CN202099045U - Device for preparing hydrogen and separating carbon dioxide (CO2) based on mixture of ferric oxide (Fe2O3) and nickel oxide (NiO) - Google Patents

Device for preparing hydrogen and separating carbon dioxide (CO2) based on mixture of ferric oxide (Fe2O3) and nickel oxide (NiO) Download PDF

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CN202099045U
CN202099045U CN2011200959161U CN201120095916U CN202099045U CN 202099045 U CN202099045 U CN 202099045U CN 2011200959161 U CN2011200959161 U CN 2011200959161U CN 201120095916 U CN201120095916 U CN 201120095916U CN 202099045 U CN202099045 U CN 202099045U
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reactor
reaction device
air
fuel reaction
fuel
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向文国
陈时熠
王东
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Southeast University
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Southeast University
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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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The utility model discloses a device for preparing hydrogen and separating carbon dioxide (CO2) based on mixture of ferric oxide (Fe2O3) and nickel oxide (NiO), which comprises a steam reactor fluidized bed, a fuel reactor and an air reactor fluidized bed. In the steam reactor fluidized bed, a steam reactor lift pipe is connected with a steam reactor base chamber through a transition section, the upper end of the steam reactor lift pipe is connected with a hydrogen cyclone separator which is connected with a third overflow tank through a blanking pipe, and the third overflow tank is connected with the air reactor base chamber. In the air reactor fluidized bed, the air reactor base chamber is connected with an air reactor lift pipe through the transition section, and the top end of the air reactor lift pipe is connected with an air cyclone separator which is connected with the fuel reactor through the blanking pipe and a second overflow tank. In the fuel reactor, a fuel reactor body is connected with a fuel reactor chamber through the transition section, the fuel reactor base chamber is connected with a first overflow tank, and the first overflow tank is connected with the steam reactor base chamber.

Description

A kind of based on Fe 2O 3-NiO mixture is produced hydrogen and separation of C O 2Device
Technical field
The present invention relates to a kind of device that utilizes fuel to produce hydrogen, particularly relate to a kind of based on Fe 2O 3-NiO mixture is produced hydrogen and separation of C O 2Device.
Background technology
The high efficiency of energy clean utilization is to realize one of sustainable development strategies of the energy.Hydrogen is as clean energy, and in the conversion process of energy, following product is water, can really realize zero release of pollutant.Hydrogen is combustion power generation, heat supply directly, perhaps is converted into electric energy through fuel cell.Along with the whole world " Oil Safety ", " Greenhouse effect " and " environment protection " problem are increasingly serious; In order to reduce interdependency to oil; Strengthen the capture of carbonic acid gas and seal up for safekeeping; Reduce the influence of greenhouse gases to environment, in the sustainable energy system in future, hydrogen is expected to become the important energy carrier.But regrettably the hydrogen of occurring in nature is to exist with the chemical combination attitude mostly, must be obtained by the conversion of carbon containing primary energy source such as other primary energy source such as Sweet natural gas, coal, biomass as secondhand energy.It is main energy consumption big country with coal that China is one, in the selection of the energy, is that main fossil oil will played the part of very important role with the coal.Fossil energy can give off a large amount of CO in the process that Hydrogen Energy transforms 2, the Greenhouse effect that cause thus cause serious destruction to ecotope.Because with the fossil oil is the CO of the hydrogen production process discharging on basis 2Amount quite huge, hydrogen will disappear as the advantage of eco-friendly clean energy.Therefore, in the fossil oil hydrogen production process, effectively separate and capture CO 2Become one of key that realizes the hydrogen manufacturing of fossil oil cleaning.
Summary of the invention
The invention provides a kind of based on Fe 2O 3-NiO mixture is produced hydrogen and separation of C O 2Device, the present invention effective separation of C O when utilizing fuel to produce hydrogen 2, have the advantage that reduces greenhouse gas emission.
Device technique scheme of the present invention is following:
A kind ofly be used for above-mentioned Fe 2O 3-NiO mixture is produced hydrogen and separation of C O 2Device, form by water vapour reactor drum fluidisation bed, fuel reaction device and air reactor fluidized-bed; Water vapour reactor drum fluidisation bed is made up of water vapour reactor drum bottom compartment, water vapour reactor drum transition section and water vapour reactor riser; The water vapour reactor riser links to each other with water vapour reactor drum bottom compartment through water vapour reactor drum transition section; The upper end of water vapour reactor riser is connected with the hydrogen cyclonic separator; The hydrogen cyclonic separator links to each other with the 3rd overflow groove through first tremie pipe, and the 3rd overflow groove is connected with the air reactor fluidized-bed; The air reactor fluidized-bed is made up of air reactor bottom compartment, air reactor transition section, air reactor riser tube, air cyclonic separator and second tremie pipe; The air reactor bottom compartment links to each other with the air reactor riser tube through the air reactor transition section; The top of air reactor riser tube links to each other with the air cyclonic separator; Described the 3rd overflow groove is connected with air reactor bottom compartment in the air reactor fluidized-bed, and the air cyclonic separator is connected with the fuel reaction device through second tremie pipe and second overflow groove; The fuel reaction device is made up of fuel reaction device main body, fuel reaction device transition section, fuel reaction device bottom compartment and first overflow groove; Fuel reaction device main body links to each other with fuel reaction device bottom compartment through fuel reaction device transition section; Fuel reaction device bottom compartment links to each other with first overflow groove; First overflow groove links to each other with water vapour reactor drum bottom compartment, and said air cyclonic separator is connected with the top of the fuel reaction device main body of fuel reaction device through second tremie pipe and second overflow groove.
Compared with prior art, the present invention has following advantage:
(1) before understanding apparatus of the present invention, at first relates to Fe 2O 3Reduction process with NiO:
Fe 2O 3The reduction order be:
Fe 2O 3→ Fe 3O 4→ FeO → Fe is higher than 570 ℃
Fe 2O 3→ FeO → Fe is lower than 570 ℃
The reduction order of NiO is merely:
NiO→Ni
Fe 2O 3Be converted into Fe 3O 4Process following:
3Fe 2O 3+H 2→2Fe 3O 4+H 2O
3Fe 2O 3+CO→2Fe 3O 4+CO 2
12Fe 2O 3+CH 4→8Fe 3O 4+CO 2+2H 2
The process that NiO is converted into Ni is following:
NiO+H 2→Ni+H 2O
NiO+CO→Ni+CO 2
4NiO+CH 4→4Ni+CO 2+2H 2O
According to chemical reaction thermodynamic principles, Fe 2O 3Be converted into Fe 3O 4Be converted into the process of Ni with NiO, be non-reversible process, i.e. fuel gas H 2, CO and CH 4Can be converted into CO fully 2And water vapour, so react when being in equilibrium state, there is not unreacted H in the exit gas 2, CO and CH 4On kinetics, the reactive behavior of NiO is higher than Fe 2O 3Reactive behavior.
Secondly, Fe 3O 4The process that is converted into FeO and Fe is following:
Fe 3O 4+CO→3FeO+CO 2
Fe 3O 4+H 2→3FeO+H 2O
4Fe 3O 4+CH 4→12FeO+CO 2+2H 2O
FeO+CO→Fe+CO 2
FeO+H 2→Fe+H 2O
4FeO+CH 4→4Fe+CO 2+2H 2O
According to chemical thermodynamics equilibrium principle, Fe 3O 4Reaction being converted into FeO and Fe is reversible reaction.Reach in reaction under the situation of equilibrium state, still have portion C O, H 2And CH 4Do not participate in reaction.
If produce hydrogen, red stone Fe 2O 3Must be reduced to FeO or Fe, and react, promptly must relate to Fe in the hydrogen production process with water vapour than lower valency 3O 4Be reduced to the reaction of FeO and Fe.According to above-mentioned thermomechanical analysis, Fe 3O 4The reaction process that is converted into FeO and Fe is reversible reaction, contains the H that does not transform fully in the gas of discharging 2, CO and CH 4, after condensation separation goes out water wherein, can't obtain purified CO 2, and this device has utilized the high reactivity of NiO reductive non-reversibility and NiO and fuel reactant gas in fuel gas, utilizes NiO to react unconverted residual fuel gas, realizes the conversion fully of fuel gas.
In the fuel reaction device, Fe 2O 3Get into from the top of fuel reaction device with NiO, from bottom overflow to the water vapour reactor drum of fuel reaction device, fuel gas then gets into from fuel reaction device bottom then.The cross-sectional area of fuel reaction device main body is greater than fuel reaction device bottom compartment, and gas-solid mixture is in the moving-bed state in fuel reaction device main body, fuel gas and Fe 2O 3With the NiO inverse motion.Fuel reaction device bottom compartment is because bed body cross-sectional area dwindles, and gas flow rate is high, and gas-solid two is in bubbling fluidization mutually.In fuel reaction device main body, Fe 2O 3Move downward with NiO, gas moves upward.The new Fe that gets into the fuel reaction device 2O 3Be reduced to Fe on top by the fuel gas that does not transform fully from the bottom with NiO 3O 4And Ni, this reaction is non-reversible process, gaseous product is merely CO 2And water vapour, after condensation separation goes out water wherein, obtain purified CO 2Fe after the reduction 3O 4Continue with Ni, in fuel reaction device bottom because the fuel gas concentration of newly advancing is high, Fe 3O 4Further be reduced to FeO and Fe.In fuel reaction device bottom compartment, because cross-sectional reactor area reduces, gas flow rate is high, and gas-solid two is in bubbling fluidization mutually, and FeO, Fe and Ni overflow to the water vapour reactor drum of going back ortho states carry out hydrogen production reaction.The fuel gas of complete reaction is not along with the CO that generates 2Rise together with water vapour, and by the new Fe that gets in fuel reaction device top 2O 3React completely with NiO and to be converted into CO 2And H 2O.Utilize Aspen Plus chemical industry software simulation, consider existing chemical chain device for producing hydrogen from the chemical reaction equilibrium angle, when fuel reaction actuator temperature during at 900 ℃, fuel reaction device inlet gas is a synthetic gas, CO and H 2Mol ratio be 1: 1, if only utilize Fe 2O 3During as oxygen carrier, exit gas is CO, H 2, CO 2And H 2The mixture of O, its mol ratio are 0.2: 0.8: 0.17: 0.83,20% CO and 17% H are promptly arranged in the fuel gas 2Fail to transform, condensation separation can not obtain purified CO after going out the water of fuel reaction device outlet 2Utilize hydrogen production process of the present invention, because NiO reductive non-reversibility, when inlet gas is synthetic gas, and CO and H 2Mol ratio be 1: 1, in the exit gas except CO 2With H 2O, CO and H 2Concentration sum less than 1%, after condensation separation goes out water wherein, CO 2The purity of discharging is up to more than 99%.
(2) with traditional ferriferous oxide three beds reaction hydrogen manufacturing separation of C O 2Compared with techniques, the fuel gas that this law has used the NiO absorption reaction not transform fully because of the ferriferous oxide drastic reduction.On kinetics, the reactive behavior of NiO is higher than Fe 2O 3, guaranteed the conversion fully of fuel gas.Simultaneously, in the design of fuel reaction device, adopted moving-bed, NiO has reacted the fuel gas that does not transform fully on fuel reaction device top, and the Ni of generation gets into fuel reaction device bottom, and Ni no longer participates in reaction, so it does not influence the drastic reduction of ferriferous oxide.Realizing having obtained to go back when fuel transforms fully the FeO and the Fe of ortho states.On thermodynamics, the Ni that goes back ortho states reacts with water vapour hardly, gets into air reactor behind the Ni process water vapour reactor drum, and the oxidizing reaction of Ni is the intensive exothermic process, and the heat of release can be by second stage employ.Simultaneously, NiO takes great amount of heat to the fuel reaction device with the form of solid sensible heat from air reactor as a kind of solid carrier, in order to keep thermo-negative reaction in the fuel reaction device.
(3) traditional gas water vapour reforming hydrogen producing be obtain after will reforming earlier with H 2And CO 2Be the gaseous product of staple, handle and the product hydrogen of acquisition certain purity through purify, the CO conversion separates purification with PSA etc. then.Compare with traditional gas water vapour reforming hydrogen producing, the present invention need not to relate to CO 2And H 2Isolating equipment, reduce to realize the related energy consumption of above technology.Through water vapour and FeO and Fe reaction generation hydrogen, resultant is purified hydrogen through cooling.
Description of drawings
Fig. 1 is for the present invention is based on Fe 2O 3-NiO mixture is produced hydrogen and separation of C O 2Setting drawing.
Embodiment
A kind of based on Fe 2O 3-NiO mixture is produced hydrogen and separation of C O 2Device, form by water vapour reactor drum fluidisation bed 1, fuel reaction device 2 and air reactor fluidized-bed 3; Water vapour reactor drum fluidisation bed 1 is made up of the water vapour reactor drum 1-1 of bottom compartment, water vapour reactor drum transition section 1-2 and water vapour reactor riser 1-3; Water vapour reactor riser 1-3 links to each other with the water vapour reactor drum 1-1 of bottom compartment through water vapour reactor drum transition section 1-2; The upper end of water vapour reactor riser 1-3 is connected with hydrogen cyclonic separator 1-4; Hydrogen cyclonic separator 1-4 links to each other with the 3rd overflow groove 4 through first tremie pipe 5, and the 3rd overflow groove 4 is connected with air reactor fluidized-bed 3; Air reactor fluidized-bed 3 is made up of the 3-1 of air reactor bottom compartment, air reactor transition section 3-2, air reactor riser tube 3-3, air cyclonic separator 3-4 and the second tremie pipe 3-5; The 3-1 of air reactor bottom compartment links to each other with air reactor riser tube 3-3 through air reactor transition section 3-2; The top of air reactor riser tube 3-3 links to each other with air cyclonic separator 3-4; Described the 3rd overflow groove 4 is connected with the 3-1 of air reactor bottom compartment in the air reactor fluidized-bed 3, and air cyclonic separator 3-4 is connected with fuel reaction device 2 through the second tremie pipe 3-5 and the second overflow groove 2-5; Fuel reaction device 2 is made up of fuel reaction device main body 2-4, fuel reaction device transition section 2-3, the fuel reaction device 2-2 of bottom compartment and the first overflow groove 2-1; Fuel reaction device main body 2-4 links to each other with the fuel reaction device 2-2 of bottom compartment through fuel reaction device transition section 2-3, and the cross-sectional area of fuel reaction device main body 2-4 is greater than the cross-sectional area of the fuel reaction device 2-2 of bottom compartment; The fuel reaction device 2-2 of bottom compartment links to each other with the first overflow groove 2-1; The first overflow groove 2-1 links to each other with the water vapour reactor drum 1-1 of bottom compartment, and said air cyclonic separator 3-4 is connected with the top of the fuel reaction device main body 2-4 of fuel reaction device 2 through the second tremie pipe 3-5 and the second overflow groove 2-5; Like accompanying drawing 1.

Claims (2)

1. one kind based on Fe 2O 3-NiO mixture is produced hydrogen and separation of C O 2Device, it is characterized in that, form by water vapour reactor drum fluidisation bed (1), fuel reaction device (2) and air reactor fluidized-bed (3); Water vapour reactor drum fluidisation bed (1) is made up of water vapour reactor drum bottom compartment (1-1), water vapour reactor drum transition section (1-2) and water vapour reactor riser (1-3); Water vapour reactor riser (1-3) links to each other with water vapour reactor drum bottom compartment (1-1) through water vapour reactor drum transition section (1-2); The upper end of water vapour reactor riser (1-3) is connected with hydrogen cyclonic separator (1-4); Hydrogen cyclonic separator (1-4) links to each other with the 3rd overflow groove (4) through first tremie pipe (5), and the 3rd overflow groove (4) is connected with air reactor fluidized-bed (3); Air reactor fluidized-bed (3) is made up of air reactor bottom compartment (3-1), air reactor transition section (3-2), air reactor riser tube (3-3), air cyclonic separator (3-4) and second tremie pipe (3-5); Air reactor bottom compartment (3-1) links to each other with air reactor riser tube (3-3) through air reactor transition section (3-2); The top of air reactor riser tube (3-3) links to each other with air cyclonic separator (3-4); Described the 3rd overflow groove (4) is connected with air reactor bottom compartment (3-1) in the air reactor fluidized-bed (3), and air cyclonic separator (3-4) is connected with fuel reaction device (2) through second tremie pipe (3-5) and second overflow groove (2-5); Fuel reaction device (2) is made up of fuel reaction device main body (2-4), fuel reaction device transition section (2-3), fuel reaction device bottom compartment (2-2) and first overflow groove (2-1); Fuel reaction device main body (2-4) links to each other with fuel reaction device bottom compartment (2-2) through fuel reaction device transition section (2-3); Fuel reaction device bottom compartment (2-2) links to each other with first overflow groove (2-1); First overflow groove (2-1) links to each other with water vapour reactor drum bottom compartment (1-1), and said air cyclonic separator (3-4) is connected with the top of the fuel reaction device main body (2-4) of fuel reaction device (2) through second tremie pipe (3-5) and second overflow groove (2-5).
2. device according to claim 1 is characterized in that the cross-sectional area of the cross-sectional area of fuel reaction device main body (2-4) greater than fuel reaction device bottom compartment (2-1).
CN2011200959161U 2011-04-02 2011-04-02 Device for preparing hydrogen and separating carbon dioxide (CO2) based on mixture of ferric oxide (Fe2O3) and nickel oxide (NiO) Expired - Fee Related CN202099045U (en)

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Application Number Priority Date Filing Date Title
CN2011200959161U CN202099045U (en) 2011-04-02 2011-04-02 Device for preparing hydrogen and separating carbon dioxide (CO2) based on mixture of ferric oxide (Fe2O3) and nickel oxide (NiO)

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Application Number Priority Date Filing Date Title
CN2011200959161U CN202099045U (en) 2011-04-02 2011-04-02 Device for preparing hydrogen and separating carbon dioxide (CO2) based on mixture of ferric oxide (Fe2O3) and nickel oxide (NiO)

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Granted publication date: 20120104

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