CN110257848A - Middle low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide - Google Patents
Middle low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide Download PDFInfo
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- CN110257848A CN110257848A CN201910494915.5A CN201910494915A CN110257848A CN 110257848 A CN110257848 A CN 110257848A CN 201910494915 A CN201910494915 A CN 201910494915A CN 110257848 A CN110257848 A CN 110257848A
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- salt
- methane
- carbon monoxide
- hydrogen
- metal
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 150000003839 salts Chemical class 0.000 title claims abstract description 81
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 230000003647 oxidation Effects 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 16
- -1 oxonium ion Chemical class 0.000 claims abstract description 16
- 230000004927 fusion Effects 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 150000003841 chloride salts Chemical class 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 150000004673 fluoride salts Chemical class 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 39
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000011033 desalting Methods 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000320 mechanical mixture Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000011195 cermet Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of melten salt electriochemistry methods that middle low-temperature oxidation methane is hydrogen and carbon monoxide, in the watery fusion salt electrolyte containing oxonium ion, using work anode, reference electrode and the three-electrode system formed to electrode, at a temperature of 400~700 DEG C, methane is passed directly to work anode surface with 50~200mL/min flow, using potentiostatic deposition, and anode potential is corrected compared with oxygen evolution potential, the electrochemical oxidation methane on work anode, generates hydrogen and carbon monoxide.Middle low-temperature molten salt pond proposed by the present invention can reduce the reaction temperature of methane portion oxidation by coupling electrochemical means, synthesis gas is converted into for industrial methane directly matches downstream Fischer-Tropsch reaction provide a technical strategies, molten salt electrolyte ionic conductivity is high in this method, the optional wide model of electrode；Particularly, oxonium ion abundant advantageously reduces anode carbon distribution in fused salt.
Description
Technical field
The invention belongs to high efficiency of energy trans-utilization fields, and in particular to a kind of middle low-temperature oxidation methane is hydrogen and an oxygen
Change the melten salt electriochemistry method of carbon.
Background technique
With the high speed development of economic society, the mankind increasingly increase the consumption of the energy, in order to effectively solve facing mankind
Energy shortage problem, it is necessary to economical and efficient utilize existing fossil energy.It is a kind of relatively abundant to be that the earth contains for natural gas
Fossil energy, other than it can be directly used as fuel and provide energy, natural gas can also be used as industrial chemicals for synthesizing
The chemical fields such as ammonia, synthesizing methanol and its derivative, but the dosage of chemical field only accounts for 8% or so of gas consumption total amount.
Main component this is mainly due to natural gas is methane, and methane can be rated as the most stable of organic molecule of structure, its activation is wanted
It is more difficult than other hydro carbons very much.But from the point of view of long term growth angle, as the reduction and exploitation difficulty of the fossil resources such as petroleum add
Greatly, natural gas is possible to that petroleum is replaced to become main energy sources and industrial chemicals, therefore the Efficient Conversion for researching and developing methane utilizes
Technology is international very popular project.Methane transformation technology can be roughly divided into direct transformation technology and indirect reformer skill
Art.Direct transformation technology includes that partial oxidation of methane takes organic oxygen-containing compound and methane oxidation coupling to produce more carbon alkane again
Hydrocarbon, alkene etc., it is considered as the route of most industrialization potential that wherein partial oxidation of methane, which takes C1 organic matter, but by-product CO
And CO2Generation be difficult to inhibit, the oxidation rate of target product methanol and formaldehyde lacks faster etc. than the oxidation rate of methane
Point is difficult to solve, and the relevant technologies still more rest on laboratory level.Methane indirect reformer technology is then first to produce from methane
Synthesis gas, then various industrial chemicals and oil product are synthesized by synthesis gas.The hydrocarbon with liquid is prepared by Fischer-Tropsch reaction due to synthesis gas
Or hydrocarbon is more mature for the technology of main fuel, therefore chooses indirect reformer technologies more industrially to utilize methane.
But indirect reformer technology still has the shortcomings that very important, including process is complex, energy consumption is high, production cost is higher etc..It makes
It is the major way that current methane is converted into synthesis gas the main reason for complicated at process is that the dry of methane, wet type are reformed (see formula
1,2), two kinds of reactions are strong endothermic reactions, and reaction carries out usually requiring 800 DEG C or more high temperature, and synthesis gas further converts
Often under middle cryogenic conditions, it is huge to cause whole energy consumption for the unmatched problem of temperature in higher temperature and two techniques
And process is complicated.
CH4+H2O=CO+3H2 ΔH298K=+206kJ/mol (1)
CH4+CO2=2CO+2H2 ΔH298K=+247kJ/mol (2)
2CH4+O2=2CO+4H2 ΔH298K=-36kJ/mol (3)
Therefore, the operating temperature that reduction methane is converted into synthesis gas has important practical significance, and the part oxygen of methane
Change technology is just hopeful to solve this problem.The partial oxidation of methane first is an exothermic reaction (see formula 3), this is anti-to reduce
Temperature is answered to provide possibility；Particularly, it is hopeful to further decrease the reaction of methane portion oxidation by coupling electrochemical means
Temperature.Methane electrochemical part oxidation at present mostly occurs in electrolytic tank of solid oxide (SOEC), is limited to soild oxide
Electrode and the too low bottleneck problem of electrolyte cryotronics conductance and ion conductance, conversion temperature will be reacted by, which still failing to, is reduced to
Middle low temperature；Particularly, cracking reaction generation simple substance carbon easily occurs for methane under hot conditions, causes anode carbon distribution to inactivate, influences electricity
The stability of chemical system under long-term working conditions.It is therefore desirable to propose a kind of electrolysis for really being able to run under middle cryogenic conditions
Pond, and fusion electrolysis pond can be run under middle cryogenic conditions, while have electrolyte ion conductance height, electrode range of choice
The advantages that wide；Developing a kind of melten salt electriochemistry method that middle low-temperature oxidation methane is hydrogen and carbon monoxide has important warp
Ji value and realistic meaning.
Summary of the invention
The present invention for existing methane conversion prepare synthesis gas need high temperature and with downstream technique process matching in terms of
Deficiency provides a kind of melten salt electriochemistry method that middle low-temperature oxidation methane is hydrogen and carbon monoxide.Using rich in oxonium ion
In anode partial oxidation occurs for middle low temperature molten salt as electrolyte, methane, and this method can utilize first under middle cryogenic conditions
Alkane prepares synthesis gas, solves methane conversion and prepares synthesis gas and needs high temperature, it is difficult to downstream Fischer-Tropsch reaction is directly matched asks
Topic realizes the purpose for reducing whole energy consumption, while realizing that the device overall structure of this method is simple, easy to use.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of middle low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, in the low temperature containing oxonium ion
In molten salt electrolyte, using work anode, reference electrode and the three-electrode system formed to electrode, in 400~700 DEG C of temperature
Under, methane is passed directly to work anode surface with 50~200mL/min flow, using potentiostatic deposition, and the anode that works
Current potential is corrected compared with oxygen evolution potential, and the electrochemical oxidation methane on work anode generates hydrogen and carbon monoxide.
The watery fusion salt electrolyte is any in carbonate, chloride salt, fluoride salt, nitrate or sulfate
Kind；Wherein, the carbonate is Li2CO3、Na2CO3、K2CO3、CaCO3Or MgCO3One of or a variety of mixed salts, the chlorination
Object salt is LiCl, NaCl, KCl, CaCl2Or MgCl2One of or a variety of mixed salts, the fluoride salt be LiF, NaF, KF,
CaF2Or MgF2One of or a variety of mixed salts, the nitrate be LiNO3、NaNO3、KNO3、Ca(NO3)2Or Mg (NO3)2In
One or more mixed salts, the sulfate are Li2SO4、Na2SO4、K2SO4、CaSO4Or MgSO4One of or a variety of mixed salts.
When the watery fusion salt electrolyte is chloride salt or fluoride salt, the oxonium ion derives from additional oxidation
Object.
When the watery fusion salt electrolyte is carbonate or nitrate or sulfate, the oxonium ion is molten from low temperature
Fused salt electrolysis matter itself or added Oxides.
The added Oxides include Li2O、Na2O、K2O、CaO、MgO、CO2Or SO2It is any one or more of.
Preferably, the watery fusion salt electrolyte is tri- kinds of LiCl, NaCl, KCl that molar ratio is 47.5:15:37.5
Chloride salt mixed salt, the fusing point of three kinds of chloride salt mixed salts are 399 DEG C；Or the watery fusion salt electrolyte is that molar ratio is
43.5:31.5:25 Li2CO3、Na2CO3、K2CO3Three kinds of carbonate mixed salts, the fusing point of three kinds of carbonate mixed salts are 393 DEG C.
The work anode is not using by fused salt heat, electrochemical corrosion or the gold that can form stable fine and close oxidation film
Category, alloy, metal oxide, cermet and perovskite type ceramic are as work anode electrode material.The work anode
Electrode material is metal Au, metal Ag, Pt metal, W metal, Ni metal, NiFe alloy, NiFeCu alloy, RuO2、Ni-YSZ、
Any one of Co-YSZ, Cu-GDC, Ru-GDC, LSM.
Described use to electrode is not made by the metal or alloy of molten salt hot corrosion or the oxidation film that can form stable densification
For to electrode material.It is described to electrode material be metal Au, metal Ag, Pt metal, W metal, Ni metal, NiFe alloy,
Any one of NiFeCu alloy.
The work anode and be sheet, netted, foamed metal structures or porous structure to the structure of electrode.
The reference electrode is Ag/Ag2SO4Or Ag/AgCl high temperature reference electrode, wherein Ag2SO4Or AgCl concentration is
0.1mol/kg, using filamentary silver as reference electrode material.
The principle of embodiment is as follows in the present invention:
In work anode oxidation reaction (see formula 4,5) occurs for carbonate or oxonium ion first, and reaction, which generates, has high oxidation
Active active oxygen, the active oxygen further aoxidize methane (see formula 6).
CO3 2--2e-=CO2+Oactive (4)
O2--2e-=Oactive (5)
CH4+Oactive=CO+2H2 (6)
The method of the present invention compared with prior art, has the following advantages and outstanding effects: 1. can be using molten salt pool
The characteristics of middle low-temperature working, coupling electrochemical technology successfully reduce the operating temperature of methane portion oxidation, are reducing energy consumption
While can preferably match with downstream Fischer-Tropsch reaction temperature.2. fused salt has higher compared to solid oxide electrolysis matter
Ionic conductivity.3. middle low-temperature working condition is unfavorable for anode carbon distribution, while oxonium ion abundant is conducive to subtract in fused salt
Few anode carbon distribution, these both contribute to improve lifetime of system.4. compared to electrolytic tank of solid oxide, electrode in molten-salt electrolysis pond
Material selection range is wider.
Detailed description of the invention
Fig. 1 is flowage structure schematic diagram of the invention；
In figure, 1. methane gas cylinder, 2. nitrogen gas cylinder, 3. pressure reducing valve, 4. gas flowmeter, 5. electrochemical workstation, 6. close
Sealing, 7. electric tube furnace, 8. alundum tube, 9. work anode, 10. corundum crucible,High temperature reference electrode,To electrode,
Fuse salt,Filter dryer,Gas-chromatography.
Fig. 2 is the work of embodiment 1 anode potentiostatic deposition curve in the present invention.
Fig. 3 is the work of embodiment 2 anode potentiostatic deposition curve in the present invention.
Fig. 4 is that the work of embodiment 1 anode potentiostatic deposition corresponds to gaseous product concentration curve in the present invention；
After electrolysis starts, electric current is stablized in 20mA cm-2, corresponding gas concentration generation significant changes: methane concentration decline
320ppm, H2Concentration rises 10ppm, and CO concentration rises 4ppm.
Fig. 5 is that the work of embodiment 2 anode potentiostatic deposition corresponds to gaseous product concentration curve in the present invention；
After electrolysis starts, electric current is stablized in 30mA cm-2, corresponding gas concentration generation significant changes: methane concentration decline
500ppm, H2Concentration rises 20ppm, and CO concentration rises 11ppm.
Specific embodiment
It is the specific implementation case based on technical solution of the present invention below, passes through following embodiment and can be more in conjunction with attached drawing
Understand the present invention well.It should be noted that the present invention is not only limited to following embodiment, those skilled in the art are according to this hair
Bright principle belongs to the model that the present invention protects to the insubstantial modifications or change in terms of the form and content of the invention made
It encloses.
[embodiment 1]
Weigh Li2CO3, Na2CO3, K2CO3(molar ratio 43.5:31.5:25) total 300g, is put into after mechanical mixture is uniform
Corundum crucible is placed in electric tube furnace, is warming up to 300 DEG C with 5 DEG C/min heating rate and is kept the temperature and removes the moisture in desalting for 24 hours,
Then 600 DEG C are warming up to and keeps the temperature half an hour to salt with 5 DEG C/min heating rate and be completely melt to form uniform mixed salt, then dropped
Temperature to 500 DEG C keep.Electric tube furnace upper and lower ends are sealed with steel flange disk, and logical by the aperture of lower section ring flange
Enter inert gas N2, corresponding flow velocity is 200mL/min.It chooses NiFe alloy (64:36) and is used as work anode material, electrode structure
For sheet.The anode that will work directly is contacted with the thin alundum tube for being passed through methane gas, integral sealing gas made of thick alundum tube
In fluid chamber, it is ensured that working electrode is located at fused salt liquid level or less.As shown in Fig. 1, fused salt will be inserted into electrode and working electrode
In electrolytic cell, while gas flow path is connected according to shown in attached drawing 1.Methane induction air flow ratio is adjusted to be 50mL/min and keep 1h, it will
Three electrodes are connected with electrochemical workstation.Potentiostatic deposition program is arranged in electrochemical workstation, and setting parameter is 1.0V vs.Ag/
Ag2SO4, and record current changes over time curve, work anode potentiostatic deposition curve as shown in Figure 2.At the same time, it opens
Online gas-chromatography on-line real-time measuremen gaseous product, the anode potentiostatic deposition that works as shown in Figure 4 correspond to gaseous product concentration
Change curve, after electrolysis starts, electric current is stablized in 20mA cm-2, corresponding gas concentration generation significant changes, methane concentration decline
320ppm, H2Concentration rises 10ppm, and CO concentration rises 4ppm.
[embodiment 2]
Weigh Li2CO3, Na2CO3, K2CO3Mixed salt quality 5% is added in (molar ratio 47.5:30.5:23) total 300g
Li2O increase fused salt in oxonium ion content, be put into corundum crucible after mechanical mixture is uniform and be placed in electric tube furnace, with 10 DEG C/
Min heating rate is warming up to 300 DEG C and keeps the temperature removes the moisture in desalting for 24 hours, is then warming up to 600 with 10 DEG C/min heating rate
DEG C and keep the temperature half an hour to salt and be completely melt to form uniform mixed salt, be then cooled to 500 DEG C of holdings.By above and below electric tube furnace two
End is sealed with steel flange disk, and is passed through inert gas N by lower section ring flange aperture2, corresponding flow velocity is 200mL/
min.Metal Au is chosen as work anode material, electrode structure is sheet, and will work anode and is passed through the thin rigid of methane gas
Jade pipe directly contacts, and integral sealing is in the gas chamber made of thick alundum tube, it is ensured that working electrode is located at fused salt liquid level or less.
As shown in Fig. 1, electrode and working electrode will be inserted into molten-salt electrolysis pond, while connects gas flow path according to shown in attached drawing 1.
It adjusts methane induction air flow ratio to be 100mL/min and keep 0.5h, three electrodes is connected with electrochemical workstation.Electrochemical workstation
Potentiostatic deposition program is set, and setting parameter is 1.0V vs.Ag/Ag2SO4, and record current changes over time curve, such as Fig. 3
Shown work anode potentiostatic deposition curve.At the same time, online gas-chromatography on-line real-time measuremen gaseous product is opened, is such as schemed
Work anode potentiostatic deposition shown in 5 corresponds to gaseous product concentration curve, and after electrolysis starts, electric current is stablized in 30mA cm-2, corresponding gas concentration generation significant changes, methane concentration decline 500ppm, H2Concentration rises 20ppm, and CO concentration rises
11ppm。
[embodiment 3]
LiCl, NaCl, the total 300g of KCl (molar ratio 47.5:15:37.5) are weighed, the Na of mixed salt quality 4% is added2O increases
Add oxonium ion content in fused salt, be put into corundum crucible after mechanical mixture is uniform and be placed in electric tube furnace, is heated up with 5 DEG C/min fast
Rate is warming up to 300 DEG C and keeps the temperature removes the moisture in desalting for 24 hours, is then warming up to 600 DEG C with 5 DEG C/min heating rate and keeps the temperature half
It hour is completely melt to form uniform mixed salt to salt, is then cooled to 400 DEG C of holdings.By electric tube furnace upper and lower ends stainless steel
Ring flange is sealed, and is passed through inert gas Ar by lower section ring flange aperture, and corresponding flow velocity is 200mL/min.Choose gold
Belong to Au and be used as work anode material, electrode structure be it is netted, the anode that will work directly connects with the thin alundum tube for being passed through methane gas
Touching, integral sealing is in the gas chamber made of thick alundum tube, it is ensured that working electrode is located at fused salt liquid level or less.Such as 1 institute of attached drawing
Show, electrode and working electrode will be inserted into molten-salt electrolysis pond, while connecting gas flow path according to shown in attached drawing 1.Adjust methane
Induction air flow ratio is 50mL/min and keeps 2h, and three electrodes are connected with electrochemical workstation.Constant potential is arranged in electrochemical workstation
It is electrolysed program, setting parameter is 1.2V vs.Ag/AgCl, and record current changes over time curve.At the same time, it opens online
Gas-chromatography on-line real-time measuremen gaseous product.After electrolysis starts, electric current is stablized in 25mA cm-2, corresponding gas concentration occurs aobvious
Variation is write, methane concentration declines 330ppm, H2Concentration rises 25ppm, and CO concentration rises 6ppm.
[embodiment 4]
LiCl, NaCl, the total 300g of KCl (molar ratio 47.5:15:37.5) are weighed, the Li of mixed salt quality 2% is added2O increases
Add oxonium ion content in fused salt, be put into corundum crucible after mechanical mixture is uniform and be placed in electric tube furnace, is heated up with 5 DEG C/min fast
Rate is warming up to 300 DEG C and keeps the temperature removes the moisture in desalting for 24 hours, is then warming up to 600 DEG C with 5 DEG C/min heating rate and keeps the temperature extremely
Salt is completely melt to form uniform mixed salt.Electric tube furnace upper and lower ends are sealed with steel flange disk, and pass through lower section
Ring flange aperture is passed through inert gas N2, corresponding flow velocity is 200mL/min.Cermet Ni-YSZ is chosen as work anode material
Material, cermet Ni-YSZ are porous structure, and the anode that will work directly is contacted with the thin alundum tube for being passed through methane gas, whole close
It is encapsulated in gas chamber made of thick alundum tube, it is ensured that working electrode is located at fused salt liquid level or less.It as shown in Fig. 1, will be to electricity
In pole and working electrode insertion molten-salt electrolysis pond, while gas flow path is connected according to shown in attached drawing 1.Adjusting methane induction air flow ratio is
100mL/min simultaneously keeps 1h, and three electrodes are connected with electrochemical workstation.Potentiostatic deposition program is arranged in electrochemical workstation,
Setting parameter is 1.2V vs.Ag/AgCl, and record current changes over time curve.At the same time, online gas-chromatography is opened
On-line real-time measuremen gaseous product.After electrolysis starts, electric current is stablized in 120mA cm-2, corresponding gas concentration generation significant changes,
Methane concentration declines 1200ppm, H2Concentration rises 980ppm, and CO concentration rises 800ppm.
[embodiment 5]
LiCl 300g is weighed, the Li of mixed salt quality 5% is added2O increases oxonium ion content in fused salt, and mechanical mixture is uniform
After be put into corundum crucible and be placed in electric tube furnace, with 5 DEG C/min heating rate be warming up to 300 DEG C and keep the temperature for 24 hours except desalting in
Moisture, be then warming up to 700 DEG C with 5 DEG C/min heating rate and keep the temperature.By electric tube furnace upper and lower ends steel flange
Disk is sealed, and is passed through inert gas Ar by lower section ring flange aperture, and corresponding flow velocity is 200mL/min.Choose foam gold
Belong to Ni as work anode material, the anode that will work directly is contacted with the thin alundum tube for being passed through methane gas, and integral sealing is in thick
In gas chamber made of alundum tube, it is ensured that working electrode is located at fused salt liquid level or less.It as shown in Fig. 1, will be to electrode and work
Make in electrode insertion molten-salt electrolysis pond, while connecting gas flow path according to shown in attached drawing 1.Adjusting methane induction air flow ratio is 200mL/
Min simultaneously keeps 1h, and three electrodes are connected with electrochemical workstation.Potentiostatic deposition program, setting ginseng is arranged in electrochemical workstation
Number is 1.5V vs.Ag/AgCl, and record current changes over time curve.At the same time, it is real online to open online gas-chromatography
When detection gas product.After electrolysis starts, electric current is stablized in 420mAcm-2, significant changes occur for corresponding gas concentration, and methane is dense
Degree decline 6500ppm, H2Concentration rises 5900ppm, and CO concentration rises 5400ppm.
The present embodiments relate to principle it is as follows:
In work anode oxidation reaction (see formula 4,5) occurs for carbonate or oxonium ion first, and reaction, which generates, has high oxidation
Active active oxygen further aoxidizes methane (see formula 6).It is selectable that this also increases work anode material to a certain extent
Range.
CO3 2--2e-=CO2+Oactive (4)
O2--2e-=Oactive (5)
CH4+Oactive=CO+2H2 (6)
The potentiostatic deposition curve and corresponding gas of the present embodiment 1 and embodiment 2 is set forth in attached drawing 2,3,4,5
Production concentration curve, as a result demonstrating and realizing that methane is electrochemically transformed based on molten-salt electrolysis Chi Zhong low temperature is the possibility of synthesis gas
Property, a technical strategies are provided for industrial methane transformation of synthetic gas direct-coupling downstream Fischer-Tropsch reaction.
Claims (10)
1. a kind of melten salt electriochemistry method that middle low-temperature oxidation methane is hydrogen and carbon monoxide, it is characterised in that: containing aerobic
In the watery fusion salt electrolyte of ion, using work anode, reference electrode and the three-electrode system formed to electrode, 400
At a temperature of~700 DEG C, methane is passed directly to work anode surface with 50~200mL/min flow, using potentiostatic deposition,
And anode potential is corrected compared with oxygen evolution potential, the electrochemical oxidation methane on work anode generates hydrogen and carbon monoxide.
2. low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, feature in as described in claim 1
Be: the watery fusion salt electrolyte is any one of carbonate, chloride salt, fluoride salt, nitrate or sulfate；
Wherein, the carbonate is Li2CO3、Na2CO3、K2CO3、CaCO3Or MgCO3One of or a variety of mixed salts, the chloride salt
For LiCl, NaCl, KCl, CaCl2Or MgCl2One of or a variety of mixed salts, the fluoride salt be LiF, NaF, KF, CaF2Or
MgF2One of or a variety of mixed salts, the nitrate be LiNO3、NaNO3、KNO3、Ca(NO3)2Or Mg (NO3)2One of or
A variety of mixed salts, the sulfate are Li2SO4、Na2SO4、K2SO4、CaSO4Or MgSO4One of or a variety of mixed salts.
3. low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, feature in as claimed in claim 2
Be: when the watery fusion salt electrolyte is chloride salt or fluoride salt, the oxonium ion derives from added Oxides.
4. low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, feature in as claimed in claim 2
Be: when the watery fusion salt electrolyte is carbonate or nitrate or sulfate, the oxonium ion derives from watery fusion
Salt electrolyte itself or added Oxides.
5. middle low-temperature oxidation methane as described in claim 3 or 4 is the melten salt electriochemistry method of hydrogen and carbon monoxide, special
Sign is: the added Oxides include Li2O、Na2O、K2O、CaO、MgO、CO2Or SO2It is any one or more of.
6. low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, feature in as claimed in claim 3
Be: the watery fusion salt electrolyte is tri- kinds of mixed salts of LiCl, NaCl, KCl that molar ratio is 47.5:15:37.5.
7. low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, feature in as claimed in claim 4
Be: the watery fusion salt electrolyte is the Li that molar ratio is 43.5:31.5:252CO3、Na2CO3、K2CO3Three kinds of mixed salts.
8. the fused salt electricity that the middle low-temperature oxidation methane as described in any one of claim 1-4,6 or 7 is hydrogen and carbon monoxide
Chemical method, it is characterised in that: the work anode electrode material be metal Au, metal Ag, Pt metal, W metal, Ni metal,
NiFe alloy, NiFeCu alloy, RuO2, any one of Ni-YSZ, Co-YSZ, Cu-GDC, Ru-GDC, LSM；It is described to electrode
Material is any one of metal Au, metal Ag, Pt metal, W metal, Ni metal, NiFe alloy, NiFeCu alloy.
9. low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, feature in as claimed in claim 8
It is: the work anode and be sheet, netted, foamed metal structures or porous structure to the structure of electrode.
10. low-temperature oxidation methane is the melten salt electriochemistry method of hydrogen and carbon monoxide, feature in as claimed in claim 9
Be: the reference electrode is Ag/Ag2SO4Or Ag/AgCl high temperature reference electrode, wherein Ag2SO4Or AgCl concentration is
0.1mol/kg, using filamentary silver as reference electrode material.
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| CN113832473A (en) * | 2021-09-10 | 2021-12-24 | 默特瑞(武汉)科技有限公司 | Molten salt electrochemical method for co-production of metal/carbon composite material and hydrogen |
| CN114057164A (en) * | 2020-07-31 | 2022-02-18 | 上海科技大学 | Reaction system for dry reforming reaction of methane |
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| CN1636862A (en) * | 2004-10-12 | 2005-07-13 | 昆明理工大学 | Method of catalytically oxidizing natural gas with lattice oxygen to prepare hydrogen in molten salt |
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