EP3532433A1 - Saures zirkoniumhydroxid - Google Patents
Saures zirkoniumhydroxidInfo
- Publication number
- EP3532433A1 EP3532433A1 EP17703790.0A EP17703790A EP3532433A1 EP 3532433 A1 EP3532433 A1 EP 3532433A1 EP 17703790 A EP17703790 A EP 17703790A EP 3532433 A1 EP3532433 A1 EP 3532433A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zirconium
- oxide
- hydroxide
- acid
- sulphate
- 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
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 230000002378 acidificating effect Effects 0.000 title description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 54
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 50
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 47
- 239000002019 doping agent Substances 0.000 claims abstract description 36
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 35
- 239000010937 tungsten Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000010452 phosphate Substances 0.000 claims abstract description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004411 aluminium Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 239000010955 niobium Substances 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011135 tin Substances 0.000 claims abstract description 16
- 229910052718 tin Inorganic materials 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002841 Lewis acid Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 8
- 239000011260 aqueous acid Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 150000003754 zirconium Chemical class 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 239000002594 sorbent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract 2
- 239000011148 porous material Substances 0.000 claims description 60
- 238000001354 calcination Methods 0.000 claims description 47
- 239000012298 atmosphere Substances 0.000 claims description 40
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 15
- -1 rare earth hydroxide Chemical class 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000001117 sulphuric acid Substances 0.000 claims description 14
- 235000011149 sulphuric acid Nutrition 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 238000004375 physisorption Methods 0.000 claims description 10
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 229960002510 mandelic acid Drugs 0.000 claims description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical class O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 6
- BDPNSNXYBGIFIE-UHFFFAOYSA-J tungsten;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[W] BDPNSNXYBGIFIE-UHFFFAOYSA-J 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical class O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 41
- HAIMOVORXAUUQK-UHFFFAOYSA-J zirconium(iv) hydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[Zr+4] HAIMOVORXAUUQK-UHFFFAOYSA-J 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000523 sample Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- 239000002002 slurry Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 238000010335 hydrothermal treatment Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical class S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- WZHCOOQXZCIUNC-UHFFFAOYSA-N cyclandelate Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C(O)C1=CC=CC=C1 WZHCOOQXZCIUNC-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000011157 data evaluation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
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- 239000012925 reference material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- 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
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/30—Tungsten
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- 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
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/06—Sulfates
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- C01G33/00—Compounds of niobium
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/50—Solid solutions
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- C01P2002/52—Solid solutions containing elements as dopants
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- 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
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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Definitions
- This invention relates to processes for preparing acidic zirconium hydroxides and oxides, compositions comprising acidic zirconium hydroxides and oxides, as well as the use of these hydroxides and oxides in catalysis and sorption applications.
- zirconium hydroxide Due to its well-known amphoteric properties, zirconium hydroxide has a strong ability for selective adsorption of wide range of different toxic anions, such as phosphates and arsenates.
- Zirconium oxides both with and without stabilisers, find applications in many different types of catalysis, including environmental, automotive and chemical catalysis applications.
- the catalytic activity of Zr0 2 in important reactions such as methanol and hydrocarbon synthesis from CO and H 2 , C0 2 and H 2 , or alcohol dehydration, has also been studied.
- Zirconium hydroxide has also been extensively used as a support for metals. It has also been incorporated in supports in order to stabilize the metal or make the metal more resistant to sintering. Stabilised zirconium hydroxide, containing sulfate or tungstate ions, has been found to exhibit a superacidic behaviour leading to a high activity for isomerization of hydrocarbons or for conversion of methanol into hydrocarbons. Silicon substitution into zirconium hydroxide has been found to enhance the acidity of the mixed oxide produced from the hydroxide. The resulting materials possess good catalytic activity at high temperatures and are currently being tested as promising methane oxidation catalysts for liquefied natural gas (LNG) fuelled engines. In relation to this area of technology, references to the elemental forms of the various dopants are generally interpreted to include their corresponding oxides. Thus, for example, silicon includes silicate and colloidal silica, tungsten includes tungstate etc.
- zirconium hydroxide materials in catalysis is mainly due to the ability to modify their physical and chemical properties by subtle processing methods and incorporation of other stabilisers. This allows fine-tuning the critical parameters of a catalyst support. Different combinations of properties are required for different applications, but having high, thermally stable, surface areas and porosities are pre-requisites for most catalyst applications. Through modification of the manufacturing process to improve the morphology of the product, changes in the balance of acid-base properties will also be observed. These properties can also be significantly impacted by inclusion of dopants such as silica, aluminium, sulphate, phosphate, molybdenum, tin, tungsten, niobium and titanium.
- dopants such as silica, aluminium, sulphate, phosphate, molybdenum, tin, tungsten, niobium and titanium.
- porosity is an important, but not critical, criterion for effective catalyst behaviour.
- An equally prominent role in final catalytic performance is played by surface acidity, which in zirconium hydroxide for example is impacted by the amount and ratio of terminal and bridging OH groups. This means that determination of the strength of acid sites, as well as their concentration and type (Bronsted/Lewis), is important in assessing the suitability of a catalyst for a particular application.
- Many different techniques are used for characterising solid surface acid properties, including visual colour changes; spectrophotometry; and amines titration etc.
- TPD Temperature- Prog rammed Desorption
- WO2004/096713 describes a method for the production of zirconium oxides and zirconium-based mixed oxides. The process involves the precipitation of zirconium hydroxide from an aqueous solution of zirconium salt by reaction with an alkali in the presence of a controlled amount of sulphate anions at a temperature of not greater than 50°C. The hydroxide is then calcined to form an essentially sulphate-free zirconium oxide.
- H1 1-292538 and 2000-247641 describe the manufacture of zirconium hydroxide from a zirconium basic sulphate by the addition of base to a slurry of the sulphate.
- the processes set out in these documents do not result in zirconium hydroxide having the improved pore volume, pore size and surface area properties of the present invention.
- the hydroxide has a surface area of at least 300m 2 /g, a total pore volume of at least 0.70cm 3 /g and an average pore size 5nm-15nm.
- It is prepared by a process which comprises the steps of: a) preparing an aqueous solution comprising sulphate anions and a zirconium salt at a specific ratio, (b) chilling the solution to below 25°C, (c) adding an alkali in order to precipitate the amorphous zirconium hydroxide, (d) filtering and washing the precipitated zirconium hydroxide with water or an alkali to remove residual sulphate and chloride, (e) hydrothermally treating the zirconium hydroxide at a pressure of less than 3 barg, and (f) drying the zirconium hydroxide.
- zirconium hydroxides or zirconium oxides as defined in the aspects of the invention set out below.
- the zirconium hydroxides or zirconium oxides may be defined as acidic.
- the majority of the acid sites of the zirconium hydroxides and zirconium oxides may also be Lewis acid sites. This may be shown by the highest intensity peaks in the DRIFT spectra of the zirconium hydroxides in the range 1700-1400cm "1 being at around 1600-1620cnT 1 and around 1440- 1450cm "1 .
- the zirconium hydroxides and zirconium oxides may have more Lewis acid sites than Br0nsted acid sites.
- the term "acid sites” is used to refer to acid species that are available for reaction. They can include Br0nsted acid sites i.e. proton donors (eg the proton on terminal surface OH groups, S0 3 H groups or other surface groups) and Lewis acid sites i.e electron acceptors (eg Zr atoms).
- the zirconium oxide or zirconium hydroxide may comprise, on an oxide basis, up to 30wt%, more particularly up to 16wt%, of a dopant comprising one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium or tin. It is noted that all zirconium oxides and zirconium oxides comprise, on an oxide basis, around 1.5-2wt% hafnium oxide or hydroxide as an impurity. This is not included in the amounts of "incidental impurities" referred to below.
- a zirconium hydroxide comprising, on an oxide basis, less than 0.1 wt% of a dopant comprising one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium or tin, wherein the zirconium hydroxide is porous and, in relation to the pores having a pore diameter of up to 155nm, at least 70% of its pore volume provided by pores having a pore diameter of 3.5-155nm as measured using the BJH method.
- the zirconium hydroxide may comprise, on an oxide basis, less than 0.1 wt% of a dopant comprising one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium, tin, a rare earth metal, or yttrium. More particularly, in relation to the pores having a pore diameter of up to 155nm, at least 75% of its pore volume may be provided by pores having a pore diameter of 3.5-155nm as measured using the BJH method.
- the zirconium hydroxide may have a total pore volume as measured by N 2 physisorption of at least 0.75cm 3 /g, more particularly at least 0.80 cm 3 /g.
- the zirconium hydroxide may have a mean pore diameter of at least 6.0nm, more particularly at least 6.5nm.
- the zirconium oxide may comprise at least 80wt% of the monoclinic phase as measured by XRD (X-Ray Diffraction) after calcination at 450°C in an air atmosphere for 2 hours, more particularly at least 82wt%.
- the zirconium hydroxide may have an acid loading of at least 1300 ⁇ 3 as measured by propylamine TPD. More particularly, the zirconium hydroxide may have T max of less than 365°C, even more particularly less than 360°C, as measured by propylamine TPD.
- This aspect of the invention also relates to zirconium oxides which are obtained or obtainable from the zirconium hydroxides defined above, generally by calcination (for example, at a temperature of 450°C or higher). More particularly, there is provided a zirconium oxide comprising, on an oxide basis, less than 0.1wt% of a dopant comprising one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium or tin, having a surface area of at least 50m 2 /g after calcination at 600°C in an air atmosphere for 2 hours, even more particularly at least 52m 2 /g.
- a dopant comprising one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium or tin
- the zirconium oxide may comprise, on an oxide basis, less than 0.1 wt% of a dopant comprising one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium, tin, a rare earth metal, or yttrium.
- the zirconium oxide may have an acid loading of at least ⁇ /g as measured by propylamine TPD after calcination at 600°C in an air atmosphere for 2 hours. More particularly, the zirconium oxide may have a total pore volume as measured by N 2 physisorption of at least 0.35cm 3 /g after calcination at 600°C in an air atmosphere for 2 hours.
- the zirconium oxide may have a mean pore diameter of at least 25.0nm after calcination at 600°C in an air atmosphere for 2 hours. More particularly, the zirconium oxide may show basicity, characterised by a C0 2 uptake of at least ⁇ at 400-600°C as measured by TPD (Temperature Programmed Desorption), even more particularly at least 16 ⁇ 3, after calcination at 600°C in an air atmosphere for 2 hours.
- TPD Tempoture Programmed Desorption
- this aspect of the invention also relates to a zirconium oxide comprising, on an oxide basis, less than 0.1 wt% of a dopant comprising one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium or tin, having a surface area of at least 15m 2 /g after calcination at 900°C in an air atmosphere for 2 hours, even more particularly at least 16m 2 /g.
- the zirconium oxide may have a total pore volume as measured by N 2 physisorption of at least 0.10cm 3 /g after calcination at 900°C in an air atmosphere for 2 hours. More particularly, the zirconium oxide may have a mean pore diameter of at least 26.0nm after calcination at 900°C in an air atmosphere for 2 hours
- the zirconium hydroxide or zirconium oxide may be, on an oxide basis, at least 98wt% pure, even more particularly at least 99wt% pure (excluding the hafnium oxide or hydroxide impurity mentioned above).
- the zirconium hydroxides, or corresponding calcined oxides also exhibit useful physical characteristics such as high pore volumes, particular relating to pore size in the range 3.5-50nm. In addition, they may show a nitrogen isotherm of type IV hysteresis loop of H3 with mesoporosity at P/P0>0.6.
- a doped zirconium oxide comprising, on an oxide basis, 0.1-30wt% of a silicon hydroxide or oxide, wherein the zirconium oxide has an NH 3 uptake of at least 3.5 ⁇ as measured by TPD, after calcination at 850°C for 2 hours. More particularly, the silicon doped zirconium oxide may have an NH 3 uptake of at least 4.0 ⁇ as measured by TPD, even more particularly at least 4.25 ⁇ after calcination at 850°C in an air atmosphere for 2 hours.
- the silicon doped zirconium oxide may have an NH 3 uptake of at least 330 ⁇ 3 as measured by TPD, more particularly at least 360 ⁇ 3, after calcination at 850°C in an air atmosphere for 2 hours.
- the silicon doped zirconium oxide may have T max of at least 280°C as measured by NH 3 TPD, more particularly at least 285°C, after calcination at 850°C in an air atmosphere for 2 hours.
- this oxide may be obtained or obtainable from the corresponding zirconium hydroxide, generally by calcination (for example, at a temperature of 450°C or higher).
- the silicon doped zirconium oxide may have an acid loading of at least 170 ⁇ 3 as measured by propylamine TPD after calcination at 850°C in an air atmosphere for 2 hours.
- this aspect of the invention also relates to a silicon doped zirconium hydroxide having a surface area of at least 540m 2 /g, a total pore volume as measured by N 2 physisorption of at least 0.90cm 3 /g, and when calcined at 850°C in an air atmosphere for 2 hours an NH 3 uptake of at least 3.5 ⁇ as measured by TPD.
- the silicon doped zirconium hydroxide or silicon doped zirconium oxide may comprise, on an oxide basis, 1-10wt% of a silicon hydroxide or oxide, even more particularly 1-5wt%, more particularly 2.5-4.5wt%.
- the remainder of the silicon doped zirconium oxide may comprise, on an oxide basis, zirconium oxide and incidental impurities up to 0.3wt%
- a doped zirconium hydroxide comprising, on an oxide basis, 0.1-30wt% of a tungsten hydroxide or oxide having a surface area of at least 400m 2 /g. More particularly, the tungsten doped zirconium hydroxide may have a surface area of at least 450m 2 /g, even more particularly at least 500m 2 /g.
- the tungsten doped zirconium hydroxide may have a total pore volume as measured by N 2 physisorption of at least 0.7cm 3 /g, more particularly at least 0.8cm 3 /g.
- this aspect of the invention also relates to tungsten doped zirconium oxides which are obtained or obtainable from the tungsten doped zirconium hydroxides defined above, generally by calcination (for example, at a temperature of 450°C or higher). More particularly, there is provided a tungsten doped zirconium oxide comprising, on an oxide basis, 0.1-30wt% of a tungsten hydroxide or oxide having an NH 3 uptake of at least 4.30 ⁇ as measured by TPD after calcination at 700°C in an air atmosphere for 2 hours.
- the tungsten doped zirconium oxide may have an NH 3 uptake of at least 420 ⁇ 3 as measured by TPD, even more particularly at least 46C ⁇ mol/g, after calcination at 700°C in an air atmosphere for 2 hours.
- the tungsten doped zirconium oxide may have an acid loading of at least 260 ⁇ , more particularly at least 280 ⁇ 3, as measured by propylamine TPD after calcination at 700°C in an air atmosphere for 2 hours.
- the tungsten doped zirconium hydroxide or tungsten doped zirconium oxide may comprise, on an oxide basis, 12-20wt% of a tungsten hydroxide or oxide, even more particularly 14-18wt%.
- the remainder of the tungsten doped zirconium oxide may comprise, on an oxide basis, zirconium oxide and incidental impurities up to 0.3wt%.
- a doped zirconium hydroxide comprising, on an oxide basis, 0.1-30wt% of a sulphate, more particularly 1-12wt%, even more particularly 1-10wt%, having a surface area of at least 375m 2 /g. More particularly, the sulphate doped zirconium hydroxide may have a surface area of at least 400m 2 /g. [0033] In particular, the sulphate doped zirconium hydroxide may have a total pore volume as measured by N 2 physisorption of at least 0.50cm 3 /g, more particularly at least 0.60cm 3 /g.
- sulphate doped the zirconium hydroxide may have a mean pore diameter of at least 5.5nm, more particularly at least 6.0nm.
- this aspect of the invention also relates to sulphate doped zirconium oxides which are obtained or obtainable from the sulphate doped zirconium hydroxides defined above, generally by calcination (for example, at a temperature of 450°C or higher).
- a sulphate doped zirconium oxide comprising, on an oxide basis, 0.1-30wt% of a sulphate having an NH 3 uptake of at least ⁇ as measured by TPD, more particularly at least ⁇ , even more particularly at least ⁇ , after calcination at 600°C in an air atmosphere for 2 hours.
- the sulphate doped zirconium oxide may comprise, on an oxide basis, 1-12wt% of a sulphate, more particularly 1- [0035]
- the sulphate doped zirconium oxide may have an acid loading of at least ⁇ , more particularly at least ⁇ , as measured by propylamine TPD after calcination at 600°C in an air atmosphere for 2 hours.
- the sulphate doped zirconium oxide may have a surface area of at least 140m 2 /g after calcination at 600°C in an air atmosphere for 2 hours, even more particularly at least 150m 2 /g.
- the zirconium oxide may have a total pore volume as measured by N 2 physisorption of at least 0.30cm 3 /g after calcination at 600°C in an air atmosphere for 2 hours, more particularly at least 0.32cm 3 /g.
- the zirconium oxide may have a mean pore diameter of at least 8.5nm, even more particularly at least 9.0nm, after calcination at 600°C in an air atmosphere for 2 hours.
- This invention relates to acidic zirconium hydroxides and acidic zirconium oxides with controlled acidic and basic properties, both in the bulk and on the surface.
- the silicon, tungsten, sulphate, phosphate, niobium, aluminium, molybdenum, titanium or tin doped zirconium hydroxide or oxide may comprise an additional dopant, specifically to help stabilise the bulk form.
- the additional dopant may comprise a rare earth hydroxide or oxide, or yttrium hydroxide or oxide, or any other transition metal hydroxide or oxide not already mentioned.
- This further dopant may be present in a concentration, on an oxide basis, of less than 25wt%, more particularly 0.1-25wt%.
- the total zirconium content of the zirconium hydroxide or zirconium oxide will not be less than 50wt % on an oxide basis.
- the zirconium hydroxides of the invention comprise less than 5% by weight cerium hydroxide, more particularly less than 2% by weight cerium hydroxide, even more particularly less than 1 % by weight cerium hydroxide. In some embodiments, the zirconium hydroxides are substantially free of cerium.
- the zirconium hydroxide, or further stabilised or doped zirconium hydroxides can be calcined to their corresponding oxides. These oxides also exhibit acidic characteristics, but some may also show strong basicity.
- the temperature at which this calcination is carried out depends on the dopant which has been added to the composition. For some dopants, too high a temperature will result in loss of that dopant from the composition.
- the calcination temperature should be less than 650°C, more particularly 400-650°C.
- the calcination temperature should be less than 850°C, more particularly 400-800°C.
- the calcination temperature may be 400-1000°C, more particularly 450-800°C.
- the zirconium hydroxides may be substantially amorphous as measured by XRD. More particularly, the zirconium hydroxides may have a d 50 particle size as measured by laser light scattering of less than 100 ⁇ , more particularly 10-50 ⁇ .
- compositions defined herein may comprise less than 250ppm of Na and/or less than 250ppm of K, more particularly less than 200ppm, even more particularly less than 125ppm.
- content of Na and/or K may be less than 50ppm.
- a catalyst, catalyst support or sorbent comprising any one of the zirconium hydroxides and/or zirconium oxides described above.
- the one or more complexing agents being an organic compound comprising at least one of the following functional groups: an amine, an organosulphate, a sulphonate, a hydroxyl, an ether or a carboxylic acid group,
- zirconium hydroxides optionally including a dopant
- the resulting materials having a higher percentage of mesopores than has previously been achieved.
- improved thermostability can be achieved, particularly for undoped zirconium hydroxides calcined at 900°C.
- the undoped zirconium hydroxides can also exhibit a higher percentage of the monoclinic phase.
- the zirconium salt may be zirconium basic carbonate or zirconium hydroxide.
- zirconium basic carbonate ZBC
- ZBC zirconium basic carbonate
- the aqueous acid may be hydrochloric acid, sulphuric acid, nitric acid or acetic acid, in particular the aqueous acid is nitric acid.
- the molar ratio of zirconium ions to nitrate ions in the solution or sol may be 1 :0.8 to 1 :2, more particularly 1 :0.8 to 1 : 1.5.
- the term complexing agent is used to mean a ligand that bonds to zirconium.
- the complexing agent may be a carboxylic acid, a dicarboxylic acid, an alpha hydroxycarboxylic acid, an amino acid, an organosulphate or a polyol.
- the complexing agent may be a multidentate, more particularly a bidentate, ligand.
- the polyol may be a polysaccharide, for example starch.
- the complexing agent may be an alpha hydroxycarboxylic acid.
- the complexing agent generally has a polar group (ie an amine, an organosulphate, a sulphonate, a hydroxyl, an ether or a carboxylic acid group) which coordinates to zirconium, and one or more hydrocarbon groups.
- the one or more hydrocarbon groups may comprise one or more aromatic substituents, more particularly one or more phenyl substituents.
- multidentate ligands coordinate effectively to metal ions.
- the combination of different functional groups within the same molecule may be advantageous to interact with different coordination environments on the metal ion; providing both steric and electronic effects.
- complexing agents with different hydrocarbon groups may be used.
- the alpha hydroxy carboxylic acid may be an aromatic (for example, phenyl) or non-aromatic alpha hydroxycarboxylic acid, more particularly mandelic or benzillic or lactic acid even more particularly mandelic acid.
- the solution formed may be heated.
- the solution may be heated to a temperature above 25°C, more particularly to at least 40°C, even more particularly at least 50°C, more particularly to a temperature in the range 50-70°C. More particularly, the solution may be heated to around 60°C.
- the pH of the solution may be increased (i.e., partially neutralised) by adding a base.
- a base may be sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, potassium hydroxide, potassium carbonate, and/or potassium hydrogen carbonate.
- step (b) may additionally comprise adding water, normally deionised water, to the heated solution. More particularly, in step (b), after the addition of the complexing agent, the solution has an equivalent zirconium content of 5-25% by weight expressed as Zr0 2 , more particularly 10-20% by weight, even more particularly 12-16% by weight, expressed as Zr0 2 .
- the equivalent zirconium content expressed as Zr0 2 means that, for example, 100g of a 15% by weight solution would have the same zirconium content as 15g of Zr0 2 .
- the heating may comprise heating the solution or sol to a temperature of 60-100°C, more particularly 80-100°C, for 1-15 hours. In particular, the heating may be carried out for 1-5 hours. More particularly, in step (c) the temperature of the solution or sol may be increased at a rate of 0.1-1.5°C/min.
- references to a heating rate including both linear (ie constant) heating rates, as well as non-liner heating rates (eg a fast initial heating rate, followed by a slower heating rate). This heating step is normally carried out in order to assist in providing optimum polymer/oligomer size for mesoporous powder preparation.
- the solution or sol may be allowed to cool, or cooled, before adding the sulphating agent. More particularly, the solution or sol may be allowed to cool, or cooled, to a temperature less than 40°C, even more particularly less than 30°C.
- Possible sulphating agents are water soluble salts of sulphate, bisulphate, sulphite, bisulphite. In particular, the sulphating agent may be sulphuric acid.
- the sulphating agent may be added such that the molar ratio of zirconium ions to sulphate ions is from 1 :0.05 to 1 :1
- the process may comprise the step of isolating the solid from the solution or sol, for example by filtering.
- the pH of the solution or sol may be increased to pH >8 by adding the base.
- the base may be sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, potassium hydroxide, potassium carbonate and/or potassium hydrogen carbonate. More particularly, in step (e) the addition of the base is to form a zirconium hydroxide precipitate.
- the pH that the solution or sol can be adjusted to depends on the base used.
- the base may be either ammonium hydroxide or an alkali metal hydroxide, more particularly sodium hydroxide.
- the maximum pH that can be achieved is normally about pH 10.5-11.
- Step (e) may be carried out at any temperature at which the solution or sol is not frozen, ie from -5°C to 95°C, more particularly, 10°C to 80°C.
- the process may comprise after step (e) the step of (f) adding a dopant.
- a dopant may be any material which stabilises the tetragonal phase of zirconia, for example as a surface stabiliser or bulk stabiliser. This phase of zirconia can provide improved catalytic performance.
- the dopant can also be used to increase the acidity of the material.
- the dopant may comprise one or more of silicon, sulphate, phosphate, tungsten, niobium, aluminium, molybdenum, titanium or tin. Even more particularly, the dopant may comprise one or more of sulphate, silicon or tungsten. Sulphate may be added in the form of sulphuric acid, ammonium sulphate, sodium sulphate or other sulphate salt; silicon may be added in the form of silica, such as aqueous colloidal silica or sodium silicate; and tungsten may be added in the form of a tungstate salt such as sodium tungstate or ammonium metatungstate. Step (f) may be carried out at any point in the process after step (e) and before the drying step mentioned below.
- the process may comprise after step (e), and before or after step (f), the step of (g) heat treating the zirconium hydroxide.
- the heat treatment may be hydrothermal treatment.
- the hydrothermal treatment may comprise heating the solution or sol to a temperature of 50-250°C, more particularly 100-250°C, for 0.5-24 hours in an autoclave.
- the process may comprise the steps of isolating, for example by filtering, and/or washing the zirconium hydroxide.
- steps may be carried out to remove chloride ions, sulphate ions, phosphate ions, nitrate ions, acetate ions, sodium ions, potassium ions, ammonium ions and/or organic residue if desired.
- levels of sulphate or phosphate ions may be reduced to 0.3% by weight or less, more particularly 0.1 % by weight or less.
- Levels of sodium, potassium and chloride ions may be reduced to 0.05% by weight or less each, more particularly 0.01 % by weight of less each, even more particularly 0.005% by weight or less each.
- Alkali metal ions may then be removed by an additional step of reslurrying the washed zirconium hydroxide and adding a mineral acid.
- the mineral acid may be nitric acid or sulphuric acid, more particularly nitric acid.
- the nitric acid concentration may be from about 10% to 60% by weight.
- the pH of the solution is generally adjusted to a pH less than 9, preferably adjusted to between pH 6.5-9.
- the process may comprise the optional step of redispersing the precipitate in an aqueous medium and heating the resulting dispersed slurry or wet cake to between 100°C and 350°C, more particularly between 100°C to 200°C.
- the process may comprise after step (e), or after steps (f) or (g) if they are carried out, the step of (h) drying the zirconium hydroxide.
- this may be by oven-drying, spray-drying or vacuum-drying. Drying may be carried out in an oxidising, inert (eg N 2 ) or reducing atmosphere. More particularly, the zirconium hydroxide may be dried at a temperature of 50-200°C. If a vacuum is used, the drying temperature can be at the lower end of this range. Without a vacuum, temperatures at the higher end of this range may be required, for example 100-150°C.
- the process may comprise after step (g), or after step (e) or (f) if step (f) and/or (g) is not carried out, the step of (h) calcining the zirconium hydroxide to form a zirconium oxide. More particularly, the calcining step may be carried out at temperature of 400-1100°C, even more particularly 600-850°C. The calcining step may be carried out for 0.5-15 hours, more particularly 2-8 hours, even more particularly 2-3 hours. The calcining step may be carried out in any gaseous atmosphere. In particular, the calcining step may be carried out in a static or flowing air atmosphere, although a reductive or neutral atmosphere could be used.
- an air atmosphere is generally preferred since this can assist in removing organic species.
- a neutral atmosphere is generally defined as one which neither oxidises nor reduces the composition in that atmosphere. This can be done by removing air or removing oxygen from the atmosphere.
- a further example of a neutral atmosphere is a nitrogen atmosphere.
- the calcination atmosphere could be that of the combustion gases generated from a gas- fired kiln. The time at temperature can depend on the thermal mass being calcined and it is necessary for consistency that adequate time at temperature is utilised to ensure the required degree of crystallinity, homogeneity, acidity and development of microstructure of the solid.
- the zirconium oxide (which may be doped) may then be formed or pressed, for example by being granulated, pelletized, tableted or extruded. These forming or pressing steps may optionally comprise adding a binder.
- the method may comprise the optional additional step of deagglomerating or milling the zirconium hydroxide or zirconium oxide. This can be done to zirconium hydroxide or oxide powder or to zirconium hydroxide or oxide in the form of a slurry(ie "wet") in an aqueous or non-aqueous liquid. This step can be carried out using known methods such as sieving, sifting, opposed air milling, impact milling, ball milling, bead milling and the like.
- the invention also relates to compositions obtainable by the above process, and applications for the use of the resulting materials, which includes but is not limited to catalysts, catalyst supports or precursors, binders, functional binders, coatings and sorbents. [0063] This invention will be further described by reference to the following Figures which are not intended to limit the scope of the invention claimed, in which:
- Figure 1 shows nitrogen adsorption isotherms for the acidic zirconium hydroxides of Comparative Example 2 and Preparative Example 2,
- Figure 2a shows NH 3 -TPD profiles for the acidic zirconium oxides of Comparative Examples 1 and 2, and Preparative Examples 1 and 2, when calcined at 600°C/2hours,
- Figure 2b shows C0 2 -TPD profiles for the acidic zirconium oxides of Comparative Examples 1 and 2, and Preparative Examples 1 and 2, when calcined at 600°C/2hours,
- Figure 3 shows XRD data for the acid zirconium hydroxides of Comparative
- Figure 5 shows TPD-MS data showing the intensity at 41 amu as a function of temperature for a) the fresh materials of Comparative Examples 1 , 2 and 5, and Preparative Examples 1 and 2; and b) the doped materials after calcination of Comparative Examples 4 and 8 and Preparative Examples 5, 6 and 7.
- Figure 6 shows DRIFT spectra of pyridine-saturated acidic zirconia samples recorded at 100°C in vacuo, for a) fresh and calcined samples of zirconium hydroxide materials from Preparative Examples 1 and 2 and Comparative Examples 1 , 2 and 5; and b) doped zirconium oxides after calcination for Preparative Examples 5-7 and Comparative Examples 4, 5 and 8.
- Figure 7 shows NH 3 -TPD profiles for the tungsten stabilised zirconium oxides of Comparative Examples 3 and 4, and Preparative Examples 5 and 8, when calcined at 700°C/2hours,
- Figure 8 shows XRD data for the tungsten stabilised zirconium oxides of Comparative Examples 3 and 4, and Preparative Examples 5 and 8, when calcined at 700°C/2hours,
- Figure 9 shows NH 3 -TPD profiles for the silica stabilised zirconium oxides of Comparative Examples 7 and 8, and Preparative Examples 7 and 10, when calcined at 850°C/2hours,
- Figure 10 shows XRD data for the silica stabilised zirconium oxides of
- Figure 11 shows NH 3 -TPD profiles for the sulphate stabilised zirconium oxides of Comparative Examples 5 and 6, and Preparative Examples 6, 9, 1 1 and 12, when calcined at 600°C/2hours,
- Figure 12 shows XRD data for the sulphate stabilised zirconium oxides of Comparative Examples 5 and 6, and Preparative Examples 6 and 9, when calcined at 600°C/2hours, and
- Figure 13 shows TG-DTA profiles for the acidic zirconium hydroxides of Comparative Examples 1 and 2, and Preparative Examples 1 and 2, when dried at 110°C.
- a slurry of zirconium basic sulphate in deionised water was prepared, containing the equivalent of 200g Zr0 2 . 28wt% aqueous sodium hydroxide was added dropwise until the solution reached pH 13. The resulting precipitated zirconium hydroxide was then filtered and washed. The wet cake was reslurried in deionised water to give 2000g of slurry and this was hydrothermally treated at 1 barg for 1 hour and then dried at 1 10°C.
- Comparative Example 2 [0068] A sample was prepared according to the method described in patent EP 1 984 301 B1.
- a sample was prepared according to Comparative Example 1 , except that prior to the hydrothermal treatment to the 2000g slurry an 8wt% aqueous solution of sodium tungstate was added to target 15.8wt% W0 3 on an oxide basis in the resulting zirconium hydroxide. This slurry was adjusted to pH 6.7 with nitric acid, and the resulting slurry was then filtered and washed with deionised water.
- a sample was prepared according to Comparative Example 2, except that prior to hydrothermal treatment 328g of 8wt% aqueous solution of sodium tungstate was added to target 15.8wt% W0 3 on an oxide basis in the resulting zirconium hydroxide. This slurry was then adjusted to pH 6.7 with nitric acid, and the resulting slurry was then filtered and washed with deionised water.
- a sample was prepared according to Comparative Example 1 , except that prior to hydrothermal treatment 390g of the wet cake was slurried in deionised water and 127.1 g of 20wt% aqueous sulphuric acid was added to target 10wt% S0 3 on an oxide basis in the resulting zirconium hydroxide.
- Comparative Example 6 A sample was prepared according to Comparative Example 2 except that prior to hydrothermal treatment 977g of the wet cake was slurried in deionised water and 180.9 g of 20wt% aqueous sulphuric acid was added to target 10%SO 3 on an oxide basis in the resulting zirconium hydroxide.
- a sample was prepared according to Comparative Example 2, except that prior to hydrothermal treatment 900g of the washed wet cake was slurried in deionised water and 22.6g of 30wt% colloidal silica solution (Ludox AS-30) was added.
- the obtained solution was mixed with 564.01 g of de-ionised water and 394.84 of 20wt% aqueous sulphuric acid was added to the mixture.
- the pH of the obtained solution was then adjusted to pH 13.0 with a dilute sodium hydroxide solution.
- the resulting slurry was then filtered and washed.
- the wet cake was then hydrothermally treated at 1 barg for 1 hour and then dried at 1 10°C.
- Preparative Example 3 A sample was prepared according to the procedures described in Preparative Example 1 , but using a lower amount of mandelic acid - 1.226 g.
- Preparative Example 4 A sample was prepared according to the procedures described in Preparative Example 2, but using a lower amount of mandelic acid - 1.226 g.
- Preparative Example 5 A sample was prepared according to Preparative Example 1 except that prior to hydrothermal treatment 1891.2g of slurry was mixed with 258g of aqueous sodium tungstate to target 15.8wt% W0 3 on an oxide basis in the resulting zirconium hydroxide. The slurry was then adjusted to pH 6.7 with a dilute nitric acid the resulting slurry was then filtered and washed with deionised water.
- a sample was prepared according to the procedure described in the Preparative Example 1 , except that dilute sulphuric acid was added after the hydrothermal treatment, but prior to drying. The sample was then dried at 1 10°C to give a target S0 3 content of 10wt% on an oxide basis.
- a sample of zirconium hydroxide wet cake was prepared according to Preparative Example 1. 12.46 g of 30 wt% colloidal silica solution (Ludox AS-30) was added prior to hydrothermal treatment. The sample was then dried at 110°C to give a target Si0 2 content of 3.5% on an oxide basis.
- Preparative Example 11 A sample was prepared according to the procedure described in Preparative Example 1 , except that prior to hydrothermal treatment 1812.7 g of the washed slurry was adjusted to pH 6.5 with a dilute sulphuric acid. This gave a resulting S0 3 content of 6.5wt% on oxide basis.
- Preparative Example 12 28g of a sample prepared according to the procedure described in the Preparative Example 1 was mixed with dilute sulphuric acid. This was then further dried at 110°C for 3 hours to give a target S0 3 content of 10 wt% on an oxide basis.
- TG-DTA thermogravimetric analysis-differential thermal analysis experiments (measurement of samples weight loss (TG) and the exothermic DTA signal (e.g. crystallisation temperature)) were carried out using a Setsys-EVO-DTA Instrument. 50mg of sample was placed into 100 ⁇ Pt crucible and heated in the temperature range 20-1000°C, with the heating rate 10°C/min in the atmosphere of 20% 0 2 /He atmosphere (flowing rate - 20ml/min). Experiment run and data analysis were performed using Data Acquisition Setsys-1750 CS Evol software.
- XRD X-Ray Diffraction
- Loss over ignition (LOI) was determined using a Vecsrar unit under constant flow of an air atmosphere. Samples (2g) were heated at a rate of 3°C/min to the desired temperature (generally 1000°C, but for tungsten doped samples this would need to be 800°C) and held at this temperature for at least 60 minutes and until no change in weight over time is observed. [00120] Acidity measurements (for pre-calcined samples)
- TPD Temperature Programmed Desorption
- the sample was then exposed to flowing helium at 100°C for 1 hr to remove any non- adsorbed NH 3 /or C0 2 from the system and to allow a steady baseline on the Thermal Conductivity Detector (TCD).
- TCD Thermal Conductivity Detector
- a TPD experiment was carried out from 100°C to the maximum temperature of the experiment at 10°C/min in flowing helium (20ml/min), with a 2hr dwell time.
- the NH 3 or C0 2 uptake is monitored based on the TCD response.
- Quantitative analysis was performed based on pulse calibration, whereby a series of pulses of known volume (527 microlitres) of 5%NH 3 /He or 5%C0 2 /He were injected into a helium carrier stream and the TCD response was recorded.
- TGA-MS Propylamine adsorption/ Thermogravimetric Analysis/Mass Spectrometry
- Table 3 - XRD phase ratio analysis for samples calcined at 450°C for 2 hours
- Table 4 surface properties of the acidic zirconium hydroxides, fresh and calcined at 600°C for 2 hours, when measured by propylamine-TPD
- Table 5 surface properties of tungsten stabilised zirconium hydroxides when calcined at 700°C for 2 hours as measured by NH 3 -TPD
- Table 7 surface properties of sulphate stabilised zirconium hydroxides when calcined at 600°C for 2 hours as measured by NH 3 -TPD.
- the process route of the invention shows improved thermostability for undoped zirconium hydroxides and corresponding oxides after calcination at high temperature (900°C), retaining good porosity with a significant portion of mesopores.
- the calcined undoped zirconium hydroxide materials show more influence by the monoclinic phase, which can be important for particular uses of the materials.
- the porosity of the doped hydroxides has also been improved in comparison with the tested benchmarks. There is a general significant increase in acidity (strength of acid sites) has been noticed for both types of materials (undoped/doped).
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PCT/GB2016/053335 WO2017072509A1 (en) | 2015-10-27 | 2016-10-27 | Zirconia-based compositions for use as three way catalysts |
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