CN105498485A - Separation method of methane from coal bed methane-air mixture and system thereof - Google Patents
Separation method of methane from coal bed methane-air mixture and system thereof Download PDFInfo
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- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
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- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及一种混空煤层气中甲烷的分离方法及其系统，属于化工技术领域。The invention relates to a method and system for separating methane in air-mixed coal bed gas, belonging to the technical field of chemical industry.
背景技术Background technique
煤层气(CoalBedMethane，简称CBM)，又称煤矿瓦斯或矿井瓦斯，产生于成煤过程，主要以吸附状态赋存于煤层中，是一种以甲烷为主要成分的非常规天然气资源。Coal Bed Methane (CBM for short), also known as coal mine gas or mine gas, is produced in the coal-forming process and mainly exists in coal seams in an adsorbed state. It is an unconventional natural gas resource with methane as the main component.
目前，开采煤层气的主要方式为地面钻井和井下抽采。地面钻井技术在国外煤层气的开发中应用比较多，而中国地质情况复杂，大部分煤层的透气性比较差，受技术以及地质条件的制约，当前中国煤层气的开发中应用比较多的还是井下抽采技术。采用直接钻井技术得到的煤层气中甲烷含量一般大于90％，与常规的天然气组成相近，可直接利用已经比较成熟的天然气预处理工艺加工净化，然后直接液化储运或加压后通入天然气管网。采用井下抽采技术得到的煤层气一般都会混入空气，甲烷含量比较低(通常体积分数在30％-80％)，目前只有很少部分的井下抽采煤层气得到了有效利用，大部分被直接排入大气中，造成了很大的资源浪费和环境污染。At present, the main methods of mining coalbed methane are surface drilling and underground extraction. Surface drilling technology is widely used in the development of coalbed methane in foreign countries. However, China's geological conditions are complex, and most of the coal seams have relatively poor air permeability. Restricted by technology and geological conditions, the current development of coalbed methane in China is mostly used underground Extraction technology. The methane content in coalbed methane obtained by direct drilling technology is generally greater than 90%, which is similar to the composition of conventional natural gas. It can be directly processed and purified by relatively mature natural gas pretreatment technology, and then directly liquefied, stored and transported or put into natural gas pipelines after pressurization network. The coalbed methane obtained by underground drainage technology is generally mixed with air, and the methane content is relatively low (usually the volume fraction is 30%-80%). Directly discharged into the atmosphere, resulting in a great waste of resources and environmental pollution.
近年来许多研究者对混空煤层气中甲烷的分离和回收进行了大量的研究，现有用于分离混空煤层气中甲烷的方法有低温深冷分离法、膜分离法、变压吸附分离法和水合物分离法。然而上述方法却存在不同的缺陷，制约了混空煤层气中甲烷的回收。In recent years, many researchers have conducted a lot of research on the separation and recovery of methane in mixed air coalbed methane. The existing methods for separating methane in air mixed coalbed methane include low-temperature cryogenic separation, membrane separation, and pressure swing adsorption separation. and hydrate separation method. However, the above methods have different defects, which restrict the recovery of methane in the mixed gas.
低温深冷分离技术是利用煤层气中各组分的沸点不同，采用低温精馏和液化的方式将各组分分离。该分离技术要求在－150℃左右进行操作，能耗较高，因为混空煤层气中含氧，需要首先进行脱氧，存在爆炸的危险；膜分离技术是根据混合气的各组分在一定压差下透过膜的传递速率不同而实现的。但是，目前所研制的膜材料对煤层气中的主要组分CH4和N2的分离效果不佳，同时也存在爆炸的危险；变压吸附分离技术是利用吸附剂在一定温度和压力下对混合气中各组分吸附能力的差异而实现的。经过几十年的发展，变压吸附分离H2、N2和O2等技术在世界范围内都已普遍使用，但目前在国内还没有使用变压吸附分离法分离混空煤层气的工业应用的实例。The low-temperature cryogenic separation technology utilizes the different boiling points of the components in coalbed methane, and separates the components by means of low-temperature rectification and liquefaction. This separation technology requires operation at around -150°C, and the energy consumption is relatively high. Because the mixed gas contains oxygen, it needs to be deoxidized first, and there is a risk of explosion. It is achieved by the difference in the transmission rate through the membrane under the difference. However, the currently developed membrane materials are not effective in separating CH 4 and N 2 , the main components in coalbed methane, and there is also a risk of explosion; It is realized by the difference in the adsorption capacity of each component in the mixed gas. After decades of development, technologies such as pressure swing adsorption separation of H 2 , N 2 and O 2 have been widely used in the world, but there is no industrial application of pressure swing adsorption separation method in China to separate mixed gas instance of .
上述三种分离技术均未实现工业化的主要原因在于混空煤层气极易爆炸，不能保证分离过程的安全。水合物分离法是一种新的分离低沸点混合气体的分离技术，原理是根据不同气体形成水合物的难易程度，从而实现混合气体中各组分的分离。现有水合物分离法能够使混空煤层气的分离在水饱和的环境下进行，但是因为水合物的分离需要在一定的压力下进行，前期对混空煤层气实施压缩升压过程中同样存在爆炸的危险同样难以采用。The main reason why the above three separation technologies have not been industrialized is that the mixed air CBM is extremely easy to explode, and the safety of the separation process cannot be guaranteed. The hydrate separation method is a new separation technology for separating low-boiling point mixed gases. The principle is to realize the separation of components in the mixed gas according to the difficulty of forming hydrates in different gases. The existing hydrate separation method can make the separation of air-mixed coalbed methane in a water-saturated environment, but because the separation of hydrates needs to be carried out under a certain pressure, there are also problems in the process of compressing and boosting the air-mixed coalbed methane in the early stage. The danger of explosion is equally difficult to adopt.
因此，如何研究出一种新的分离方法，实现混空煤层气中甲烷的分离和利用，很有必要。Therefore, it is very necessary to develop a new separation method to realize the separation and utilization of methane in mixed gas.
发明内容Contents of the invention
本发明所解决的技术问题在于，提供一种混空煤层气中甲烷的分离方法及其系统，该方法不需要现有水合物分离法分离混空煤层气中甲烷需要对混空煤层气压缩升压的步骤，避免了混空煤层气压缩过程和高压流动过程爆炸的危险，具有操作安全、实际工业应用可行性强的优点。The technical problem to be solved by the present invention is to provide a method and system for separating methane in mixed air coalbed methane. The pressure step avoids the risk of explosion during the compression process of the mixed gas and the high-pressure flow process, and has the advantages of safe operation and strong feasibility for practical industrial application.
本发明提供了一种混空煤层气中甲烷的分离方法，包括使混空煤层气发生水合反应，并收集甲烷富气的过程，其中，The invention provides a method for separating methane from mixed air-filled coalbed methane, including the process of hydrating the mixed air-filled coalbed methane and collecting methane-enriched gas, wherein,
实现水合反应的水合反应器具有以下结构：水合反应器腔体沿水合物工作液流动方向具有入口段、喉管段和稳定段，且喉管段的流通面积均小于入口段和稳定段的流通面积，该水合反应器腔体对应于喉管段的侧壁开设有进气口；The hydration reactor for realizing the hydration reaction has the following structure: the cavity of the hydration reactor has an inlet section, a throat section and a stabilizing section along the flow direction of the hydrate working fluid, and the flow area of the throat section is smaller than that of the inlet section and the stabilizing section, The hydration reactor cavity is provided with an air inlet corresponding to the side wall of the throat section;
所述分离方法包括：将水合物工作液从入口段送入所述水合反应器中，使混空煤层气通过进气口与水合反应器连通，利用流经喉管段的水合物工作液产生的吸力将待分离混空煤层气吸入水合反应器，并使二者在流至稳定段过程中被混合而发生水合反应，生成水合物浆液和甲烷贫气；The separation method includes: feeding the hydrate working fluid from the inlet section into the hydration reactor, making the mixed air gas connected to the hydration reactor through the air inlet, and utilizing the hydrate working fluid flowing through the throat section to produce Suction sucks the mixed air into the hydration reactor to be separated, and causes the two to be mixed in the process of flowing to the stabilization section for hydration reaction to generate hydrate slurry and methane-depleted gas;
将所述水合物浆液和甲烷贫气送入水合物分离器，使所述甲烷贫气从水合物分离器的顶部出口排出而被收集，将所述水合物浆液经水合物分离器的底部出口送入水合物化解器实施化解，分离并收集甲烷富气，化解出的脱除气体的水合物工作液供水合反应循环使用。The hydrate slurry and methane-depleted gas are sent to the hydrate separator, the methane-depleted gas is discharged from the top outlet of the hydrate separator to be collected, and the hydrate slurry is passed through the bottom outlet of the hydrate separator Send it to the hydrate decomposer for decompression, separate and collect the methane-rich gas, and degas the hydrate working fluid from degassing for hydration reaction recycling.
上述混空煤层气中甲烷的分离方法，主要利用了流体力学的原理，利用水合物工作液在水合反应器中的不同位置的流动与压力的变化规律，实现了混空煤层气的吸入、自升压以及水合分离的过程。具体表现在：将水合物工作液从水合反应器的入口段注入，当其到达水合反应器的喉管段时，由于流通截面积急剧缩小，从而使其流速突然增大，使水合反应器内的静压快速降低，在压力差的作用下，混空煤层气被吸入了水合反应器中与水合物工作液混合，当混空煤层气与水合物工作液到达水合反应器的稳定段时，由于流通截面积的扩大，从而使流体的静压升高，当流体的静压大于水合物的生成压力时，混空煤层气中的甲烷与水合物工作液发生水合反应，形成水合物浆液，而混空煤层气中所含空气的一部分气相得到富集形成甲烷贫气。The above separation method of methane in the mixed air-gas is mainly based on the principle of fluid mechanics, and utilizes the flow and pressure variation of the hydrate working fluid in different positions in the hydration reactor to realize the inhalation of the air-mixed coalbed methane, automatic The process of pressurization and hydration separation. Specifically, when the hydrate working fluid is injected from the inlet section of the hydration reactor, when it reaches the throat section of the hydration reactor, the flow rate suddenly increases due to the sharp reduction of the cross-sectional area of the hydration reactor. The static pressure drops rapidly. Under the action of pressure difference, the mixed air CBM is sucked into the hydration reactor and mixed with the hydrate working fluid. When the mixed air CBM and hydrate working fluid reach the stable section of the hydration reactor, due to The expansion of the cross-sectional area of the flow increases the static pressure of the fluid. When the static pressure of the fluid is greater than the hydrate formation pressure, the methane in the mixed gas hydrate and the hydrate working fluid undergo a hydration reaction to form a hydrate slurry. Part of the gas phase of the air contained in the mixed air coalbed methane is enriched to form methane-depleted gas.
在本发明的具体实施方式中，使水合物工作液进入水合反应器时的温度为4-15℃，压力为0.6-5.1MPa。该温度和压力下的水合物工作液更有利于在其流经喉管段形成压力差，从而有利于混空煤层气被吸入气体水合反应器的稳定段，使之与水合物工作液进行水合反应，形成水合物浆液。In a specific embodiment of the present invention, when the hydrate working fluid enters the hydration reactor, the temperature is 4-15° C., and the pressure is 0.6-5.1 MPa. The hydrate working fluid at this temperature and pressure is more conducive to forming a pressure difference when it flows through the throat section, so that the mixed air gas is sucked into the stable section of the gas hydration reactor, so that it can undergo hydration reaction with the hydrate working fluid , forming a hydrate slurry.
在本发明的具体实施方式中，所述水合反应器的入口段的管道内径为15-50mm，所述喉管段的内径与所述入口段的管道内径比值为0.05-0.5，所述进气口的直径与所述喉管段的内径比值为0.2-0.5；In a specific embodiment of the present invention, the inner diameter of the inlet section of the hydration reactor is 15-50 mm, the ratio of the inner diameter of the throat section to the inner diameter of the inlet section is 0.05-0.5, and the air inlet The ratio of the diameter to the inner diameter of the throat section is 0.2-0.5;
所述入口段的长度与所述入口段的管道内径比值为1-3，所述喉管段长度与所述喉管段的内径比值为1-2.5，所述稳定段的长度与所述入口段的管道内径比值为3-5。The ratio of the length of the inlet section to the inner diameter of the inlet section is 1-3, the ratio of the length of the throat section to the inner diameter of the throat section is 1-2.5, and the length of the stable section to the inner diameter of the inlet section The pipe inner diameter ratio is 3-5.
在本发明的具体实施方式中，所述水合物分离器的操作温度为4-15℃，操作压力为0.6-5.1MPa。在水合物分离器中控制上述操作温度和操作压力可以使水合物浆液和混空煤层气中的空气尽可能的分离完全，实现气相和液相的分离。In a specific embodiment of the present invention, the operating temperature of the hydrate separator is 4-15° C., and the operating pressure is 0.6-5.1 MPa. Controlling the above-mentioned operating temperature and operating pressure in the hydrate separator can make the hydrate slurry and the air in the mixed coalbed methane completely separated as much as possible, and realize the separation of gas phase and liquid phase.
在本发明的具体实施方式中，所述水合物化解器的操作温度为8-23℃，操作压力为0.1-2.1MPa。在水合物化解器中控制上述操作温度和压力可以使水合物浆液尽可能的完全化解得到甲烷富气和脱除气体的水合物工作液，实现混空煤层气中甲烷和空气的分离。In a specific embodiment of the present invention, the operating temperature of the hydrate decomposer is 8-23° C., and the operating pressure is 0.1-2.1 MPa. Controlling the above operating temperature and pressure in the hydrate decomposer can make the hydrate slurry decompose as completely as possible to obtain methane-enriched and degassed hydrate working fluid, and realize the separation of methane and air in the mixed air coalbed methane.
在本发明的具体实施方式中，待分离混空煤层气被吸入水合反应器前的压力小于0.6MPa。In a specific embodiment of the present invention, the pressure of the air-mixed coalbed gas to be separated before being sucked into the hydration reactor is less than 0.6 MPa.
本发明还提供了实现上述混空煤层气中甲烷的分离方法的系统，所述系统包括水合物工作液储罐、水合反应器、水合物分离器、水合物化解器、加热器和/或减压阀；The present invention also provides a system for realizing the separation method of methane in the above air-mixed coalbed methane. The system includes a hydrate working fluid storage tank, a hydration reactor, a hydrate separator, a hydrate decomposer, a heater and/or Pressure valve;
其中，水合反应器腔体沿水合物工作液流动方向具有入口段、喉管段和稳定段，且喉管段的流通面积均小于入口段和稳定段的流通面积，该水合反应器腔体对应于喉管段的侧壁开设有进气口；Among them, the hydration reactor cavity has an inlet section, a throat section, and a stabilization section along the flow direction of the hydrate working fluid, and the flow area of the throat section is smaller than that of the inlet section and the stabilization section. The hydration reactor cavity corresponds to the throat section. The side wall of the pipe section is provided with an air inlet;
所述水合物工作液储罐设有入口和出口，所述水合物工作液储罐的出口与所述水合反应器的入口段连通；The hydrate working fluid storage tank is provided with an inlet and an outlet, and the outlet of the hydrate working fluid storage tank communicates with the inlet section of the hydration reactor;
所述水合反应器稳定段设有用于排出水合物浆液和甲烷贫气的出口，其与所述水合物分离器的入口连通，所述水合物分离器的顶部设有甲烷贫气排放口，底部设有水合物浆液出口；The stable section of the hydration reactor is provided with an outlet for discharging hydrate slurry and methane-depleted gas, which communicates with the inlet of the hydrate separator. The top of the hydrate separator is provided with a methane-depleted gas discharge port, and the bottom is Equipped with a hydrate slurry outlet;
所述水合物分离器的水合物浆液出口与水合物化解器的入口连通，且二者间设置有加热器和/或减压阀，所述水合物化解器的脱除气体的水合物工作液出口与所述水合物工作液储罐的入口连通。The hydrate slurry outlet of the hydrate separator communicates with the inlet of the hydrate decomposer, and a heater and/or pressure relief valve is arranged between the two, and the degassed hydrate working fluid of the hydrate decomposer The outlet communicates with the inlet of the hydrate working fluid storage tank.
在上述系统中，所述水合反应器的入口段的管道内径为15-50mm，所述喉管段的内径与所述入口段的管道内径比值为0.05-0.5，所述进气口的直径与所述喉管段的内径比值为0.2-0.5；In the above system, the inner diameter of the inlet section of the hydration reactor is 15-50 mm, the ratio of the inner diameter of the throat section to the inner diameter of the inlet section is 0.05-0.5, and the diameter of the air inlet and the inner diameter of the inlet section are 0.05-0.5. The inner diameter ratio of the throat section is 0.2-0.5;
所述入口段的长度与所述入口段的管道内径比值为1-3，所述喉管段长度与所述喉管段的内径比值为1-2.5，所述稳定段的长度与所述入口段的管道内径比值为3-5。The ratio of the length of the inlet section to the inner diameter of the inlet section is 1-3, the ratio of the length of the throat section to the inner diameter of the throat section is 1-2.5, and the length of the stable section to the inner diameter of the inlet section The pipe inner diameter ratio is 3-5.
本发明提供的混空煤层气中甲烷的分离方法，采用了构造改良的水合反应器，巧妙地借助水合反应器中流通面积改变提供混空煤层气所需要的水合条件(水合生成压力)，即，在利用水合物工作液流过喉管段所产生的压力降(甚至达到局部真空)将混空煤层气吸入水合反应器后，并在流向稳定段过程中由于压力增大以及二者在压力驱动下的充分混合而促使混空煤层气中的甲烷尽可能全部发生水合，达到分离甲烷的目的。相比于目前对混空煤层气进行分离的工艺，本发明的分离方法不需要对待分离的混空煤层气进行压缩升压，不仅省去了压缩设备的投入，大幅降低了能耗，水合反应时也无需额外的搅拌机构，而且对操作空间及操作工序的要求都显著降低，实现了混空煤层气中甲烷的分离，为该技术的工业化应用提供了可能。The method for separating methane in the mixed air coalbed methane provided by the present invention adopts a structurally improved hydration reactor, and skillfully provides the required hydration conditions (hydration generation pressure) for the air mixed coalbed methane by changing the flow area in the hydration reactor, that is, , after using the pressure drop (even reaching partial vacuum) generated by the hydrate working fluid flowing through the throat section to suck the mixed air into the hydration reactor, and in the process of flowing to the stable section due to the pressure increase and the pressure-driven Under the sufficient mixing, the methane in the mixed coalbed methane can be hydrated as much as possible, so as to achieve the purpose of methane separation. Compared with the current process for separating mixed air-filled coalbed methane, the separation method of the present invention does not need to compress and boost the mixed air-filled coalbed methane to be separated, which not only saves the investment in compression equipment, but also greatly reduces energy consumption. There is no need for an additional stirring mechanism, and the requirements for operating space and operating procedures are significantly reduced, and the separation of methane in the mixed air coalbed methane is realized, which provides the possibility for the industrial application of this technology.
附图说明Description of drawings
图1是本发明分离混空煤层气中甲烷的工艺流程图。Fig. 1 is a process flow chart of the present invention for separating methane in air-mixed coalbed methane.
图2是本发明分离混空煤层气中甲烷系统中的水合反应器。Fig. 2 is the hydration reactor in the methane separation system of the present invention for separating mixed air from coalbed methane.
附图标记：Reference signs:
1-水合物工作液储罐；2-水合反应器；3-水合物分离器；4-水合物化解器；5-高压泵；6-冷却器；7-加热器；8-减压阀；9-水合物工作液；10-混空煤层气；1-Hydrate working fluid storage tank; 2-Hydration reactor; 3-Hydrate separator; 4-Hydrate decomposer; 5-High pressure pump; 6-Cooler; 7-Heater; 8-Decompression valve; 9-hydrate working fluid; 10-mixed gas;
01-入口段；02-喉管段；03-扩大段；04-进气口。01-inlet section; 02-throat section; 03-expansion section; 04-air inlet.
具体实施方式detailed description
为使本发明实施例的目的、技术方案和优点更加清楚，下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all Example. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明混空煤层气中甲烷的分离方法，包括使混空煤层气发生水合反应，并收集甲烷富气的过程，其中，The method for separating methane from mixed air-filled coalbed methane of the present invention includes the process of causing hydration reaction of mixed air-filled coalbed methane and collecting methane-enriched gas, wherein,
实现水合反应的水合反应器如图2所示，具有以下结构：水合反应器腔体沿水合物工作液流动方向具有入口段01、喉管段02和稳定段03，且喉管段02的流通面积均小于入口段01和稳定段03的流通面积，该水合反应器腔体对应于喉管段02的侧壁开设有进气口04；其中，水合反应器的入口段01的管道内径为15-50mm，喉管段02的内径与入口段01的管道内径比值为0.05-0.5，进气口04的直径与喉管段02的内径比值为0.2-0.5；入口段01的长度与入口段01的管道内径比值为1-3，喉管段02长度与喉管段02的内径比值为1-2.5，稳定段03的长度与入口段01的管道内径比值为3-5。The hydration reactor that realizes the hydration reaction is shown in Figure 2, and has the following structure: the cavity of the hydration reactor has an inlet section 01, a throat section 02, and a stabilizing section 03 along the flow direction of the hydrate working fluid, and the flow area of the throat section 02 is equal to Smaller than the flow area of the inlet section 01 and the stable section 03, the hydration reactor cavity is provided with an air inlet 04 corresponding to the side wall of the throat section 02; wherein, the inner diameter of the pipeline of the inlet section 01 of the hydration reactor is 15-50 mm, The ratio of the inner diameter of the throat section 02 to the inner diameter of the inlet section 01 is 0.05-0.5, the ratio of the diameter of the air inlet 04 to the inner diameter of the throat section 02 is 0.2-0.5; the ratio of the length of the inlet section 01 to the inner diameter of the inlet section 01 is 1-3, the ratio of the length of the throat section 02 to the inner diameter of the throat section 02 is 1-2.5, and the ratio of the length of the stabilizing section 03 to the inner diameter of the inlet section 01 is 3-5.
如图1所示，本发明混空煤层气中甲烷的分离方法包括：将水合物工作液储罐1中的水合物工作液9经高压泵5和冷却器6后，从入口段01送入水合反应器2中，使水合物工作液9进入水合反应2时的温度为4-15℃，压力为0.6-5.1MPa。使混空煤层气10通过进气口04与水合反应器2连通，待分离混空煤层气10被吸入水合反应器2前的压力小于0.6MPa，利用流经喉管段02的水合物工作液9产生的吸力将待分离混空煤层气10吸入水合反应器2，并使二者在流至稳定段03过程中被混合而发生水合反应，生成水合物浆液和甲烷贫气；As shown in Figure 1, the method for separating methane in the mixed air-filled coalbed methane of the present invention includes: sending the hydrate working fluid 9 in the hydrate working fluid storage tank 1 through the high-pressure pump 5 and the cooler 6, and then sending it into the hydrate from the inlet section 01 In the hydration reactor 2, when the hydrate working fluid 9 enters the hydration reaction 2, the temperature is 4-15° C., and the pressure is 0.6-5.1 MPa. Make the air-mixed coalbed methane 10 communicate with the hydration reactor 2 through the air inlet 04, the pressure before the air-mixed coalbed methane 10 to be separated is sucked into the hydration reactor 2 is less than 0.6 MPa, and the hydrate working fluid 9 flowing through the throat section 02 is used The generated suction draws the mixed empty coalbed gas 10 to be separated into the hydration reactor 2, and causes the two to be mixed in the process of flowing to the stabilization section 03 to undergo a hydration reaction to generate hydrate slurry and methane-depleted gas;
将水合物浆液和甲烷贫气送入水合物分离器3，水合物分离器3的操作温度为4-15℃，操作压力为0.6-5.1Mpa，使甲烷贫气从水合物分离器3的顶部出口排出而被收集，将水合物浆液经水合物分离器3的底部出口，经加热器7和减压阀8后送入水合物化解器4实施化解，水合物化解器4的操作温度为8-23℃，操作压力为0.1-2.1Mpa，分离并收集甲烷富气，化解出的脱除气体的水合物工作液返回水合物工作液罐1中供水合反应循环使用。The hydrate slurry and methane-depleted gas are sent to the hydrate separator 3, the operating temperature of the hydrate separator 3 is 4-15°C, and the operating pressure is 0.6-5.1Mpa, so that the methane-depleted gas flows from the top of the hydrate separator 3 The outlet is discharged and collected, and the hydrate slurry is sent to the hydrate decomposer 4 for decomposition through the bottom outlet of the hydrate separator 3, the heater 7 and the pressure reducing valve 8, and the operating temperature of the hydrate decomposer 4 is 8 -23°C, operating pressure 0.1-2.1Mpa, separate and collect methane-enriched gas, degassed hydrate working fluid decomposed and returned to hydrate working fluid tank 1 for hydration reaction cycle use.
在本发明中，水合物工作液的选择可以根据混空煤层气中甲烷浓度的高低而选择，可以是四丁基溴化铵或者四丁基氟化铵的水溶液，也可以是添加了能够提高水合物生成速度的其它的化学物质，这些物质的加入与否和浓度的高低均不影响本发明的技术方案。In the present invention, the choice of hydrate working fluid can be selected according to the level of methane concentration in the mixed air coalbed methane, it can be an aqueous solution of tetrabutylammonium bromide or tetrabutylammonium fluoride, or it can be added to increase the Other chemical substances related to the hydrate formation rate, the addition of these substances and the level of concentration will not affect the technical solution of the present invention.
实施例1Example 1
水合物工作液为四丁基溴化铵(英文缩写：TBAB)，其浓度为10wt％；Hydrate working fluid is tetrabutylammonium bromide (English abbreviation: TBAB), and its concentration is 10wt%;
混空煤层气的组成如下表1所示：The composition of mixed gas is shown in Table 1 below:
表1混空煤层气的组成Table 1 Composition of mixed air CBM
采用如图1所示的分离混空煤层气中甲烷的工艺流程和图2的水合反应器，其具体过程请参照上述分离方法的说明，涉及的工艺参数如下：The process flow for separating methane in air-mixed coalbed methane as shown in Figure 1 and the hydration reactor shown in Figure 2 are used. For the specific process, please refer to the description of the above separation method. The process parameters involved are as follows:
1)混空煤层气的压力为0.5MPa。1) The pressure of mixed air CBM is 0.5MPa.
2)水合物工作液进入水合反应器时的温度为8℃，压力为3.0MPa。2) When the hydrate working fluid enters the hydration reactor, the temperature is 8°C and the pressure is 3.0MPa.
3)水合物工作液经过水合反应器的喉管段的压力为0.4MPa。3) The pressure of the hydrate working fluid passing through the throat section of the hydration reactor is 0.4MPa.
4)水合物工作液与混空煤层气中的甲烷形成的流体在水合反应器的稳定段的压力为2.5MPa。4) The pressure of the fluid formed by the hydrate working fluid and the methane in the mixed gas in the stable section of the hydration reactor is 2.5 MPa.
5)水合物分离器的操作温度为9℃，操作压力为2.4MPa。5) The operating temperature of the hydrate separator is 9°C and the operating pressure is 2.4MPa.
6)水合物化解器的操作温度为10℃，操作压力为0.2MPa。6) The operating temperature of the hydrate decomposer is 10°C and the operating pressure is 0.2MPa.
经图1的工艺流程分离得到的甲烷贫气和甲烷富气的组成，如下表2所示：The compositions of methane-depleted gas and methane-rich gas separated by the process flow in Fig. 1 are shown in Table 2 below:
表2甲烷富气和甲烷贫气的组成Table 2 Composition of methane-rich gas and methane-poor gas
由表2所示，甲烷富气中甲烷的摩尔分率为63.782mol％，甲烷的回收率达到83％，该结果表明：上述水合物分离法能够有效将混空煤层气中甲烷进行分离。As shown in Table 2, the mole fraction of methane in the methane-rich gas is 63.782mol%, and the recovery rate of methane reaches 83%. The results show that the above-mentioned hydrate separation method can effectively separate the methane in the mixed air coalbed methane.
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still be Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent replacements are made to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.
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