EP3993896A1 - Process for removing carbon monoxide and/or gaseous sulfur compounds from hydrogen gas and/or aliphatic hydrocarbons - Google Patents
Process for removing carbon monoxide and/or gaseous sulfur compounds from hydrogen gas and/or aliphatic hydrocarbonsInfo
- Publication number
- EP3993896A1 EP3993896A1 EP20746946.1A EP20746946A EP3993896A1 EP 3993896 A1 EP3993896 A1 EP 3993896A1 EP 20746946 A EP20746946 A EP 20746946A EP 3993896 A1 EP3993896 A1 EP 3993896A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metals
- metal
- carbon monoxide
- complex metal
- sulfur compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 150000003464 sulfur compounds Chemical class 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims abstract description 12
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 title claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 62
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 15
- 150000002739 metals Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- -1 metal salts Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 101100108446 Mus musculus Aifm3 gene Proteins 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 229910052987 metal hydride Inorganic materials 0.000 description 9
- 150000004681 metal hydrides Chemical class 0.000 description 9
- 150000004678 hydrides Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 239000003570 air Substances 0.000 description 3
- 239000012080 ambient air Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- BIZCJSDBWZTASZ-UHFFFAOYSA-N iodine pentoxide Inorganic materials O=I(=O)OI(=O)=O BIZCJSDBWZTASZ-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- RZCJSVRGPHXBSM-UHFFFAOYSA-N 8-chloro-[1,3]dioxolo[4,5-g]quinazoline Chemical compound C1=C2C(Cl)=NC=NC2=CC2=C1OCO2 RZCJSVRGPHXBSM-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0675—Removal of sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/209—Other metals
- B01D2255/2092—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a method for removing carbon monoxide and / or gaseous sulfur compounds from hydrogen gas and / or aliphatic hydrocarbons, preferably at low temperatures, with the aid of complex metal-aluminum hydrides.
- Hydrogen is the most important energy carrier for fuel cells.
- the polymer electrolyte fuel cell has gained importance as a low-temperature fuel cell in recent years.
- the polymer electrolyte fuel cell (“Polymer Electrolyte Fuel Cell" - PEFC - colloquially mostly called PEM - works at operating temperatures below 100 ° C.
- a characteristic feature of the polymer electrolyte fuel cell is the thin, gas-tight, proton-conducting, solid polymer membrane as the electrolyte. Acid groups are integrated into this plastic skin, ie the protons diffuse through the membrane, as in all acidic cells, from the anode to the cathode, where they recombine together with the oxygen ions to form water.
- the water content of currently available perfluorinated polymer membranes eg made from NAFION ®
- the electrical contact from the electrodes to the bipolar plates takes place via metallic or carbon-containing current conductors.
- the noble metal catalysts and electrolytes used require a comparatively high level of fuel gas purity. Only H 2 can be used as the fuel gas.
- the oxidizing agent is 0 2 , and unlike other fuel cells, air operation is also possible; this significantly expands the application possibilities of the PEFC.
- carbon monoxide (CO) is only tolerated in very small quantities of ⁇ 0.2 ppm, since it acts as a catalyst poison just like sulfur compounds.
- Hydrogen hardly occurs in pure form on earth and is therefore generated with energy expenditure.
- a manufacturing process often used in industry is the steam reforming of natural gas or hydrocarbons from other sources. The hydrogen is gradually withdrawn from the hydrocarbon chains using the various reforming processes. By-products include Carbon monoxide, nitrogen oxides and sulfur dioxide. If the gas produced during the reforming is in a low-temperature
- the fuel cell If the fuel cell is to be conducted, it must first be cleaned of carbon monoxide. For thermodynamic reasons, carbon monoxide is also formed during reforming and, like sulfur compounds, is a poison for the catalysts of the fuel cell. In the processes in the prior art, cleaning is carried out in the so-called water-gas shift reactor and in the reactor for preferential oxidation carried out. However, these processes are rather expensive and there is therefore a need for a simplified process for the production of hydrogen gas or gaseous aliphatic hydrocarbons from which catalyst poisons such as CO or sulfur compounds have been removed.
- the invention relates to a method for removing carbon monoxide and / or gaseous sulfur compounds from a gas containing carbon monoxide and / or gaseous sulfur compounds, in which the gas, selected from hydrogen gas and / or one or more gaseous aliphatic hydrocarbons or a mixture thereof, in a
- the reaction can be carried out in a vessel designed as a reaction vessel for a batch reaction or, preferably, as a reaction vessel for a continuous reaction into which the gas to be purified is introduced, brought into contact with the complex metal-aluminum hydride and after the reaction is passed out of the reaction vessel.
- This makes it possible to design the reaction vessel in the form of a permeable filter unit which is filled with one or more complex metal-aluminum hydrides of the formulas I to III.
- Such a through-flow filter unit can advantageously be used as a filter cartridge, in particular in front of fuel cells, in order to To protect the catalyst from the catalyst poisons in the hydrogen gas used.
- a through-flow filter unit can have an indicator display, which shows the degree of loading of the filter unit and allows timely replacement.
- the invention also relates to a fuel cell with at least one such filter unit according to the invention through which a flow can flow.
- the gas flow can be diverted depending on the degree of loading of a first filter unit to at least one second filter unit arranged "parallel" in the gas flow, so that continuous operation of the fuel cell is made possible.
- the first filter unit can be subjected to a step for recycling the complex metal hydride.
- Me stands for one or more arbitrary alkali or alkaline earth metals from the periodic table of the elements.
- the complex hydride used can be fully or only partially dehydrated. According to the invention, dehydrogenated is understood to mean that the hydrogen bound to the metal has been removed from the metal hydride by measures for dehydrogenation such as, for example, heating up to the decomposition temperature.
- the aforementioned complex hydrides can be mixed with one or more metals as metal compounds such as metal salts, for example metal halides, or also as metal in particle form, in order to increase the reactivity of the metal-aluminum hydrides.
- metals are transition metals from groups 3, 4, 5, 6, 7, 8, 9, 10, 11, in particular Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, La, Ce, Pr and Nd, or alloys or mixtures of these metals with one another or with aluminum, or compounds of these metals, for example as a metal salt such as metal halide, in the form of very small particles with a high degree of distribution, for example with particle sizes approx.
- metals such as Ti, Zr, Sc, Y, and rare earth metals.
- the metals can be produced from different precursors directly by reduction in-situ with the complex metal hydride or ex-situ by various reduction processes. In-situ production is preferred.
- Additives such as carbon (graphite, spheroidal carbon, activated carbon) in particle form with a particle size of 10 nm to 1000 nm or metal powders such as Al powder with particle sizes of 10 nm to 1000 nm can be added to the complex hydride or the mixture of metal and complex hydride in order to achieve a good distribution of catalyst and complex hydride on the surface of the particles.
- the complex hydrides described above, which have been partially oxidized, can also be used. The oxidation occurs through contact with oxygen (air), for example simply in air.
- the CO-containing hydrogen gas is passed in a reactor over the metal hydride powder composed of complex hydride and catalyst in flow or also in batch operation and is thus brought into contact with the latter.
- the contact can also take place in a fluidized bed reactor or in a closed reaction vessel such as in an autoclave.
- the flow rates of the CO-containing hydrogen gas are selected in a continuous operation so that a complete reaction and adsorption on the complex metal hydride takes place, and are usually 1.5 L / hg (complex metal hydride).
- the pressure in the reaction vessel is not critical and can be in the range of normal pressure from about 0.1 to 15 MPa.
- the reaction temperature is generally between -20 ° and 250 ° C. The invention is explained further with reference to the attached FIGS. 1 to 5 and the production examples.
- Figures 1 to 4 show the course of tests for the method according to the invention in comparison with a method not according to the invention.
- FIG. 4 illustrates the reusability of a flow tube filled with a complex metal-aluminum hydride used in the process according to the invention, which was subjected to a step to remove the adsorbed carbon monoxide, for example under the action of ambient air on the complex metal-aluminum hydride.
- FIG. 5 shows the test apparatus and serves to explain the test method.
- the test apparatus consists of the absorption tube 4, filled with a complex aluminum hydride, the storage vessel 5 for the gas mixture used, a mass flow meter 6, a vacuum pump 7 and an IR spectrometer 8 to control the CO concentration in the gas mixture.
- the individual work processes can be carried out under inert conditions via valves 1, 2 and 3.
- valve 2 Before starting the measurement, the entire apparatus is evacuated through valve 2 with valves 1 and 3 closed. Valve 2 is then closed and the apparatus is filled with an inert gas via valve 3. The gas mixture is supplied with valves 1 and 3 open, the gas flow being adjusted to the required amount of gas with the aid of the mass flow controller 6. After the gas mixture has flowed through the absorption tube 4, the CO concentration is determined with the aid of the IR spectrometer 8.
- a reduction in the absorption capacity of the complex aluminum hydrides when removing impurities from hydrogen gas can be made visible in a simple manner by means of a color reaction in a window cartridge in the direction of flow after the absorption tube 4 in front of the valve 1 and thus controlled.
- the released iodine causes a discoloration of the carrier material on which the color reaction takes place. This enables visual observation and control of a decreasing absorption capacity, and the absorption tube can be replaced in good time.
- Two or more absorption tubes 4 are preferably arranged in parallel in the direction of flow, and when the absorption capacity decreases, the gas flow can be switched from one to another absorption tube 4.
- FIG. 4 illustrates the reusability of a flow tube filled with a complex metal-aluminum hydride used in the method according to the invention, which was subjected to a step for removing the adsorbed carbon monoxide, for example under the action of ambient air on the complex metal-aluminum hydride.
- the gas concentration was determined with the aid of a gas-filled optopneumatic detector.
- the particle sizes were determined either by laser diffraction or, in the case of very small particles, by means of TEM analyzes (transmission electron microscopy). Manufacturing example
- Na 3 AlH 6 is ground with TiCl 3 (2-4 mol%) and, if necessary, other additives in a ball mill.
- the material obtained in this way is used to remove CO from hydrogen gas.
- Other impurities such as C0 2 , H 2 O and S compounds can also be eliminated from hydrogen gas using this process.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Fuel Cell (AREA)
- Gas Separation By Absorption (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102019211379.6A DE102019211379A1 (en) | 2019-07-30 | 2019-07-30 | Process for removing carbon monoxide and / or gaseous sulfur compounds from hydrogen gas and / or aliphatic hydrocarbons |
PCT/EP2020/071066 WO2021018809A1 (en) | 2019-07-30 | 2020-07-26 | Process for removing carbon dioxide and/or gaseous sulfur compounds from hydrogen gas and/or aliphatic hydrocarbons |
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EP3993896A1 true EP3993896A1 (en) | 2022-05-11 |
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US (1) | US20220266195A1 (en) |
EP (1) | EP3993896A1 (en) |
JP (1) | JP2022543750A (en) |
KR (1) | KR20220040477A (en) |
CN (1) | CN114302765B (en) |
CA (1) | CA3145150A1 (en) |
DE (1) | DE102019211379A1 (en) |
WO (1) | WO2021018809A1 (en) |
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US5702838A (en) * | 1995-08-18 | 1997-12-30 | Matsushita Electric Industrial Co., Ltd. | Fuel cell device equipped with catalyst material for removing carbon monoxide and method for removing carbon monoxide |
DE10163697A1 (en) * | 2001-12-21 | 2003-07-03 | Studiengesellschaft Kohle Mbh | Reversible storage of hydrogen with the help of doped alkali metal aluminum hydrides |
WO2003079470A1 (en) * | 2002-03-20 | 2003-09-25 | Matsushita Electric Industrial Co., Ltd. | Fuel cell |
JP2004097859A (en) * | 2002-09-04 | 2004-04-02 | Tokyo Inst Of Technol | Catalyst and method for eliminating carbon monoxide |
US7160343B2 (en) * | 2003-05-16 | 2007-01-09 | General Motors Corporation | Systems and methods for carbon monoxide clean-up |
WO2007055663A1 (en) * | 2005-11-14 | 2007-05-18 | Agency For Science, Technology And Research | Highly dispersed metal calatysts |
KR100745743B1 (en) * | 2006-10-25 | 2007-08-02 | 삼성에스디아이 주식회사 | Carbon monoxide removing system and fuel processor and fuel cell comprising the same |
SG174814A1 (en) * | 2007-09-21 | 2011-10-28 | Memc Electronic Materials | Processes for purification of silicon tetrafluoride |
EP2560226A1 (en) * | 2011-08-19 | 2013-02-20 | Technical University of Denmark | Method and system for purification of gas/liquid streams for fuel cells or electrolysis cells |
US10414989B2 (en) * | 2016-04-15 | 2019-09-17 | Baker Hughes, A Ge Company, Llc | Chemical process for sulfur reduction of hydrocarbons |
CN109499261A (en) * | 2018-12-03 | 2019-03-22 | 四川天科技股份有限公司 | The removing system and method for CO in a kind of used in proton exchange membrane fuel cell hydrogen |
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CN114302765B (en) | 2024-06-11 |
CA3145150A1 (en) | 2021-02-04 |
WO2021018809A8 (en) | 2021-12-30 |
JP2022543750A (en) | 2022-10-14 |
CN114302765A (en) | 2022-04-08 |
US20220266195A1 (en) | 2022-08-25 |
KR20220040477A (en) | 2022-03-30 |
WO2021018809A1 (en) | 2021-02-04 |
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