by air cryogenic separation technology or air pressure swing adsorption technology2In addition, high purity N is produced2，O2And N2The molar ratio of (A) to (B) is 1: 2-2.5; o is2As combustion improver into CH4A flameless combustion process; n is a radical of hydrogen2H separated from hydrogen separation tube2Preparation of ammonia gas NH by ammonia synthesis3Product, remainder N2For purging the apparatus; ammonia gas NH3The product can be used as chemical raw material or H2Chemical carrier when transporting over long distance.
3. The method for the efficient utilization of the methane-rich gas according to claim 1, wherein the pretreatment of the methane comprises separation and desulfurization, wherein the methane is derived from natural gas generated in oil production of oil and gas fields and methane separated from associated gas; said CO2Use of the product as dioxide for CCS-EORCarbon.
4. The method for efficiently utilizing the methane-rich gas according to claim 1, wherein the steam methane reforming reaction is performed by using a nickel-based catalyst, and the nickel-based catalyst catalyzes methane and steam to perform the steam methane reforming reaction, so as to generate carbon dioxide and hydrogen; the reforming reaction temperature of the methane steam is controlled to be 550-600 ℃, and the reaction pressure is 0.5-2 MPa.
5. The method for efficiently utilizing a methane-rich gas according to claim 1, wherein CH is contained in a mixed gas of methane and steam4And H2The molar ratio of O is =1: 3-5.
6. The method for efficiently utilizing a methane-rich gas according to claim 1, wherein the H obtained in the hydrogen purification and storage step2The storage mode of the product is a high-pressure hydrogen form of 20-70 MPa or a liquid hydrogen form or an ammonia synthesis process to prepare an ammonia product, wherein the ammonia product is used as H2Chemical carrier when transported over a long distance of over 200 km.
7. The method for high efficiency utilization of methane-rich gas as claimed in claim 1, wherein during the premixing in step 3), CO is controlled2In such an amount that O is present in the flameless combustion chamber2The volume percentage concentration of the methane is controlled to be 9-12%, and the volume percentage concentration of the methane is controlled to be 50-60%.
8. A system for efficiently utilizing a methane-rich gas by carrying out the method according to any one of claims 1 to 7, comprising:
a first mixing preheater for mixing and preheating of methane and steam; the heat of preheating comes from CH4Heat generated by flameless combustion;
a methane steam reforming reactor connected with the first mixing preheater and used for performing methane steam reforming reaction, wherein the methane steam reforming reactor is a tubular type reverse reactorReactors, which are uniformly arranged in CH4In the flameless combustion chamber, a nickel-based catalyst is filled in the methane steam reforming reactor, and a plurality of hydrogen separation pipes are arranged in the methane steam reforming reactor; the heat of the methane steam reforming reaction is totally from CH4CH of flameless combustion chamber4Heat generated by flameless combustion; during the methane steam reforming reaction, the hydrogen separation pipe separates high-purity hydrogen in situ;
a hydrogen separation device for purifying the hydrogen separated by the hydrogen separation tube in the methane steam reforming reactor to obtain H2A product;
the liquid water heat exchanger is used for recovering the heat of the carbon dioxide-rich tail gas obtained by the methane steam reforming reactor and preparing steam to supply to the first mixing preheater; feeding the cooled tail gas rich in carbon dioxide into CO2A separation device;
CO2separation apparatus for purifying CO2To obtain CO2Producing a product;
a second mixing preheater for mixing and preheating methane and carbon dioxide;
CH4a flameless combustion chamber which uses high-purity oxygen as a combustion improver and is used for mixing the mixed gas from the second mixing preheater and the mixed gas from the CO2The separated tail gas of the separation device is subjected to flameless combustion, and the heat generated by the combustion is supplied to the mixing preheater and the methane steam reforming reactor which is uniformly arranged in CH4A flameless combustion chamber; and
cooler for separating CH4CO produced by flameless combustion chamber2And H2O, wherein H is separated off by condensation2O feed liquid water heat exchanger; CO obtained by separation2Feeding the CO2And (4) separating equipment.
9. The methane-rich gas efficient utilization system according to claim 8, further comprising:
a methane pretreatment device for purifying methane gas and performing desulfurization treatment, wherein the pretreated methane is supplied to a first mixing preheater and a second mixing preheater;
air cryogenic separation system or air pressure swing adsorption system for producing high purity oxygen and high purity nitrogen, wherein the high purity oxygen is used to supply CH4A flameless combustion chamber; the purity of the high-purity oxygen is more than 99%, and the purity of the high-purity nitrogen is more than 99%.
10. The methane-rich gas efficient utilization system according to claim 9, further comprising:
ammonia synthesis system for separating H from hydrogen2The product reacts with high-purity nitrogen obtained by an air cryogenic separation system or an air pressure swing adsorption system to obtain ammonia gas, and the ammonia gas is used as a chemical carrier for long-distance hydrogen transportation.
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