CN114772551B - 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 a methane-rich gas. Book (I)The invention uses natural gas of oil field and main component methane CH in associated gas 4 For producing carbon dioxide CO 2 The raw materials of (2) solve the problems of CO of carbon dioxide capture oil displacement and sequestration and the enhanced recovery ratio technology CCS-EOR nearby 2 Source problem, and reduction of CO in the system by using membrane reactor and flameless combustion technology 2 Difficulty of trapping and trapping cost. Use of membrane reactor for enhanced CH in steam reforming of methane 4 The conversion rate of (3) is improved 2 The yield of (2). In addition, nitrogen N generated during air separation 2 Through an ammonia synthesis process with H 2 Synthesis of ammonia NH 3 Product, ammonia NH 3 The product can be used as chemical raw material, and can also be liquefied into liquid ammonia for long-distance transportation. Liquid ammonia as H 2 Chemical carrier during long-distance transportation (more than or equal to 200 km) and further solves the problem of H 2 The problem of difficult long-distance (more than or equal to 200 km) transportation.
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.
EOR (oil-out-of-oil) technology as technology for effectively improving recovery efficiency of crude oilOne of the means is that the recovery ratio of crude oil can be generally increased by 10-15%, and the production life of an oil well can be prolonged 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 field 2 The 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 used 2 As raw material gas, with methane CH 4 React to produce carbon monoxide CO and hydrogen H 2 . However, this patent fails to provide the CO required for EOR 2 。
Publication No. CN 113818842A: 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 gas 4 Is subjected to steam reforming to produce H 2 And CO 2 . Preparation of H 2 And the reaction by-product CO is removed 2 And the shale gas is reinjected to the stratum, so that the efficient development of the shale gas is realized. However, no specific reference is made to combustion methods for burning shale gas to heat a methane reforming reactor. 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 mixed 2 CO capture in tail gas with other inert gases 2 Greatly 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 generate methane steam reforming reaction by using a nickel-based catalyst at the temperature of 400-550 ℃ and under the pressure of 0.5-2MPa to generate carbon dioxide and hydrogen. And (3) separating high-purity hydrogen in situ while performing methane steam reforming reaction by using a membrane reactor based on a hydrogen separation membrane, and separating carbon dioxide required for oil displacement by introducing residual gas into a carbon dioxide separation system. (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 synthesized into ammonia gas with the hydrogen generated by methane steam reforming reaction. 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 CH 4 Supplying 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; hydrogen obtained by separation enters a hydrogen purification and storage process to prepare H 2 A product;
2) Separation of H from steam methane reforming reactor 2 The residual carbon dioxide-rich tail gas exchanges heat with liquid water and then enters CO 2 Purification/liquefaction/storage process; in CO 2 In the purification/liquefaction/storage process, CO 2 Is separated, purified and liquefied to produce CO 2 Producing a product;
3）CH 4 in the flameless combustion process, the methane is pretreated and comes from CO 2 CO part of purification/liquefaction/storage process 2 Premixing, 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 combustion chamber nozzle 2 Into a flameless combustion chamber, CH 4 Flameless combustion to produce combustion tail gas CO 2 And H 2 O；CH 4 The heat generated by the flameless combustion is provided to the methane steam reforming reactor;
4）CH 4 CO produced in flameless combustion processes 2 And H 2 Cooling the mixed gas of O, and then obtaining H 2 Condensing and recycling O; CO 2 2 Then enter CO 2 Purification/liquefaction/storage procedures.
As a preferable embodiment of the present invention, said CH 4 O required for flameless combustion 2 Is 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 technology 2 In addition, high purity N is produced 2 ，O 2 And N 2 The molar ratio of (A) to (B) is 1:2 to 2.5; o is 2 As combustion improver into CH 4 A flameless combustion process; n is a radical of 2 H separated from hydrogen separation tube 2 Preparation of ammonia gas NH by ammonia synthesis 3 Product, remainder N 2 For purging the apparatus; ammonia NH 3 The product can be used as chemical raw material or as H 2 Chemical carrier when transporting over long distance.
As a preferred embodiment of the present invention, the pretreatment of methane from natural gas produced during oil production in 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 temperature of the methane steam reforming reaction is controlled to be 550-600 ℃, and the reaction pressure is 0.5-2Mpa.
As a preferable embodiment of the present invention, methane and waterIn a mixture of steam, CH 4 And H 2 The molar ratio of O =1 to 5.
As a preferred embodiment of the present invention, H obtained in the hydrogen purification and storage step 2 The storage mode of the product can be a high-pressure hydrogen form of 20-70MPa or a liquid hydrogen form or an ammonia synthesis procedure to prepare an ammonia product, wherein the ammonia product is used as H 2 Chemical carrier when transported over a long distance of over 200 km.
As a preferred embodiment of the present invention, said CO 2 The 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 controlled 2 In such an amount that O is present in the flameless combustion chamber 2 The volume percentage concentration of the methane is controlled to be 9 to 12 percent, and the volume percentage concentration of the methane is controlled to be 50 to 60 percent.
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 CH 4 Heat generated by flameless combustion;
a methane steam reforming reactor connected with the first mixing preheater for performing a methane steam reforming reaction, wherein the methane steam reforming reactor is a tubular reactor and is uniformly arranged on CH 4 In 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 CH 4 CH of flameless combustion chamber 4 Heat 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 H 2 Producing a product;
a liquid water heat exchanger for recovering heat of the carbon dioxide rich tail gas obtained from the methane steam reforming reactor and preparing steam to supply to the first mixing deviceCombining a preheater; feeding the cooled tail gas rich in carbon dioxide into CO 2 A separation device;
CO 2 separation apparatus for purifying CO 2 To obtain CO 2 Producing a product;
a second mixing preheater for mixing and preheating methane and carbon dioxide;
CH 4 a 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 CO 2 The 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 CH 4 A flameless combustion chamber; and
cooler for separating CH 4 CO produced by flameless combustion chamber 2 And H 2 O, wherein H is separated off by condensation 2 O feed liquid water heat exchanger; CO obtained by separation 2 Feeding in the CO 2 And (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, 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 CH 4 A 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 hydrogen 2 The 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 C in natural gas/associated gas of oil and gas fieldsH 4 As CO production 2 Raw materials. Nearby ensure CO 2 CO required for oil displacement 2 Source of, simultaneously reducing CO 2 Storage costs and long distance transportation costs.
2) Membrane reactor steam reforming CH 4 Compared with the traditional methane steam reforming mode, the method can separate high-purity hydrogen H in situ 2 Not only reduce the subsequent H 2 Pressure of separation/purification, and increase of CH 4 The conversion of (2). The mixed gas (containing CO) after hydrogen separation (the separation rate is more than or equal to 90 percent) 2 ，CH 4 ，H 2 Water vapor) cooling to remove water vapor, wherein CO is contained 2 The content can reach 70.4%, and the trapping energy consumption and cost are low.
3) The heat source required by the system is CH 4 Flameless combustion is provided, with only CO being produced after flameless combustion 2 And H 2 O, condensation of H 2 Obtaining high-purity CO after O 2 . Due to no nitrogen N 2 And 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 process 2 The (more than or equal to 99 percent) is generated by air cryogenic separation technology or pressure swing adsorption technology to produce O 2 While obtaining high purity N 2 。N 2 H produced by reforming reaction with methane steam 2 Synthesis of ammonia NH 3 。NH 3 The chemical carrier used as hydrogen storage is easy to compress into liquid ammonia and is convenient for long-distance (more than or equal to 200 km) transportation.
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 features of the embodiments of the present invention can be combined correspondingly 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 technology 2 Problem of origin while producing hydrogen H 2 And with ammonia NH 3 The 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. The reaction 1 is a methane steam reforming reaction, the reaction 2 is a water-vapor conversion reaction, and the reaction 3 integrates the reaction 1 and the reaction 2. Conventionally, SMR reactions have been carried out on immobilized nickel catalysts (e.g., ni/Si) 3 N 4 ，Ni/Al 2 O 3 ，Ni/SiO 2 ，Ni-Co/SiO 2 Etc.) in a multi-tubular reactor. The reaction temperature is increased to 800 to 850 ℃, the pressure is controlled to be 1.6 to 4.1MPa, and the molar ratio of water to carbon is CH 4 : H 2 O =1: 2 to 4. Since both reactions 1 and 2 are reversible reactions, limited by the thermodynamic equilibrium, usually CH 4 The conversion of (A) is only about 78%.
Reaction 1: CH (CH) 4 + H 2 O ⇌ CO + 3H 2 ∆H 298K = 206 kJ/mol
Reaction 2: CO + H 2 O ⇌ CO 2 + H 2 ∆H 298K = -41 kJ/mol
Reaction 3: CH (CH) 4 + 2H 2 O ⇌ CO 2 + 4H 2 ∆H 298K = 165 kJ/mol
The invention uses a hydrogen separation membrane (E.g., carbon, silica, palladium-based composite membranes) tubular membrane reactors to increase CH 4 Thereby increasing CO 2 And H 2 The yield of (2). Because the hydrogen separation membrane has selective permeability to hydrogen, the hydrogen separation membrane can realize the H generated by the reaction 2 Carrying out in-situ separation to promote the reaction 1 and the reaction 2 to generate H continuously 2 The reaction is carried out in the direction of (1). Thus greatly improving CH 4 The 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 O 2 Rather than air. Due to the absence of nitrogen N in the air 2 And 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 1ppm. So that combustion as shown in reaction 4 produces only carbon dioxide CO 2 And water H 2 And O. At this time, CO 2 The concentration is high, and the trapping cost is low;
reaction 4: CH (CH) 4 + 2O 2 → CO 2 +2 H 2 O ∆H 298K = -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 amount influences the separation rate of the hydrogen separation membrane in the tubular membrane reactor, the hydrogen partial pressure difference between the two sides of the hydrogen separation membrane is the largest when the hydrogen generation amount is sufficient, and the membrane separation efficiency is the highest at the moment. 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 CO 2 Trapping costs, and also reducing system heating fuel CH 4 In the amount of (i) CH 4 For steam reforming without total consumptionComplete CH 4 Increase and further generate more H 2 。
The heat source required by the system is CH 4 Flameless combustion provides high purity O for use in flameless combustion processes 2 The (99 percent or more) is generated by air cryogenic separation technology or pressure swing adsorption technology. In the separation of high purity O 2 While separating out N 2 H produced by reforming methane steam 2 Synthesis of ammonia NH 3 。NH 3 As 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 H 2 。
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 CH 4 After pretreatment such as separation/desulfurization, the mixture enters a mixer and is fully mixed with steam to form mixed gas with the water-carbon molar ratio CH 4 : H 2 O =1, 3 to 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. Under the catalysis of a nickel-based catalyst, the reaction temperature is controlled to be 600 to 750 ℃, and the reaction pressure is 0.5MPa to 2MPa. The mixed gas undergoes a reforming reaction to form carbon dioxide CO 2 Carbon monoxide CO and hydrogen H 2 。
（2）CH 4 After pretreatment such as separation/desulfurization, the mixture is firstly mixed with CO 2 The gases are premixed. The mixed gas and the smoke generated by flameless combustion carry out heat exchange, and the temperature reaches 500 to 550 ℃. Combustor nozzle CH 4 Mixed gas and oxygen O 2 Into a flameless combustion chamber, when O in the combustion chamber 2 The concentration of (B) is controlled to be 9 to 12 percent. CH (CH) 4 After complete combustion, CO is produced 2 And H 2 O。CH 4 The heat generated by the flameless combustion provides the steam reforming reaction of methane. CH (CH) 4 CO required for flameless combustion premixing 2 From CO in the system 2 Separation and purification apparatus, desired O 2 By cryogenic separation of air or by pressure swing of airProviding an adsorption technology.
(3) H produced by reaction in a steam methane reforming reactor 2 Separated out through a hydrogen separation pipe in the reactor and enters H 2 Purification and storage procedure to prepare H 2 And (5) producing the product. H 2 The storage mode can be a high-pressure hydrogen form of 20 to 70MPa or a liquid hydrogen form.
(4) Separation of H from steam methane reforming reactor 2 The remaining carbon dioxide-rich CO 2 Exchanging heat between the tail gas and liquid water to change the tail gas into water vapor at 100 to 200 ℃, and introducing the water vapor into CO 2 Purification/liquefaction/storage procedures. CO 2 2 Is separated, purified and liquefied to produce CO 2 And (5) producing the product. The remaining gas (including CH) 4 ，CO，H 2 ) Into CH 4 A flameless combustion process, which is completely oxidized to generate CO 2 And H 2 O。
（5）CH 4 CO produced by flameless combustion chamber 2 /H 2 The O mixed gas is firstly mixed with CH to be fed into the flameless combustion chamber 4 /CO 2 Exchanging heat of the mixed gas, then cooling and recovering liquid water H 2 And (O). The recovered liquid water can be heated to supplement the steam required for steam reforming of methane. CO 2 2 Then enter CO 2 Purification/liquefaction/storage process, CO 2 Is purified and liquefied to produce CO 2 And (5) producing the product.
Production of high-purity oxygen O by air cryogenic separation technology or air pressure swing adsorption technology 2 And high purity nitrogen N 2 ，O 2 And N 2 The molar ratio of (A) to (B) is 1:2 to 2.5.O is 2 As combustion improver into CH 4 And (4) a flameless combustion process. N is a radical of 2 And H 2 Preparation of ammonia gas NH by ammonia synthesis 3 ，NH 3 Can be used as chemical raw material and H 2 Chemical carrier when transporting over long distance (more than or equal to 200 km).
In an alternative embodiment of the present invention, the process described above, the methane may be separated from the natural gas or associated gas from the oil field by using pressure swing adsorption separation techniques. The air separation plant uses cryogenic separation of air or pressure swing adsorption separation. According to the amount of oxygen or nitrogen usedOne of the gases used in an amount exceeding 3000Nm 3 H, using cryogenic air separation technology. If both are used in an amount of less than 3000Nm 3 And/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.
In one embodiment of the present invention, as shown in fig. 1-5, 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 CO 2 Separation equipment, second hybrid preheater and CH 4 A 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 CH 4 Heat 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 CH 4 In the flameless combustion chamber, in order to make the combustion more uniform, the methane steam reforming reactor 1 and the combustion chamber nozzles 2 are arranged alternately and uniformly (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 CH 4 CH of flameless combustion chamber 4 Heat 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 out 2 ；
A hydrogen separation device for separating hydrogen H obtained by the separation of the hydrogen separation tube in the methane steam reforming reactor 2 Purifying to obtain H 2 Producing a product;
liquid water heat exchanger for recoveryThe heat of the carbon dioxide-rich tail gas obtained by the methane steam reforming reactor is used for preparing steam and supplying the steam to the first mixing preheater; feeding the cooled tail gas rich in carbon dioxide into CO 2 A separation device;
CO 2 separation apparatus for purifying CO 2 To obtain CO 2 A product;
a second mixing preheater for mixing and preheating methane and carbon dioxide;
wherein the second mixing preheater is premixed with CO 2 The purpose of (1) includes:
1) Will CH 4 Oxygen O in flameless combustion chamber 2 The volume percentage concentration of the (C) is controlled to be 9 to 12 percent, and the requirement of the flameless combustion on the low-oxygen reaction is met (generally lower than 15 percent).
2) Due to CO 2 Inert gases not participating in combustion reaction, CO 2 Homogeneous dilution of CH 4 And O 2 And the combustion temperature of each part in the flameless combustion chamber is ensured to be consistent.
3) Using CO 2 Controlling CH in a combustion chamber 4 The combustion rate of (2). Prevent the hydrogen separation membrane from being damaged by overhigh temperature.
The preheating aims to improve the heat utilization efficiency of methane flameless combustion and reduce the consumption of methane during combustion.
CH 4 A 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 CO 2 The 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 CH 4 A flameless combustion chamber; and
cooler for separating CH 4 CO produced by flameless combustion chamber 2 And H 2 O, wherein H is separated off by condensation 2 O is supplied to the liquid water heat exchanger; CO obtained by separation 2 Feeding the CO 2 And (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;
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 CH 4 A 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%.
Ammonia synthesis system for separating H from hydrogen 2 The 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 operating steadily, methane CH is consumed per hour 4 449.9 kg total, 400.0 kg CH 4 And 1350.0 kg of water vapor (not less than 150 ℃) are fed into the steam reforming membrane reactor to react, the reaction temperature is 500 ℃, and the pressure is 0.5 MPa. CH (CH) 4 Conversion of (2) was 98.1%, i.e. 392.0 kg CH 4 Conversion to carbon dioxide CO 2 Carbon monoxide CO and hydrogen H 2 . 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 out 2 175.6 kg，H 2 The separation rate was 90%. Unseparated H 2 With rich CO 2 The tail gas exchanges heat with liquid water to prepare water vapor with the temperature of 100 to 200 ℃, and then the water vapor enters CO 2 And (4) separating equipment. 1036.4 kg CO were separated 2 Then, the residual gas (including CO and H) 2 & CH 4 ) Entering a flameless combustion process and mixing with 49.9 kg of CH 4 And sufficient pure oxygen to recover CO after complete combustion 2 And H 2 O, the heat generated provides for the use of steam reforming of methane. CO produced by flameless combustion 2 And H 2 The O is cooled through heat exchange, and 305.9 kg of H is recycled 2 O, remaining 176.2 kg CO 2 Into CO 2 And (4) separating equipment. Pure oxygen O for flameless combustion 2 Is provided by air pressure swing adsorption separation equipment, and at the same time, the equipment also provides pure nitrogen N 2 Produced byO 2 /N 2 The molar ratio is 1:2.5.n is a radical of 2 And H 2 About 994.9 kg of ammonia NH can be prepared by the reaction 3 . To sum up, CH is added every hour after the system is stably operated 4 The consumption of (2) was 449.9 kg, and 1212.6 kg of CO was captured 2 And produce 994.9 kg of NH 3 The comprehensive thermal efficiency is about 75 percent.
When the system is in steady operation, methane CH is consumed per hour 4 1442.3 kg in total, wherein 1280.0 kg of CH 4 And 3850.0 kg of water vapor (not less than 150 ℃) enters the steam reforming membrane reactor to react, the reaction temperature is 500 ℃, and the pressure is 0.5 MPa. CH (CH) 4 Has a conversion of 98.9%, i.e. 1254.4 kg CH 4 Conversion to carbon dioxide CO 2 Carbon monoxide CO and hydrogen H 2 . 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 out 2 562.9 kg，H 2 The separation rate was 90%. Unseparated H 2 With rich CO 2 The tail gas exchanges heat with liquid water to prepare water vapor with the temperature of 100 to 200 ℃, and then the water vapor enters CO 2 And (4) separating equipment. 3377.6 kg of CO were separated off 2 Then, the residual gas (including CO and H) 2 & CH 4 ) Entering a flameless combustion process and mixing 179.0 kg of CH 4 And sufficient pure oxygen to recover CO after complete combustion 2 And H 2 O, the heat generated provides for the use of steam reforming of methane. CO produced by flameless combustion 2 And H 2 The O is cooled by heat exchange, and 978.9 kg of H is recovered 2 O, remainder 524.8 kg CO 2 Into CO 2 And (4) separating the devices. Pure oxygen O for flameless combustion 2 Is provided by air pressure swing adsorption separation equipment, and simultaneously the equipment also provides pure nitrogen N 2 Generation of O 2 /N 2 The molar ratio is 1:2.5.n is a radical of 2 And H 2 About 3189.9 kg of ammonia NH can be prepared by the reaction 3 . To sum up, CH is added every hour after the system is stably operated 4 The consumption of (2) was 1442.3 kg and 3902.4 kg of CO were captured 2 And produced 3189.9 kg of NH 3 The 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 without departing from the spirit and scope of the invention.
Claims (7)
1. A method for efficiently utilizing methane-rich gas is characterized by comprising the following steps:
the methane is fully mixed with the steam after being pretreated to form mixed gas, and the mixed gas enters a methane steam reforming reactor after being preheated; preheating the mixed gas to 550-600 ℃; under the catalytic action of a nickel-based catalyst, the reaction temperature is controlled to be 600 to 750 ℃, and the reaction pressure is 0.5MPa to 2MP a; the methane steam reforming reactor is a tubular reactor which is uniformly distributed in CH 4 In the flameless combustion chamber, the methane steam reforming reactor and the combustion chamber nozzle are alternately and uniformly arranged; the mixed gas is subjected to reforming reaction to generate carbon dioxide, carbon monoxide and hydrogen; the steam methane reforming reactor uses CH 4 The heat is supplied by flameless combustion, and the heat of the methane steam reforming reaction is totally derived from CH 4 CH of flameless combustion chamber 4 Heat generated by flameless combustion; 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 H 2 Producing a product;
separation of H from steam methane reforming reactor 2 The residual tail gas rich in carbon dioxide firstly exchanges heat with liquid water to prepare steam with the temperature of 100-200 ℃, and then enters CO 2 Purification/liquefaction/storage process; in CO 2 In the purification/liquefaction/storage process, CO 2 Is separated, purified and liquefied to produce CO 2 Product, residual gas into CH 4 The flameless combustion process is carried out with complete oxidation treatment;
CH 4 in the flameless combustion process, the methane is pretreated and then mixed with the methaneFrom CO 2 Part of CO of purification/liquefaction/storage process 2 Premixing, performing heat exchange between the mixed gas and smoke generated by flameless combustion at the temperature of 500-550 ℃, and using a nozzle of a combustion chamber to preheat the mixed gas and oxygen O 2 Injecting into flameless combustion chamber, and controlling CO 2 In such an amount that O is present in the flameless combustion chamber 2 The volume percentage concentration of the methane is controlled to be 9 to 12 percent, and the volume percentage concentration of the methane is controlled to be 50 to 60 percent; CH (CH) 4 Flameless combustion to produce CO 2 And H 2 O；CH 4 The heat generated by the flameless combustion is provided for the methane steam reforming reactor for the methane steam reforming reaction; CH (CH) 4 O required for flameless combustion 2 Is provided by air cryogenic separation technology or air pressure swing adsorption technology;
CH 4 CO produced by flameless combustion processes 2 And H 2 Cooling the mixed gas of O, and then, H 2 Condensing and recovering O, and using the O as a raw material for exchanging heat with the carbon dioxide-rich tail gas to generate steam; CO 2 2 Then enter CO 2 Purification/liquefaction/storage procedure, CO 2 Is separated, purified and liquefied to produce CO 2 Producing a product;
the pretreatment of methane comprises separation and desulfurization, wherein the methane is from natural gas generated in oil exploitation of oil and gas fields and methane separated from associated gas; said CO 2 The product is used as carbon dioxide for CCS-EOR.
2. The method for high efficiency utilization of methane-rich gas according to claim 1, characterized in that said cryogenic air separation or pressure swing adsorption is used to produce O 2 In addition, high purity N is produced 2 ，O 2 And N 2 The molar ratio of (A) to (B) is 1:2 to 2.5; o is 2 As combustion improver into CH 4 A flameless combustion process; n is a radical of hydrogen 2 H separated from hydrogen separation tube 2 Preparation of ammonia gas NH by ammonia synthesis 3 Product, remainder N 2 For purging the apparatus; ammonia NH 3 The product can be used as chemical raw material or H 2 Chemical carrier when delivered over long distance.
3. The method for efficiently utilizing a methane-rich gas according to claim 1, wherein CH is contained in a mixed gas of methane and steam 4 And H 2 The molar ratio of O =1 to 5.
4. The method for efficiently utilizing a methane-rich gas according to claim 1, wherein the H obtained in the hydrogen purification and storage step 2 The storage mode of the product is a high-pressure hydrogen form of 20-70MPa or a liquid hydrogen form or an ammonia synthesis procedure to prepare an ammonia product, wherein the ammonia product is used as H 2 Chemical carrier when transported over a long distance of over 200 km.
5. A methane-rich gas high-efficiency utilization system for implementing the method of any one of claims 1 to 4, characterized by comprising:
a first mixing preheater for mixing and preheating of methane and steam; the heat of preheating comes from CH 4 Heat 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 CH 4 In the flameless combustion chamber, the methane steam reforming reactor and the combustion chamber nozzle are alternately and uniformly arranged; the methane steam reforming reactor is filled with a nickel-based catalyst and is also internally provided with a plurality of hydrogen separation pipes; the heat of the methane steam reforming reaction is totally from CH 4 CH of flameless combustion chamber 4 Heat 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 H 2 Producing 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; after cooling downFeeding the carbon dioxide rich tail gas into CO 2 A separation device;
CO 2 separation apparatus for purifying CO 2 To obtain CO 2 Producing a product;
a second mixing preheater for mixing and preheating methane and carbon dioxide;
CH 4 a 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 CO 2 The 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 CH 4 A flameless combustion chamber; and
cooler for separating CH 4 CO produced by flameless combustion chamber 2 And H 2 O, wherein H is separated off by condensation 2 O is supplied to the liquid water heat exchanger; CO obtained by separation 2 Feeding in the CO 2 And (4) separating the devices.
6. The methane-rich gas efficient utilization system of claim 5, 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 CH 4 A 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%.
7. The methane-rich gas efficient utilization system according to claim 6, further comprising:
ammonia synthesis system for separating H from hydrogen 2 The product reacts with high-purity nitrogen obtained by an air cryogenic separation system or an air pressure swing adsorption system to obtain ammonia, and the ammonia is transported for a long distance as hydrogenAnd (4) chemical carrier for transfusion.
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