EP3762350A1 - Manganese-doped nickel methanization catalysts having elevated sulphur resistance - Google Patents
Manganese-doped nickel methanization catalysts having elevated sulphur resistanceInfo
- Publication number
- EP3762350A1 EP3762350A1 EP19711029.9A EP19711029A EP3762350A1 EP 3762350 A1 EP3762350 A1 EP 3762350A1 EP 19711029 A EP19711029 A EP 19711029A EP 3762350 A1 EP3762350 A1 EP 3762350A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- sulfur
- ppb
- range
- reactant stream
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052759 nickel Inorganic materials 0.000 title claims description 25
- 239000005864 Sulphur Substances 0.000 title abstract 4
- 230000002211 methanization Effects 0.000 title abstract 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 69
- 238000000034 method Methods 0.000 claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 71
- 239000011593 sulfur Substances 0.000 claims description 69
- 230000008569 process Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011572 manganese Substances 0.000 abstract description 35
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 238000002411 thermogravimetry Methods 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000009849 deactivation Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 231100000572 poisoning Toxicity 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 3
- 239000010414 supernatant solution Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000012482 calibration solution Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- -1 oxygen anions Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/045—Regeneration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
Definitions
- the energy supply through the so-called renewable energy photovoltaic and wind energy suffers from the problem of weather and daytime dependent fluctuations in electricity production.
- a way has to be found to intercept weather and time-dependent fluctuations in electricity production.
- One potential method of chemically storing energy is the power-to-gas process, which uses excess electricity to split water into hydrogen and oxygen by electrolysis. What hydrogen, in which the energy is stored after the electrolysis of water, can be stored even with great effort or transported to the consumer.
- the hydrogen is converted into methane and water in the methanation reaction with carbon dioxide, which acts as a climate-damaging greenhouse gas in the atmosphere.
- Methane can be easily stored in existing infrastructures, which have capacities for storage in the range of several months, can be transported almost lossless over longer distances and can be reconverted in times of energy demand.
- the methanation reaction which involves high energy release and is usually catalyzed, is at the heart of the process.
- the high exothermicity of the reaction (-165 kJ / mol) gives rise to two direct problems.
- ther modynamic equilibrium limits the maximum achievable yield of methane.
- a purity of 95% is necessary in Germany. This results in the demand for a high catalyst activity, so that at industrially applied reaction pressures at low temperatures higher yields of methane can be achieved.
- Ni 3 S 2 Heazlewoodite
- Ni 3 S 4 Polydymite
- the methanation reaction is also of key importance in large-scale SNG (synthetic natural gas) plants based on coal gasification.
- the hydrogen which is recovered by the coal gasification and the subsequent shift reaction (C0 + H 2 O-> -C0 2 + H 2 ) is purified, for example by wet scrubbing with cold methanol, and contains low sulfur loads of the order of ⁇ 100 ppb , However, even these low sulfur levels can adversely affect the life of subsequent synthesis reactors.
- Catalysts with an increased sulfur resistance could reduce the pre-cleaning effort or increase the service life of the synthesis reactor, with a positive effect on the profitability of the overall system.
- US 4132672 A discloses an improved process for the conversion of hydrogen and carbon monoxide to a methane-enriched gas using a supported nickel catalyst obtained by the addition of a small percentage of iridium metal, typically 0.1 to 1, 0 wt .-% is promoted. This promoted catalyst is very active in methanation and has good resistance to sulfur compound poisoning.
- This object is achieved by a method for the methanation of carbon monoxide and / or the carbon dioxide, in a reactant stream containing carbon monoxide and / or carbon dioxide, hydrogen and more than 1 ppb sulfur, using a catalyst, the alumina, a Ni Active composition and Mn, characterized in that the molar Ni / Mn ratio in the catalyst in the range between 1, 0 and 15.0, preferably between 2.0 and 12.0, particularly preferably between 3.0 and 10.0 , or more preferably in the range between 3.5 and 5.5 or 7.5 and 9.5.
- a Mn-containing Ni catalyst has a high sulfur resistance and a high sulfur capacity.
- the catalyst used in the process according to the invention shows, in addition to its improved ability to catalyze the methanation reaction ("sulfur resistance") despite the presence of sulfur, at the same time the ability to absorb or irreversibly bind sulfur (“sulfur capacity”) ,
- the invention relates to a process for the methanation of carbon monoxide and / or the carbon dioxide, in a reactant stream containing carbon monoxide and / or carbon dioxide, hydrogen and more than 1 ppb sulfur, wherein the educt stream is passed through a reactor with a catalyst, wherein the catalyst comprises a Ni active composition and Mn, with a molar Ni / Mn ratio in the catalyst in the range between 1, 0 and 15.0, preferably between 2.0 and 12.0, particularly preferably between 3.0 and 10.0, or more preferably in the range between 3.5 and 5.5 or 7.5 and 9.5, characterized in that the cata- capacitor absorbs the sulfur contained in the reactant stream and simultaneously catalyzes the methanation reaction.
- the invention relates to the use of a catalyst comprising alumina, a Ni-active composition and Mn, characterized in that the molar Ni / Mn ratio in the catalyst in the range between 1, 0 and 15.0, preferably between 2.0 and 12 , 0, more preferably between 3.0 and 10.0, or more preferably in the range between 3.5 and 5.5 or 7.5 and 9.5, for the methanation of carbon monoxide and / or carbon dioxide with gaseous hydrogen in the presence of more than 1 ppb of sulfur.
- the catalyst absorbs more than 70%, more preferably more than 80%, of the sulfur present in the reactant stream, ie during the process the product stream contains 70 or 80% less sulfur than the educt stream. It is particularly preferred that during the process according to the invention the catalyst completely absorbs the sulfur in the educt stream, then the product stream no longer contains any sulfur.
- the catalyst according to the invention is particularly suitable for the methanation of carbon monoxide and / or carbon dioxide by hydrogen in the presence of more than 1 ppb, preferably more than 4 ppb, more preferably more than 10 ppb of sulfur.
- One ppb sulfur corresponds to one billionth of the volume fraction (10 9 ) of the sulfur-containing molecule, it being approximately assumed that each sulfur-containing molecule has only one sulfur atom.
- the sulfur content in the process according to the invention is between 1 ppb and 300 ppm, preferably 4 ppb to 10 ppm of sulfur.
- One ppm sulfur in this case corresponds to one millionth part by volume (10 6 ) of the sulfur-containing molecule, assuming approximately that each sulfur-containing molecule has only one sulfur atom.
- the methanation of carbon dioxide can be represented by the following reaction equation:
- the methanation of carbon monoxide can be represented by the following reaction equation:
- the methanation is generally carried out at temperatures of 180 ° C to 600 ° C.
- the reactant gas which contains carbon dioxide or carbon monoxide or a mixture of both, is brought into contact with the catalyst at a temperature above 180 ° C. to 600 ° C.
- the catalyst contains alumina, a Ni active composition and Mn, the Ni / Mn ratio, in particular in the case of the coprecipitated catalyst, in the range between 2.0 and 6.0, more preferably between 3.5 and 5.5, or more preferably in the range between 4.0 and 5.0.
- the Ni / Mn ratio is, in particular in the case of the catalyst represented by impregnation, in the range between 6.0 and 10.0, preferably between 7.5 and 9.5 and particularly preferably between 8.0 and 9.0.
- the alumina need not be stoichiometric Al 2 O 3, but may be a non-stoichiometric alumina, preferably gamma Al 2 O 3.
- the promoter Mn may be wholly or partially contained in the Ni active material.
- the catalyst can contain further promoters in addition to Mn, but it can also exclusively contain the promoter Mn.
- the oxidation states of Al, Ni and the promoters can vary depending on the treatment of the catalyst. Al, Ni and the promoters are typically present as metal cations (eg Al 3+ , Ni 2+ , Mn 2+ , Mn 4+ ). After calcination, eg in air, high oxidation states or the maximum oxidation states can be achieved. If the catalyst is reduced at temperatures above room temperature, for example under reaction conditions with hydrogen, Al, Ni and the promoters can assume lower oxidation states or occur partially or completely in the oxidation state O. The charge balance to the metal cations is carried out by oxygen anions (O 2 ).
- the catalyst according to the invention may contain other components in addition to aluminum oxide (AIO x with x ⁇ 1, 5) Ni, and Mn (as well as the Sauerstoffanio NEN necessary for charge equalization), but it can also hen exclusively from alumina, Ni and Mn best.
- the Ni-active composition may contain further promoters in addition to Mn, but it may also contain exclusively the promoter Mn.
- the Ni active composition contains none of the elements selected from B, Ta, In, Cu, Ce, Cr, Bi, Fe, P, Sb, Sn, Si, Ti, Zr, Co, Rh, Ru, Ag, Ir, Pd and Pt.
- the Ni active material contains no noble metal.
- the atomic (ie molar) Al / Ni ratio is preferably greater than 2, particularly preferably greater than 2.7, in particular the molar Al / Ni ratio between 2 and 9 is preferably between 2.3 and 5 ,
- the molar Al / Ni ratio is preferably between 0.1 and 0.9, preferably between 0.3 and 0.7, more preferably the molar Al / Ni ratio is approximately 0, 45th
- the catalysts according to the invention may advantageously have crystallites in the Ni active composition with a diameter of less than 20 nm, preferably less than 10 nm.
- the Ni active material may also be wholly or substantially of crystallites with a Diameter below 20 nm, preferably below 10 nm exist.
- the Ni active material is preferably present in a metallic state.
- the C0 2 uptake capacity of the catalysts at 35 ° C may be greater than 150 pmol / g and is preferably in the range between 150 and 350 pmol / g, more preferably between 180 and 260 pmol / g.
- the BET surface area (SBET) of the catalyst according to the invention may be greater than 100 m 2 / g, preferably greater than 200 m 2 / g, or in the range between 100 and
- the specific metal surface area (Swiet) of the catalyst according to the invention is preferably greater than 10 m 2 / g, preferably greater than 20 m 2 / g and preferably in the range between 20 m 2 / g and 70 m 2 / g.
- the specific metal surface area (Swiet) is preferably in the range between 30 and 70 m 2 / g, more preferably between 40 and 60 m 2 / g.
- the specific metal surface area (Swiet) is in the range between 20 and 80 m 2 / g, preferably between 25 and 70 m 2 / g or between 30 and 60 m 2 / g.
- the catalyst used in the process according to the invention is preferably present in a reactor and forms a catalyst bed therein.
- the reactor is flowed through with the educt gas and thus comes into contact with the catalyst.
- the reactor is heated so that the required reaction temperature of the catalyst is achieved.
- the catalyst acts due to its increased sulfur capacity in addition to its catalytic function at the same time as a sulfur trap ("trap" function).
- the catalyst inlet to the reactor inlet in the catalyst bed will absorb the sulfur and thus protect the subsequent catalyst from sulfur poisoning.
- the sulfur-loaded catalyst at least partially retains its activity in the methanation reaction.
- the catalyst used in the process according to the invention has the advantage of an increased sulfur absorption capacity, so that in addition to the function as methanation catalyst, the function is realized as a sulfur trap. As a result of the improved function as sulfur trap, the function as a methanation catalyst is subsequently increased.
- the sulfur contained in the educt gas completely absorbed in the front region of the catalyst bed, so that in the rear loading area of the catalyst bed, the educt gas contains no more sulfur and accordingly there is no deactivation by sulfur sulfur.
- the catalyst used in the process according to the invention can be prepared by coprecipitation. In the preparation of the catalyst by coprecipitation, at least one solution containing Al, Ni and Mn in dissolved form is added with a precipitating reagent to obtain a precipitate.
- the preparation of the catalysts by coprecipitation comprises, for example, the following steps:
- the solution from step a) is an aqueous solution and Al, Ni and Mn are present dissolved in the aqueous solution as ionic compounds.
- the catalyst according to the invention can also be prepared by impregnation. Then the catalyst according to the invention is e.g. by simultaneous impregnation of nickel and manganese onto a suitable alumina support. The effect of improved sulfur resistance and sulfur capacity is observed for both precipitated (co-precipitated) and impregnated catalysts. Normally, impregnated catalysts can not be produced with as high Ni contents as precipitated catalysts, since nickel uptake during impregnation is limited by the volume of the pores of the aluminum oxide.
- Figure 2 Mass increase by sulfur uptake of the catalysts A to C during the catalytic test reaction, normalized to the weight of catalyst (Test 1).
- Figure 3 Decrease in activity relative to sulfur uptake during the catalytic test reaction (Test 1, assuming nickel sulfide is formed).
- FIG. 4 Decrease in the activity of catalysts A and B during the catalytic test reaction (test 2).
- the determination of the composition of the calcined catalysts was carried out by means of inductively coupled plasma optical emission spectroscopy (ICP-OES). 50 mg of catalyst were dissolved in 50 ml of 1 molar phosphoric acid (VWR, pA) at 60 ° C. To dissolve any brownstone formed, 50 mg Na 2 S0 3 (Sigma Aldrich, pA) was added to the solution. After cooling, the solutions were diluted 1/10, added to the same concentration with Na 2 SO 3 and filtered by means of 0.1 pm filters (Pall). The calibration solutions were measured at 1, 10 and 50 mg l _1 (Merck). Determination of metal concentrations was performed using an Agilent 700 ICP-OES.
- the specific surface area of the catalysts was determined by N 2 -BET analysis on a NOVA 4000e (Quantachrome). For this purpose, 100 mg of catalyst were degassed for 3 hours at 120 ° C and then adsorption and Desorptionsiso- therme in the p / p 0 range of 0.007 to 1 recorded. To determine the BET surface area, the data points in the p / p 0 range of 0.007 to 0.28 were used.
- the pore distribution and the pore volume of the catalyst particles were determined using a mercury porosimeter: Pascal 440 from Thermo Electron Corporation according to DIN 66133. there previously, the sample was evacuated for 30 minutes at room temperature. Samples in the range of 600 to 900 mg were measured and the pressure increased to 2000 bar.
- Chemisorption experiments were performed on an Autosorb 1C (Quantachrome). Before the measurement, 100 mg of catalyst were activated at 500 ° C in 10% H 2 in N 2 for 6 hours. The heating ramp was 2 Kmin -1 .
- the determination of the metal surface was carried out according to DIN 66136-2 (Ver., 2007-01) and was carried out by means of H 2 chemisorption at 35 ° C. For this purpose, 20 adsorption points were recorded equidistant from 40 mmHg to 800 mmHg. The equilibration time for the adsorption was 2 min, the thermal equilibrium 10 min. To determine the metal surface, a metal atom / H stoichiometry of 1 was used. For C0 2 chemisorption measurements, the equilibration time for adsorption was set to 10 min with otherwise unchanged parameters. Before recording the chemisorption data, any kinetic inhibition of C0 2 chemisorption under these conditions was experimentally excluded. Metal surfaces and CO 2 uptake capacities were extrapolated to a pressure of 0 mmHg according to the extrapolation method.
- the catalysts A and B were prepared by coprecipitation at a loading of 50 wt% nickel, which for catalyst A at a molar ratio of aluminum to nickel of 0.75 and for the manganese-containing catalyst B to a molar Al / Ni ratio 0 , 47 leads.
- manganese (II) nitrate was added to the salt solution of nickel and aluminum nitrate during catalyst synthesis.
- the purity of all chemicals used was pa Water was purified by a millipore filter system and the degree of purity verified by conductivity measurements.
- the synthesis was carried out in a double-walled, 3 l stirred tank. The double jacket, which was filled with water, allowed the temperature of the synthesis batch to be adjusted to 30 ° C.
- the precipitation reagent used was a volume-identical mixture of the solutions 0.5M NaOH and 0.5M Na 2 C0 3 , for the metering of which a titrator was used.
- the suspension was aged overnight in the mother liquor, the precipitate was then filtered off and washed with H 2 0 until the filtrate had a neutral pH. After drying at 80 ° C in a drying oven overnight, the dried precipitate (precursor) was heated at a heating rate of 5 K min -1 to 450 ° C and calcined for 6 hours under synthetic air.
- Catalyst C was prepared but triple impregnation each with subsequent calcination.
- 3022.0 grams of Ni (N0 3) 2 were 2 x 4H 2 0 (98.5%) presented x 6H 2 0 (98%), 307.9 g of Mn (N0 3).
- deionized water was made up to a volume of about 2900 ml and stirred by means of propeller stirrer until a clear solution was present. It was then made up to the required total volume of 3441 ml with deionised water.
- Second Impregnation The once impregnated extrudates were placed in a sealable container. 1 147.0 ml of impregnating solution were added slowly and in small amounts, which corresponds to the maximum amount of solution at which no supernatant solution forms. In between, the container was repeatedly closed and shaken / homogenized. When the complete solution was added, shaking was continued for a further two minutes.
- Second Calcination The impregnated extrudates were transferred into porcelain dishes and heated at 2 ° C / min to 120 ° C and dried at this temperature for 6 h in air. Thereafter, the WUR impregnated extrudates were heated at 2 ° C / min to 240 ° C and calcined in air at this temperature for 4 h.
- Third Impregnation The twice impregnated extrudates were placed in a sealable container. Slowly and in small quantities, 944.3 ml of impregnating solution were added, which corresponds to the maximum amount of solution at which it does not yet form a supernatant solution. In between, the container was repeatedly closed and shaken / homogenized. When the complete solution was added, shaking was continued for a further two minutes.
- thermogravimetric analysis was used (TGA).
- TGA thermogravimetric analysis
- the catalytic activity was evaluated by determining the product gas composition.
- a partial stream of the product gas was analyzed with a mass spectrometer. The results are shown under "Catalytic Test Reactions", "Test 1" and "Test 2".
- the experimental conditions were kept constant in order to ensure the comparability of the various catalysts investigated during the test series. Since the catalysts are obtained in an oxidic form from the synthesis, they must first be reduced in the H2 stream before starting the tests in order to produce the catalytically active, metallic phases. The reduction takes place until the weight remains constant.
- the specified weights of the catalysts are based on this weight after the reduction, which is lower than the original weight by the conversion of NiO into Ni or MnO 2 in Mn:
- Test 1 Catalyst A: 1.27 g
- Catalyst B 0.93 g of catalyst C: 0.90 g. Shown is the normalized H 2 conversion (0 corresponds to 0% conversion, 1 corresponds to 100% conversion).
- catalyst A is a comparative sample without manganese
- the catalysts contain 5 B and C manganese.
- the three catalysts have the properties summarized in Table 1 together.
- Table 2 Determination of sulfur uptake on the basis of TGA analysis and the subsequent chemical analysis of the used catalysts after removal from the experimental reactor.
- the different weight of Ka catalyst in test 1 was not considered. In order to correct this, the results were normalized to the initial weight in the results shown in FIG.
- the results shown in FIG. 3 show that catalysts B and C are more suitable for use in sulfur-containing gas streams.
- the x-axis corresponds to the uptake of sulfur with respect to the nickel mass present and the y-axis of the catalytic activity. It was postulated that the absorbed sulfur is bound as NiS, which, however, is not analytically proven, but was only used for clarification.
- the catalyst B according to the invention exhibits a higher activity than the catalyst A for the same sulfur loading, and the catalyst C shows a similar activity.
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