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CN101566103A - Power cycle method using hydrogen as fuel - Google Patents

Power cycle method using hydrogen as fuel Download PDF

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Publication number
CN101566103A
CN101566103A CNA2008101049950A CN200810104995A CN101566103A CN 101566103 A CN101566103 A CN 101566103A CN A2008101049950 A CNA2008101049950 A CN A2008101049950A CN 200810104995 A CN200810104995 A CN 200810104995A CN 101566103 A CN101566103 A CN 101566103A
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gas
hydrogen
turbine
reaction
temperature
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郑丹星
王志方
侯智
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

本发明提出一种以氢为燃料的动力循环方法。将H2和CO2逆变换反应用于以氢为燃料的O2/CO2动力循环的化学回热，富含氢气的气体原料与加压的CO2循环气混合；混合气体进入逆变换反应器发生吸热化学反应，生成水蒸汽和CO，反应所需热量由透平的高温排气提供；反应产生的气体与加压氧气分别进入燃烧室，生成高温高压的水蒸汽和CO2；高温气体经过燃气轮机透平发电；透平的高温排气先为逆变换反应器提供热量，再向余热回收系统排热，然后经进一步冷却和冷凝，分出其中的H2O；剩余的CO2循环气经过冷却和增压，返回循环气混合器。本发明通过逆变换反应的化学回热、余热制冷和进气冷却技术实现了氢气的高效利用，可以高效联产电和冷。The invention proposes a power cycle method using hydrogen as fuel. The H2 and CO2 inverse shift reaction is used for the chemical recuperation of hydrogen-fueled O2 / CO2 power cycle, the hydrogen-rich gas feedstock is mixed with the pressurized CO2 cycle gas; the mixed gas enters the inverse shift reaction The endothermic chemical reaction occurs in the reactor to generate water vapor and CO 2 , and the heat required for the reaction is provided by the high-temperature exhaust gas of the turbine; the gas generated by the reaction and the pressurized oxygen enter the combustion chamber respectively to generate high-temperature and high-pressure water vapor and CO 2 ; The gas passes through the gas turbine turbine to generate electricity; the high-temperature exhaust gas from the turbine first provides heat for the reverse conversion reactor, and then discharges heat to the waste heat recovery system, and then after further cooling and condensation, the H 2 O is separated; the remaining CO 2 is circulated The gas is cooled and pressurized, and returned to the recycle gas mixer. The invention realizes the efficient utilization of hydrogen through the chemical heat recovery of reverse conversion reaction, waste heat refrigeration and intake air cooling, and can efficiently co-produce electricity and cooling.

Description

A kind of is the power circulation method of fuel with hydrogen
Technical field
The present invention proposes a kind of is the power circulation method of fuel with hydrogen.Be specifically related to H 2And CO 2The O of reverse shift reaction chemical back heating 2/ CO 2Power cycle can be used for the utilization of gas industry hydrogen containing tail gas.
Background technique
In the gas industry such as oil refining, rock gas, petroleum gas, installation for blast furnace gas, chemical product processing with multiple hydrogen containing tail gas and waste gas.The High Purity Hydrogen air-flow that the concentration and separation of process hydrogen obtains.For example, gas by partial oxidation of natural/combustion decomposition system C 2H 2Technology is produced C 2H 2The a large amount of hydrogen-rich synthetic gas of by-product (wherein contains 54% H approximately simultaneously 2, 46% CO).And for example in the oil refinery dry gas, also contain a large amount of hydrogen.Hydrogen provides a valid approach as industrial cycle power for the utilization of hydrogen rich off gas.(Sugisita H, Mori H, Uematsua K.Study of thermodynamic cycle and system configurations of hydrogencombustion turbines.Int J Hydrogen Energy 1998 such as Sugisita H; 23 (8): 705-712) proposed a kind of H based on hydrogen fuel 2/ O 2Combined cycle.Pure oxygen and pure H 2After the supercharging, enter the firing chamber, the water vapor that reaction generates enters the turbine expansion work done together with the water vapor that is injected into the firing chamber.This system's turbine high-temperature exhaust air waste heat only is used to add hot feed, and generating efficiency is 54.3%.At present, there are some difficult points in the hydrogen-oxygen combined cycle on using, and key is that the development of hydrogen fuel gas turbine also exists some difficulties, mainly concentrates on fuel system, control system and firing chamber, and in addition, material, cooling and operation etc. also need to work hard.
O 2/ CO 2Circulation is a kind of, and the power cycle mode that adopts fuel to burn in oxygen atmosphere is characterised in that with the pure oxygen to be oxygenant, and cycle fluid is CO 2, fuel and pure oxygen burning have only CO 2Generate with water vapor, can separable water outlet and gaseous state CO through the cooling condensation 2People such as Degtiarev (Degtiarev V L, Grybovsky V P.Carbon dioxide semi-closed power plant.Author sertif.Bull:USSR.1971) have at first proposed the O of accurate zero-emission 2/ CO 2Circulation system.O 2/ CO 2The energy consumption of the circulatory system mainly is at making oxygen by air separation process and CO 2On the power consumption of compression gas compressor.Chemical back heating in the power cycle be a kind of turbine high-temperature exhaust air waste heat efficiently utilize method, turbine high-temperature exhaust air waste heat is converted into the combustion heat value of endothermic reaction products by the chemical reaction of heat absorption.US2002/0095931, having proposed a kind of is the power cycle of fuel with methyl alcohol.The heat absorption reaction recovery gas turbine high-temperature exhaust air waste heat that this circulation has adopted methanol steam to reform.It is the power circulation system of fuel with methane that CN1869418 proposes a kind of.By O 2/ CO 2Chemical back heating power cycle and ammonia absorption type cooling cycle system constitute, and methane CO has been adopted in this circulation 2The heat absorption reaction recovery gas turbine high-temperature exhaust air waste heat of reforming.Also adopt ammonia water absorbing circularly cooling technology and as CO 2Circulating air compressor air inlet machine cooling technology, the system generating efficiency of making reaches 49.6%.
In view of H 2And CO 2The power cycle of reverse shift reaction chemical back heating is not appeared in the newspapers.
Summary of the invention
It is the power circulation method of fuel with hydrogen that the present invention proposes a kind of, with H 2And CO 2It is the O of fuel that reverse shift reaction is used for hydrogen 2/ CO 2The chemical back heating of power cycle absorbs turbine high-temperature exhaust air refrigeration by residual neat recovering system simultaneously, system's cold is provided, thereby improves the generating efficiency of power circulation system, also has the function of electricity, cold coproduction simultaneously.
What the present invention proposed is the power circulation method of fuel with hydrogen, with CO 2Being cycle fluid, is oxygenant with the pure oxygen, is rich in the gas raw material of hydrogen and the CO of pressurization 2Circulating air mixes in the circulating air mixer, H 2With CO 2Mol ratio is 1: 3～1: 30; Mixed gas enters the reverse shift reaction device heat absorption inverse transformation chemical reaction takes place, and reaction temperature is 500 ℃～1000 ℃, and reaction pressure is 0.5～5.0MPa, generates CO and water vapor, and reaction institute calorific requirement is provided by the high-temperature exhaust air of turbine; CO gas and pressurised oxygen that reaction produces enter the firing chamber respectively, and burning generates water vapor and CO 2High-temperature gas; The high-temperature gas passes gas turbine for turbine power generation; The high-temperature exhaust air of turbine provides heat for the reverse shift reaction device earlier, again to the residual neat recovering system heat extraction, through further cooling and condensation of water cooler, tells H wherein then 2O; Remaining CO 2Circulating air returns the circulating air mixer through supercooling and supercharging.
In the circulation method of the present invention, the raw material H of reverse shift reaction 2Can be pure hydrogen, also can be the hydrogen-rich gas in the gas industry such as oil refining, rock gas, petroleum gas, installation for blast furnace gas, chemical product processing, the High Purity Hydrogen air-flow that the concentration and separation of process hydrogen obtains.Thereby for the high efficiente callback of hydrogen containing tail gas and waste gas provides the new mode of utilizing.The described gas raw material of hydrogen and the CO of pressurization of being rich in 2Carry out reverse shift reaction after the mixing, the conversion ratio of hydrogen in reaction can reach more than 60%.
In the circulation method of the present invention, the temperature that the turbine high-temperature exhaust air entered and left the reverse shift reaction device is respectively 500 ℃～1000 ℃ and 150 ℃～300 ℃.Thereby realized utilizing the chemical reaction that absorbs heat to reclaim the used heat of a part of turbine high-temperature exhaust air.
In the circulation method of the present invention, the turbine high-temperature exhaust air is cooled to 120 ℃～150 ℃ to the residual neat recovering system heat extraction, more further through being cooled to 10 ℃～50 ℃ at cooler; Enter separator then, isolate H 2O.CO 2Circulating air further is cooled to-20 ℃～20 ℃ by residual neat recovering system; Through CO 2The compression of circulating air gas compressor secondary is pressurized to 0.5～5.0MPa, returns the circulating air mixer.
In the circulation method of the present invention, described heat recovery is an ammonia absorption type refrigeration circulation.It is by the heat supply of turbine high-temperature exhaust air, and the cold of its generation is used for CO 2The cooling of circulating air compressor air inlet machine.Ammonia absorption type refrigeration circulation is to be realized by the common circulatory system, mainly by connecting to form with lower member: by the rectifying column of turbine high-temperature exhaust air heat supply, condenser, to CO 2The vaporizer of circulating air compressor air inlet machine cooler cooling, the vaporizer to extraneous cooling, adsorber, throttle valve and solution circulation pump constitute.
Effect of the present invention: the present invention is with H 2And CO 2It is the O of fuel that reverse shift reaction is used for hydrogen 2/ CO 2The chemical back heating of power cycle; Simultaneously the turbine high-temperature exhaust air is used for ammonia water absorbing circulation utilizing waste heat for refrigeration, the cold of generation is used for CO 2Circulation compressor air inlet machine cooling makes the generating efficiency of system reach 55.8% and (has considered to isolate O from air 2The power consumption of air separation process), be higher than 54.3% of hydrogen-oxygen combined cycle.
When realizing efficient power generation, the present invention produces cold with turbine high-temperature exhaust air utilizing waste heat for refrigeration, except being used for CO by ammonia water absorbing circuit residual neat recovering system 2The cooling of circulation compressor air inlet machine, outwards output.Realized the efficient coproduction of cold-peace electricity.
The present invention is as a kind of technology of resource recirculation, and to the high efficiente callback utilization of hydrogen containing tail gas and waste gas, energy saving is significant.Power cycle adopts CO 2Being working medium, is a kind of CO of helping 2What reduce discharging utilizes mode.
Description of drawings
Fig. 1 is a power circulation system schematic flow sheet of the present invention
Embodiment:
As shown in Figure 1: system of the present invention is fuel with hydrogen, CO 2Being cycle fluid, is oxygenant with the pure oxygen, by the CO of hydrogen 2Inverse transformation, O 2/ CO 2Chemical back heating power cycle and ammonia absorption type cooling cycle system combine and form, and system is mainly by connecting to form with lower member: respectively to pure oxygen, CO 2The compressor 1,2 of gas compression; H by turbine exhaust heat supply 2And CO 2Reverse shift reaction device 5; CO 2Circulating air mixer 9; The firing chamber 3 of reverse shift reaction gas and pure oxygen generation combustion reaction; The turbine 4 and the generator of high-temperature gas expansion working; Ammonia absorption type refrigerated heat exchanger 6 by turbine exhaust heat supply; Condensation separation goes out CO from the turbine exhaust 2The separator 7 of gas and liquid water; The cold cool cycles CO that utilizes the ammonia absorption type refrigeration to produce 2Charge air cooler 8; CO 2Circulating air gas compressor interstage cooler 10, aqua ammonia pump 11, cooler 12 and heat exchanger 13.
In the above-mentioned circulatory system, carry out power circulation method: from the hydrogen of Hydrogen Line after 14 superchargings of hydrogen-pressure mechanism of qi, and through CO 2The CO of circulating air gas compressor 2 compression superchargings 2According to 1: 3～1: 30 ratio of mol ratio at CO 2Mix in the circulating air mixer 9, enter reverse shift reaction device 5,500 ℃～1000 ℃ of temperature, reverse shift reaction takes place down in reaction pressure 0.5～5.0MPa, and the reverse shift reaction equation is:
H 2+CO 2＝CO+H 2O
The inverse transformation product generates CO, enters firing chamber 3 then, and with the pure oxygen generation combustion reactions under 1000 ℃～1500 ℃ through 1 supercharging of pure oxygen gas compressor, the combustion reaction equation is:
2CO+O 2→2CO 2
2H 2+O 2→2H 2O
The high-temperature gas that burning produces at first enters turbine 4 expansion workings.The turbine exhaust is introduced into 5 heat exchange of reverse shift reaction device, and for reverse shift reaction provides heat, self temperature is reduced to 150 ℃～300 ℃; Enter the single-stage circuit ammonia absorption type refrigeration circulatory system then, in heat exchanger 6, be further cooled, enter separator 7 last turbine exhaust is cooled to 10 ℃～50 ℃ in cooler 12 after, isolate CO to 120 ℃～150 ℃ 2Gas and liquid H 2O.Liquid H 2O reclaims, CO 2Circulating air is through the ammonia absorption type refrigeration circulatory system, at CO 2Be cooled to-20 ℃～20 ℃ in the charge air cooler 8 after CO 2The compression of circulating air gas compressor secondary is pressurized to 0.5～5.0MPa, returns circulating air mixer 9.Part is used for cooling off the CO that enters before the gas compressor in the cold that the ammonia absorption type refrigeration circulatory system provides 2, remaining part is by heat exchanger 13-2 output system.
Further open to the present invention by the following examples, but the invention is not restricted to this embodiment.
Embodiment 1:
In the circulatory system, from Hydrogen Line 1kgs -1The hydrogen of flow and is cooled to 0 ℃ and through CO at cooler 2The compression of circulating air gas compressor secondary is pressurized to the CO of 1MPa 2According to 1: 9 ratio of mol ratio at CO 2Mix in the circulating air mixer, enter the reverse shift reaction device, reverse shift reaction takes place down at 860 ℃, the inverse transformation product generates CO (content 6.2%), enter the firing chamber then, with the pure oxygen generation combustion reaction that is pressurized to 1MPa through the pure oxygen gas compressor, 1300 ℃ of high-temperature gases that burning produces at first enter the turbine expansion work done.The turbine exhaust is introduced into the heat exchange of reverse shift reaction device, and for reverse shift reaction provides heat, self temperature is reduced to 200 ℃; Enter the single-stage circuit ammonia absorption type refrigeration circulatory system then, in heat exchanger, be further cooled to 135 ℃.Enter separator last turbine exhaust is cooled to 30 ℃ in cooler after, isolate CO 2Gas and liquid H 2O.Liquid H 2O reclaims, CO 2Circulating air is through the ammonia absorption type refrigeration circulatory system, at CO 2Be circulated to CO after being cooled to 0 ℃ in the charge air cooler 2The circulating air gas compressor.In the cold that the ammonia absorption type refrigeration circulatory system provides, 5.34MW is used for cooling off the CO that enters before the gas compressor 2, 1.19MW is by the heat exchanger output system.Among the embodiment, the concrete operational condition of each equipment is as follows: the gas compressor isentropic efficiency is 0.86, and burner efficiency is 0.99, and the turbine isentropic efficiency is 0.89, and the minimum heat transfer temperature difference of chemical back heating reverse shift reaction device is 20 ℃; The minimum heat transfer temperature difference of heat recovery is 20 ℃, and the compressor air inlet machine crushing is 1%, calms the anger than being 10, and the firing chamber crushing is 3%, reverse shift reaction device both sides crushing 3%, and the cooler crushing is 2%, electromechanical efficiency is 98%.Ammonia water absorbing circularly cooling condition: heat source temperature is 120 ℃, and cooling water temperature is 25 ℃, and cryogenic temperature is 5 ℃, and coefficient of refrigeration is 0.55, and generator pressure is 1.5MPa.Empty branch wasted work is: 0.9MJ/kgO 2(0.1MPa, 15 ℃, purity is 99.5%), and the turbine intake temperature is when being 1300 ℃, the present invention realizes that performance is shown in the data of table 1.
Table 1 entire system performance
Illustrate: generating efficiency=(turbine output power-system consumption power)/(hydrogen gas consumption * hydrogen Lower heat value 119.62MJ/kg).

Claims (4)

1、一种以氢为燃料的动力循环方法，以CO2为循环工质，以纯氧为氧化剂，其特征在于：富含氢气的气体原料与加压的CO2循环气在循环气混合器中混合，H2与CO2摩尔比为1∶3～1∶30；混合气体进入逆变换反应器发生吸热逆变换化学反应，反应温度为500℃～1000℃，反应压力为0.5～5.0MPa，生成CO和水蒸汽，反应所需热量由透平的高温排气提供；反应产生的CO气体与加压氧气分别进入燃烧室，燃烧生成水蒸汽和CO2高温气体；高温气体经过燃气轮机透平发电；透平的高温排气先为逆变换反应器提供热量，再向余热回收系统排热，然后经水冷器进一步冷却和冷凝，分出其中的H2O；剩余的CO2循环气经过冷却和增压，返回循环气混合器。1. A power cycle method using hydrogen as fuel, with CO2 as the circulating working medium and pure oxygen as the oxidant, characterized in that: the gaseous raw material rich in hydrogen and the pressurized CO2 recycle gas in the recycle gas mixer Mixing, the molar ratio of H2 and CO2 is 1:3~1:30; the mixed gas enters the inverse conversion reactor to undergo an endothermic inverse conversion chemical reaction, the reaction temperature is 500°C~1000°C, and the reaction pressure is 0.5~5.0MPa, Generate CO and water vapor, and the heat required for the reaction is provided by the high-temperature exhaust gas of the turbine; the CO gas and pressurized oxygen produced by the reaction enter the combustion chamber respectively, and burn to generate water vapor and CO 2 high-temperature gas; the high-temperature gas passes through the gas turbine turbine to generate electricity ; The high-temperature exhaust gas from the turbine first provides heat for the reverse conversion reactor, and then discharges heat to the waste heat recovery system, and then is further cooled and condensed by a water cooler, and the H 2 O is separated out; the remaining CO 2 circulating gas is cooled and Pressurize and return to the recycle gas mixer. 2、根据权利要求1的方法，其特征在于，所述的富含氢气的气体原料是气体工业中的富氢气体，经过氢的富集分离得到的高纯氢气流。2. The method according to claim 1, characterized in that the hydrogen-rich gas raw material is a hydrogen-rich gas in the gas industry, a high-purity hydrogen stream obtained through hydrogen enrichment and separation. 3、根据权利要求1的方法，其特征在于，所述的透平高温排气向余热回收系统排热，降温至120℃～150℃，再经在冷却器降温至10℃～50℃；然后进入分离器，分离出H2O，剩余的CO2循环气被余热回收系统冷却至-20℃～20℃，经CO2循环气压气机二级压缩增压至0.5～5.0MPa，返回循环气混合器。3. The method according to claim 1, characterized in that the high-temperature exhaust gas from the turbine is discharged to the waste heat recovery system, the temperature is lowered to 120°C-150°C, and then cooled to 10°C-50°C in a cooler; and then Enter the separator, separate out H2O , and the remaining CO2 circulating gas is cooled to -20℃～20℃ by the waste heat recovery system, compressed and pressurized by the CO2 circulating air compressor to 0.5～5.0MPa in the second stage, and returned to the circulating gas mixer. 4、根据权利要求1的方法，其特征在于，所述的余热回收为氨水吸收式制冷循环，由透平高温排气供热，其产生的冷量用于CO2循环气压气机进气冷却。4. The method according to claim 1, characterized in that said waste heat recovery is ammonia water absorption refrigeration cycle, heat is supplied by the high-temperature exhaust gas of the turbine, and the cooling capacity generated by it is used for cooling the intake air of the CO2 circulating air compressor .
CNA2008101049950A 2008-04-25 2008-04-25 Power cycle method using hydrogen as fuel Pending CN101566103A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105258384A (en) * 2015-11-26 2016-01-20 中国科学院工程热物理研究所 Combined cooling heating and power system integrating thermochemical process
CN105433819A (en) * 2014-08-27 2016-03-30 上海合既得动氢机器有限公司 Hydrogen barbecue oven
JP2020097941A (en) * 2013-03-15 2020-06-25 パルマー ラボ，エルエルシー High efficiency power generation system and method using carbon dioxide circulating working fluid
CN114718730A (en) * 2022-04-19 2022-07-08 西安交通大学 A hydrogen-fired gas turbine system and control method for converting ammonia into hydrogen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020097941A (en) * 2013-03-15 2020-06-25 パルマー ラボ，エルエルシー High efficiency power generation system and method using carbon dioxide circulating working fluid
CN105433819A (en) * 2014-08-27 2016-03-30 上海合既得动氢机器有限公司 Hydrogen barbecue oven
CN105258384A (en) * 2015-11-26 2016-01-20 中国科学院工程热物理研究所 Combined cooling heating and power system integrating thermochemical process
CN114718730A (en) * 2022-04-19 2022-07-08 西安交通大学 A hydrogen-fired gas turbine system and control method for converting ammonia into hydrogen
CN114718730B (en) * 2022-04-19 2023-06-30 西安交通大学 Hydrogen-burning gas turbine system for converting ammonia into hydrogen and control method

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Application publication date: 20091028