CN101915163A - A method and equipment for oxyfuel combustion using hydrogen fuel and a gas turbine - Google Patents
A method and equipment for oxyfuel combustion using hydrogen fuel and a gas turbine Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 42
- 239000000446 fuel Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000005611 electricity Effects 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 239000000809 air pollutant Substances 0.000 abstract description 3
- 231100001243 air pollutant Toxicity 0.000 abstract description 3
- 239000003245 coal Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 238000002309 gasification Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- 238000010248 power generation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
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Abstract
Description
技术领域：本发明涉及一种利用能源方法及设备，尤其是一种使用氢气燃料和燃气轮机进行氧燃料燃烧的方法及装备，属于能源科技领域。Technical field: The present invention relates to a method and equipment for utilizing energy, especially a method and equipment for oxyfuel combustion using hydrogen fuel and a gas turbine, belonging to the field of energy science and technology.
背景技术：我国是以煤炭为主要一次能源的国家，煤炭占据一次能源的65％以上。目前我国煤炭产量和消费总量均列世界首位，而且煤炭产量仍在上升，2009年已经达到近25亿吨。我国大部分电力依靠燃煤电厂产生，每年由于燃煤产生大量的大气污染物的排放，目前我国二氧化硫和氮氧化物的排放均为世界首位。因此，我国面临能源供应安全和环境保护的双重压力，洁净煤技术的发展刻不容缓。根据我国的实际情况，煤基多联产和IGCC以及煤的液化技术将是我国煤炭清洁利用的主流技术，在保障我国能源供应安全方面将发挥巨大作用。Background technology: my country is a country with coal as the main primary energy, and coal accounts for more than 65% of the primary energy. At present, my country's coal production and total consumption both rank first in the world, and coal production is still rising, reaching nearly 2.5 billion tons in 2009. Most of my country's electricity is generated by coal-fired power plants. Every year, a large amount of air pollutants are emitted due to coal combustion. At present, my country's emissions of sulfur dioxide and nitrogen oxides rank first in the world. Therefore, my country is facing the dual pressure of energy supply security and environmental protection, and the development of clean coal technology is urgent. According to the actual situation of our country, coal-based polygeneration, IGCC and coal liquefaction technology will be the mainstream technology of coal clean utilization in my country, and will play a huge role in ensuring the security of my country's energy supply.
目前技术采用的是氢气与空气的燃烧或富氢气燃气做燃气轮机的燃料，并进行了一些热力学分析。包括西门子公司也正在进行氢气燃气轮机清洁燃烧过程的研究。这些技术目前采用纯氢气和空气以及纯氧为燃烧体系，面临的直接问题是燃气轮机对纯氢燃烧产生的极高温度的容忍程度。一些研究人员提出采用超高温陶瓷为燃气轮机部件，另外一些技术提出第一代氢气燃气轮机技术采用空气为助燃气体。这些均处在概念性研究阶段，同时，虽然尾气中主要产物是水蒸气和氮气，减少了碳排放，但因燃烧温度过高而存在热力氮氧化物生成量增加而导致NOx的排放增加的问题。因此，第一代氢气燃气轮机技术的工业应用难以进行。The current technology uses the combustion of hydrogen and air or hydrogen-rich gas as the fuel of the gas turbine, and some thermodynamic analysis has been carried out. Including Siemens is also conducting research on the clean combustion process of hydrogen gas turbines. These technologies currently use pure hydrogen, air and pure oxygen as the combustion system, and the immediate problem they face is the tolerance of the gas turbine to the extremely high temperature generated by the combustion of pure hydrogen. Some researchers proposed to use ultra-high temperature ceramics as gas turbine components, and some other technologies proposed that the first generation of hydrogen gas turbine technology use air as a combustion gas. These are all in the conceptual research stage. At the same time, although the main products in the tail gas are water vapor and nitrogen, which reduces carbon emissions, there is a problem of increased thermal nitrogen oxide generation due to excessive combustion temperature, resulting in increased NOx emissions. . Therefore, the industrial application of the first-generation hydrogen gas turbine technology is difficult.
发明内容：针对上述现有技术的不足，本发明提供了一种使用氢气燃料和燃气轮机进行氧燃料燃烧的方法及装备。Summary of the invention: In view of the shortcomings of the above-mentioned prior art, the present invention provides a method and equipment for oxy-fuel combustion using hydrogen fuel and a gas turbine.
为实现上述目的，本发明采用的技术方案是：一种使用氢气燃料和燃气轮机进行氧燃料燃烧的方法，采用纯氢气为燃料，以纯氧和再循环高温水蒸气的混合物为助燃气体(氧气分压为15-45％)，在燃气轮机燃烧室中进行氧燃料燃烧，从而产生高温高压水蒸气，驱动燃气透平发电。出口的蒸汽进入蒸汽透平进一步产生电力。In order to achieve the above object, the technical solution adopted in the present invention is: a method of using hydrogen fuel and a gas turbine to carry out oxyfuel combustion, adopting pure hydrogen as fuel, and using a mixture of pure oxygen and recirculated high-temperature water vapor as a combustion-supporting gas (oxygen partial pressure 15-45%), oxygen-fuel combustion is carried out in the combustion chamber of the gas turbine, thereby generating high-temperature and high-pressure water vapor, which drives the gas turbine to generate electricity. The exported steam enters the steam turbine to further generate electricity.
一种使用氢气燃料和燃气轮机进行氧燃料燃烧的装备，包括空分装置，纯氧缓冲罐，压气机，纯氢气源，燃烧室，燃气透平，第一发电机，第二发电机和蒸汽透平，水蒸气再循环装置。空分装置与纯氧缓冲罐连接。纯氧缓冲罐与压气机连接。再循环水蒸气管道连接在纯氧缓冲罐和压气机之间。燃烧室入口端与纯氢气源和压气机连接，出口端与燃气透平连接。第一发电机与燃气透平连接。燃气透平与蒸汽透平连接，蒸汽透平与第二发电机连接。An equipment for oxyfuel combustion using hydrogen fuel and a gas turbine, including an air separation unit, a pure oxygen buffer tank, a compressor, a pure hydrogen source, a combustion chamber, a gas turbine, a first generator, a second generator and a steam turbine Flat, water vapor recirculation unit. The air separation unit is connected with the pure oxygen buffer tank. The pure oxygen buffer tank is connected with the compressor. The recirculating water vapor pipeline is connected between the pure oxygen buffer tank and the compressor. The inlet end of the combustion chamber is connected with the pure hydrogen source and the compressor, and the outlet end is connected with the gas turbine. The first generator is connected to the gas turbine. The gas turbine is connected to the steam turbine, and the steam turbine is connected to the second generator.
本发明通过燃气-蒸汽联合发电，提高发电效率。由于尾气中只有水蒸气，很容易得到进一步利用，因此，该技术装备将不产生空气污染物，属于零污染排放系统。利用本发明提出的技术，燃气轮机部件不需要在超高温条件下工作，同时还解决在空气燃烧条件下热力氮氧化物生成量增加的问题，因此具有很大的推广优势。The invention improves power generation efficiency through gas-steam combined power generation. Since there is only water vapor in the tail gas, it is easy to be further utilized. Therefore, this technical equipment will not produce air pollutants and belongs to a zero-pollution emission system. Utilizing the technology proposed by the invention, gas turbine components do not need to work under ultra-high temperature conditions, and at the same time solve the problem of increased thermal nitrogen oxide generation under air combustion conditions, so it has great promotion advantages.
附图说明：Description of drawings:
图1是使用氢气燃料和燃气轮机进行氧燃料燃烧的方法流程图。Figure 1 is a flowchart of a method for oxyfuel combustion using hydrogen fuel and a gas turbine.
图2是使用氢气燃料和燃气轮机进行氧燃料燃烧设备的组成和原理框图。Fig. 2 is a composition and principle block diagram of an oxy-fuel combustion equipment using hydrogen fuel and a gas turbine.
图3是基于煤气化制氢、氢气为燃料的燃气轮机氧燃料燃烧的零碳排放新型多联产工艺和技术流程框图。Figure 3 is a block diagram of a new zero-carbon emission polygeneration process and technical process based on coal gasification hydrogen production and gas turbine oxyfuel combustion with hydrogen as fuel.
具体实施方式：Detailed ways:
如图1所示：一种使用氢气燃料和燃气轮机进行氧燃料燃烧的方法，该技术的核心部分是采用纯氢气为燃料，以纯氧和再循环高温水蒸气的混合物为助燃气体(氧气分压为15-45％)，在燃气轮机燃烧室中进行氧燃料燃烧，从而产生高温高压水蒸气，驱动燃气透平发电。出口的蒸汽进入蒸汽透平进一步产生电力。通过燃气-蒸汽联合发电，提高发电效率。As shown in Figure 1: a method of using hydrogen fuel and gas turbine for oxyfuel combustion, the core part of this technology is to use pure hydrogen as fuel, and use a mixture of pure oxygen and recirculated high-temperature water vapor as a combustion-supporting gas (oxygen partial pressure is 15-45%), oxygen-fuel combustion is carried out in the combustion chamber of the gas turbine, thereby generating high-temperature and high-pressure water vapor, which drives the gas turbine to generate electricity. The exported steam enters the steam turbine to further generate electricity. Improve power generation efficiency through gas-steam combined power generation.
如图2所示：1为空分装置，2为纯氧缓冲罐，3为压气机，4为纯氢气源，5为燃气轮机的燃烧室，6为燃气透平，7为第一发电机，8为蒸汽透平，9为第二发电机。空气(0.1MPa，25℃)进入空分装置1，产生的纯氧经过纯氧缓冲罐2进入压气机3。水蒸气再循环装置产生的再循环水蒸气(0.1MPa，200-400℃)与纯氧混合后进入压气机3，产生的高压助燃混合气体(氧气和水蒸气，1.4MPa，200-300℃)进入燃气轮机燃烧室5。来自纯氢气源4的氢气(1.4MPa，25℃)也同时进入燃烧室5，与氧气燃烧，产生高温燃气(1.4MPa，1200-1500℃)，从而驱动燃气透平轮机涡轮，从而驱动与其相连接的第一发电机7产生电力。控制燃烧室中氢气和氧气的比例而实现氧燃料条件下的贫氧燃烧，使从燃气轮机出口产生的尾气为水蒸气和极少量氢气的混合物(0.4MPa，500-600℃)。高温蒸汽进一步进入蒸汽透平8，驱动蒸汽轮机和与其相连接的第二发电机9进一步产生电力，从而实现燃气轮机和蒸汽轮机的联合循环。蒸汽轮机出口的尾气为水蒸气和极少量氢气混合物(0.1MPa，200-300℃)，构成余热蒸汽。部分余热蒸汽通过再循环回到压气机3，与来自纯氧缓冲罐2的纯氧构成氧燃料的助燃气体，另外一部分通过再循环到达煤气化单元，从而作为气化剂加以有效利用。剩余的余热蒸汽可用于产生余热。经过高效利用水蒸气的余热，使系统的整体热效率提高。在系统运行过程中不产生任何碳排放和氮氧化物的排放，因此是高效零污染分布式能源系统。As shown in Figure 2: 1 is the air separation unit, 2 is the pure oxygen buffer tank, 3 is the compressor, 4 is the pure hydrogen source, 5 is the combustion chamber of the gas turbine, 6 is the gas turbine, 7 is the first generator, 8 is a steam turbine, and 9 is a second generator. Air (0.1MPa, 25°C) enters the
如图3所示：利用本发明提出的技术可以实现基于煤气化制氢、氢气为燃料的燃气轮机氧燃料燃烧、燃气轮机和蒸汽轮机联合循环的零碳排放新型多联产系统。系统中利用水蒸气和氧气的混合物作为气化剂对褐煤(或生物质)进行气化。气化后的产物为氢气和一氧化碳的混合物，经过净化和重整后产生氢气和二氧化碳的混合物，通过气体分离装置(高温膜分离系统)将二氧化碳分离出来，从而得到纯氢燃料。分离出的高纯食品级二氧化碳可用于工业生产(如食品或饮料)，也可直接用于封存。纯氢燃料则进入燃气轮机燃烧产生高温蒸气，通过上述本发明提出的燃气轮机和蒸汽轮机联合循环系统产生电力。系统生产的纯氢还可以用于请燃料电池产生电力或作为其他工业原料。As shown in Figure 3: the technology proposed in the present invention can realize a new zero-carbon emission polygeneration system based on coal gasification hydrogen production, gas turbine oxyfuel combustion with hydrogen as fuel, and gas turbine and steam turbine combined cycle. In the system, a mixture of water vapor and oxygen is used as a gasification agent to gasify lignite (or biomass). The gasified product is a mixture of hydrogen and carbon monoxide, which is purified and reformed to produce a mixture of hydrogen and carbon dioxide, and the carbon dioxide is separated through a gas separation device (high temperature membrane separation system) to obtain pure hydrogen fuel. The separated high-purity food-grade carbon dioxide can be used in industrial production (such as food or beverage), and can also be directly used for storage. The pure hydrogen fuel enters the gas turbine for combustion to generate high-temperature steam, and electricity is generated through the combined cycle system of the gas turbine and steam turbine proposed by the present invention. The pure hydrogen produced by the system can also be used to generate electricity from fuel cells or as other industrial raw materials.
系统的原理Principle of the system
煤气化制氢过程采用目前成熟的煤气化技术。煤气化制氢主要通过两步进行，及褐煤的气化过程和气体的净化及重整(水煤气变换反应)。The coal gasification hydrogen production process adopts the current mature coal gasification technology. Coal gasification hydrogen production is mainly carried out in two steps, and the lignite gasification process and gas purification and reforming (water gas shift reaction).
1)煤气化过程1) Coal gasification process
以煤气化制氢为目标的气化工艺主要是利用煤与高温水蒸气反应，从而产生一氧化碳和氢气的混合物。主要反应方程式为：The gasification process aimed at producing hydrogen from coal gasification mainly uses coal to react with high-temperature steam to produce a mixture of carbon monoxide and hydrogen. The main reaction equation is:
C(s)+H2O(g)→H2(g)+CO(g)C(s)+ H2O (g)→ H2 (g)+CO(g)
在本发明技术工艺中，采用褐煤在中低温下进行气化反应，气化剂采用纯氧和水蒸气的混合物，以提高反应效率，产物为一氧化碳和氢气的混合气，但CO的含量相当较高。反应的方程式如下：In the technical process of the present invention, lignite is used to carry out the gasification reaction at a medium and low temperature, and the gasification agent is a mixture of pure oxygen and water vapor to improve the reaction efficiency. The product is a mixture of carbon monoxide and hydrogen, but the content of CO is quite low. high. The equation for the reaction is as follows:
3C(s)+H2O(g)+O2(g)→H2(g)+3CO(g)3C(s)+ H2O (g)+ O2 (g)→ H2 (g)+3CO(g)
产物中的CO将在水煤气变换反应中进行转换。The CO in the product will be converted in the water gas shift reaction.
2)水煤气变换反应2) Water gas shift reaction
煤气化气体产物的重整是通过水煤气变换反应实现的。水煤气变换反应在催化条件下与400-600摄氏度下在水煤气变换反应器中进行，催化剂采用以半焦为载体的纳米铁基催化剂，主要活性组分为Fe3O4.水煤气变换反应的方程式如下：The reforming of coal gasification gas products is achieved through the water gas shift reaction. The water-gas shift reaction is carried out in a water-gas shift reactor at 400-600 degrees Celsius under catalytic conditions. The catalyst is a nano-iron-based catalyst supported by semi-coke, and the main active component is Fe 3 O 4 . The equation of the water-gas shift reaction is as follows :
CO(g)+H2O(g)→H2(g)+CO2(g)CO(g)+ H2O (g)→ H2 (g)+ CO2 (g)
重整后气化产物为氢气和二氧化碳，为下一步的气体分离做准备。The reformed gasification products are hydrogen and carbon dioxide, which are prepared for the next step of gas separation.
3)氢气和二氧化碳的分离3) Separation of hydrogen and carbon dioxide
水煤气变换反应产生的氢气和二氧化碳的混合物采用常规的高温膜分离设备进行分离。分离出的纯二氧化碳可以用于工业生产(如食品和饮料)以及石油强化回收等，多余的则通过压缩后进行深埋。因此，系统将实现零碳排放。The mixture of hydrogen and carbon dioxide produced by the water gas shift reaction is separated by conventional high-temperature membrane separation equipment. The separated pure carbon dioxide can be used in industrial production (such as food and beverage) and enhanced oil recovery, etc., and the excess is compressed and buried deep. Therefore, the system will achieve zero carbon emissions.
4)燃气轮机燃烧室中的燃烧反应4) Combustion reaction in gas turbine combustor
分离的纯氢进入燃气轮机燃烧室，与氧气和高温水蒸气的混合物实现氧燃料燃烧。反应方程式如下：The separated pure hydrogen enters the combustor of the gas turbine, and the mixture with oxygen and high-temperature water vapor realizes oxy-fuel combustion. The reaction equation is as follows:
O2(g)+H2(g)→H2O(g) O2 (g)+ H2 (g)→ H2O (g)
由于燃烧时助燃气体为高温水蒸气和氧气的混合物，因此可以在大大提高系统燃烧效率的同时，消除热力氮氧化物的生成，因此系统不会产生氮氧化物的排放。Since the combustion-supporting gas is a mixture of high-temperature water vapor and oxygen during combustion, it can greatly improve the combustion efficiency of the system while eliminating the generation of thermal nitrogen oxides, so the system will not produce nitrogen oxide emissions.
5)电力的产生5) Generation of electricity
系统中的电力的生产通过三种方式：燃气透平驱动发电机；蒸汽轮机透平驱动发电机；氢燃料电池产生电力。Electricity in the system is produced in three ways: a gas turbine drives a generator; a steam turbine drives a generator; and a hydrogen fuel cell generates electricity.
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