CN101734620A - Method for producing hydrogen gas by methane-rich plasma - Google Patents
Method for producing hydrogen gas by methane-rich plasma Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
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Abstract
一种富甲烷气等离子体制氢气的方法是将富甲烷气先与反应高温尾气换热,再与等离子裂解气化反应器器壁换热,后进入等离子裂解气化反应器内与等离子发生器产生的等离子体射流相作用,生成以氢气为主要成分的气体。该方法克服了传统工艺需要催化剂,催化剂易发生析碳,硫、卤素、砷中毒的难题,同时也解决了等离子体制氢过程中能耗较高以及反应器器壁的保护的问题。本发明工艺流程短、操作简单、热效率高,环境污染小,适用于燃气化工领域与等离子化工领域。A method for producing hydrogen from methane-enriched gas plasma is to first exchange heat with methane-enriched gas with high-temperature reaction tail gas, then exchange heat with the wall of the plasma cracking gasification reactor, and then enter the plasma cracking gasification reactor to produce hydrogen with the plasma generator. The plasma jet interacts with each other to generate a gas with hydrogen as the main component. This method overcomes the problems that the traditional process requires a catalyst, and the catalyst is prone to carbon deposition, sulfur, halogen, and arsenic poisoning, and also solves the problems of high energy consumption and reactor wall protection in the process of plasma hydrogen production. The invention has short technological process, simple operation, high thermal efficiency and little environmental pollution, and is suitable for the fields of gas chemical industry and plasma chemical industry.
Description
技术领域technical field
本发明涉及一种甲烷气制氢气的方法,特别是一种用富甲烷气在等离子体射流作用下制得氢气的方法。The invention relates to a method for producing hydrogen from methane, in particular to a method for producing hydrogen with methane-enriched gas under the action of a plasma jet.
技术背景technical background
氢气的应用领域很广,主要是用于生产合成氨、甲醇以及石油炼制过程的加氢反应。此外,在电子工业、冶金工业、食品加工、浮法玻璃、精细化工合成、航空航天工业等领域也有很多的应用。随着社会对环境质量的日益重视,汽油柴油中允许的硫化物、芳烃化合物的含量逐步降低,这使氢气的需求量呈增长态势。氢作为一种清洁燃料气,具有很高的燃烧热值,而且燃烧后的产物是水,不会对环境排放温室气体,因此是一种较理想的二次能源。另外,氢能源的使用也会增加市场对氢气的需求,尤其是氢气作为化工合成的中间产品气或原料气,近些年来越来越多的科研机构在着力于研究以氢为能源的燃料电池的开发和利用。Hydrogen is used in a wide range of fields, mainly for hydrogenation reactions in the production of synthetic ammonia, methanol, and petroleum refining. In addition, there are many applications in the fields of electronics industry, metallurgical industry, food processing, float glass, fine chemical synthesis, aerospace industry and so on. As society pays more and more attention to environmental quality, the content of sulfide and aromatic compounds allowed in gasoline and diesel is gradually reduced, which makes the demand for hydrogen increase. As a clean fuel gas, hydrogen has a high combustion calorific value, and the product of combustion is water, which will not emit greenhouse gases to the environment, so it is an ideal secondary energy source. In addition, the use of hydrogen energy will also increase the market demand for hydrogen, especially hydrogen as an intermediate product gas or raw material gas for chemical synthesis. In recent years, more and more scientific research institutions are focusing on the research of fuel cells using hydrogen as energy. development and utilization.
以富甲烷气为原料制氢方法主要有四种:甲烷的水蒸气重整法、甲烷的部分氧化法、甲烷的二氧化碳重整法以及甲烷的非催化部分氧化法。水蒸气重整法是现有制取氢气的主要方法。其中三种方法的工艺过程都需要催化系统,催化剂都容易发生析碳,以及硫、卤素、砷中毒。非催化部分氧化法则需要纯氧或富氧空气,同时将相当一部分氢转化为水,减少了氢气的产率。甲烷是自然界中最稳定的有机分子之一,甲烷中的碳氢键键能大,结构相当牢固,所以在甲烷制氢气过程中,碳氢键的断裂需要大量的能量,因此,传统甲烷转化制氢一般需要催化剂,且反应器庞大,富含活性粒子等离子体的引入,解决了该问题,但高品位的等离子体能量的有效利用又成了问题。如果利用不好,将造成新的能量浪费。There are four main methods for producing hydrogen from methane-enriched gas: steam reforming of methane, partial oxidation of methane, carbon dioxide reforming of methane, and non-catalytic partial oxidation of methane. Steam reforming is the main method for producing hydrogen. The technological processes of the three methods all require a catalytic system, and the catalysts are prone to carbon deposition, as well as sulfur, halogen, and arsenic poisoning. The non-catalytic partial oxidation method requires pure oxygen or oxygen-enriched air, and at the same time converts a considerable portion of hydrogen into water, reducing the yield of hydrogen. Methane is one of the most stable organic molecules in nature. The carbon-hydrogen bond energy in methane is large and the structure is quite strong. Therefore, in the process of producing hydrogen from methane, the breaking of carbon-hydrogen bonds requires a lot of energy. Therefore, the traditional methane conversion system Hydrogen generally needs a catalyst, and the reactor is huge, and the introduction of plasma rich in active particles solves this problem, but the effective utilization of high-grade plasma energy becomes a problem again. If it is not utilized properly, it will cause new waste of energy.
电弧热等离子体,属于热等离子体,其射流具有能量高度集中、超高温、富含激发态的原子、分子,电子等活性粒子、速度和压力梯度高的特点,等离子体射流等非常适宜作为超高温超短接触反应的热源,将等离子体技术与甲烷转化相结合的等离子体制氢工艺,克服了传统甲烷转化工艺的许多缺点,具有流程短、不需要催化剂等特点。由于能耗的原因,至今没有工业化。等离子体制氢工艺中由于反应器温度较高,反应后气体的温度也高,通常要用换热器来回收其中的热量。美国专利US6,881,363在等离子反应器中设置了逆流换热器来预热部分空气或部分燃料,从而降低了能量供给。但问题是该换热器存在气流分布不均,同时换热器紧邻等离子体电弧容易造成换热器内积碳,严重影响换热效果和换热器寿命,甚至在换热器通过气体流量较大时造成等离子体电弧熄灭,系统停止运行。Arc thermal plasma belongs to thermal plasma. Its jet has the characteristics of highly concentrated energy, ultra-high temperature, rich in excited state atoms, molecules, electrons and other active particles, and high velocity and pressure gradient. Plasma jet is very suitable as super The heat source of high-temperature ultra-short contact reaction, the plasma hydrogen production process combining plasma technology and methane conversion, overcomes many shortcomings of the traditional methane conversion process, and has the characteristics of short process and no need for catalysts. Due to energy consumption, it has not been industrialized so far. In the plasma hydrogen production process, due to the high temperature of the reactor and the high temperature of the gas after the reaction, a heat exchanger is usually used to recover the heat therein. In US Pat. No. 6,881,363, a counterflow heat exchanger is arranged in the plasma reactor to preheat part of the air or part of the fuel, thereby reducing the energy supply. But the problem is that the heat exchanger has uneven air flow distribution. At the same time, the heat exchanger is close to the plasma arc, which is easy to cause carbon deposits in the heat exchanger, which seriously affects the heat exchange effect and the life of the heat exchanger. Even when the gas flow through the heat exchanger is relatively low When it is large, the plasma arc is extinguished and the system stops running.
美国专利US7,597,860在等离子体反应器以下连有一列管式换热器,用来降低富氢气体的温度,预热空气、原料气或两者的混合气,达到降低能耗的目的。在该发明中,反应产生的富氢气体经过催化剂床层后温度较低,对原料气的预热效果较差;经预热后的原料气通过反应器外的连管进入等离子体发生器两极之间的高频放电区域,在连管中被预热的气体又会有一定热量损失;如果被预热气体气量较大或由于加热造成气流湍动,电弧及系统的稳定运行就会被破坏。U.S. Patent No. 7,597,860 connects a row of tubular heat exchangers below the plasma reactor to reduce the temperature of hydrogen-rich gas, preheat air, raw gas or a mixture of the two, and reduce energy consumption. In this invention, the hydrogen-rich gas produced by the reaction has a lower temperature after passing through the catalyst bed, and the preheating effect on the raw material gas is poor; the preheated raw gas enters the two poles of the plasma generator through the connecting pipe outside the reactor In the high-frequency discharge area between the pipes, the preheated gas in the connecting pipe will have a certain amount of heat loss; if the preheated gas volume is large or the air flow is turbulent due to heating, the stable operation of the arc and the system will be destroyed. .
上述现有技术中,将等离子体制氢后的尾气进入催化剂床层,可以提高氢气的产率,但是催化剂容易中毒,为了克服催化剂中毒的问题,需要净化原料气和等离子发生器的工作气体,这样又使得工艺流程复杂。In the above-mentioned prior art, the tail gas after hydrogen production by plasma enters the catalyst bed, which can increase the yield of hydrogen, but the catalyst is easily poisoned. In order to overcome the problem of catalyst poisoning, it is necessary to purify the raw material gas and the working gas of the plasma generator. It also makes the technological process complicated.
发明内容Contents of the invention
为了克服上述现有技术的不足,本发明提供一种富甲烷气等离子体制氢气的方法。In order to overcome the deficiencies of the prior art above, the present invention provides a method for producing hydrogen from methane-enriched gas plasma.
本发明富甲烷气等离子体制氢气的方法是将富甲烷气或其混合气先与反应尾气换热,然后与等离子反应器器壁换热,再进入等离子反应器内与等离子体发生器产生的等离子体射流相互作用,生成以氢气为主要成分的气体。该方法的具体步骤如下:The method for producing hydrogen from methane-enriched gas plasma in the present invention is to first exchange heat with methane-enriched gas or its mixed gas with reaction tail gas, then exchange heat with the wall of the plasma reactor, and then enter the plasma reactor to interact with the plasma generated by the plasma generator. The body jet interacts to generate a gas with hydrogen as the main component. The concrete steps of this method are as follows:
I.甲烷含量在10%~100%的富甲烷气,或其与水蒸气、二氧化碳的混合气,进入等离子体反应器下部的换热器内,与反应后的600℃-1500℃的富氢气体进行换热,富甲烷气或混合气被加热到300℃-600℃;I. Methane-rich gas with a methane content of 10% to 100%, or its mixture with water vapor and carbon dioxide, enters the heat exchanger at the lower part of the plasma reactor, and reacts with the hydrogen-rich gas at a temperature of 600°C-1500°C The gas is heat exchanged, and the methane-enriched gas or mixed gas is heated to 300°C-600°C;
II.被加热的富甲烷气或混合气进入等离子体反应器器壁内的换热器与等离子体反应器器壁换热,富甲烷气或混合气被二次加热后,温度升至600℃-1200℃;II. The heated methane-rich gas or mixed gas enters the heat exchanger in the wall of the plasma reactor to exchange heat with the wall of the plasma reactor. After the methane-rich gas or mixed gas is heated again, the temperature rises to 600°C -1200℃;
III.被二次加热的富甲烷气或混合气进入等离子反应器,在反应区与2500℃-5000℃的等离子发生器产生的富含活性粒子的等离子体射流相作用,在常压下0.5-500ms内生成以氢气为主要成分的富氢气体,该富氢气体与反应器器壁、富甲烷气或混合气换热后温度降至200℃-300℃;III. The second-heated methane-enriched gas or mixed gas enters the plasma reactor, and interacts with the plasma jet rich in active particles generated by the plasma generator at 2500°C-5000°C in the reaction zone. Under normal pressure, 0.5- Generate hydrogen-rich gas with hydrogen as the main component within 500ms, and the temperature of the hydrogen-rich gas will drop to 200°C-300°C after heat exchange with the reactor wall, methane-rich gas or mixed gas;
IV.降温后的富氢气体进入分离器,分离出固体杂质,然后进一步分离制得以氢气。IV. The cooled hydrogen-rich gas enters the separator to separate solid impurities, and then further separates to obtain hydrogen.
在上述技术方案中,所述的富甲烷气是天然气、煤层气、焦炉煤气或者是其任意的混合气;所述的富甲烷气或其混合气与等离子体反应器器壁换热是通过埋藏在等离子体反应器内壁耐火保温材料层中的螺旋管换热器进行换热;所述的等离子发生器是是非移动型电弧等离子发生器;所述的等离子发生器的工作气体是氢气、氩气、氧气、二氧化碳、氮气、水蒸气和空气中的一种或其任意混合气。In the above technical scheme, the methane-enriched gas is natural gas, coal bed methane, coke oven gas or any mixture thereof; the heat exchange between the methane-enriched gas or its mixture and the wall of the plasma reactor is carried out through The spiral tube heat exchanger buried in the refractory insulation material layer on the inner wall of the plasma reactor performs heat exchange; the plasma generator is a non-moving arc plasma generator; the working gas of the plasma generator is hydrogen, argon One or any mixture of gas, oxygen, carbon dioxide, nitrogen, water vapor and air.
本发明用富甲烷气在等离子体射流作用下制氢的方法,与现有等离子体转化甲烷制氢气的方法相比,富甲烷气或混合气在进入等离子体反应器反应前,被反应后的富氢气体和等离子体反应器器壁二次预热,富甲烷气或混合气被预热活化后,再进入反应器与等离子体射流作用反应,充分利用了富含高活性粒子(离子、电子、原子、激发态的分子等)的等离子体射流能量,提高了化学反应的反应温度和反应速率。在该反应过程中,反应器器壁的散热损失由于内设了换热器而被有效降低,产品高温富氢气体的能量被充分利用,由于富甲烷气被预热活化,有效地解决了富甲烷气制氢时所需要的等离子体能耗高的问题,即在等离子体能量不变时,有效地提高了富甲烷气的处理量;在该反应过程中,反应器壁的热能连续不断地被耐火保温层吸收,有效地保护了反应器,延长了反应器的寿命。而且由于采用了上下部换热器集成在等离子体反应器中,缩短了工艺流程,简化了操作方法。The present invention uses methane-enriched gas to produce hydrogen under the action of plasma jets. Compared with the existing method of converting methane into hydrogen by plasma, methane-enriched gas or mixed gas is reacted before entering the plasma reactor. The hydrogen-rich gas and the plasma reactor wall are preheated twice. After the methane-rich gas or mixed gas is preheated and activated, it enters the reactor and reacts with the plasma jet, making full use of the particles rich in high activity (ions, electrons, etc. , atoms, excited state molecules, etc.) plasma jet energy increases the reaction temperature and reaction rate of chemical reactions. During the reaction process, the heat loss of the reactor wall is effectively reduced due to the built-in heat exchanger, and the energy of the product high-temperature hydrogen-rich gas is fully utilized. Since the methane-rich gas is preheated and activated, it effectively solves the problem of hydrogen-rich gas. The problem of high plasma energy consumption required for the production of hydrogen from methane gas, that is, when the plasma energy is constant, the processing capacity of methane-rich gas is effectively increased; during the reaction process, the thermal energy of the reactor wall is continuously absorbed The refractory insulation layer absorbs, effectively protects the reactor and prolongs the life of the reactor. Moreover, because the upper and lower heat exchangers are integrated in the plasma reactor, the process flow is shortened and the operation method is simplified.
本发明制氢的工艺方法中,省掉了富甲烷气、混合气和工作气的净化脱硫工艺,避免了使用催化剂,克服了催化剂中毒的难题。同时,提高了富甲烷气制氢气的能量利用效率,解决了等离子体法制氢能耗较高的问题,又兼顾了保护等离子体反应器,保证了等离子体制氢系统的正常稳定运行。In the hydrogen production method of the present invention, the purification and desulfurization process of methane-enriched gas, mixed gas and working gas is omitted, the use of catalyst is avoided, and the problem of catalyst poisoning is overcome. At the same time, the energy utilization efficiency of hydrogen production from methane-enriched gas is improved, the problem of high energy consumption of hydrogen production by plasma method is solved, and the protection of plasma reactor is also taken into account to ensure the normal and stable operation of the plasma hydrogen production system.
本发明制氢的工艺方法中,可以根据所制得富氢原料气的不同用途,按照需要可以采用不同成份的混合气和不同的等离子发生器的工作气体制得不同成分含量的以氢为主要成分的目标原料气。In the hydrogen production method of the present invention, according to the different uses of the obtained hydrogen-rich raw material gas, mixed gases of different components and working gases of different plasma generators can be used to obtain hydrogen-based gas with different component contents. Composition of the target feed gas.
本发明制氢的工艺方法中,通过计量各种富甲烷气、混合气、等离子发生器的工作气,分离出的固体杂质的富氢气体温度、压力、流量,并采用气相色谱测得富氢气体中的各种成分的百分含量,计算得出本发明方法制氢,其甲烷转化率达到了90%-99.9%,氢气的产率达到了80%-95%(在未使用水蒸气的情况下),在使用水蒸气的情况下,氢气的产率超过了100%(收率的计算不包括水蒸气中的氢),氢气的比能耗降低了11MJ/kg。In the process method of hydrogen production of the present invention, by metering various methane-enriched gases, mixed gas, and working gas of the plasma generator, the temperature, pressure, and flow rate of the hydrogen-enriched gas of the separated solid impurities are measured, and the hydrogen-enriched gas is measured by gas chromatography The percentage composition of various components in the gas calculates that the inventive method produces hydrogen, and its methane conversion rate has reached 90%-99.9%, and the productive rate of hydrogen has reached 80%-95% (in the absence of using steam case), under the situation of using steam, the productive rate of hydrogen has exceeded 100% (the calculation of yield does not include the hydrogen in steam), and the specific energy consumption of hydrogen has reduced 11MJ/kg.
附图说明Description of drawings
图1是本发明富甲烷气在等离子体作用下制氢气方法的装置结构示意图Fig. 1 is the schematic diagram of the device structure of the method for producing hydrogen from methane-enriched gas of the present invention under the action of plasma
图中:1:等离子体电源;2:等离子体发生器;3:等离子体工作气体;4:等离子体射流;5:耐火保温材料;6:等离子体反应器;7:保温层;8:富甲烷气或混合气;9:下部换热器;10;上部换热器;11:预热活化后的富甲烷气或混合气;12:冷却后的富氢气体;13:气体分离器;14:分离出固体杂质的富氢气体。In the figure: 1: plasma power supply; 2: plasma generator; 3: plasma working gas; 4: plasma jet; 5: refractory insulation material; 6: plasma reactor; 7: insulation layer; 8: rich Methane gas or mixed gas; 9: lower heat exchanger; 10; upper heat exchanger; 11: methane-rich gas or mixed gas after preheating and activation; 12: hydrogen-rich gas after cooling; 13: gas separator; 14 : Hydrogen-rich gas with solid impurities separated.
具体实施方式Detailed ways
本发明一种用富甲烷气在等离子体射流作用下制氢气的方法,根据其所制得富氢原料气的不同用途,按照需要可以采用成份不同的混合气和不同的等离子发生器的工作气体,例如:如果需要纯氢,使用甲烷纯度较高的天然气或煤层气作为原料,采用氢气作为工作气体,该过程还可以生成副产物纳米级的炭黑,同时不产生温室气体二氧化碳排放,是一个显著的低碳过程,由于氢气起弧有困难,可以在等离子发生器的工作气体中掺入一定比例的氩气,便于起弧和稳定电弧;如果需要制合成气,用来合成甲醇等含氧化合物,可以采用富甲烷气加二氧化碳,或富甲烷气加水蒸气,或富甲烷气加二氧化碳加水蒸气作为混合气,其中的富甲烷气可以是天然气、煤层气、焦炉煤气或者是其任意混合。采用含氧气体作为等离子体发生器的工作气体,如氧气,二氧化碳、氧气,或空气,或水蒸气,或氧气加水蒸气,或空气加氧气等,含氧气体的加入比例,视混合气气体成份的氢碳比和所需要的合成气的氢碳比而定;如果需要合成氨,采用富甲烷气作为原料,含氮气体如氮气,空气作为等离子体发生器的工作气体。氧气和空气的使用可以为等离子体制氢这一过程提供更多的能量,减少反应对等离子体能量的依赖程度,当然这样做会有一氧化碳和二氧化碳生成。由于上述混合气成份及等离子体工作气种类较多,而由氧气、二氧化碳、氧气、空气、水蒸气和氩气所能组成的混合气的种类更多,在本发明中不必一一列举,下面就具体实施方式的典型例结合附图进行详细描述,本领域的技术人员在阅读了具体实施例后,能够实现本发明是下显而易见的,同时其所述效果也能够得到体现。The present invention is a method for producing hydrogen by using methane-enriched gas under the action of plasma jet. According to the different uses of the hydrogen-enriched raw material gas, mixed gas with different components and working gas of different plasma generators can be used as required. , for example: if pure hydrogen is required, natural gas or coal bed methane with high methane purity is used as raw material, and hydrogen is used as working gas. This process can also generate nano-scale carbon black as a by-product, and at the same time does not produce greenhouse gas carbon dioxide emissions. It is a Significant low-carbon process, due to the difficulty of hydrogen arc starting, a certain proportion of argon can be mixed into the working gas of the plasma generator to facilitate arc starting and stable arc; if it is necessary to make synthesis gas, it can be used to synthesize methanol and other oxygen-containing Compounds can be mixed with methane-rich gas plus carbon dioxide, or methane-rich gas plus water vapor, or methane-rich gas plus carbon dioxide plus water vapor, wherein the methane-rich gas can be natural gas, coal bed methane, coke oven gas or any mixture thereof. Oxygen-containing gas is used as the working gas of the plasma generator, such as oxygen, carbon dioxide, oxygen, or air, or water vapor, or oxygen plus water vapor, or air plus oxygen, etc. The proportion of oxygen-containing gas depends on the gas composition of the mixture. The hydrogen-to-carbon ratio depends on the hydrogen-to-carbon ratio of the required synthesis gas; if it is necessary to synthesize ammonia, use methane-rich gas as the raw material, nitrogen-containing gas such as nitrogen, and air as the working gas of the plasma generator. The use of oxygen and air can provide more energy for the process of plasma hydrogen production, reducing the dependence of the reaction on plasma energy. Of course, carbon monoxide and carbon dioxide will be generated in this way. Because there are many types of the above-mentioned mixed gas components and plasma working gas, and there are more kinds of mixed gas that can be formed by oxygen, carbon dioxide, oxygen, air, water vapor and argon, it is not necessary to list them one by one in the present invention. Typical examples of specific implementations will be described in detail with reference to the accompanying drawings. After reading the specific embodiments, it will be obvious to those skilled in the art that the present invention can be realized, and at the same time, the effects can also be realized.
实施例1Example 1
如图1,在实施本发明制氢的方法时,打开阀门将甲烷含量为98%的天然气8送入等离子体反应器下部的换热器9中,将压缩氢气3送至等离子发生器2中,启动高频点火装置点燃等离子发生器电弧,形成等离子体射流4。等到系统达到稳定状态,进入等离子体反应器6下部换热器9的天然气8,与等离子体反应后的高温富氢气体换热,天然气被加热到300℃-600℃,被加热的天然气继续在等离子体反应器6上部的螺旋管换热器与等离子体反应器6的器壁换热,天然气二次被加热预活化,温度升至600℃-900℃,预热活化后的天然气11进入等离子反应器6内,在反应区内与等离子发生器产生的富含活性粒子的温度高达3000℃-4000℃的等离子体射流4相作用,在常压下小于100ms的时间里生成以氢气为主要成分的富氢气体,温度为900℃-1200℃富氢气体进入等离子气体反应器的下部与换热器9换热,降温后的富氢气体温度降至200℃-300℃,冷却后的富氢气体12经过气固分离器13,分离出富氢气体中副产物炭黑,气固分离器为常用的分离设备,如旋风分离器、布袋除尘器,除尘后的富氢气体14含氢量为达90%-98%,其余为少量的甲烷、一氧化碳、氮气等,富氢气体按照常规的方法,如膜分离、变压吸附分离出氢气,部分作为产品输出,部分作为等离子体发生器的工作气体使用。As shown in Figure 1, when implementing the method for hydrogen production of the present invention, the valve is opened to send natural gas 8 with a methane content of 98% into the
为了降低能耗,保护反应器,在反应器6的内壁敷有耐火保温材料5,反应器上部的换热器10埋设在其中,除了能保护反应器6的器壁,延长耐火材料的寿命;此外,反应器的外壁采用保温材料7包覆同样是为了降低反应器热损失。In order to reduce energy consumption and protect the reactor, the inner wall of the
实施例2Example 2
如图1,在实施本发明制氢的方法时,打开阀门将甲烷含量为98%的煤层气8进入等离子体反应器下部的换热器9,将压缩氮气3送至等离子发生器2,启动高频点火装置点燃等离子发生器电弧,形成等离子体射流4。等到系统达到稳态,进入等离子体反应器下部换热器9的煤层气,与等离子体反应后的900℃-1300℃气体换热,煤层气被加热到300℃-600℃,被加热的煤层气继续在上部换热器10与等离子体反应器器壁换热,煤层气二次被加热预活化,温度升至600℃-900℃,预热活化的煤层气11进入等离子反应器6内,在反应区内与等离子发生器产生的富含活性粒子的温度高达3500℃-4500℃的等离子体射流4相作用,在常压下小于100ms的时间里生成以氢气为主要成分的富氢气体,富氢气体进入等离子气体反应器的下部,在下部换热器9中换热,温度降至200℃-300℃,经过气固分离器13,分离出富氢气体12中副产物炭黑,气固分离器13为常用的分离设备,如旋风分离器、布袋除尘器,除尘后的富氢气体14中氢气和氮气的量为达90%-97%,其余为少量的甲烷、一氧化碳等,氢气与氮气的比例2.7-3。富氢气体14进入气体分离系统,该分离系统为目前合成氨工厂常规的分离净化工艺,分离出一氧化碳、二氧化碳、硫化氢等气体后,作为合成氨的原料气。As shown in Fig. 1, when implementing the method for hydrogen production of the present invention, the valve is opened to allow coalbed methane 8 with a methane content of 98% to enter the
为了降低能耗,保护反应器,在反应器6的内壁设置有耐火保温材料5,反应器上部的换热器10就埋设在其中,除了能保护反应器6器壁,延长耐火材料的寿命;此外,反应器的外壁采用保温材料7包覆同样是为了降低反应器热损失。In order to reduce energy consumption and protect the reactor, a
实施例3Example 3
如图1,在实施本发明制氢的方法时,将甲烷含量为26.3%,氢气含量为55.6%的焦炉煤气与二氧化碳混合后形成的混合气8进入等离子体反应器6下部的换热器9,将水蒸气与氧气的混合作为工作气体3送至等离子发生器2,启动高频点火装置点燃等离子发生器电弧,形成等离子体射流4。等到系统达到稳态,进入等离子体反应器6下部换热器的混合气,与等离子体反应后的1000℃-1500℃气体换热,混合气被加热到300℃-800℃,被加热的混合气继续与等离子体反应器器壁换热,混合气被二次被加热,温度升至600℃-1000℃,预热活化后的混合气11进入等离子反应器内,在反应区内与等离子发生器产生的富含活性粒子的温度高达2000℃-3500℃的等离子体射流相作用,在常压下小于100ms的时间里生成以氢气为主要成分的气体,富氢气体进入等离子气体反应器的下部,与下部换热器9换热,温度降至200℃-300℃以下,降温后的富氢气体12经过气固分离器13,分离出富氢气体中少量的炭黑,气固分离器为常用的分离设备,如旋风分离器、布袋除尘器,除尘后的富氢气体14中氢气与一氧化碳的含量达92%-98%,氢气与一氧化碳的比例为1.8-2.3,其余为少量的一氧化碳、二氧化碳、氮气等,富氢气体按照常规的方法,如低温甲醇洗,除去二氧化碳、硫化氢等气体,作为合成气输出用于生产甲醇、二甲醚、烯烃等燃料或化工原料。As shown in Fig. 1, when implementing the method for hydrogen production of the present invention, the mixed gas 8 formed by mixing coke oven gas with a methane content of 26.3% and a hydrogen content of 55.6% with carbon dioxide enters the heat exchanger at the bottom of the
为了降低能耗,保护反应器,在反应器6的内壁敷有耐火保温材料5,反应器上部的换热器10就埋设在其中,除了能保护反应器6器壁,延长耐火材料的寿命;此外,反应器的外壁采用保温材料7包覆同样是为了降低反应器热损失。In order to reduce energy consumption and protect the reactor, the inner wall of the
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