WO2002038267A2 - Fe-doped silica catalyst - Google Patents
Fe-doped silica catalyst Download PDFInfo
- Publication number
- WO2002038267A2 WO2002038267A2 PCT/EP2001/012728 EP0112728W WO0238267A2 WO 2002038267 A2 WO2002038267 A2 WO 2002038267A2 EP 0112728 W EP0112728 W EP 0112728W WO 0238267 A2 WO0238267 A2 WO 0238267A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- weight
- silica carrier
- silica
- content
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 78
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000011068 loading method Methods 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000003345 natural gas Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005372 silanol group Chemical group 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract 6
- 230000008569 process Effects 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910002547 FeII Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 230000000063 preceeding effect Effects 0.000 claims 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 241000894007 species Species 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000875 corresponding effect Effects 0.000 description 11
- 238000004435 EPR spectroscopy Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 230000001737 promoting effect Effects 0.000 description 8
- -1 Fe2+ ions Chemical class 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010943 off-gassing Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates to an Fe-doped silica catalyst which is particularly suitable for the partial oxidation of methane to formaldehyde ( PO) , a process for the preparation of such catalyst and its use in MPO.
- Formaldehyde is currently produced by two commercial processes: a) oxidation-dehydrogenation of CH 3 OH with air on an Ag catalyst and b) oxidation of CH3OH with air on a metal oxide catalyst (Formox process) , about a third of the total demand of methanol being the feedstock for such process.
- the common technology for manufacturing formaldehyde consists of a multi-step process starting from methane via CO/H2 to methanol and formaldehyde. This is a highly costly and energy-intensive sequence process for converting natural gas into a commodity chemical.
- EP 0 492 813 A2 discloses a process for oxidation of alkanes to alcohols wherein a C ⁇ to C4 alkane is contacted with an oxygen containing gas at elevated temperature in the presence of a molybdenum oxide-containing catalyst.
- US Patent No. 4,918,249 discloses and claims silicometallate molecular sieves and their use as catalysts in the oxidation of alkanes.
- the silicometallates claimed contain iron in the structural framework of the crystalline silicometallate.
- British Patent No. 1 398 385 discloses improvements in or relating to the oxidation of gases which consist principally of hydrocarbons, wherein the oxydation catalyst generally comprises molybdenum or tungsten oxide, together with the oxide of a different metal of variable valency, the oxides being present either in combination, or free, or both.
- US Patent No. 4,727,198 describes a method for making formaldehyde from methane and a molecular oxygen containing ga& by using a silica supported catalyst having less than 350 ppm by weight of sodium and having a catalytically effective amount of v 2 o 5 -
- US Patent No. 3,996,294 describes a method for oxidizing methane to formaldehyde using silicon dioxide as catalyst, the silicon dioxide having a large internal surface area. Other metal oxides may be mixed with the silicon dioxide.
- the silica carrier of the present catalyst may be prepared by any convenient method, including precipitation, sol-gel preparation and pyrolysis. These methods are known to the skilled person and need not to be further discussed herein. A comparison of the performance in MPO of several silica samples may be found in A. Parmaliana, V. Sokolovskii, D. Miceli, F. Arena and N. Giordano, J. Catal . 148 (1994) 514. Thus, in previous studies, the activity of silica catalysts was correlated with both the concentration of strain siloxane bridges and densities of surface sites under steady state conditions. In general, the perfomance of the silica carriers in MPO is related to the preparation method resulting in the following reactivity scale: Precipitation > sol-gel > pyrolysis .
- the silica carrier may be prepared by the methods described in R.K. Her “The Chemistry of Silica” (John Wiley, N.Y., 1979) and CN. Satterfield “Heterogeneous Catalysis in Practice” (McGraw Hill, N.Y., 1991) which are explicitly incorporated by reference .
- the silica carrier is amorphous.
- amorphous silica carriers are generally resulting in higher productivity values of the corresponding Fe-loaded catalyst than those with a crystalline silica carrier.
- the silanol group content is between 0.1 to 2/nra 2 of the surface of the silica carrier where a fraction- of such groups gives rise to the formation of strained siloxane bridges under MPO reaction conditions.
- the content of impurities of the silica carrier should be limited and will preferably be 0 to 0,1 weight%, calculated as oxides and based on the total weight of the silica carrier. Also, it is important to limit the alumina impurities to 0 to 1 weight% calculated as I2O 3 and based on the total weight of the silica carrier, as higher levels of impurities will lead to acidic Al-centers which impair the selectivity of the catalyst. Silica carriers fulfilling the above requirements are known to the skilled person.
- the iron loading of the catalyst should correspond to a Fe-content of 0,01 to 5 weight%, calculated as Fe 2 ⁇ 3 and based on the total weight of the catalyst, preferably 0,03 to 1,5 weight . It was unexpectedly found that the highest HCHO productivity values are associated with optimum Fe-loading corresponding to Fe 2 ⁇ 3 -contents of 0,1 to 1,0 weight%.
- the preferred Fe-loading corresponds to 0,01 to 10, preferably 0,02 to 2 Fe-atoms/nm 2 of the surface area of the silica carrier.
- the isolated Fe 2+ / + -ions are capable of transferring one oxygen atom at one time and are therefore particularly suitable for selective (partial) oxidation.
- aggregated Fe 2 ⁇ 3 t ⁇ oieties may transfer more than one oxygen atom at the same time and therefore tend to favour complete oxidation of the hydrocarbons .
- the selectivity and HCHO productivity values of the catalysts are mainly dependent on the presence of isolated Fe 2+ / 3+ -centers on the surface of the Fe/Si ⁇ 2-cata- lyst.
- the' desired isolated Fe 3+ -ions may be present at Fe-loadings of between 0,01 to 5 weight%, in particular between 0,02 to 3 weight%.
- the above Fe-contents of 0,03 to 1,5 weight% are most preferred.
- the specific surface was determined by the BET-method (ASTM D 3663 - 84 ) .
- the pore volume was determined by nitrogen adsorption at -196°C (method ASTM D 4645-88) .
- defined partial CCI 4 steam pressures were adjusted by mixing CCI4 with paraffin.
- EPR Electron paramagnetic resonance
- Signals A and B were normalised with respect to the corresponding maximum value recorded for all the samples.
- values are evaluated from the heights of the signal in the spectra recorded at 77 K; the values for signal B are evaluated by integration of the spectra obtained at room temperature .
- Fe content has been determined by Atomic Adsorption Spectro- scopy (AAS) at A 248,3 n after dissolving the catalyst sample in HF aqueous solution..
- AAS Atomic Adsorption Spectro- scopy
- a method for preparation of a Fe-doped silica (Si0 ) catalyst comprising the steps of:
- the catalyst may be used for the oxidation, in particular, the partial oxidation of hydrocarbons .
- the preferred use is the partial oxidation of methane or natural gas to formaldehyde and/or methanol with oxygen or air in ' the range 550-800°C.
- the catalyst of the present invention may also be used in other reactions such as the oxidative dehydrogenation of alkanes to olefins and/or oxygenated products.
- silica supported iron catalysts (samples Fx-M5) was prepared by the "incipient wetness" method, described in the following.
- An amount of Fe(N0 3 ) 3 corresponding to the desired final loading of Fe, was dissolved in 50 ml of distilled water at pH close to 2.
- a silica supported iron catalyst (sample A) was prepared by the "adsorption-precipitation" method, described in the following.
- the suspension was vigorously stirred and kept under a nitrogen flow to remove any oxygen dissolved in the water and prevent any further air admission.
- a silica supported iron catalyst (sample B) was prepared by the "adsorption-precipitation" method, described in the following.
- Six grams of a powdered "precipitated" silica sample (Si 4-5P grade, Akzo product, S.A- BET ⁇ O 0 tn 2 xg -1 ) was contacted with a 0.3 litres volume of distilled water adjusting the resulting pH to a value of about 2.5.
- the suspension was vigorously stirred and kept under a nitrogen flow to remove any oxygen dissolved in the water and prevent any further air admission.
- a silica supported iron catalysts (sample C) was prepared by the "adsorption-precipitation" method, described in the following. Ten grams of a powdered "precipitated" silica sample (Si 4-5P grade, Akzo Product, S. - BET ⁇ 400 n 2 xg _1 ) was contacted with a 0.3 litres volume of distilled water with a resulting pH of about 4.5. The suspension was vigorously stirred and kept under a nitrogen flow to remove any oxygen dissolved in the water and prevent any further air admission.
- a conventional high vacuum line ( ⁇ 10 "4 torr) was employed for the different treatments. Spectra were recorded after outgassing of the samples at r.t. and 500°C.
- the large anisotropy and width of signal D indicate that the species responsible for the signal are submitted to strong anisotropic fields due to magnetic interactions between the spins forming the corresponding oxidic phases.
- the higher linewidth of signal D with respect to signal B could be due to differences in the type of oxidic .phase, which in the case of signal D might correspond to Fe 3 0 4 , formed by reduction of relatively larger Fe 2 0 3 particles present in the sample F5-SI.
- EPR data show the presence of different, oxidized iron species, whose degree of aggregation grows with iron content.
- Figure 2B presenting the relative intensities of EPR signals A and B for the differently loaded Fx-SI samples, signals that low doped F3-SI sample is characterised by the highest concentration of isolated Fe 3+ species (signal A) , while the highest extent of aggregated species is present on the highly loaded F5-SI sample.
- Isolated Fe 3+ species small clusters of Fe 2 0 3 and large Fe 2 0 3 particles are present on the surface of Fe/Si0 2 catalysts ; such species are characterised by different coordination, reducibility and catalytic functionality.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01990385A EP1337328A2 (en) | 2000-11-03 | 2001-11-02 | Fe-doped silica catalyst |
AU2002229530A AU2002229530A1 (en) | 2000-11-03 | 2001-11-02 | Fe-doped silica catalyst |
US10/415,795 US20040038811A1 (en) | 2000-11-03 | 2001-11-02 | Fe-doped silica catalyst |
NO20031992A NO20031992L (en) | 2000-11-03 | 2003-05-02 | Fe-doped silica catalyst |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10054457A DE10054457A1 (en) | 2000-11-03 | 2000-11-03 | Catalyst for oxidation of methane to formaldehyde and methanol comprises a silica support having a specified iron content |
DE10054457.6 | 2000-11-03 |
Publications (2)
Publication Number | Publication Date |
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WO2002038267A2 true WO2002038267A2 (en) | 2002-05-16 |
WO2002038267A3 WO2002038267A3 (en) | 2002-08-01 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2001/012728 WO2002038267A2 (en) | 2000-11-03 | 2001-11-02 | Fe-doped silica catalyst |
Country Status (6)
Country | Link |
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US (1) | US20040038811A1 (en) |
EP (1) | EP1337328A2 (en) |
AU (1) | AU2002229530A1 (en) |
DE (1) | DE10054457A1 (en) |
NO (1) | NO20031992L (en) |
WO (1) | WO2002038267A2 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1447124A1 (en) * | 2003-02-04 | 2004-08-18 | Gastec N.V. | Supported catalyst system for removing sulfur compounds from gases |
DE102004051008A1 (en) * | 2004-10-20 | 2006-04-27 | Universität Karlsruhe (Th) | Process for the oxidation of methane to formaldehyde |
US7705059B2 (en) * | 2005-04-15 | 2010-04-27 | University Of Southern California | Selective oxidative conversion of methane to methanol, dimethyl ether and derived products |
DE102006058813A1 (en) * | 2006-12-13 | 2008-06-19 | Wacker Chemie Ag | Process for the preparation of stable, highly pure moldings from fumed metal oxides without the addition of binders |
CN101961650B (en) * | 2010-09-10 | 2012-08-29 | 常州大学 | Zirconium base catalyst, preparation method and application in preparation of anhydrous formaldehyde |
US20130085295A1 (en) * | 2011-10-03 | 2013-04-04 | Celanese International Corporation | Processes for producing acrylic acids and acrylates |
CN103464195B (en) * | 2013-09-26 | 2015-08-19 | 中国海洋石油总公司 | A kind of expanding agent introduces the methane oxidation methanol oxidation agent method of active component |
CN112705188B (en) * | 2019-10-24 | 2022-07-08 | 中国石油化工股份有限公司 | Method for synthesizing methyl acrylate |
US11780786B2 (en) | 2020-09-14 | 2023-10-10 | Chevron Phillips Chemical Company Lp | Transition metal-catalyzed production of alcohol and carbonyl compounds from hydrocarbons |
CN115722230B (en) * | 2021-08-26 | 2024-09-20 | 广东工业大学 | Embedded water-heating-resistant NiSn-CS nano catalyst and preparation method and application thereof |
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US3491020A (en) * | 1967-02-14 | 1970-01-20 | Gulf Research Development Co | Sweetening process utilizing a catalyst composite with available lattice oxygen |
US4427578A (en) * | 1981-08-18 | 1984-01-24 | Coal Industry (Patents) Limited | Amorphous silica-based catalyst and process for its production |
US4918249A (en) * | 1989-04-17 | 1990-04-17 | Sun Refining And Marketing Company | Silicometallate molecular sieves and their use as catalysts in oxidation of alkanes |
EP0492697A1 (en) * | 1990-12-21 | 1992-07-01 | ENIRICERCHE S.p.A. | Catalytically active gel and a process for its preparation |
Family Cites Families (9)
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NL143139B (en) * | 1967-04-14 | 1974-09-16 | Stamicarbon | PROCESS FOR PREPARING A CARRIER CATALYST BY TREATING A CARRIER WITH A SOLUTION OF A SALT OF A CATALYTIC ACTIVE ELEMENT. |
DE2404737A1 (en) * | 1974-02-01 | 1975-08-21 | Bayer Ag | PROCESS FOR PRODUCING FORMALDEHYDE |
US4040982A (en) * | 1976-01-12 | 1977-08-09 | Nalco Chemical Company | Ozonization catalyst |
FR2481254A1 (en) * | 1980-04-23 | 1981-10-30 | Elf Aquitaine | PROCESS FOR THE CATALYTIC INCINERATION OF WASTE GASES CONTAINING LOW CONCENTRATION AT LEAST ONE COMPOUND OF SULFUR SELECTED AMONG COS, CS2, AND MERCAPTANS AND POSSIBLY AT LEAST ONE MEMBER OF THE GROUP FORMED BY H2S, SO2, SULFUR AND / OR VESICULAR SULFUR |
DE3131255C2 (en) * | 1981-08-07 | 1986-02-13 | VEG-Gasinstituut N.V., Apeldoorn | Process for the preparation of a ferric oxide catalyst or absorbent |
US4705771A (en) * | 1985-04-16 | 1987-11-10 | W. R. Grace & Co. | Process and catalyst for the production of formaldehyde from methane |
US4727198A (en) * | 1987-03-12 | 1988-02-23 | W. R. Grace & Co. | Process for the production of formaldehyde from methane |
DE3938056C2 (en) * | 1988-11-18 | 1994-11-10 | Mitsubishi Motors Corp | Oxygen sensor |
US6037295A (en) * | 1998-03-25 | 2000-03-14 | Council Of Scientific & Industrial Research | Process for the preparation of a new catalyst useful for producing alkylated aromatic amines |
-
2000
- 2000-11-03 DE DE10054457A patent/DE10054457A1/en not_active Withdrawn
-
2001
- 2001-11-02 EP EP01990385A patent/EP1337328A2/en not_active Withdrawn
- 2001-11-02 WO PCT/EP2001/012728 patent/WO2002038267A2/en not_active Application Discontinuation
- 2001-11-02 AU AU2002229530A patent/AU2002229530A1/en not_active Abandoned
- 2001-11-02 US US10/415,795 patent/US20040038811A1/en not_active Abandoned
-
2003
- 2003-05-02 NO NO20031992A patent/NO20031992L/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US3491020A (en) * | 1967-02-14 | 1970-01-20 | Gulf Research Development Co | Sweetening process utilizing a catalyst composite with available lattice oxygen |
US4427578A (en) * | 1981-08-18 | 1984-01-24 | Coal Industry (Patents) Limited | Amorphous silica-based catalyst and process for its production |
US4918249A (en) * | 1989-04-17 | 1990-04-17 | Sun Refining And Marketing Company | Silicometallate molecular sieves and their use as catalysts in oxidation of alkanes |
EP0492697A1 (en) * | 1990-12-21 | 1992-07-01 | ENIRICERCHE S.p.A. | Catalytically active gel and a process for its preparation |
Also Published As
Publication number | Publication date |
---|---|
AU2002229530A1 (en) | 2002-05-21 |
NO20031992L (en) | 2003-06-02 |
US20040038811A1 (en) | 2004-02-26 |
EP1337328A2 (en) | 2003-08-27 |
NO20031992D0 (en) | 2003-05-02 |
DE10054457A1 (en) | 2002-05-08 |
WO2002038267A3 (en) | 2002-08-01 |
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