CN105567325A - Spinel compound-carbonate mixture system for solar energy photo-thermal chemical conversion, preparation and application thereof - Google Patents
Spinel compound-carbonate mixture system for solar energy photo-thermal chemical conversion, preparation and application thereof Download PDFInfo
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- CN105567325A CN105567325A CN201410539425.XA CN201410539425A CN105567325A CN 105567325 A CN105567325 A CN 105567325A CN 201410539425 A CN201410539425 A CN 201410539425A CN 105567325 A CN105567325 A CN 105567325A
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a method for production of H2 and CO with carbonate and a spinel compound as cyclic active materials by means of multistep thermochemical cyclic decomposition of water or CO2. The main steps include: 1) synthesizing active materials and mixing the two materials; 2) heating the mixed materials to certain temperature and introducing H2O or CO2 to generate H2 and CO; 3) dispersing the 2) treated active materials in deionized water, introducing CO2 to conduct hydrolysis, and performing separation to obtain a hydrolyzed active species; and 4) heating the 3) treated active material to certain temperature to carry out oxygen evolution reaction. According to the invention, hydrolysis reaction is utilized to treat the active species producing H2 for the first time, the oxygen production reaction can be carried out more smoothly, and the feasibility of the cycle system is improved. The cycle system has low reaction temperature, utilizes solar energy as the heat source, adopts H2O and CO2 as the raw materials, and is clean and pollution-free.
Description
Technical field
The present invention relates to multistep processes thermochemical cycle decomposition water and carbonic acid gas.The mixture system being specifically related to form using catalytic removal of nox and basic metal or alkaline earth metal carbonate, as active material system, by multistep thermochemical cycle decomposition water and carbonic acid gas, produces hydrogen and carbon monoxide.This system utilizes sun power as thermal source, by water and carbon dioxide decomposition under low temperature (500-1000 DEG C), in energy-saving and emission-reduction and environment protection, has boundless application prospect.
Background technology
Under the background of energy dilemma and ecocrisis; the unsustainable sex expression of fossil energy more and more obvious; the problems such as the Greenhouse effect that excessive use fossil energy produces, environmental pollution become increasingly conspicuous, such that research and development is clean, eco-friendly renewable energy source system is extremely urgent.China is current is CO
2second big country of quantity discharged, CO
2quantity discharged, in the very fast situation increased, is subject to increasing environmental protection pressure and international community's pressure.Sun power has cleanliness without any pollution, the many merits such as inexhaustible, renewable, utilizes sun power water to be changed into hydrogen and oxygen avoids pollution problem from source, utilizes sun power by greenhouse gases CO in addition
2be converted into the chemical fuel being convenient to store and can also alleviate Greenhouse effect.In recent years, the development and application of this type of science and technology is subject to the extensive concern of international community.
Multistep thermochemical cycle decomposition H
2o/CO
2technology is that a class set sun power transforms and chemical fuel is produced in gordian technique integrally, is one of focus of current new energy development and research field.Compare the temperature of reaction of two-step approach thermochemical cycle more than 1000 DEG C, multistep processes thermochemical cycle has the low clear superiority of temperature of reaction, and namely most of multistep processes thermochemical cycle can complete below 1000 DEG C.A kind of more common multistep circulation pattern is as follows:
H
2O+A→0.5H
2+AO
AO+B→0.5O
2+AB
AB→A+B
A material is H
2o reduces, and produces hydrogen and oxide compound AO; B substance is oxidized AO, produces oxygen and compd A B; There is replacement(metathesis)reaction under certain condition in the 3rd step compd A B, produces A and B; Circulation is completed by three reactions steps.H
2o is O by this Cycle-decomposition
2and H
2, H in this circulation
2o is unique input raw material, and O
2and H
2it is output material.The mixed system of spinels oxide compound and carbonate is the multistep thermochemical cycle of the type designed based on above-mentioned mentality of designing.But multistep circulation is diversified, is not limited only to above-mentioned circulation model.Classical multistep circulation has that nonmetallic compound circulates, metal/metal oxide circulate with halogen or acid and metal oxide circulate with basic cpd, and wherein S-I circulates, Fe-Cl circulation, and it is that more typical multistep circulates that Cu-Cl circulates.
Beghi, G.E. propose S-I circulation (Int.J.HydrogenEnergy, 1986,11 (12): 761-771) the earliest, and the principal reaction step of this circulation is as shown below.Its temperature of reaction is obviously low than two step circulations, and maximum temperature is only 850 DEG C.But acid system is very large to the corrosion of material, and HI and H
2sO
4separation also consume energy very much.Zhang, Y. etc. (Industrial & EngineeringChemistryResearch, 2014,53,3021-3028) conduct in-depth research the BunsenReaction related in S-I circulation recently.Mainly have studied SO
2flow velocity, molar fraction; I
2content; Water-contents etc. are on the impact of Liquid liquid Separation process, and experimental result shows to work as SO
2molar fraction more than 0.12, I
2/ H
2best HI and H can be obtained when the mol ratio of O is more than 0.284
2sO
4the side reaction of separating effect and minimum degree.
TolgaBalta. under waiting (Energy, 2010,35,3263-3272) to study the reaction conditionss such as differing temps in great detail, Cu-Cl circulates four reactions steps to the performance impact of the whole recycle system, and calculates production capacity and exergic efficiency.The greatest problem that this circulation faces is the corrodibility of acidic substance to material.
Tamaura, Y. etc. (SolarEnergy, 1999,65,55-57) have studied MnFe at first
2o
4with Na
2cO
3multistep circulation, this multistep circulation can be completed by three steps.The subject matter that this system faces is unfavorable in product oxygen reaction kinetics, and speed of reaction is excessively slow.(JournalofSolidStateChemistry, 2008,181, the 1992-1997 such as Seralessandri, L.; ScriptaMaterialia, 2006,55,875-877) oxygen reaction is produced to this circulation be studied, find the crystalline structure and the CO that produce reaction product after hydrogen
2dividing potential drop on reduction reaction impact large especially.It is very unfavorable that our repetition experimental result also shows to produce oxygen reaction, is difficult to observe O under usual conditions
2generation, circulation pattern haves much room for improvement.Each species that Varsano, F. etc. (SolidStateIonics, 2011,187,19-26) utilize XRD technical Analysis reaction process to generate.They propose oxygen generator reason and carry out in two steps, i.e. CO
2first be combined with sodium ion and generate Na
2cO
3, sodium ion is partly separated, and former compound structure is subsided, and then the reaction of product oxygen is carried out smoothly.Whether can the separation of sodium ion be complete the key point of producing oxygen reaction in a word.(JournalofPhysicsandChemistryofSolids, 2001,62, the 1341-1347 such as Kaneko, H.; Energy, 2001,26,919-929) adopt and add Fe
2o
3the extraction accelerating sodium ion goes out.The method facilitates significantly produces oxygen reaction, but the Fe of how separating residual after completing circulation
2o
3it is again a problem.
In recent years, Xu, B. etc. (ProcNatlAcadSci, 2012,109 (24): 9260-9264) report Mn
3o
4-Na
2cO
3multistep circulating system.Na is used compared with circulation similar before
2cO
3alternative NaOH alleviates the corrosion strength of system, reduces the requirement to material.The circulation of metal oxide and basic cpd is that the low temperature multistep of class extensive application potentiality circulates in summary.
Summary of the invention
The present invention aims to provide carbonate (A
xcO
3) and catalytic removal of nox (MN
2o
4) mixed active material is at multistep processes thermochemical cycle decomposition H
2o or CO
2in application.The mixing material of different carbonate and different spinel compound composition can optionally decomposing H
2o or CO
2in one or both, produce H simultaneously
2and CO.
Object of the present invention also based on improving and optimizing this system Recycle design, thus improves the feasibility of this type of circulating reaction system.Another object of the present invention is to carbonate and catalytic removal of nox mixing material water of decomposition or CO
2reaction parameter be optimized, optimum reaction conditions is provided.
For achieving the above object, the invention provides following aspect:
Carbonate (A of the present invention
xcO
3) and catalytic removal of nox MN
2o
4mixed system, is characterized in that described carbonate A
xcO
3middle A is one or two or more kinds in Li, Na, K, Be, Mg, Ca, Sr, Ba, MN
2o
4middle M, N are one in Mn, Fe, Co or more than two kinds.Get carbonate and spinel compound according to the mol ratio of 3:2, adopt the blending means of direct mechanical grinding to mix, until fully mix.
The preparation method of described catalytic removal of nox is co-precipitation hydrothermal method, and high-temp solid reacts, and micro emulsion reacts, the one in egg white sol-gel method.
Described co-precipitation hydrothermal method concrete steps are as follows: the salt MCl taking M
xor M (NO
3)
x0.01-50mmol, takes the salt NCl of N according to mol ratio N:M=2:1
yor N (NO
3)
y, be dissolved in 50-300mL deionized water, add the NaOH solution that 30mL concentration is 0.1-10mol/L, stir; Be transferred in 300mL water heating kettle, range of reaction temperature is 80 DEG C-200 DEG C, and the reaction times is 3-28h; Be cooled to room temperature after hydro-thermal reaction completes, the dry 6-12h of filtration washing final vacuum, vacuum drying temperature is 50-80 DEG C;
Described high-temp solid reaction concrete steps are as follows: the carbonate M (CO taking M
3)
x0.01-50mmol, takes the oxide compound N of N according to mol ratio N:M=2:1
yo
z, be 200mL/min in total flux, gas volume ratio is: air (0-100%) and CO
2(100-0%) be heated to 1100 DEG C under mixed atmosphere, keep 7h, former atmosphere protection borehole cooling is to room temperature;
Described micro emulsion reaction concrete steps are as follows: the salt MCl taking M
xor M (NO
3)
x0.01-50mmol, takes the salt NCl of N according to mol ratio N:M=2:1
yor N (NO
3)
y, be dissolved in 50-300mL deionized water, stir; Add the NaDBS solution of 60mL0.4M subsequently; Add 300-500mL toluene solution, continuously stirring 12-24h, form uniform microemulsion system; Add the NaOH solution that 80mL concentration is 0.1-2mol/L, continue to stir 2h; Ar protects lower 60-100 DEG C of aging 1.5h; Filtration washing, 50-80 DEG C of dry 6-12h; 320-600 DEG C of roasting 1-2h, obtains state of oxidation spinel compound.
Described egg white sol-gel method concrete steps are as follows: get the egg white solution that 30-120mL stirs, and add 50-200mL deionized water dilution egg white solution, take the salt MCl of M
xor M (NO
3)
x0.01-50mmol, takes the salt NCl of N according to mol ratio N:M=2:1
yor N (NO
3)
y, metal-salt is added in the egg white solution after dilution, stirs and be evaporated to glue, to be transferred in retort furnace roasting 5h under 500 DEG C of conditions, to obtain the spinel compound of the state of oxidation.
Described carbonate and catalytic removal of nox mixed system can be applicable to H
2o and CO
2multistep decompose, this process is made up of following multiple reactions steps:
A. spinel compound MN is synthesized
2o
4, utilize the methods such as grinding that carbonate and catalytic removal of nox bi-material are mixed;
B. the active material system of mixing is heated to 500 ~ 1000 DEG C under an ar atmosphere, after constant temperature process 2-3h, brings H into by Ar
2o or CO
2in one or both; Or by CO
2bring H into
2o; Or pass into CO separately
2; Produce H
2and CO;
C. be dispersed in water by the active material after b process, the content obtaining active material is the mixed solution of 1-10wt%, and continuously stirring also passes into CO
2be hydrolyzed reaction, is separated drying and obtains the active specy after being hydrolyzed;
D. the active specy after c process is heated to 500 ~ 1000 DEG C under an ar atmosphere, carries out putting oxygen reaction, complete and produce the circulation of oxygen product hydrogen.
The product hydrogen of this circulating reaction produces oxygen reaction to carry out in fixed-bed reactor.
The composition structure of described fixed-bed reactor is: comprise a silica tube, the corundum crucible of upper end open, bottom of which has holes is provided with in silica tube, a support silica tube is provided with below corundum crucible, corundum crucible is positioned the special position in outer silica tube by the support silica tube below it, the top of the inner bottom stomidium of corundum crucible is provided with silica wool, and silica wool lays Al
2o
3filler, Al
2o
3filler is filled with active material, uses Al more successively
2o
3filler, silica wool are sealed up for safekeeping.
The present invention has the following advantages:
1. the present invention utilizes hydrolysis reaction process to produce H first
2after active specy, improve the kinetic property producing oxygen reaction, substantially increase and produce oxygen speed of reaction, making to produce oxygen reaction can more successfully carry out, and improves the feasibility of this circulating system.
2. active material system of the present invention (500-1000 DEG C) can complete the reaction of product oxygen under lower reduction temperature.
3. active material system provided by the invention, can utilize heat of high temperature that focused solar energy produces as energy derive, with H
2o or CO
2as reaction raw materials, produce H
2and CO, without other any by products, be sustainable and Conversion of energy system that is cleanliness without any pollution.
Accompanying drawing explanation
The structure diagram of fixed-bed reactor shown in Fig. 1, wherein 1: silica tube; 2: support silica tube; 3: sealing connection; 4: corundum crucible; 5: active material.
Fig. 2 is the MnFe of synthesis of different hydro-thermal time
2o
4xRD figure, XRD diffraction peak shows the MnFe synthesized
2o
4there is typical spinel structure.
Fig. 3 is MnFe
2o
4aMP.AMp.Amp Na
2cO
3hydrogen-producing speed-time changing curve, integration obtains hydrogen output 34.9mlH
2/ gMnFe
2o
4.
Fig. 4 is that hydrolysate produces oxygen rate-time change curve, and integration obtains oxygen output 16.2mlO
2/ g hydrolysate.
Fig. 5 is circulation products XRD figure, and XRD diffraction peak confirms to produce hydrogen, produces the rear MnFe of oxygen cycle reaction
2o
4regenerated.
Fig. 6 is active material MnFe
2o
4aMP.AMp.Amp Na
2cO
3hydrolysate produces oxygen curve, obtains oxygen output 17.1mlO after integration
2/ g hydrolysate.
Embodiment
Fixed-bed reactor structure diagram is shown in accompanying drawing 1.During application, get about 0.2g mixed active material and be placed in corundum crucible, sample load mode is described above, and reactor material is silica tube, and reaction tubes (silica tube) internal diameter is 17mm, and reaction product gas-chromatography carries out on-line analysis.Embodiment 1
Take 1.9791g Manganous chloride tetrahydrate (10mmol), 5.4058g iron(ic) chloride (20mmol) is dissolved in 200ml deionized water, stirred at ambient temperature 30min; Taking 4.8gNaOH is dissolved in 30ml deionized water; Under Keep agitation, NaOH solution is added drop-wise in metal salt solution, continues to stir 30min to even; Be transferred to 180 DEG C of hydro-thermal reaction 3h in 300ml water heating kettle; Filtration washing, 60 DEG C of vacuum-drying 6h, obtain spinel compound MnFe
2o
4.Hydrothermal conditions is set to respectively the MnFe that 5h, 6h, 8h, 12h, 14h, 18h, 24h, 28h obtain different time Hydrothermal Synthesis
2o
4material, XRD figure shows this serial MnFe
2o
4material has typical spinel structure (accompanying drawing 2).Na is taken according to the mol ratio of 3:2
2cO
3with the MnFe of 6h Hydrothermal Synthesis
2o
4material, adopts the blending means of direct mechanical grinding to mix, repeatedly grinds, until fully mix.
Embodiment 2
Take 1.9791g Manganous chloride tetrahydrate (10mmol), 5.4058g iron(ic) chloride (20mmol) is dissolved in 200ml deionized water, stirred at ambient temperature 30min; Take 3.2gNaOH, be dissolved in 30ml deionized water; Under Keep agitation, NaOH solution is added drop-wise in metal salt solution, continues to stir 30min to even; Be transferred to 180 DEG C of reaction 6h in 300ml water heating kettle; Filtration washing, 60 DEG C of vacuum-drying 6h, obtain spinel compound MnFe
2o
4.Change the consumption of NaOH, take 4.8g, 6.4g, 8.0g, 9.6gNaOH respectively, after process, obtain the MnFe of Different Alkali concentration Hydrothermal Synthesis as stated above
2o
4material.Na is taken according to the mol ratio of 3:2
2cO
3with the MnFe adding 3.2gNaOH synthesis
2o
4material, adopts the blending means of direct mechanical grinding to mix, repeatedly grinds, until fully mix.
Embodiment 3
Take 1.9791g Manganous chloride tetrahydrate (10mmol), 5.4058g iron(ic) chloride (20mmol) is dissolved in 200ml deionized water, stirred at ambient temperature 30min; Take 4.8gNaOH, be dissolved in 30ml deionized water; Under Keep agitation, NaOH solution is added drop-wise in metal salt solution, continues to stir 30min to even; Be transferred in 300ml water heating kettle, 160 DEG C of reaction 6h; Filtration washing, 60 DEG C of vacuum-drying 6h, obtain spinel compound MnFe
2o
4.Change hydrothermal treatment consists temperature, be set to 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 180 DEG C, 200 DEG C respectively, after process, obtain the MnFe of differing temps Hydrothermal Synthesis as stated above
2o
4material.Na is taken according to the mol ratio of 3:2
2cO
3with the MnFe of 160 DEG C of Hydrothermal Synthesiss
2o
4material, adopts the blending means of direct mechanical grinding to mix, repeatedly grinds, until fully mix.
Embodiment 4
Take 1.1495gMnCO
3(10mmol) and 1.5969gFe
2o
3(10mmol), mix with mortar, and fully grind.At 25% air & 75%CO
2atmosphere under with the heating rate to 1100 DEG C of 20 DEG C/min, keep 7 hours, former atmosphere protection borehole cooling is to room temperature.MnFe is obtained after products therefrom grinding evenly
2o
4material.Change air (0-100%) and CO
2(100-0%) volume ratio, the MnFe synthesized under obtaining a series of different atmosphere
2o
4material.Na is taken according to the mol ratio of 3:2
2cO
3with 25% air & 75%CO
2atmosphere under the MnFe that synthesizes
2o
4material, adopts the blending means of direct mechanical grinding to mix, repeatedly grinds, until fully mix.
Embodiment 5
Get the egg white solution that 30ml stirs, add 50ml deionized water dilution egg white solution, 3.579g manganous nitrate (20mmol) and 16.16g iron nitrate (40mmol) is taken according to the molar ratio of 1:2, metal-salt is added in the egg white solution after dilution under stirring, glue is evaporated to after stirring, to be transferred in retort furnace at 500 DEG C roasting 5 hours, to obtain spongiform spinel compound MnFe
2o
4material.Na is taken according to the mol ratio of 3:2
2cO
3and MnFe
2o
4material, adopts the blending means of direct mechanical grinding to mix, repeatedly grinds, until fully mix.
Embodiment 6
Take 1.7895g manganous nitrate (10mmol) and 8.080g iron nitrate (20mmol) according to the molar ratio of 1:2, be dissolved in 50ml deionized water, stir; Add the NaDBS solution of 60ml0.4M subsequently; Add 500ml toluene solution, continuously stirring 24 hours, forms uniform microemulsion system; The concentration adding 80ml is the NaOH solution of 1mol/L, continues to stir 2h; Ar protects lower 100 DEG C of aging 1.5h; Filtration washing is dry; 500 DEG C of roastings obtain state of oxidation spinel compound MnFe
2o
4material.Na is taken according to the mol ratio of 3:2
2cO
3and MnFe
2o
4material, adopts the blending means of direct mechanical grinding to mix, repeatedly grinds, until fully mix.
Embodiment 7
Take the MnFe of 6h Hydrothermal Synthesis in about 0.2g embodiment 1
2o
4with Na
2cO
3mixing material after mechanical mill, dress sample is placed in reaction tubes.Be heated to 800 DEG C with the temperature rise rate of 20 DEG C/min from room temperature under an ar atmosphere, after constant temperature process 2.5h, pass into water vapour, temperature of reaction remains on 800 DEG C, produces H-H reaction and terminates in 3h.Accompanying drawing 3 is MnFe of hydro-thermal 6h synthesis in embodiment 1
2o
4produce the rate-time change curve of H-H reaction.The reaction product of producing after hydrogen taken out, be scattered in deionized water after grinding evenly, wherein pressed powder content is 2wt%.This mixed solution is heated to 80 DEG C, and continuously stirring also passes into CO
2water Under solution reaction 3h, will hydrolysis gained solid product be separated, vacuum-drying.Take the active specy 0.4g of hydrolysis gained, dress sample is placed in reaction tubes, is heated to 800 DEG C under an ar atmosphere with the temperature rise rate of 20 DEG C/min from room temperature, carries out the reaction of product oxygen, and constant temperature process 30min produces oxygen and reacted.Accompanying drawing 4 is the MnFe executing hydro-thermal 6h synthesis in example 1
2o
4the product oxygen speed of reaction-time changing curve of hydrolysate after product H-H reaction.Active material completes regeneration, the MnFe after regeneration by product hydrogen, product oxygen cycle
2o
4carry out product hydrogen successively again, produce oxygen cycle reaction.After the XRD figure of circulating reaction product shows to circulate, active material is regenerated (accompanying drawing 5).
Embodiment 8
Take the mixing material of about 0.2g embodiment 5 gained, dress sample is placed in reaction tubes.Be heated to 800 DEG C with the temperature rise rate of 20 DEG C/min under an ar atmosphere, after constant temperature process 2.5h, be cooled to room temperature.Be scattered in 50ml deionized water after reaction product is taken out grinding, pass into CO
2, hydrolysis reaction 3h at 80 DEG C of temperature, is separated dry hydrolysate.Hydrolysate is reinstalled former reaction tubes, is heated to 800 DEG C under an ar atmosphere with the temperature rise rate of 20 DEG C/min, carry out the reaction of product oxygen, constant temperature process 30min produces oxygen reaction and terminates (accompanying drawing 6).Produce oxygen after product to process with embodiment 7, carry out product hydrogen and produce oxygen cycle reaction.
In sum, the present invention has synthesized a series of spinel type (MN
2o
4) compound, this kind of material and carbonate (A
xcO
3) can by multistep processes reaction by H after mixing
2o or CO
2be decomposed into H
2and CO.Patent of the present invention is improved further and has been developed carbonate (A
xcO
3) and catalytic removal of nox (MN
2o
4) system multistep thermochemical cycle mode, utilize hydrolysis reaction first to process and produce H
2after active specy, make produce oxygen reaction more successfully carry out, improve the feasibility of this circulating system.Multistep processes thermochemical cycle system of the present invention, temperature of reaction low (500-1000 DEG C), can utilize heat of high temperature that focused solar energy produces as energy derive, with H
2o and CO
2as input raw material, output H
2and CO, cleanliness without any pollution, is expected to become and reduces H by sun power
2o and CO
2, the effective technology of preparative chemistry fuel (synthetic gas).
Claims (6)
1. for the catalytic removal of nox of solar energy thermochemical study and a mixture system for carbonate, it is characterized in that: described mixed system is by carbonate A
xcO
3with catalytic removal of nox MN
2o
4composition.
2. mixed system according to claim 1, is characterized in that: described carbonate A
xcO
3in, A is one or two or more kinds in Li, Na, K, Be, Mg, Ca, Sr, Ba; Described catalytic removal of nox MN
2o
4in, M, N are one or two or more kinds in transient metal Mn, Fe, Co.
3. mixed system according to claim 1 and 2, is characterized in that: described catalytic removal of nox MN
2o
4preparation method be co-precipitation hydrothermal method, high-temp solid react, micro emulsion react, the one in egg white sol-gel method;
Thermoprecipitation hydrothermal method is made up of following steps altogether:
Take the salt MCl of M
xor M (NO
3)
x0.01-50mmol, takes the salt NCl of N according to mol ratio N:M=2:1
yor N (NO
3)
y, be dissolved in 50-300mL deionized water, add the NaOH solution that 30mL concentration is 0.1-10mol/L, stir; Be transferred in 300mL water heating kettle, range of reaction temperature is 80 DEG C-200 DEG C, and the reaction times is 3-28h; Be cooled to room temperature after hydro-thermal reaction completes, the dry 6-12h of filtration washing final vacuum, vacuum drying temperature is 50-80 DEG C;
High-temp solid reaction concrete steps are as follows:
Take the carbonate M (CO of M
3)
x0.01-50mmol, takes the oxide compound N of N according to mol ratio N:M=2:1
yo
z, be 200mL/min in total flux, gas volume ratio is: air (0-100%) and CO
2(100-0%) be heated to 1100 DEG C under mixed atmosphere, keep 7h, former atmosphere protection borehole cooling is to room temperature;
The concrete reaction of micro emulsion reaction is as follows:
Take the salt MCl of M
xor M (NO
3)
x0.01-50mmol, takes the salt NCl of N according to mol ratio N:M=2:1
yor N (NO
3)
y, be dissolved in 50-300mL deionized water, stir; Add the NaDBS solution of 60mL0.4M subsequently; Add 300-500mL toluene solution, continuously stirring 12-24h, form uniform microemulsion system; Add the NaOH solution that 80mL concentration is 0.1-2mol/L, continue to stir 2h; Ar protects lower 60-100 DEG C of aging 1.5h; Filtration washing, 50-80 DEG C of dry 6-12h; 320-600 DEG C of roasting 1-2h, obtains state of oxidation spinel compound;
Egg white sol-gel method concrete steps are as follows:
Get the egg white solution that 30-120mL stirs, and add 50-200mL deionized water dilution egg white solution, take the salt MCl of M
xor M (NO
3)
x0.01-50mmol, takes the salt NCl of N according to mol ratio N:M=2:1
yor N (NO
3)
y, metal-salt is added in the egg white solution after dilution, stirs and be evaporated to glue, to be transferred in retort furnace roasting 5h under 500 DEG C of conditions, to obtain the spinel compound of the state of oxidation.
4. the catalytic removal of nox described in a claim 1,2 or 3 and the preparation method of carbonate mixed system, it is characterized in that: the blending means adopted is direct mechanical ground and mixed method, namely carbonate and spinel compound is taken according to mol ratio 3:2, fully mix in mortar, repeatedly grind, until fully grinding is even, or adopt ball mill grinding even.
5. an application for the catalytic removal of nox described in claim 1,2 or 3 and the mixed system of carbonate, is characterized in that: described mixed system can be used for multistep processes thermochemical cycle decomposition H
2o or CO
2, this circulation is made up of following polystep reaction:
A. spinel compound MN is synthesized
2o
4, utilize the methods such as grinding that carbonate and catalytic removal of nox bi-material are mixed;
B. the active material system of mixing is heated to 500 ~ 1000 DEG C under an ar atmosphere, after constant temperature process 2-3h, brings H into by Ar
2o or CO
2in one or both; Or by CO
2bring H into
2o; Or pass into CO separately
2; Produce H
2and CO;
C. be dispersed in water by the active material after b process, the content obtaining active material is the mixed solution of 1-10wt%, and continuously stirring also passes into CO
2be hydrolyzed reaction, is separated drying and obtains the active specy after being hydrolyzed;
D. the active specy after c process is heated to 500 ~ 1000 DEG C under an ar atmosphere, carries out putting oxygen reaction, complete and produce the circulation of oxygen product hydrogen.
6. application according to claim 5, is characterized in that:
In described circulating reaction, produce step b and steps d in hydrogen, the reaction of producing oxygen and claim 5 and carry out in fixed-bed reactor; The composition structure of described fixed-bed reactor is: comprise a silica tube, the corundum crucible of upper end open, bottom of which has holes is provided with in silica tube, a support silica tube is provided with below corundum crucible, corundum crucible is positioned the specific position in outer silica tube by the support silica tube below it, the top of the inner bottom stomidium of corundum crucible is provided with silica wool, and silica wool lays Al
2o
3filler, Al
2o
3filler is filled with active material, uses Al more successively
2o
3filler, silica wool are sealed up for safekeeping.
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