CN110234431A - 具有增大的比表面积以及更高的将乙烷氧化脱氢为乙烯的活性的MoVNbTe催化剂的合成 - Google Patents
具有增大的比表面积以及更高的将乙烷氧化脱氢为乙烯的活性的MoVNbTe催化剂的合成 Download PDFInfo
- Publication number
- CN110234431A CN110234431A CN201880009414.7A CN201880009414A CN110234431A CN 110234431 A CN110234431 A CN 110234431A CN 201880009414 A CN201880009414 A CN 201880009414A CN 110234431 A CN110234431 A CN 110234431A
- Authority
- CN
- China
- Prior art keywords
- mixed oxide
- precursor compound
- oxide material
- mixture
- tellurium
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims description 66
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 10
- 239000005977 Ethylene Substances 0.000 title claims description 10
- 230000015572 biosynthetic process Effects 0.000 title description 19
- 238000003786 synthesis reaction Methods 0.000 title description 18
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 32
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010955 niobium Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011733 molybdenum Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 229910017488 Cu K Inorganic materials 0.000 claims abstract description 7
- 229910017541 Cu-K Inorganic materials 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 230000003647 oxidation Effects 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 229910004273 TeO3 Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 21
- 235000006408 oxalic acid Nutrition 0.000 abstract description 7
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 13
- 238000009826 distribution Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- 229910003069 TeO2 Inorganic materials 0.000 description 3
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012154 double-distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052715 tantalum 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
- 101100493713 Caenorhabditis elegans bath-45 gene Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 propane ammonia oxygen Chemical compound 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 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
- B01J35/635—0.5-1.0 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
-
- 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
-
- 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
- B01J37/033—Using Hydrolysis
-
- 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
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
- B01J2523/55—Vanadium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
- B01J2523/56—Niobium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
- B01J2523/64—Tellurium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
- B01J2523/68—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- 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
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
-
- 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
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/20—Vanadium, niobium or tantalum
- C07C2523/22—Vanadium
-
- 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
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/057—Selenium or tellurium; Compounds thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种混合氧化物材料,包括元素钼、钒、铌和碲,所述混合氧化物材料在使用Cu‑Kα辐射时在XRD中具有如下的衍射反射h、i、k和l,其顶点位于衍射角度(2θ)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l),其特征在于,所述混合氧化物材料具有>0.1cm3/g的孔体积。本发明的混合氧化物材料通过包括以下步骤的方法来制备:a)制备初始化合物的混合物,所述混合物包含钼、钒、铌和二氧化碲作为包含碲的初始化合物以及草酸和至少一种另外的含氧配体,所述含氧配体选自二羧酸和二醇的组,b)在100℃至300℃的温度下以水热法处理所述初始化合物的混合物,c)将包含在从步骤b)产生的悬浮液中的混合氧化物材料分离出来并干燥。
Description
本发明涉及一种包含钼、钒、碲和铌的新型混合氧化物材料,以及所述混合氧化物材料作为用于将乙烷氧化脱氢为乙烯或将丙烷氧化为丙烯酸的催化剂的用途,并且涉及一种用于制备所述混合氧化物材料的方法。
用于将丙烷氧化为丙烯酸或用于将乙烷氧化脱氢为乙烯的MoVNbTe混合氧化物是现有技术。超过200项专利和大量的科技公开物涉及基于MoVNbTe混合氧化物的催化剂。用周期表的其他金属来增强这种混合氧化物是已知的。在此,最高的前述的丙烯酸产率为60%而乙烯产率为约80%。
基于四种元素的用于催化剂的MoVNbTe基体系首先由三菱提出,用于将丙烷氨氧化成丙烯腈(1989年,EP 318295 A1)以及氧化成丙烯酸(1994年,EP 608838 A2)。在JPH07-053414(三菱)中公开了一种催化方法,用于在低温下通过氧化氢化乙烷而制备乙烯,该方法具有高产率和高选择性。这种用于通过在提高的温度下在催化剂组合物存在下将乙烷与包含氧分子的气体进行接触以制备乙烯的方法包括:使该催化剂组合物包含混合金属氧化物,所述混合金属氧化物具有钼、钒、碲和氧作为主要成分并且显示出基本上具有以下相对峰强度的粉末X射线衍射谱:2θ(+-0.4°),相对强度:22.1°(100),28,2°(400-3),36,2°(80-3),45.1°(40-3),50°(50-3)。
MoVNbTe催化剂主要由两种斜方晶系的相组成,被称为“M1”和“M2”(T.Ushikubo,K.Oshima,A.Kayou,M.Hatano,Studies in Surface Science and Catalysis 112,(1997),473)。M1相在选择性氧化反应中展现出重要作用。
根据P.De Santo等人,Z.Kristallogr.219(2004)152,用于选择性氧化的MoVNbTe混合氧化物中的主要相M1和M2例如能够用以下结构式描述:
M1:Mo1V0.15Te0.12Nb0.128O3.7或Mo7.8V1.2Te0.937Nb1O28.9
M2:*Mo1V0.32Te0.42Nb0.08O4.6或Mo4.31V1.36Te1.81Nb0.33O19.81
这两种主要相还能以略微不同的化学计量比存在。钒以及钼都在由氧原子形成的八面体的中心并且因此在所述结构中是部分可交换的,使得相同的结构(例如M1相)也可以具有更高的钒含量。在此方面的详细研究可以在P.Botella等人,Solid State Science 7(2005)507-519中找到。特别地,M2相对于乙烷的氧化脱氢是无活性的(见J.S.Valente等人,ACS Catal.4(2014),1292-1301特别是第1293页)。因此,对于乙烷的氧化脱氢而言所希望的是由尽可能纯的M1相组成的催化剂。因此尝试还以干净且分离的方式制备这些晶相。
EP 529853 A2公开了一种适合用于从烷烃制备腈的催化剂,其中所述催化剂具有经验式MoVbTecXxOn,其中X为Nb、Ta、W、Ti、Al、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ni、Pd、Pt、Sb、Bi、B和Ce中的至少一种,b为0.01至1.0,c为0.01至1.0;x为0.01至1.0,且n为如下的数:根据这个数,金属元素的总价数得以满足并且所述催化剂在其X射线衍射图案中在以下的2θ角度下具有X射线衍射峰:衍射角为2θ(22.1°+/-0.3°,28.2°+/-0.3°,36.2°+/-0.3°,45.2°+/-0.3°,50.0°+/-0.3°)。
JP H07-232071公开了在使用烷烃作为原材料以及某种催化剂的情况下在相对较低的温度下且以高产率制备腈的方法。所述催化剂的主要组分是由钼、钒、碲、氧和X(X选自铌、钽等的组中的一种或多种元素)形成的混合金属氧化物,其中主要组分(即除了氧以外)的比率通过式I至IV表达:I)0.25<rMo<0.98,II)0.003<rV<0.50,III)0.003<rTe<0.50,IV)0≤rX<0.5,(rMo、rV、rTe和rX分别为钼、钒、碲和X的摩尔比例)并且在XRD中,这种混合氧化物的XRD带显示在不同的2θ角度9.0°±0.3°,22.1°±0.3°,27.3°±0.3°,29.2°±0.3°和35.4°±0.3°。据此可以如下地制备腈:在不存在卤化物质的情况在低温下以高产率将烷烃例如与水等在反应体系中进行转化。
用于制备纯M1相的其他卓有成效的实验是基于将M2相从相混合物中溶出。这种实验例如记载在EP 1301457 A2、EP 1558569 A1或WO 2009106474 A2中。
A.C.Sanfiz等人,Top.Catal.50(2008)19-32描述了水热法合成MoVNbTe氧化物。在这种合成中,仅仅从可溶性化合物出发。通常使用碲酸Te(OH)6作为碲的可溶性化合物。在最常见的氧化物型碲化合物TeO2中,碲具有+4氧化态。然而二氧化碲(TeO2)难溶于水。但在碲酸中,碲具有+6氧化态。即在制备碲酸时,碲必须被氧化成高价。常见的合成通过用过氧化氢氧化氧化碲来进行,这在大规模下带来了安全性问题,因为过氧化氢在自身分解时歧化为水和氧气。因此很难大量制备碲酸。
在MoVNbTe混合氧化物的合成中使用的Nb成分一般是草酸铌铵。相反,氧化铌是难溶的并且因此仅有条件地适合用作初始化合物。
Watanabe(Applied Catal.A General,194-195(2000)479-485)尤其说明了从低溶解度的前体MoO3、V2O5和TeO2进行水热法合成。水热法合成产生了用于氨氧化催化剂的前体,在煅烧之后所述催化剂与通过已知的干式方法制备的催化剂相比具有两倍高的活性。通过固体反应制备的混合氧化物显示出了更低的活性。所建议的是,通过水热法制备的催化剂的较高活性主要与较大的表面积有关。
即,在不使用碲酸的情况下,MoVNbTe混合氧化物的合成具有明显成本更低廉的潜力。
WO 2005120702 A1记载了一种用于水热法制备由Mo和V组成的多金属物质的方法,所述方法基本上仅使用来自氧化物型多金属物质的元素成分的氧化物、水合氧化物、含氧酸和氢氧化物的组的初始物质,其中包含在初始物质中的元素成分的一部分具有低于最高氧化数的氧化数。
WO 2013021034 A1涉及一种用于使烃类氧化和/或氧化脱氢的催化剂材料,尤其用于将丙烷选择性氧化成丙烯酸,所述催化剂包括a)钼(Mo),b)钒(V),c)铌(Nb),d)碲(Te),e)锰(Mn)和钴,其中选自锰和钴中的至少一种元素与钼的摩尔比在0.01至0.2、优选0.02至0.15且特别优选0.03:1至0.1:1的范围内。此外,给出了一种用于使烃类氧化和/或氧化脱氢的催化剂,所述催化剂材料或催化剂的用途,一种用于制备使烃类氧化和/或氧化脱氢的催化剂材料的方法,以及一种用于将丙烷选择性氧化为丙烯酸的方法。
WO 2008068332 A1涉及新型的中孔混合金属氧化物催化剂以及一种用于其制备的方法以及其作为用于氧化烃类或氧化已部分氧化的烃类的用途。此公开文献尤其涉及包含至少两种、优选至少三种不同金属种类的混合氧化物催化剂,其中至少一种金属种类属于过渡金属组;涉及一种用于制备此类催化剂的方法,所述方法包括经由“中性模板”途径的制备步骤和在基本上纯氧气气氛中在介于300至700℃之间的温度下的煅烧步骤;并且涉及此类催化剂作为氧化催化剂的用途,用于制备氧化的烃类且尤其用于将丙烷选择性氧化或氨氧化成丙烯酸和丙烯腈。优选的催化剂包括元素Mo、V、Te和Nb。
在现有技术中描述的M1相的合成是指,在初始材料转化之后,首先在高温处理的范围内(典型地高于500℃)在惰性气体下形成M1相(“活化”)。在本发明的范围内,已经发现了一种用于形成高纯度M1相的合成方法,所述合成方法省去了最终的高温处理。
因此本发明的目的是找到一种包含钼、钒、碲和铌的混合氧化物材料(“MoVTeNb混合氧化物”),所述材料具有M1相和尽可能大的比表面积。本发明的目的还在于找到一种MoVTeNb混合氧化物,所述混合氧化物作为用于氧化烷烃的催化剂材料具有尽可能高的活性。
本发明的目的通过一种混合氧化物材料实现,所述混合氧化物材料包括元素钼、钒、铌和碲,所述混合氧化物材料在使用Cu-Kα辐射时在XRD中具有如下的衍射反射h、i、k和l,其顶点位于衍射角度(2θ)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l),其特征在于,所述混合氧化物材料具有>0.1cm3/g的孔体积。
本发明的MoVTeNb混合氧化物通过一种用于制备混合氧化物材料的方法制备,所述方法包括以下步骤:
a)制备初始化合物的混合物,所述混合物包含含钼、钒、铌和碲的初始化合物以及草酸和至少一种另外的含氧配体,在所述包含碲的初始化合物中碲以+4的氧化态存在,
b)在100至300℃的温度下以水热法处理所述初始化合物的混合物,以获得产物悬浮液,
c)将包含在从步骤b)产生的产物悬浮液中的所述混合氧化物材料分离出来并干燥。
所述初始化合物为含有钼、钒、碲和铌的水热合成反应物(前体化合物)。这些反应物分别包含元素钼、钒、碲或铌中的一种或多种。
包含钼的初始化合物可以例如为七钼酸铵或三氧化钼,包含钒的初始化合物可以例如为偏钒酸铵、硫酸氧钒或五氧化二钒,包含铌的初始化合物可以例如为草酸铌铵或草酸铌或氧化铌。根据本发明的包含碲的初始化合物为其中碲以+4氧化态(即作为碲(IV)阳离子)存在的初始化合物,如在二氧化碲中或者式Mx n+TeO3的化合物(其中n=1或2,并且x=2/n),其中M为碱金属或碱土金属,例如Na2TeO3。特别优选地,所述包含碲的初始化合物为二氧化碲,它可以任意的水合度存在。
本发明的制备方法的优点在于,成功地从不溶且价格低廉的氧化物,例如MoO3、V2O5、Nb2O5和TeO2以及草酸与至少一种另外的含氧配体的组合合成M1相。已经证明二羧酸和二醇以及具有两个相邻的分别具有羟基的碳原子的有机化合物特别适合作为另外的含氧配体(也就是说,除了草酸之外)。特别优选作为另外的含氧配体的是使用柠檬酸和二醇的混合物。
草酸优选应在初始化合物的混合物中以1:0.01至1:1、优选1:0.08至1:0.4、更优选1:0.15至1:0.25的Mo/草酸比存在。
所述至少一种另外的含氧配体或者所有其他的含氧配体总共应在初始化合物的混合物中以1:0.01至1:1、优选1:0.025至1:0.2、更优选1:0.05至1:0.1的Mo/含氧配体之比存在。
此外,出人意料地,本发明的合成在水热法合成和干燥之后已经提供了M1相,而不需要在高于400℃的温度下的能量密集的高温处理。在本发明的合成中重要的是,与文献中相反,在所述方法中在水热法合成之后不需要在氮气下煅烧。
本发明的M1相合成的另一个优点是通过水热法合成造成的初始物质的高转化效率。倘若反应物的化学计量比在Mo/V/Nb/Te=1:0.22:0.1:0.1至1:0.3:0.17:0.17的范围内变动,则Mo、V、Nb和Te就几乎完全转化为M1相,使得所有金属的小于100ppm保留在母液中。
M1相的可能的化学计量比是由文献中充分已知的并且能够通过式Mo1VaNbbTecOx来表示,其中a=0.2至0.3,b=0.1至0.2,c=0.1至0.25且x为取决于金属(Mo、V、Nb和Te)的氧化态而造成电荷平衡的数值。
优选地,在合成期间不存在铵离子。本发明的制备方法允许合成具有M1相的MoVNbTe混合氧化物。在此,在干燥之后形成具有大于0.1cm3/g的孔体积和大于20m2/g且特别优选大于30m2/g的高比表面积的MoVNbTe混合氧化物。本发明的MoVNbTe混合氧化物因此特别适合作为催化剂材料,因为对于催化应用通常期望大的孔体积和大的比表面积。
初始化合物的混合物优选作为水性悬浮液存在并且随后被水热处理。术语“水热法”主要涉及用于在水存在下且在提高的温度和/或提高的压力下(例如在高压釜中)制备催化剂材料的反应条件。在此,压力可以在5至30bar、优选10至27bar的范围内。示例性的压力范围为11至20bar。
通过水热处理(步骤b))获得了包含MoVNbTe混合氧化物作为固体的产物悬浮液。在本发明的方法中,可以在步骤c)中分离出悬浮液的形成本发明MoVNbTe混合氧化物的固体,在一个或多个步骤中进行过滤(例如通过过滤掉母液)。干燥可以在一个步骤中进行或在两个步骤中在流动或静止空气中进行。在此,第一干燥步骤优选在60至150℃(特别优选在80至120℃)下进行,第二干燥步骤可以在200至400℃下进行。另外,本发明方法的步骤c)可以包含一个或多个清洗、煅烧(热处理)和/或研磨的步骤。煅烧可以在200至500℃下、优选250℃至350℃下在空气中进行。
本发明的MoVNbTe混合氧化物可以用作用于将烃类氧化和/或氧化脱氢(“ODH”)的催化剂材料,尤其用于将乙烷氧化脱氢为乙烯。
所述催化剂或催化剂材料为根据本发明方法制备的且能以不同方式用于商业催化剂中的MoVNbTe混合氧化物。例如其可以通过制片而被加工成催化剂片料,然后可以将其填入反应器中。
优选地使用通过本发明方法获得的、没有进一步煅烧的(即在干燥之后直接使用)MoVNbTe混合氧化物作为催化剂材料。
所述催化剂材料还可以与适合的粘结剂一起被加工成挤出物(片料、成型体、蜂窝体等)。可以使用本领域技术人员熟悉的且表现为适合的粘结剂作为粘结剂。优选的粘结剂尤其为伪勃姆石以及硅酸盐类粘结剂,如胶体氧化硅或氧化硅溶胶。
所述催化剂材料另外可以与其他成分一起、优选与粘结剂、特别优选与有机粘结剂(例如有机粘合剂、聚合物、树脂或蜡)一起被加工成载体涂层(Washcoat),所述载体涂层可以施加到金属或陶瓷载体上。在某些情况下可以进行额外的浸渍步骤或煅烧步骤。
本发明的MoVNbTe混合氧化物在实施例中作为催化剂材料使用并且因此在实验说明中有时被称为催化剂。
图1:来自实施例1的本发明催化剂的X射线衍射图。
图2:来自对比实施例1的对比催化剂的X射线衍射图。
图3:活化之后的来自对比实施例2的对比催化剂的X射线衍射图。
图4:活化之前的来自对比实施例2的对比催化剂的X射线衍射图。
图5:根据实施例1的催化剂的孔分布。
图6:根据对比实施例1的催化剂的孔分布。
图7:根据对比实施例2的这些催化剂的孔分布。
图8:在乙烷的ODH反应中催化剂的活性。
图9:根据实施例2的催化剂的孔分布。
图10:在ODH反应中来自实施例2的催化剂的活性。
可以看到,图1中本发明催化剂的X射线衍射图(XRD)在(2θ=)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l)处具有M1相的典型反射(在使用Cu-Kα辐射时)。它们比通过活化处理的对比实施例(图2和3)中的更宽。更大的宽度通过更小的晶粒尺寸而得以解释,这伴随着更大的比表面积。在图4中可以看到,在没有活化的情况下,仅能清晰辨别在22.5°处的表示层间距的反射。只有在活化之后(图3),该催化剂才同样显示出M1相的典型反射。
表征方法:
为了测定本发明催化剂的参数,使用了以下方法:
1.BET表面积:
测定根据DIN 66131按照BET方法进行;BET方法的公开内容也可以在J.Am.Chem.Soc.60.309(1938)中找到。测量在Sorptomatic 1990设备上在77K进行。在测量之前将样品在523K抽真空2小时。根据BET方法的等温线的线性回归在p/p0=0.01-0.3(p0=730Torr)的压力范围内进行。
2.N2孔分布
在Sorptomatic仪器或TriStar 3000仪器上在77K下借助于氮气吸附测量来进行孔径分布测量。在测量之前将样品在523K下抽真空2小时。测定了吸附和脱附等温线并且将其用于根据Barrett-Joyner-Halenda方法(BJH)进行分析。
3.粉末X射线衍射测量法(XRD)
通过粉末X射线衍射测量法(XRD)来确定X射线衍射图并且根据Scherrer公式来进行评价。
在配备有Medipix PIXcel 3D检测器的PANalytical Empyrean上,在Θ-Θ几何形状中在2Θ=5-70°的角度范围内记录衍射图。X射线管产生Cu-K辐射。通过在入射X射束的辐照路径中使用Ni过滤器来抑制Cu-Kβ辐射,使得在样品处仅具有15.4nm波长(E=8.04778keV)的Cu-Kα辐射被衍射。源侧的辐照路径的高度通过自动的发散狭缝(可编程发散狭缝-PDS)进行适配,使得样品在长度为12mm的整个角度区域上都被辐照。检测器侧的X射束的宽度通过固定的挡板限制在10mm。水平方向的发散通过使用0.4rad的Soller狭缝来最小化。
类似于源侧的辐照路径,检测器侧的辐照路径的高度借助于自动的抗折射狭缝(可编程抗散射狭缝-PASS)进行适配,使得在长度为12mm的整个角度区域上在样品上都检测到反射的X射线。
依据存在的量不同,样品在无定形的硅样品盘上制备或作为平板样品以制片的方式制备。
实施例:
实施例1:
在100mL的PTFE烧杯中放入75mL的双蒸馏水,滴加177.8mg的单乙二醇并且随后使5397.9mg的MoO3、1023.9mg的V2O5、599.1mg的TeO2、549.5mg的Nb205·xH2O(Nb=63.45重量%)、540.9mg的柠檬酸和338.3mg的草酸形成悬浮液。将特氟龙烧杯封闭并转移到不锈钢高压釜罩壳中。将其压力密封地封闭并且在预热到190℃的烘箱中夹持在水平旋转的轴上。在48小时之后将高压釜壳从烘箱中取出并且立即在流动水中淬火并且随后在冰浴中冷却45分钟。
所产生的产物悬浮液通过滤纸(孔宽3μm)过滤并且固体用200mL双蒸馏水清洗。
将如此获得的产物在干燥箱中在80℃下干燥16小时并且之后在手动研钵中磨碎。
实现了6.2g的固体产量。产物的BET表面积为83.3m2/g,产物具有0.2cm3/g的孔体积以及在图5中所示的孔分布。
实施例2:
合成如在实施例1下描述地来进行,除了在80℃下干燥16小时之后在400℃下进行另一个干燥步骤3小时。产物的BET表面积为59.0m2/g,产物具有0.176cm3/g的孔体积以及在图9中所示的孔分布。
从图10中可以看到,在420℃下催化剂具有9xl0-6mol g-1 催化剂s-1的乙烯形成速率,拥有与来自实施例1的仅在80℃下干燥的催化剂(图8)大致相同的活性。即,活性损失只有在高于400℃的温度范围内才出现。
对比实施例1:
使在实施例1中描述的催化剂在管式炉中经受热处理(活化)。为此将1g经干燥的固体转移到陶瓷舟中,使得其底部约2mm高被粉末覆盖。
活化在600℃下进行2小时(加热速率10℃/分钟,N2:100mL/分钟)。此处理之后,BET表面积为7.3m2/g,产物具有0.013cm3/g的孔体积以及在图6中所示的孔分布。
对比实施例2:
在高压釜(40L)中预先放入3.3L蒸馏水并且在搅拌下加热到80℃。在此期间添加725.58g的四水合七钼酸铵(来自HC Starck)并且将其溶解(AHM溶液)。在三个5L玻璃烧杯中分别将1.65L蒸馏水在磁力搅拌器的搅拌下通过控温同样加热到80℃。然后在这些玻璃烧杯中分别加入405.10g的水合硫酸氧钒(来自GfE,V含量:21.2%)、185.59g草酸铌铵(HCStarck,Nb含量:20.6%)以及94.14g碲酸(V溶液、Te溶液和Nb溶液)并且将它们溶解。
随后借助于软管泵将V溶液、然后Te溶液且最后Nb溶液泵送到AHM溶液中(泵送时间:V溶液:4.5分钟,190rpm,软管直径8x5mm,Nb溶液:6分钟,130rpm,软管直径:8x5mm)。
所产生的悬浮液在80℃下继续搅拌10分钟。在沉淀时搅拌器的速度为90rpm。
随后用氮气覆盖,其方式为,在高压釜中用氮气升高压力直至约6bar并且将泄放阀打开,直至在N2压力下流过高压釜(5分钟)。在结束时通过排气阀将压力再次泄放到直至1bar的残余压力。
在40L高压釜中在175℃下通过锚式搅拌器在90rpm的搅拌速度下进行水热法合成20小时(加热时间:3小时)。
在合成之后借助于真空泵通过蓝带滤纸过滤并且将滤饼用5L蒸馏水清洗。
在80℃下在干燥箱中干燥3天并且随后在冲击磨机中磨碎,其中获得了0.8kg的固体产量。
在280℃下煅烧4小时(加热速率5℃/分钟,空气:1L/分钟)。
在蒸馏器中在600℃下在N2通流中活化2小时(加热速率5℃/分钟,N2:0.5L/分钟)。
产品具有13m2/g的BET表面积和0.055cm3/g的孔体积以及在图7中所示的孔分布。
对比实施例3:
将来自对比实施例2的催化剂在280℃煅烧4小时之后直接使用。没有在600℃下在氮气中活化2小时。
实施例3:
在管式反应器中在大气压力下在330至420℃的温度范围内对来自实施例1和对比实施例1和2的催化剂在乙烷的氧化脱氢过程(“ODH”)中的催化活性进行研究。为此将各25mg(实施例1和对比实施例1)或200mg(对比实施例2)的催化剂(粒径150-212μm)用碳化硅(粒径150-212μm)以1:5的质量比稀释。在催化剂床的上方和下方填入分别由250mg的相同粒径碳化硅形成的层并且通过石英棉塞将管式反应器的末端封闭。
在实验开始之前用惰性气体冲刷反应器并且随后在50sccm的氦气流下加热到330℃。在达到所希望的温度并且稳定一小时之后,切换到反应混合物。
进入气体组成为在50sccm的总体积流量下C2H6/O2/He=9.1/9.1/81.8(v/v)。
对产物气流的分析在配备有Haysep N柱和Haysep Q柱、分子筛柱5A和热导率检测器的气相色谱中进行。
在图8中展示了在上述条件下的乙烯形成速率。
按照催化剂质量标准化催化剂活性,根据现有技术来自可溶前体化合物(对比实施例2)的催化剂显示出了最低的活性。对比实施例1根据本专利的新方法制备,但是仍然在600℃下煅烧。本发明的催化剂在没有最终的高温处理的情况下展现出最高的催化活性。
表1:
BET[m<sup>2</sup>/g] | 孔体积[cm<sup>3</sup>/g] | |
实施例1 | 83.3 | 0.2 |
实施例2 | 59.0 | 0.176 |
对比实施例1 | 7.3 | 0.013 |
对比实施例2 | 13 | 0.055 |
对比实施例3 | (69)(几乎无定形) |
表1比较了本发明催化剂与对比实施例的BET表面积和孔体积。
Claims (14)
1.混合氧化物材料,包括元素钼、钒、铌和碲,所述混合氧化物材料在使用Cu-Kα辐射时在XRD中具有如下的衍射反射h、i、k和l,其顶点位于衍射角度(2·)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l),其特征在于,所述混合氧化物材料具有大于0.1cm3/g的孔体积。
2.根据权利要求1所述的混合氧化物材料,其特征在于,所述混合氧化物材料具有大于30m2/g的BET表面积。
3.根据以上权利要求之一所述的混合氧化物材料,其特征在于,所述混合氧化物材料具有的小于10nm的孔的体积大于0.2cm3/g。
4.根据以上权利要求之一所述的混合氧化物材料,其特征在于,摩尔比Mo:Te≤11,并且摩尔比Mo:Nb≤11。
5.用于制备根据以上权利要求之一所述的混合氧化物材料的方法,包括以下步骤:
a)制备初始化合物的混合物,所述混合物包含含有钼、钒、铌和碲的初始化合物以及草酸和至少一种另外的含氧配体,在含碲的初始化合物中碲以+4的氧化态存在,
b)在100℃至300℃的温度下以水热法处理所述初始化合物的混合物,以获得产物悬浮液,
c)将包含在从步骤b)产生的产物悬浮液中的混合氧化物材料分离出来并干燥。
6.根据权利要求5所述的方法,其特征在于,所述包含碲的初始化合物为氧化碲或者式Mx n+TeO3的化合物,其中n=1或2并且x=2/n,其中M为碱金属或碱土金属。
7.根据权利要求5或6所述的方法,其特征在于,所述初始化合物的混合物作为水性悬浮液存在。
8.根据权利要求5至7之一所述的方法,其特征在于,所述初始化合物的混合物包含二羧酸、二醇、或其他的在相邻位置中具有两个羟基的化合物作为另外的含氧配体。
9.根据权利要求5至8之一所述的方法,其特征在于,所述初始化合物的混合物包含三氧化钼。
10.根据权利要求5至9之一所述的方法,其特征在于,所述初始化合物的混合物包含五氧化二钒。
11.根据权利要求5至10之一所述的方法,其特征在于,所述初始化合物的混合物包含柠檬酸作为另外的含氧配体。
12.根据权利要求5至11之一所述的方法,其特征在于,所述初始化合物的混合物包含柠檬酸和二醇作为另外的含氧配体。
13.根据权利要求1至4所述的混合氧化物材料作为用于将乙烷氧化脱氢为乙烯的催化剂材料的用途。
14.根据权利要求1至4所述的混合氧化物材料作为用于将丙烷氧化为丙烯酸的催化剂材料的用途。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102017000865.5 | 2017-01-31 | ||
DE102017000865.5A DE102017000865A1 (de) | 2017-01-31 | 2017-01-31 | Synthese eines MoVNbTe-Katalysators mit erhöhter spezifischer Oberfläche und höherer Aktivität für die oxidative Dehyxdrierung von Ethan zu Ethylen |
PCT/EP2018/052012 WO2018141653A1 (de) | 2017-01-31 | 2018-01-26 | Synthese eines movnbte-katalysators mit erhöhter spezifischer oberfläche und höherer aktivität für die oxidative dehydrierung von ethan zu ethylen |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110234431A true CN110234431A (zh) | 2019-09-13 |
CN110234431B CN110234431B (zh) | 2023-03-24 |
Family
ID=62200392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201880009414.7A Active CN110234431B (zh) | 2017-01-31 | 2018-01-26 | 具有增大的比表面积以及更高的将乙烷氧化脱氢为乙烯的活性的MoVNbTe催化剂的合成 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11161096B2 (zh) |
EP (1) | EP3576874A1 (zh) |
JP (1) | JP6917463B2 (zh) |
KR (1) | KR102316669B1 (zh) |
CN (1) | CN110234431B (zh) |
DE (1) | DE102017000865A1 (zh) |
WO (1) | WO2018141653A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114787110A (zh) * | 2019-12-20 | 2022-07-22 | 诺瓦化学品(国际)股份有限公司 | 从氧化脱氢过程中去除一氧化碳、氧气和乙炔 |
CN114950475A (zh) * | 2022-06-06 | 2022-08-30 | 河北大学 | 一种高熵二维催化剂的低温制备方法和应用 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102017000848A1 (de) * | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur Herstellung molybdänhaltiger Mischoxidmaterialien |
DE102017000861A1 (de) * | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Synthese eines MoVTeNb-Katalysators aus preisgünstigen Metalloxiden |
DE102017000862A1 (de) * | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Synthese eines MoVNbTe-Katalysators mit reduziertem Gehalt an Niob und Tellur und höherer Aktivität für die oxidative Dehydrierung von Ethan |
EP3897975A1 (en) | 2018-12-19 | 2021-10-27 | Shell Internationale Research Maatschappij B.V. | Catalyst for alkane oxidative dehydrogenation and/or alkene oxidation |
DE102021202505A1 (de) | 2021-03-15 | 2022-09-15 | Clariant International Ltd. | Verfahren und Anlage zur Herstellung einer Zielverbindung |
DE102021005596A1 (de) | 2021-11-11 | 2023-05-11 | Alexander Damps | Verfahren zur oxidativen Aromatisierung von kurzkettigen Alkanen |
US11890594B2 (en) | 2021-12-30 | 2024-02-06 | Uop Llc | Chemical homogeneity and catalytic performance of mixed-metal oxide catalysts |
CN115676782A (zh) * | 2022-12-06 | 2023-02-03 | 武汉船用电力推进装置研究所(中国船舶重工集团公司第七一二研究所) | 一种碲粉为原料制备超细二氧化碲的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1705638A (zh) * | 2002-10-17 | 2005-12-07 | 巴斯福股份公司 | 多金属氧化物材料 |
US20120016171A1 (en) * | 2009-02-26 | 2012-01-19 | Nova Chemicals (International) S.A. | Supported oxidative dehydrogenation catalyst |
DE102011109774A1 (de) * | 2011-08-09 | 2013-02-14 | Süd-Chemie AG | Katalysatormaterial für die Oxidation von Kohlenwasserstoffen |
DE102011109816A1 (de) * | 2011-08-09 | 2013-02-14 | Süd-Chemie AG | Katalysatormaterial für die Oxidation von Kohlenwasserstoffen |
CN103285888A (zh) * | 2013-04-18 | 2013-09-11 | 沈阳化工大学 | 一种用于丙烯一步氧化制备丙烯酸反应的催化剂及其制备方法 |
CN104549373A (zh) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | 低碳烷烃氨氧化催化剂 |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2608768B2 (ja) | 1987-11-25 | 1997-05-14 | 三菱化学株式会社 | ニトリルの製造法 |
DE69208565T2 (de) | 1991-08-08 | 1996-09-26 | Mitsubishi Chem Corp | Katalysator und Verfahren zur Herstellung von Nitrilen |
DE69402567T2 (de) | 1993-01-28 | 1997-11-27 | Mitsubishi Chem Corp | Methode zur Herstellung einer ungesättigten Carbonsäure |
JP3484729B2 (ja) | 1993-06-11 | 2004-01-06 | 三菱化学株式会社 | エチレンの製造方法 |
JP3500682B2 (ja) | 1994-02-23 | 2004-02-23 | 三菱化学株式会社 | アルカンよりニトリルを製造するための触媒 |
JP3576251B2 (ja) | 1995-02-17 | 2004-10-13 | 井上玩具煙火株式会社 | 噴き出し花火 |
US5945368A (en) | 1995-10-02 | 1999-08-31 | Huntsman Petrochemical Corporation | Molybdenum-modified vanadium-phosphorus oxide catalysts for the production of maleic anhydride |
JP2000143244A (ja) | 1998-07-24 | 2000-05-23 | Mitsubishi Chemicals Corp | 複合金属酸化物の製造方法 |
CN1232504C (zh) | 1999-10-18 | 2005-12-21 | 三菱丽阳株式会社 | 生产丙烯腈的方法、其中所用的催化剂及其制备方法 |
DE10119933A1 (de) | 2001-04-23 | 2002-10-24 | Basf Ag | Verfahren zur Herstellung von Acrylsäure durch heterogen katalysierte Gasphasenoxidation von Propan |
CN1323998C (zh) | 2000-07-18 | 2007-07-04 | 巴斯福股份公司 | 通过丙烷的非均相催化的气相氧化制备丙烯酸的方法 |
TW574071B (en) | 2001-06-14 | 2004-02-01 | Rohm & Haas | Mixed metal oxide catalyst |
EP1598112A3 (en) | 2001-06-14 | 2005-11-30 | Rohm and Haas Company | Process for preparing a mixed metal oxide catalyst by vapor deposition |
US7038082B2 (en) | 2002-10-17 | 2006-05-02 | Basf Aktiengesellschaft | Preparation of a multimetal oxide material |
US20050027295A1 (en) | 2003-08-01 | 2005-02-03 | Yang Lin Min | Interlocking nail |
BRPI0509988A (pt) * | 2004-04-30 | 2007-10-16 | Basf Ag | processo para preparar ácido acrìlico por oxidação parcial heterogeneamente catalisada de pelo menos um composto precursor de hidrocarboneto c3 |
JP5517407B2 (ja) | 2004-06-09 | 2014-06-11 | ビーエーエスエフ ソシエタス・ヨーロピア | 多金属酸化物材料の製造方法 |
DE102004027999A1 (de) | 2004-06-09 | 2005-01-27 | Basf Ag | Verfahren zur Herstellung einer Multimetalloxidmasse |
US7009075B2 (en) | 2004-06-30 | 2006-03-07 | Saudi Basic Industries Corporation | Process for the selective conversion of alkanes to unsaturated carboxylic acids |
EP1930074A1 (en) | 2006-12-08 | 2008-06-11 | Robert Prof. Dr. Schlögl | Novel mesoporous mixed metal oxide catalyst and method for the preparation thereof |
WO2009106474A2 (en) | 2008-02-25 | 2009-09-03 | Olaf Timpe | Phase-enriched movtenb mixed oxide catalyst and methods for the preparation thereof |
EP2781262B1 (en) | 2013-03-22 | 2020-05-27 | Clariant International Ltd | Removable protective coating for the receipt of a dust free catalyst |
JP6498749B2 (ja) | 2015-03-26 | 2019-04-10 | 旭化成株式会社 | 触媒の製造方法、及び不飽和ニトリルの製造方法 |
JP6777848B2 (ja) | 2016-07-08 | 2020-10-28 | 富士通株式会社 | 制御装置、及びストレージ装置 |
-
2017
- 2017-01-31 DE DE102017000865.5A patent/DE102017000865A1/de active Pending
-
2018
- 2018-01-26 US US16/480,736 patent/US11161096B2/en active Active
- 2018-01-26 CN CN201880009414.7A patent/CN110234431B/zh active Active
- 2018-01-26 WO PCT/EP2018/052012 patent/WO2018141653A1/de unknown
- 2018-01-26 KR KR1020197025651A patent/KR102316669B1/ko active IP Right Grant
- 2018-01-26 EP EP18725740.7A patent/EP3576874A1/de active Pending
- 2018-01-26 JP JP2019540555A patent/JP6917463B2/ja active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1705638A (zh) * | 2002-10-17 | 2005-12-07 | 巴斯福股份公司 | 多金属氧化物材料 |
US20120016171A1 (en) * | 2009-02-26 | 2012-01-19 | Nova Chemicals (International) S.A. | Supported oxidative dehydrogenation catalyst |
DE102011109774A1 (de) * | 2011-08-09 | 2013-02-14 | Süd-Chemie AG | Katalysatormaterial für die Oxidation von Kohlenwasserstoffen |
DE102011109816A1 (de) * | 2011-08-09 | 2013-02-14 | Süd-Chemie AG | Katalysatormaterial für die Oxidation von Kohlenwasserstoffen |
US20140336411A1 (en) * | 2011-08-09 | 2014-11-13 | Clariant Produkte (Deutschland) Gmbh | Catalyst for the oxidation of hydrocarbons consisting of molybdenum, vanadium, niobium, tellurium, manganese and cobalt |
US20150148563A1 (en) * | 2011-08-09 | 2015-05-28 | Clariant Produkte (Deutschland) Gmbh | Catalyst Material for the Oxidation of Hydrocarbons |
CN103285888A (zh) * | 2013-04-18 | 2013-09-11 | 沈阳化工大学 | 一种用于丙烯一步氧化制备丙烯酸反应的催化剂及其制备方法 |
CN104549373A (zh) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | 低碳烷烃氨氧化催化剂 |
Non-Patent Citations (1)
Title |
---|
T.T.NGUYEN AT AL.: "Optimizing the efficiency of MoVTeNbO catalysts for ethane oxidative dehydrogenation to ethylene", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114787110A (zh) * | 2019-12-20 | 2022-07-22 | 诺瓦化学品(国际)股份有限公司 | 从氧化脱氢过程中去除一氧化碳、氧气和乙炔 |
CN114950475A (zh) * | 2022-06-06 | 2022-08-30 | 河北大学 | 一种高熵二维催化剂的低温制备方法和应用 |
CN114950475B (zh) * | 2022-06-06 | 2023-12-19 | 河北大学 | 一种高熵二维催化剂的低温制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
WO2018141653A1 (de) | 2018-08-09 |
KR20190112793A (ko) | 2019-10-07 |
JP2020506862A (ja) | 2020-03-05 |
EP3576874A1 (de) | 2019-12-11 |
DE102017000865A1 (de) | 2018-08-02 |
JP6917463B2 (ja) | 2021-08-11 |
KR102316669B1 (ko) | 2021-10-27 |
CN110234431B (zh) | 2023-03-24 |
US20200139349A1 (en) | 2020-05-07 |
US11161096B2 (en) | 2021-11-02 |
WO2018141653A8 (de) | 2019-02-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110234431A (zh) | 具有增大的比表面积以及更高的将乙烷氧化脱氢为乙烯的活性的MoVNbTe催化剂的合成 | |
CN110461472A (zh) | 由廉价金属氧化物合成MoVTeNb催化剂 | |
JP6876813B2 (ja) | ニオブおよびテルルの低下した含有量ならびにエタンの酸化的脱水素化に対するより高い活性を有するMoVNbTe触媒の合成 | |
US11007509B2 (en) | Method for producing mixed oxide materials containing molybdenum | |
CA2655841C (en) | Supported oxidative dehydrogenation catalyst | |
EP1871522B8 (en) | Process for preparing improved catalysts for selective oxidation of propane into acrylic acid | |
JP4197254B2 (ja) | プロパンの不均一系触媒部分酸化によるアクリル酸の製法 | |
JP7108620B2 (ja) | プロピレンアンモ酸化触媒の製造のための新規合成方法 | |
JP7089531B2 (ja) | プロピレンアンモ酸化触媒を調製するための方法 | |
JP7314122B2 (ja) | エタンのエチレンへの酸化的脱水素のためのMoVNbTeシェル触媒の合成 | |
WO2018127767A1 (en) | Double peroxide treatment of oxidative dehydrogenation catalyst | |
CN112469803B (zh) | 氧化脱氢催化剂组合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |