CN116395691A - CO in carbon emission source realized by chemical-looping hydrogen production technology 2 System and method of trapping - Google Patents
CO in carbon emission source realized by chemical-looping hydrogen production technology 2 System and method of trapping Download PDFInfo
- Publication number
- CN116395691A CN116395691A CN202310358407.0A CN202310358407A CN116395691A CN 116395691 A CN116395691 A CN 116395691A CN 202310358407 A CN202310358407 A CN 202310358407A CN 116395691 A CN116395691 A CN 116395691A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- reactor
- unit
- oxygen carrier
- hydrogen production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 98
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005516 engineering process Methods 0.000 title claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 226
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 113
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 112
- 239000000446 fuel Substances 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 230000008569 process Effects 0.000 claims abstract description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003546 flue gas Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000005265 energy consumption Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 92
- 239000001301 oxygen Substances 0.000 claims description 92
- 229910052760 oxygen Inorganic materials 0.000 claims description 92
- 238000000926 separation method Methods 0.000 claims description 52
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- 230000003647 oxidation Effects 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 29
- 239000012752 auxiliary agent Substances 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 28
- 238000002485 combustion reaction Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000003345 natural gas Substances 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000001926 trapping method Methods 0.000 claims description 6
- 230000002950 deficient Effects 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 20
- 239000002918 waste heat Substances 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
- C01B3/063—Cyclic methods
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Carbon And Carbon Compounds (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a method for realizing CO in a carbon emission source by utilizing a chemical-looping hydrogen production technology 2 System and method for capturing heat released in fuel chemical looping hydrogen production process as carbon emission source CO 2 CO in the trapping process 2 The release unit provides energy and simultaneously utilizes the water vapor generated by the reduction reaction to reduce CO 2 Partial pressure of carbon dioxide in the release unit, facilitating CO 2 CO evolution by the release unit 2 . The method can reduce CO in carbon emission source 2 The high-efficiency conversion of fuel chemical energy is realized while the energy consumption is captured, compared with the method for respectively carrying out the hydrogen production of fuel chemical chains and the CO capturing in the flue gas 2 The equipment investment cost can be reduced.
Description
Technical Field
The present invention relates to CO 2 The technical field of trapping, in particular to a method for realizing CO in a carbon emission source by utilizing a chemical-looping hydrogen production technology 2 Systems and methods of trapping.
Background
Human activities cause a substantial increase in greenhouse gases in the atmosphere, thereby causing a series of serious climate problems. Reducing the emission of greenhouse gases and slowing down the greenhouse effect. CO 2 Is the main gas causing the greenhouse effect, and conventional CO 2 The trapping includes pre-combustion, post-combustion trapping, oxygen-enriched combustion and other processes, and the post-combustion trapping is due to N in air 2 Dilution of (c) results in CO in flue gas 2 The concentration of (2) is lower, resulting in high energy consumption of the existing post-combustion capture,CO is needed after gasification or reforming and water gas shift before combustion 2 Separation, relatively complex fuel conversion process, oxygen-enriched combustion realizing high concentration CO in flue gas at the cost of separating pure oxygen 2 Expensive air separation units and high air separation energy consumption are the main factors leading to high capture costs for the oxycombustion technology route. In addition, for cement and refining industries, a large amount of steam and electricity are consumed by adopting post-combustion trapping, an additional cogeneration system is needed to be newly built, or the requirement of trapping energy consumption is met by recycling high-temperature heat power generation through calcium cycle pure oxygen combustion, so that further improvement of trapping cost is caused, and further research and development of a technology capable of reducing carbon trapping cost is needed.
Disclosure of Invention
Aiming at the problems of high energy consumption and high trapping cost caused by low energy utilization efficiency in the trapping process of a low-concentration emission source, the invention aims to provide a method for realizing CO in a carbon emission source by utilizing a chemical-looping hydrogen production technology 2 The second purpose of the trapping system is to provide a method for realizing CO in a carbon emission source by utilizing a chemical-looping hydrogen production technology 2 And (5) a trapping method. The invention takes the heat released by an air reactor or a hydrogen production process as an emission source CO 2 The trapped desorption process provides energy; at the same time, the fuel is produced into CO 2 And H 2 O is used as the driving force of the release process, so that the equilibrium partial pressure of the regeneration process is reduced, and the reaction temperature of the release unit is lowered. The invention realizes the fuel CO while producing hydrogen with high efficiency 2 And emission source CO 2 Is captured with low energy consumption.
In order to achieve the above purpose, the invention adopts the following specific scheme:
in a first aspect, CO in a carbon emissions source is achieved using chemical looping hydrogen production technology 2 The system for trapping comprises a carbonization reactor, a calcination reactor, an air reactor, a fuel reactor and a hydrogen production reactor;
the carbonization reactor is communicated with the calcination reactor, the calcination reactor is also respectively communicated with the air reactor, the fuel reactor and the hydrogen production reactor, the fuel reactor is also respectively communicated with the air reactor and the hydrogen production reactor, and the hydrogen production reactor is also communicated with the air reactor;
the carbonization reactor is used as a carbon dioxide combining unit, and the carbon dioxide separating auxiliary agent is used for capturing CO in a low-concentration emission source 2 The carbon dioxide separation aid is then combined with CO 2 The carbon dioxide combined carrier obtained after that is sent to a calcination reactor;
the calcination reactor is used as a carbon dioxide release unit, the partial pressure of carbon dioxide is reduced by utilizing a reaction product in the fuel reactor, the carbon dioxide is combined with a carrier to be decomposed into a carbon dioxide separation auxiliary agent and release carbon dioxide and water vapor, the carbon dioxide with high purity can be obtained by separation after condensation, and the carbon dioxide separation auxiliary agent is sent back to the carbonization reactor to form auxiliary agent circulation;
the air reactor is used as an oxidation unit, air reacts with the intermediate metal oxygen carrier at high temperature to obtain an oxidation state oxygen carrier and oxygen-deficient air, and simultaneously, heat is released; the oxidation state oxygen carrier is sent into a fuel reactor, and the released heat is sent into a calcination reactor to supply heat for a carbon dioxide release unit;
the fuel reactor is used as a reduction unit, and the oxidation state oxygen carrier reacts with fuel at high temperature to obtain the reduction state oxygen carrier and generate CO 2 And water vapor, after gas-solid separation, the reduced oxygen carrier is sent into a hydrogen production reactor, CO 2 And steam is introduced into the calcination reactor;
the hydrogen production reactor is used as a hydrogen production unit, steam is introduced, and a reduced oxygen carrier is utilized to react with the steam to obtain an intermediate oxygen carrier, generate hydrogen and release heat; the intermediate state oxygen carrier is sent into an air reactor to form oxygen carrier circulation, and released heat is sent into a calcination reactor to supply heat for a carbon dioxide release unit;
in the circulation of the auxiliary agent, caO/CaCO is adopted 3 Desorbing carbon dioxide;
in the oxygen carrier circulation, fe is adopted 2 O 3 -Fe 3 O 4 FeO as oxygen carrier;
in the system, the heat released by the air reactor or/and the hydrogen production reactor is used as emission source CO 2 Desorption process for trappingProviding energy; simultaneously CO, a reaction product generated from fuel in a fuel reactor 2 And H 2 O acts as the driving force for the release process.
In a second aspect, CO in a carbon emission source is realized by using a chemical looping hydrogen production technology 2 Method for trapping, which can simultaneously realize high-efficiency conversion of fuel to hydrogen, carbon components of fuel and low-energy consumption CO of carbon emission source of flue gas 2 The trapping method comprises the following steps:
(1) Introducing the flue gas into a carbon dioxide combining unit filled with a carbon dioxide separation auxiliary agent, capturing carbon dioxide in the flue gas by the carbon dioxide separation auxiliary agent, and performing gas-solid or gas-liquid separation to obtain a decarburized flue gas and carbon dioxide combining carrier; the carbon dioxide combined carrier is a product obtained by combining a carbon dioxide separation auxiliary agent and carbon dioxide;
(2) Delivering the carbon dioxide combined carrier obtained in the step (1) to a carbon dioxide release unit, and introducing a reduction unit product to reduce CO by changing reaction conditions 2 Partial pressure, decomposing the carbon dioxide combined carrier into a carbon dioxide separation auxiliary agent and releasing carbon dioxide to obtain carbon dioxide and water vapor, condensing and separating to obtain high-purity carbon dioxide, and returning the carbon dioxide separation auxiliary agent to the step (1) to form auxiliary agent circulation;
(3) Introducing air and an intermediate metal oxygen carrier into an oxidation unit, obtaining an oxidation state oxygen carrier and oxygen-deficient air under the high-temperature reaction condition, and releasing heat at the same time; the released heat provides energy for the carbon dioxide release unit of step (2);
(4) Feeding the oxidized metal oxygen carrier obtained in the step (3) and fuel into a reduction unit together, and reacting the oxidized metal oxygen carrier and the fuel under the high-temperature reaction condition to obtain the reduced metal oxygen carrier and generate CO 2 And water, after gas-solid separation, sending the reducing gas product into a carbon dioxide release unit in the step (2) to reduce the partial pressure of carbon dioxide;
(5) The reduced metal oxygen carrier obtained in the step (4) and water vapor are sent to a hydrogen production unit, the reduced metal oxygen carrier is oxidized into an intermediate metal oxygen carrier in the hydrogen production unit and hydrogen is generated at the same time, after gas-solid separation, a gas product is condensed to obtain high-purity hydrogen, the intermediate metal oxygen carrier is sent to an oxidation unit in the step (3) to form an oxygen carrier circulation, and the heat released by the hydrogen production unit is used for generating electricity or providing energy for a carbon dioxide release unit;
(6) The carbon dioxide combining unit, the hydrogen production unit and the oxidation unit are all exothermic processes, and the carbon dioxide releasing unit and the reduction unit are endothermic processes; the heat required by the reduction unit is provided by the heat carried by the oxygen carrier of the oxidation unit, and the heat required by the carbon dioxide release unit is provided by selecting the heat of the oxidation unit or the hydrogen production unit according to the release temperature.
Preferably, in the step (1), the flue gas introduced into the carbon dioxide combining unit comprises CO in the technical processes of power plant flue gas, cement, chemical industry, steel and the like 2 Is a gas of (a) a gas of (b).
Preferably, in the step (1), the carbon dioxide separation aid is an absorbent or adsorbent such as CaO or MgO.
Preferably, in the step (4), the fuel fed into the reduction unit includes gas, liquid or solid having a heat value such as coal, natural gas, synthesis gas, biomass, coke oven gas, etc.; further, the ratio of oxidized metal oxygen carrier to fuel ensures complete conversion of the reduction unit fuel to CO 2 And H 2 O. Product CO of the reduction unit 2 And H 2 O enters CO 2 The release unit reduces the equilibrium partial pressure of CO2 release.
Preferably, the oxygen carrier is a metal oxygen carrier. Further, the oxygen carrier comprises Fe, feO, co, ni or Cu and the like.
Preferably, the reaction temperature of the carbon dioxide binding unit is 40-800 ℃.
Preferably, the reaction temperature of the carbon dioxide releasing unit is 800-950 ℃.
Preferably, the reaction temperature of the oxidation unit is 800-1200 ℃.
Preferably, the reaction temperature of the reduction unit is 600-1000 ℃.
Preferably, the reaction temperature of the hydrogen production unit is 500-900 ℃.
Preferably, the oxidation unitAnd the heat released by the hydrogen production unit is based on CO 2 Temperature matching of the release unit to the CO 2 And a release unit.
The beneficial effects of the invention are as follows:
the invention utilizes the heat released by the oxidation reaction unit or the hydrogen production reaction unit in the fuel chemical-looping hydrogen production process to provide energy for the reduction reaction unit and the carbon dioxide release unit, thereby realizing self-heating of the process; meanwhile, the partial pressure of carbon dioxide is reduced by utilizing the vapor generated by the reduction reaction, which is beneficial to driving the precipitation of carbon dioxide in the carbon dioxide release unit; the invention realizes the trapping of CO by the fuel hydrogen production unit and the carbon emission source by adjusting the proportion of the circulating carrier 2 Energy matching between cells. The invention can realize the zero energy consumption trapping of carbon dioxide in the fuel conversion process and reduce the energy consumption of carbon dioxide trapped by an emission source while realizing the high-efficiency hydrogen production of the fuel, compared with the method for respectively carrying out the chemical-looping hydrogen production of the fuel and trapping CO in the flue gas 2 The equipment investment can be reduced.
Drawings
FIG. 1 shows the coupling of fuel chemical looping hydrogen to realize CO in carbon emission source flue gas 2 Schematic diagram of trapping method.
FIG. 2 shows the coupling fuel chemical looping hydrogen production of the invention to realize CO in carbon emission source flue gas 2 A typical process flow schematic of the trapping process.
FIG. 3 is a representative process flow diagram of selected reference objects of the present invention for performing a fuel hydrogen production process and carbon emission source flue gas CO, respectively 2 A simple combination of trapping processes.
FIG. 4 is a representative process flow of selected reference objects of the present invention, which is a calcium cycling post-combustion capture process.
Detailed Description
Carbon emission source CO capture 2 In order to solve the problems of high cost and high energy consumption, particularly the capture of carbon dioxide in low-concentration carbon emission sources consumes a large amount of energy, and for low-concentration emission sources of factories such as cement, refining and the like, a newly built cogeneration power plant is required to provide steam and electric power or recycle high-temperature heat through calcium cycle pure oxygen combustion to generate electricity so as to meet the energy requirement of the capture process,causing CO 2 The trapping cost is high. The invention cancels the air separation unit which originally provides energy in the calcium circulating pure oxygen combustion process, realizes the fuel CO while producing hydrogen with high efficiency 2 And a low concentration emission source CO 2 Is captured with low energy consumption.
Fossil fuel realizes low-carbon hydrogen production by chemical-looping hydrogen production and simultaneously is emission source CO 2 The trapping provides the required energy.
And (3) refining specific working units:
the three reactors are all insulated in the original three-reactor chemical-looping hydrogen production process; the invention realizes the energy supply for the release process in the post-combustion trapping unit by adjusting the carrier proportion and the reaction condition of the reactor;
the original technology after combustion only uses heat to drive the release process to desorb CO 2 The method comprises the steps of carrying out a first treatment on the surface of the The invention utilizes the product of the chemical-looping hydrogen production process to drive the release process, can reduce the release temperature of the release process, and simultaneously provides partial energy.
The technical scheme of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention and the accompanying drawings.
Example 1
As shown in FIG. 1, the method of the present invention involves a chemical looping hydrogen production cycle and CO 2 And (5) separating and recycling the auxiliary agent.
In CO 2 In the auxiliary agent separation circulation, the emission source flue gas enters a carbon dioxide combination unit after passing through a desulfurization and denitrification purification unit and the like, wherein the carbon dioxide separation auxiliary agent can react with carbon dioxide in the emission source flue gas to absorb the carbon dioxide in the flue gas, the reaction temperature of the carbon dioxide combination unit is 40-800 ℃, the pressure is normal pressure or high pressure, the carbon dioxide combination carrier is obtained after the carbon dioxide is captured by the carbon dioxide separation auxiliary agent, and the decarbonized flue gas is separated from solid through a gas-solid separator to capture the carbon dioxide in the emission source flue gas. The carbon dioxide combined carrier separated from the decarbonized flue gas enters a carbon dioxide releasing unit, the carbon dioxide releasing unit is powered by heat released by an oxidizing unit or a hydrogen producing unit, and simultaneously the carbon dioxide is oxidized under the drive of a reduction product of a reducing unitThe carbon-combined carrier is decomposed into a carbon dioxide separation auxiliary agent and carbon dioxide, the reaction temperature of the carbon dioxide release unit is 800-950 ℃ according to different carriers, the carbon dioxide separation auxiliary agent is circulated back to the carbon dioxide combining unit after gas-solid separation, and the obtained gas product is condensed and separated to obtain high-purity carbon dioxide.
The chemical-looping hydrogen production cycle comprises an oxidation unit, a reduction unit and a hydrogen production unit, wherein in the oxidation unit, air reacts with an intermediate oxygen carrier to release heat, the reaction temperature is 800-1200 ℃, the reaction pressure is normal pressure or high pressure, and the heat released in the process can provide a carbon dioxide release unit or generate high-temperature steam after heat recovery and generate power through thermodynamic cycle. The air reacts with the intermediate oxygen carrier to obtain oxygen-deficient air and an oxidation state oxygen carrier, the oxidation state oxygen carrier is sent into a reduction unit to react with fuel after gas-solid separation, the reaction temperature is 600-1000 ℃, the reaction pressure is normal pressure or high pressure, and in the reduction unit, the oxidation state oxygen carrier is reduced into a reduction state by the fuel to simultaneously generate carbon dioxide and H 2 O, after gas-solid separation, the gas reduction product is sent into CO 2 The release unit drives CO 2 And (3) releasing the solid reduced oxygen carrier, and sending the solid reduced oxygen carrier into a hydrogen production unit to react with water vapor to produce hydrogen. The hydrogen production unit is characterized in that the reduced oxygen carrier is oxidized by water vapor to generate hydrogen, the reaction temperature of the hydrogen production unit is 500-900 ℃, and the pressure is normal pressure or high pressure. The obtained product is separated from the gas by a gas-solid separator and condensed to obtain a hydrogen product, and the separated reduced metal oxygen carrier is sent into an oxidation unit to form an oxygen carrier circulation.
FIG. 2 is a schematic illustration of the chemical looping hydrogen production technique of the present invention for achieving CO in a carbon emissions source 2 Schematic of a typical process flow of trapping. As shown in FIG. 2, in this exemplary embodiment, caO/CaCO are selected separately 3 And Fe (Fe) 2 O 3 -Fe 3 O 4 FeO as CO 2 Separating carrier and oxygen carrier for chemical-looping hydrogen production, and taking natural gas as typical fuel. Firstly, the flue gas reacts with CaO carrier in a carbonization unit, and part of CaO reacts with CO in the flue gas 2 Reacting to generate CaCO 3 Through gas-solid separationThereafter, comprises CaCO 3 The solid is sent into a calcination reactor and CaCO is driven by the gas products of the high temperature and fuel reactor 3 Decomposition into CO 2 And CaO, after gas-solid separation, the CaO is sent back to the carbonization unit to absorb CO in the flue gas again 2 While the gaseous product (mainly CO 2 And water) is further condensed and separated after heat recovery to obtain high-purity CO 2 Because the calcination reactor and the carbonization reaction have higher temperature and release heat in the carbonization reaction, sensible heat carried by the decarbonization flue gas and the calcination reaction gas product and the heat released in the carbonization reaction are recovered through the waste heat boiler, and high-temperature steam is generated to drive the steam turbine to do work. Since the calcination reaction absorbs heat, the heat required is provided by the oxidation process in an air reactor in which the intermediate oxygen carrier Fe 3 O 4 Oxidized by preheated air into oxidation state oxygen carrier Fe 2 O 3 The air is preheated by the heat recovery mode after the air-solid separation, the air with the oxygen-poor after the heat recovery is directly discharged into the atmosphere or is further utilized by heat, and the oxygen carrier Fe in oxidation state is obtained 2 O 3 Then the fuel is fed to the fuel reactor to react with natural gas. In the fuel reactor, the natural gas will oxidize the oxygen carrier Fe 2 O 3 Reducing into reduced oxygen carrier FeO and generating CO as main component 2 And H 2 The gas product of O is sent into a calcination reactor to drive CaCO after gas-solid separation 3 Decomposing and delivering the reduced oxygen carrier FeO into a hydrogen production reactor to react with water vapor. In the hydrogen production reactor, the water vapor oxidizes the reduced oxygen carrier FeO into intermediate oxygen carrier Fe 3 O 4 Generating hydrogen, performing gas-solid separation, recovering heat of gas product (mainly steam and hydrogen) by preheating reactant, and further condensing to obtain high-purity hydrogen and intermediate oxygen carrier Fe 3 O 4 Then the mixture is sent into an air reactor for oxidation reaction, and oxygen carrier circulation is completed.
In this exemplary case, the relevant reaction conditions are selected as follows: wherein the temperature of the carbonization reactor is 650 ℃, and the CaO and the CO of the carbonization reactor 2 The molar ratio of (2) was 4.25, caO is converted into 20%, the temperature of the calcination reactor is 900 ℃, the temperature of the air reactor is 950 ℃, the fuel reactor and the hydrogen production reactor are both insulated, the waste heat boiler adopts a three-pressure reheating technology, the temperature of the waste heat boiler is 126bar/566 ℃, the temperature of the waste heat boiler is 26bar/566 ℃, the temperature of the waste heat boiler is 5.5bar/305 ℃, the exhaust gas temperature of the waste heat boiler is 125 ℃, and the pressure of the waste heat boiler is micro positive pressure.
In order to further illustrate the beneficial effects of the present invention, reference 1 was further selected as a reference. The process flow diagram of comparative example 1 is shown in fig. 3.
FIG. 3 is a representative process flow diagram of selected comparative examples of the present invention in which CO in flue gas is performed in parallel 2 Trapping and fuel chemical looping to produce hydrogen. As shown in figure 3, natural gas is split and then enters a fuel chemical-looping hydrogen production unit and chemical-looping combustion coupling calcium circulation CO capturing unit respectively 2 A unit. In a fuel chemical-looping hydrogen production unit, in an air reactor, intermediate oxygen carrier Fe 3 O 4 Oxidized by preheated air into oxidation state oxygen carrier Fe 2 O 3 The air is preheated by the heat recovery mode after the air-solid separation, the air with the oxygen-poor after the heat recovery is directly discharged into the atmosphere or is further utilized by heat, and the oxygen carrier Fe in oxidation state is obtained 2 O 3 Then the fuel is fed to the fuel reactor to react with natural gas. In the fuel reactor, the natural gas will oxidize the oxygen carrier Fe 2 O 3 Reducing into reduced oxygen carrier FeO and generating CO as main component 2 And H 2 After gas-solid separation, the gas product of O is sent to a waste heat boiler to recover heat and generate electricity to do work, and the reduced oxygen carrier FeO is sent to a hydrogen production reactor to react with water vapor. In the hydrogen production reactor, the water vapor oxidizes the reduced oxygen carrier FeO into intermediate oxygen carrier Fe 3 O 4 Generating hydrogen, performing gas-solid separation, recovering heat of gas product (mainly steam and hydrogen) by preheating reactant, and further condensing to obtain high-purity hydrogen and intermediate oxygen carrier Fe 3 O 4 Then the mixture is sent into an air reactor for oxidation reaction, and oxygen carrier circulation is completed.
Combustion in chemical chainCoupled calcium recycle capture of CO 2 In the process, the flue gas reacts with CaO carrier in a carbonization unit, and part of CaO reacts with CO in the flue gas 2 Reacting to generate CaCO 3 After gas-solid separation, comprises CaCO 3 The solid is sent into a calcination reactor and CaCO is driven by the gas product of the fuel reactor in the high-temperature and chemical-looping combustion process 3 Decomposition into CO 2 And CaO, after gas-solid separation, the CaO is sent back to the carbonization unit to absorb CO in the flue gas again 2 While the gaseous product (mainly CO 2 And water) is further condensed and separated after heat recovery to obtain high-purity CO 2 . Because the calcination reaction absorbs heat, the heat is supplied by the chemical looping combustion process, and Fe is adopted in the chemical looping combustion process 3 O 4 /Fe 2 O 3 Fe as oxygen carrier in an air reactor 3 O 4 React with air to produce Fe 2 O 3 The heat released in the process is provided for a calcination reactor, and Fe is obtained after gas-solid separation 2 O 3 Feeding into a fuel reactor to react with natural gas to generate CO as a main component 2 And H 2 The gas product of O is sent to a calcining unit to drive CaCO after gas-solid separation 3 Decomposing, solid oxygen carrier Fe 3 O 4 And (5) feeding the mixture into an air reactor to complete a chemical looping combustion cycle. And the sensible heat of the flue gas in each process and the reaction heat in the carbonization process are recovered by adopting a waste heat boiler.
In comparative example 1, the relevant reaction conditions were selected as follows: wherein chemical looping combustion is coupled with calcium recycle to capture CO 2 In the unit, the temperature of the carbonization reactor is 650 ℃, and the CaO and the CO of the carbonization reactor 2 The molar ratio of (2) was 4.25, caO converted to 20%, the temperature of the calcination reactor was 900 ℃, the air reactor temperature was 950 ℃, and the fuel reactor was adiabatic. In the fuel chemical-looping hydrogen production reactor, the air reactor temperature, the fuel reactor and the hydrogen production reactor are all insulated. The waste heat boiler adopts a three-pressure reheating technology, the temperature is 126bar/566 ℃, the temperature is 26bar/566 ℃, the temperature is 5.5bar/305 ℃, the exhaust gas temperature of the waste heat boiler is 125 ℃, and the pressure is micro-positive pressure.
Natural gas and flue gas composition based on typical examples and comparative example 1As shown in tables 1 and 2, the performance pairs are shown in table 3. Typical examples are for the same natural gas, flue gas input and the same CO as comparative examples 2 In the case of the trapped amount, the energy efficiency was 7.1 percent higher than that of comparative example 1, and the energy utilization effect was good.
Table 1 input natural gas composition
| Project | Unit (B) | Numerical value |
| Temperature (temperature) | ℃ | 15 |
| Pressure of | bar | 1.013 |
| Molar flow rate | kmol/h | 2067.7 |
| Low heat value | MJ/kg | 45.3 |
| Composition (volume fraction) | ||
| CH 4 | ％ | 79.75 |
| C 2 H 6 | ％ | 9.68 |
| C 3 H 8 | ％ | 4.45 |
| C 4 H 10 | ％ | 2.37 |
| CO 2 | ％ | 2.92 |
| N 2 | ％ | 0.83 |
Table 2 input smoke composition
Table 3 performance comparison
| Project | Examples | Comparative example 1 |
| Input device | ||
| Natural gas (MW) | 535.5 | 535.5 |
| Flue gas (kmol/h) | 14716.1 | 14716.1 |
| Output of | ||
| Hydrogen (MW) | 332.6 | 270.1 |
| Electric power (MW) | 54.8 | 79.2 |
| Energy efficiency (%) | 72.3 | 65.2 |
| CO 2 Trapping quantity (kg/s) | 58.8 | 58.8 |
* Energy efficiency = (hydrogen output + power output)/(natural gas input)
The invention discloses a method for realizing CO in a carbon emission source by utilizing a chemical-looping hydrogen production technology 2 The trapping method uses the heat released in the fuel chemical-looping hydrogen production process (the heat released by the oxidation unit or the hydrogen production unit) as a carbon emission source CO 2 CO in the trapping process 2 The release unit provides energy and simultaneously utilizes the water vapor generated by the reduction reaction to reduce CO 2 Partial pressure of carbon dioxide in the release unit, facilitating CO 2 CO evolution by the release unit 2 Thereby improving the efficiency of the system by 5-8 percentage points.
Comparative example 2: the conventional post-combustion technology takes the combustion heat supply of calcium circulating pure oxygen as a reference object, and a trapping flow chart after the calcium circulating combustion is shown in fig. 4. In this comparative example, the relevant reaction conditions were chosen as follows: wherein the temperature of the carbonization reactor is 650 ℃, and the CaO and the CO of the carbonization reactor 2 The molar ratio of (2) is 4.25, caO is converted into 20%, the temperature of the calcination reactor is 900 ℃, the fuel is natural gas, the oxygen purity of the air separation unit is 95%, and the power consumption of the air separation unit is 180kWh/tO 2 The waste heat boiler adopts a three-pressure reheating technology, the temperature is 126bar/566 ℃, the temperature is 26bar/566 ℃, the temperature is 5.5bar/305 ℃, the exhaust gas temperature of the waste heat boiler is 125 ℃, and the pressure is micro-positive pressure. The results are compared as shown in Table 4 below.
Table 4 comparison of results
It should be noted that the above-mentioned embodiments are to be understood as illustrative, and not limiting, the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made to the present invention without departing from its spirit or scope.
Claims (10)
1. CO in carbon emission source realized by chemical-looping hydrogen production technology 2 A system of trapping, characterized by: comprises a carbonization reactor, a calcination reactor, an air reactor, a fuel reactor and a hydrogen production reactor;
the carbonization reactor is communicated with the calcination reactor, the calcination reactor is also respectively communicated with the air reactor, the fuel reactor and the hydrogen production reactor, the fuel reactor is also respectively communicated with the air reactor and the hydrogen production reactor, and the hydrogen production reactor is also communicated with the air reactor;
the carbonization reactor is used as a carbon dioxide combining unit, and the carbon dioxide separating auxiliary agent is used for capturing CO in a low-concentration emission source 2 The carbon dioxide separation aid is then combined with CO 2 The carbon dioxide combined carrier obtained after that is sent to a calcination reactor;
the calcination reactor is used as a carbon dioxide release unit, the partial pressure of carbon dioxide is reduced by utilizing a reaction product in the fuel reactor, the carbon dioxide is combined with a carrier to be decomposed into a carbon dioxide separation auxiliary agent and release carbon dioxide and water vapor, the carbon dioxide with high purity can be obtained by separation after condensation, and the carbon dioxide separation auxiliary agent is sent back to the carbonization reactor to form auxiliary agent circulation;
the air reactor is used as an oxidation unit, air reacts with the intermediate metal oxygen carrier at high temperature to obtain an oxidation state oxygen carrier and oxygen-deficient air, and simultaneously, heat is released; the oxidation state oxygen carrier is sent into a fuel reactor, and the released heat is sent into a calcination reactor to supply heat for a carbon dioxide release unit;
the fuel reactor is used as a reduction unitReacting the oxidized oxygen carrier with fuel at high temperature to obtain reduced oxygen carrier and generate CO 2 And water vapor, after gas-solid separation, the reduced oxygen carrier is sent into a hydrogen production reactor, CO 2 And steam is introduced into the calcination reactor;
the hydrogen production reactor is used as a hydrogen production unit, steam is introduced, and a reduced oxygen carrier is utilized to react with the steam to obtain an intermediate oxygen carrier, generate hydrogen and release heat; the intermediate state oxygen carrier is sent into an air reactor to form oxygen carrier circulation, and released heat is sent into a calcination reactor to supply heat for a carbon dioxide release unit;
in the system, the heat released by the air reactor or/and the hydrogen production reactor is used as emission source CO 2 The trapped desorption process provides energy; simultaneously CO, a reaction product generated from fuel in a fuel reactor 2 And H 2 O acts as the driving force for the release process.
2. The system according to claim 1, wherein: in the circulation of the auxiliary agent, caO/CaCO is adopted 3 Desorbing carbon dioxide; in the oxygen carrier cycle, fe is adopted 2 O 3 -Fe 3 O 4 FeO as oxygen carrier.
3. CO in carbon emission source realized by chemical-looping hydrogen production technology 2 The trapping method is characterized in that: the method is applied to the system of claim 1, and realizes the efficient conversion of fuel to hydrogen, the carbon component of the fuel and the low-energy consumption CO of the carbon emission source of the flue gas after combustion 2 The trapping method comprises the following steps:
(1) Introducing the flue gas into a carbon dioxide combining unit filled with a carbon dioxide separation auxiliary agent, capturing carbon dioxide in the flue gas by the carbon dioxide separation auxiliary agent, and performing gas-solid or gas-liquid separation to obtain a decarburized flue gas and carbon dioxide combining carrier; the carbon dioxide combined carrier is a product obtained by combining a carbon dioxide separation auxiliary agent and carbon dioxide;
(2) Feeding the carbon dioxide-bonded carrier obtained in the step (1) into a carbon dioxide releasing unit by changing the reaction barPart, introducing reduction unit product to reduce CO 2 Partial pressure, decomposing the carbon dioxide combined carrier into a carbon dioxide separation auxiliary agent and releasing carbon dioxide to obtain carbon dioxide and water vapor, condensing and separating to obtain high-purity carbon dioxide, and returning the carbon dioxide separation auxiliary agent to the step (1) to form auxiliary agent circulation;
(3) Introducing air and an intermediate metal oxygen carrier into an oxidation unit, obtaining an oxidation state oxygen carrier and oxygen-deficient air under the high-temperature reaction condition, and releasing heat at the same time; the released heat provides energy for the carbon dioxide release unit of step (2);
(4) Feeding the oxidized metal oxygen carrier obtained in the step (3) and fuel into a reduction unit together, and reacting the oxidized metal oxygen carrier and the fuel under the high-temperature reaction condition to obtain the reduced metal oxygen carrier and generate CO 2 And water, after gas-solid separation, sending the reducing gas product into a carbon dioxide release unit in the step (2) to reduce the partial pressure of carbon dioxide;
(5) The reduced metal oxygen carrier obtained in the step (4) and water vapor are sent to a hydrogen production unit, the reduced metal oxygen carrier is oxidized into an intermediate metal oxygen carrier in the hydrogen production unit and hydrogen is generated at the same time, after gas-solid separation, a gas product is condensed to obtain high-purity hydrogen, the intermediate metal oxygen carrier is sent to an oxidation unit in the step (3) to form an oxygen carrier circulation, and the heat released by the hydrogen production unit is used for generating electricity or providing energy for a carbon dioxide release unit;
(6) The carbon dioxide combining unit, the hydrogen production unit and the oxidation unit are all exothermic processes, and the carbon dioxide releasing unit and the reduction unit are endothermic processes; the heat required by the reduction unit is provided by the heat carried by the oxygen carrier of the oxidation unit, and the heat required by the carbon dioxide release unit is provided by selecting the heat of the oxidation unit or the hydrogen production unit according to the release temperature.
4. A method according to claim 3, characterized in that: in the step (1), the flue gas introduced into the carbon dioxide combining unit is CO-containing generated in the process of power plant flue gas, cement, chemical industry or steel processing technology 2 Is a gas of (a) a gas of (b).
5. A method according to claim 3, characterized in that: in the step (4), the fuel fed to the reduction unit is a gas, liquid or solid having a heat value.
6. The method according to claim 5, wherein: the fuel is coal, natural gas, synthetic gas, biomass or coke oven gas.
7. A method according to claim 3, characterized in that: in step (4), the ratio of the oxidized metal oxygen carrier to the fuel ensures complete conversion of the reduction unit fuel to CO 2 And H 2 O。
8. A method according to claim 3, characterized in that: the reaction temperature of the carbon dioxide combining unit is 40-800 ℃; the reaction temperature of the carbon dioxide releasing unit is 800-950 ℃.
9. A method according to claim 3, characterized in that: the reaction temperature of the oxidation unit is 800-1200 ℃; the reaction temperature of the reduction unit is 600-1000 ℃; the reaction temperature of the hydrogen production unit is 500-900 ℃.
10. A method according to claim 3, characterized in that: the heat released by the oxidation unit and the hydrogen production unit is matched and provided for the carbon dioxide release unit according to the temperature of the carbon dioxide release unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310358407.0A CN116395691A (en) | 2023-04-06 | 2023-04-06 | CO in carbon emission source realized by chemical-looping hydrogen production technology 2 System and method of trapping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310358407.0A CN116395691A (en) | 2023-04-06 | 2023-04-06 | CO in carbon emission source realized by chemical-looping hydrogen production technology 2 System and method of trapping |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116395691A true CN116395691A (en) | 2023-07-07 |
Family
ID=87019453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310358407.0A Pending CN116395691A (en) | 2023-04-06 | 2023-04-06 | CO in carbon emission source realized by chemical-looping hydrogen production technology 2 System and method of trapping |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116395691A (en) |
-
2023
- 2023-04-06 CN CN202310358407.0A patent/CN116395691A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101285004B (en) | Multifunctional energy resource system | |
| RU2007137645A (en) | SYSTEMS AND METHODS USING A FUEL PROCESSOR WITHOUT MIXING | |
| JPH0593519A (en) | Power generation plant comprising gasification | |
| CN112374458A (en) | Method and device for producing hydrogen from blast furnace gas in iron-making | |
| CN111847381B (en) | Method and device for preparing hydrogen from industrial waste gas | |
| CN112079333B (en) | Chain reaction hydrogen production system and hydrogen production method | |
| CN113736943A (en) | Direct reduction method for producing sponge iron by converting hydrocarbon-rich gas | |
| US20180162729A1 (en) | Power generation using hydrogen fuel with economical carbon dioxide capture | |
| CN111482068A (en) | Method for sustainable energy production in a power plant comprising solid oxide fuel cells | |
| AU2018217734B2 (en) | Power generation using hydrogen fuel with economical carbon dioxide capture | |
| CN107098312B (en) | Method for preparing synthesis gas by using flue gas | |
| CN109266373B (en) | Coal chemical industry power poly-generation system based on calcium-based compound | |
| CN116395691A (en) | CO in carbon emission source realized by chemical-looping hydrogen production technology 2 System and method of trapping | |
| Abbas et al. | A Ca-Cu chemical loop process for CO2 capture in steel mills: system performance analysis | |
| CN210092233U (en) | Molten carbonate fuel cell and calcium circulation integrated system | |
| CN217264848U (en) | Device for preparing hydrogen by utilizing low-carbon coal | |
| CN216572397U (en) | Coking and flue gas treatment system | |
| CN215208467U (en) | Coupling chemical chain reaction and CO2High-efficiency low-energy-consumption hydrogen electric heating cold poly-generation system for separation and trapping | |
| CN111748672B (en) | Short-process low-cost CO preparation method by converter gas2And high-value application system and process | |
| CN213326721U (en) | Natural gas hydrogen production product purification system | |
| US7232472B2 (en) | Method for the treatment of coal | |
| CN101333463B (en) | Oxygen supplying and hydrogen making process from iron base oxygen carrier of three-linked transport bed | |
| CN107337178B (en) | Process for recycling PSA desorption gas and catalytic regeneration flue gas of oil refinery | |
| CN118079589A (en) | CO based on fuel staged conversion coupling chemical looping combustion2Trapping method and system | |
| CN221619009U (en) | High-pressure chemical chain coupling calcium circulation carbon dioxide trapping system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |