CN109863121A - 酸性氢氧化锆 - Google Patents
酸性氢氧化锆 Download PDFInfo
- Publication number
- CN109863121A CN109863121A CN201780065346.1A CN201780065346A CN109863121A CN 109863121 A CN109863121 A CN 109863121A CN 201780065346 A CN201780065346 A CN 201780065346A CN 109863121 A CN109863121 A CN 109863121A
- Authority
- CN
- China
- Prior art keywords
- zirconium
- oxide
- hydroxide
- dopant
- zirconium hydroxide
- 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
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- 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 119
- 239000002253 acid Substances 0.000 title claims description 32
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 95
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 51
- 239000002019 doping agent Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010937 tungsten Substances 0.000 claims abstract description 25
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 239000004411 aluminium Substances 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- 239000010955 niobium Substances 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
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002841 Lewis acid Substances 0.000 claims abstract description 8
- 239000011260 aqueous acid Substances 0.000 claims abstract description 8
- 230000001180 sulfating effect Effects 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 150000004028 organic sulfates Chemical group 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims abstract description 4
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- 125000001033 ether group Chemical group 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 125000000524 functional group Chemical group 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
- 238000001354 calcination Methods 0.000 claims description 56
- 239000012298 atmosphere Substances 0.000 claims description 46
- 239000011148 porous material Substances 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052726 zirconium Inorganic materials 0.000 claims description 26
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 25
- 238000005259 measurement Methods 0.000 claims description 25
- 238000010521 absorption reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- -1 hydrogen Zirconium oxide Chemical class 0.000 claims description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 6
- NFJORKYTEPFHEF-UHFFFAOYSA-J [W+4].[OH-].[OH-].[OH-].[OH-] Chemical compound [W+4].[OH-].[OH-].[OH-].[OH-] NFJORKYTEPFHEF-UHFFFAOYSA-J 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen 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
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007848 Bronsted acid Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- WZHCOOQXZCIUNC-UHFFFAOYSA-N cyclandelate Chemical class C1C(C)(C)CC(C)CC1OC(=O)C(O)C1=CC=CC=C1 WZHCOOQXZCIUNC-UHFFFAOYSA-N 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 239000000523 sample Substances 0.000 description 45
- 239000000243 solution Substances 0.000 description 45
- 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 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 18
- 238000001027 hydrothermal synthesis Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 229910021653 sulphate ion Inorganic materials 0.000 description 14
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 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 description 6
- 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 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 description 6
- 239000002585 base Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 229960002510 mandelic acid Drugs 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000001179 sorption measurement Methods 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011734 sodium Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000000908 ammonium hydroxide 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
- 239000008119 colloidal silica 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
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 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
- 239000013078 crystal Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 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
- DFIPXJGORSQQQD-UHFFFAOYSA-N hafnium;tetrahydrate Chemical compound O.O.O.O.[Hf] DFIPXJGORSQQQD-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000002045 lasting effect Effects 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
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
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- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 238000001107 thermogravimetry coupled to mass spectrometry Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- 208000003556 Dry Eye Syndromes Diseases 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 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
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 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
- 229940000489 arsenate Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
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Classifications
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Abstract
本发明涉及氢氧化锆或氧化锆,该氢氧化锆或氧化锆基于氧化物包含至多30wt%的掺杂剂,该掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,并且该氢氧化锆或氧化锆具有酸位点,其中酸位点中的大多数是路易斯酸位点。此外,本发明涉及包含氢氧化锆或氧化锆的催化剂、催化剂载体或前体、粘合剂、功能性粘合剂、涂层或吸附剂。本发明还涉及用于制备氢氧化锆的工艺,该工艺包括以下步骤:(a)将锆盐溶解在含水酸中,(b)向所得溶液或溶胶中加入一种或更多种络合剂,所述一种或更多种络合剂是包含以下官能团中的至少一种的有机化合物:胺基团、有机硫酸酯基团、磺酸酯基团、羟基基团、醚基团或羧酸基团,(c)加热在步骤(b)中形成的溶液或溶胶,(d)加入硫酸化剂,和(e)加入碱以形成氢氧化锆,以及(f)任选地加入掺杂剂。
Description
本发明涉及用于制备酸性氢氧化锆和氧化锆的工艺、包含酸性氢氧化锆和氧化锆的组合物,以及这些氢氧化物和氧化物在催化和吸附应用中的用途。
背景
由于其众所周知的两性性质,氢氧化锆具有强的选择性吸附大范围的不同有毒阴离子例如磷酸根和砷酸根的能力。
氧化锆,在具有和不具有稳定剂的情况下,均应用于许多不同类型的催化,包括环境催化、汽车催化和化学催化应用。还已经研究了ZrO2在重要反应中的催化活性,所述重要反应例如由CO和H2、CO2和H2或醇脱水来合成甲醇和烃。
氢氧化锆还已经被广泛地用作金属的载体。氢氧化锆还已经被并入载体中,以便稳定金属或使金属更耐烧结。已经发现,含有硫酸根离子或钨酸根离子的稳定的氢氧化锆表现出超强酸行为(superacidic behaviour),导致对于烃的异构化或对于甲醇转化为烃的高活性。已经发现,硅取代进入氢氧化锆增强了由氢氧化物产生的混合氧化物的酸度。所得材料在高温具有良好的催化活性,并且目前正在作为用于液化天然气(LNG)燃料发动机的有前途的甲烷氧化催化剂而被测试。关于该技术领域,提及的各种掺杂剂的元素形式通常被解释为包括它们的相应的氧化物。因此,例如,硅包括硅酸盐和胶体二氧化硅,钨包括钨酸盐等。
氢氧化锆材料在催化中的商业成功主要是由于通过精细加工方法和并入其他稳定剂来改变其物理和化学性质的能力。这允许微调催化剂载体的关键参数。不同的应用需要不同的性质的组合,但具有高的、热稳定的表面积和孔隙率是大多数催化剂应用的先决条件。通过改变制造工艺来改善产物的形态,还将观察到酸-碱性质平衡的变化。这些性质还显著地受到包含掺杂剂的影响,所述掺杂剂例如二氧化硅、铝、硫酸盐、磷酸盐、钼、锡、钨、铌和钛。
因此,清楚的是,孔隙率是有效催化剂行为的重要但非关键的标准。表面酸度在最终催化性能中起到同样突出的作用,例如氢氧化锆中的表面酸度受到末端OH基团和桥接OH基团的量和比率的影响。这意味着确定酸位点(acid site)的强度以及它们的浓度和类型(布朗斯台德/路易斯)对于评估催化剂对特定应用的适用性是重要的。许多不同的技术用于表征固体表面酸性质,包括视觉颜色变化;分光光度法和胺滴定等。
气态的碱特别是吡啶的吸附,结合红外(IR)分析,已经被公认为使表面上的酸类型合格(qualify)的一般实践。对于此存在两个主要原因。首先,它有助于评估催化剂表面上的酸位点的总浓度,因为从气相中吸附的碱的量与固体表面上的酸位点的浓度密切相关。其次,对应于不同的络合物的形成的不同的IR吸附带允许区分氧化锆表面上的活性位点的性质。
程序升温脱附(TPD)是广泛用于表征氧化物表面上的酸/碱位点的另一种众所周知的技术。TPD可以有助于确定氢氧化锆上的活性位点的量和强度,这对于理解和预测催化剂的性能至关重要。
氢氧化锆和氧化锆的性质通常密切地依赖于制备方法。WO2004/096713描述了用于生产氧化锆和锆基混合氧化物的方法。该工艺包括在不高于50℃的温度,在受控量的硫酸根阴离子的存在下,通过与碱反应,从锆盐的水溶液中沉淀氢氧化锆。然后煅烧该氢氧化物以形成基本上不含硫酸盐的氧化锆。日本专利申请公布第H11-292538号和第2000-247641号描述了通过向碱式硫酸锆的浆料中加入碱由碱式硫酸锆制备氢氧化锆。然而,这些文献中阐述的工艺未导致具有本发明的改进的孔体积、孔尺寸和表面积性质的氢氧化锆。
WO2007/088326中描述了无定形氢氧化锆的改进的孔隙率性质及其生产方法。该氢氧化物具有至少300m2/g的表面积,至少0.70cm3/g的总孔体积,以及5nm-15nm的平均孔尺寸。它通过包括以下步骤的工艺来制备:a)制备包含特定比率的硫酸根阴离子和锆盐的水溶液,(b)将溶液冷却至低于25℃,(c)加入碱以便沉淀无定形氢氧化锆,(d)过滤并且用水或碱洗涤沉淀的氢氧化锆以除去残余的硫酸盐和氯化物,(e)在小于3barg的压力水热处理氢氧化锆,以及(f)干燥氢氧化锆。
尽管WO2007/088326中描述了无定形材料的改进的孔隙率特性,但已经在寻求煅烧的材料的热稳定性改进、定制的多孔结构/晶体结构的设计(包括产生一定尺寸的孔的可能性和相含量)和比表面(酸/碱)性质。
发明陈述
根据本发明,提供了如以下阐述的本发明的方面中定义的氢氧化锆或氧化锆。关于本发明的所有方面,氢氧化锆或氧化锆可以被定义为酸性的。氢氧化锆和氧化锆的大多数酸位点也可以是路易斯酸位点。这可以通过氢氧化锆在1700cm-1-1400cm-1范围内的DRIFT光谱中的处于约1600cm-1-1620cm-1和约1440cm-1-1450cm-1的最高强度峰来示出。更特别地,氢氧化锆和氧化锆可以具有比布朗斯台德酸位点更多的路易斯酸位点。这可以通过氢氧化锆在DRIFT光谱中的处于约1600cm-1-1620cm-1和约1440cm-1-1450cm-1的峰比处于约1630cm-1-1640cm-1和约1530cm-1-1550cm-1的峰更高来示出。在本发明的上下文中,术语“酸位点”用于指可用于反应的酸物质。它们可以包括布朗斯台德酸位点,即质子供体(例如在末端表面OH基团、SO3H基团或其他表面基团上的质子)和路易斯酸位点,即电子受体(例如Zr原子)。氧化锆或氢氧化锆可以基于氧化物包含至多30wt%,更特别地至多16wt%的掺杂剂,该掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种。应注意,所有氧化锆和氧化锆基于氧化物包含约1.5wt%-2wt%的氧化铪或氢氧化铪作为杂质。这不包括在以下提及的“附带杂质”的量中。
根据本发明的一个方面,提供了氢氧化锆,该氢氧化锆基于氧化物包含少于0.1wt%的掺杂剂,该掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,其中该氢氧化锆是多孔的,并且关于具有至多155nm的孔径的孔,其孔体积的至少70%由具有按照使用BJH方法测量的3.5nm-155nm的孔径的孔提供。特别地,氢氧化锆可以基于氧化物包含少于0.1wt%的掺杂剂,该掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛、锡、稀土金属或钇中的一种或更多种。更特别地,关于具有至多155nm的孔径的孔,其孔体积的至少75%可以由具有按照使用BJH方法测量的3.5nm-155nm的孔径的孔提供。特别地,关于具有至多155nm的孔径的孔,其孔体积的小于30%,更特别地小于25%,可以由具有按照使用BJH方法测量的小于3.5nm的孔径的孔提供。在本发明的上下文中,3.5nm-155nm的孔径被定义为介孔的/大孔的,并且小于3.5nm的孔径被定义为微孔的。
特别地,氢氧化锆可以具有按照通过N2物理吸附测量的至少0.75cm3/g,更特别地至少0.80cm3/g的总孔体积。特别地,氢氧化锆可以具有至少6.0nm,更特别地至少6.5nm的平均孔径。
特别地,氧化锆在450℃在空气气氛中煅烧持续2小时之后,可以包括按照通过XRD(X射线衍射)测量的至少80wt%,更特别地至少82wt%的单斜相。
特别地,氢氧化锆可以具有按照通过丙胺TPD测量的至少1300μmol/g的酸负载量(acid loading)。更特别地,氢氧化锆可以具有按照通过丙胺TPD测量的低于365℃,甚至更特别地低于360℃的Tmax。
本发明的该方面还涉及氧化锆,该氧化锆通常通过煅烧(例如,在450℃或更高的温度),由上文定义的氢氧化锆获得或可获得。更特别地,提供了氧化锆,该氧化锆基于氧化物包含少于0.1wt%的掺杂剂,该掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,该氧化锆在600℃在空气气氛中煅烧持续2小时之后具有至少50m2/g,甚至更特别地至少52m2/g的表面积。更特别地,氧化锆可以基于氧化物包含少于0.1wt%的掺杂剂,该掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛、锡、稀土金属或钇中的一种或更多种。特别地,氧化锆在600℃在空气气氛中煅烧持续2小时之后,可以具有按照通过丙胺TPD测量的至少100μmol/g的酸负载量。更特别地,氧化锆在600℃在空气气氛中煅烧持续2小时之后,可以具有按照通过N2物理吸附测量的至少0.35cm3/g的总孔体积。特别地,氧化锆在600℃在空气气氛中煅烧持续2小时之后,可以具有至少25.0nm的平均孔径。更特别地,氧化锆可以显示碱度,其特征在于在600℃在空气气氛中煅烧持续2小时之后,按照通过TPD(程序升温脱附)测量的在400℃-600℃时至少14μmol/g,甚至更特别地至少16μmol/g的CO2吸收量(CO2uptake)。
此外,本发明的该方面还涉及氧化锆,该氧化锆基于氧化物包含少于0.1wt%的掺杂剂,该掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,该氧化锆在900℃在空气气氛中煅烧持续2小时之后具有至少15m2/g,甚至更特别地至少16m2/g的表面积。特别地,氧化锆在900℃在空气气氛中煅烧持续2小时之后,可以具有按照通过N2物理吸附测量的至少0.10cm3/g的总孔体积。更特别地,氧化锆在900℃在空气气氛中煅烧持续2小时之后,可以具有至少26.0nm的平均孔径。
更特别地,氢氧化锆或氧化锆基于氧化物可以是至少98wt%纯,甚至更特别地至少99wt%纯(不包括上文提及的氧化铪或氢氧化铪杂质)。
氢氧化锆或相应的煅烧的氧化物还表现出有用的物理特性,例如高的孔体积,特别是与在3.5nm-50nm范围内的孔尺寸相关的孔体积。此外,它们可以示出H3的IV型滞后环(hysteresis loop)的氮等温线,在P/P0>0.6时具有介孔性。
根据本发明的第二方面,提供了掺杂的氧化锆,该掺杂的氧化锆基于氧化物包含0.1wt%-30wt%的氢氧化硅或氧化硅,其中该氧化锆在850℃煅烧持续2小时之后具有按照通过TPD测量的至少3.5μmol/m2的NH3吸收量(NH3uptake)。更特别地,硅掺杂的氧化锆在850℃在空气气氛中煅烧持续2小时之后,可以具有按照通过TPD测量的至少4.0μmol/m2,甚至更特别地至少4.25μmol/m2的NH3吸收量。特别地,硅掺杂的氧化锆在850℃在空气气氛中煅烧持续2小时之后,可以具有按照通过TPD测量的至少330μmol/g,更特别地至少360μmol/g的NH3吸收量。特别地,硅掺杂的氧化锆在850℃在空气气氛中煅烧持续2小时之后,可以具有按照通过NH3TPD测量的至少280℃,更特别地至少285℃的Tmax。如上所述,这种氧化物可以通常通过煅烧(例如,在450℃或更高的温度),由相应的氢氧化锆获得或可获得。
特别地,硅掺杂的氧化锆在850℃在空气气氛中煅烧持续2小时之后,可以具有按照通过丙胺TPD测量的至少170μmol/g的酸负载量。
此外,本发明的该方面还涉及硅掺杂的氢氧化锆,该硅掺杂的氢氧化锆具有至少540m2/g的表面积、按照通过N2物理吸附测量的至少0.90cm3/g的总孔体积,以及当在850℃在空气气氛中煅烧持续2小时时按照通过TPD测量的至少3.5μmol/m2的NH3吸收量。
更特别地,硅掺杂的氢氧化锆或硅掺杂的氧化锆可以基于氧化物包含1wt%-10wt%,甚至更特别地1wt%-5wt%,更特别地2.5wt%-4.5wt%的氢氧化硅或氧化硅。特别地,硅掺杂的氧化锆的剩余部分可以基于氧化物包含氧化锆和至多0.3wt%的附带杂质。
根据本发明的第三方面,提供了掺杂的氢氧化锆,该掺杂的氢氧化锆基于氧化物包含0.1wt%-30wt%的氢氧化钨或氧化钨,具有至少400m2/g的表面积。更特别地,钨掺杂的氢氧化锆可以具有至少450m2/g,甚至更特别地至少500m2/g的表面积。
特别地,钨掺杂的氢氧化锆可以具有按照通过N2物理吸附测量的至少0.7cm3/g,更特别地至少0.8cm3/g的总孔体积。
特别地,本发明的该方面还涉及钨掺杂的氧化锆,该钨掺杂的氧化锆通常通过煅烧(例如,在450℃或更高的温度),由上文定义的钨掺杂的氢氧化锆获得或可获得。更特别地,提供了钨掺杂的氧化锆,该钨掺杂的氧化锆基于氧化物包含0.1wt%-30wt%的氢氧化钨或氧化钨,在700℃在空气气氛中煅烧持续2小时之后具有按照通过TPD测量的至少4.30μmol/m2的NH3吸收量。更特别地,钨掺杂的氧化锆在700℃在空气气氛中煅烧持续2小时之后,可以具有按照通过TPD测量的至少420μmol/g,甚至更特别地至少460μmol/g的NH3吸收量。
特别地,钨掺杂的氧化锆在700℃在空气气氛中煅烧持续2小时之后,可以具有按照通过丙胺TPD测量的至少260μmol/g,更特别地至少280μmol/g的酸负载量。
更特别地,钨掺杂的氢氧化锆或钨掺杂的氧化锆可以基于氧化物包含12wt%-20wt%,甚至更特别地14wt%-18wt%的氢氧化钨或氧化钨。特别地,钨掺杂的氧化锆的剩余部分可以基于氧化物包含氧化锆和至多0.3wt%的附带杂质。
根据本发明的第四方面,提供了掺杂的氢氧化锆,该掺杂的氢氧化锆基于氧化物包含0.1wt%-30wt%,更特别地1wt%-12wt%,甚至更特别地1wt%-10wt%的硫酸盐,具有至少375m2/g的表面积。更特别地,硫酸盐掺杂的氢氧化锆可以具有至少400m2/g的表面积。
特别地,硫酸盐掺杂的氢氧化锆可以具有按照通过N2物理吸附测量的至少0.50cm3/g,更特别地至少0.60cm3/g的总孔体积。特别地,硫酸盐掺杂的氢氧化锆可以具有至少5.5nm,更特别地至少6.0nm的平均孔径。
特别地,本发明的该方面还涉及硫酸盐掺杂的氧化锆,该硫酸盐掺杂的氧化锆通常通过煅烧(例如,在450℃或更高的温度),由上文定义的硫酸盐掺杂的氢氧化锆获得或可获得。更特别地,提供了硫酸盐掺杂的氧化锆,该硫酸盐掺杂的氧化锆基于氧化物包含0.1wt%-30wt%的硫酸盐,在600℃在空气气氛中煅烧持续2小时之后具有按照通过TPD测量的至少800μmol/g、更特别地至少850μmol/g、甚至更特别地至少900μmol/g的NH3吸收量。特别地,硫酸盐掺杂的氧化锆可以基于氧化物包含1wt%-12wt%,更特别地1wt%-10wt%的硫酸盐。
特别地,硫酸盐掺杂的氧化锆在600℃在空气气氛中煅烧持续2小时之后,可以具有按照通过丙胺TPD测量的至少800μmol/g,更特别地至少900μmol/g的酸负载量。
更特别地,硫酸盐掺杂的氧化锆在600℃在空气气氛中煅烧持续2小时之后,可以具有至少140m2/g,甚至更特别地至少150m2/g的表面积。特别地,氧化锆在600℃在空气气氛中煅烧持续2小时之后,可以具有按照通过N2物理吸附测量的至少0.30cm3/g,更特别地至少0.32cm3/g的总孔体积。更特别地,氧化锆在600℃在空气气氛中煅烧持续2小时之后,可以具有至少8.5nm,甚至更特别地至少9.0nm的平均孔径。
本发明涉及在本体中和表面上均具有受控的酸碱性(acidic and basicproperty)的酸性氢氧化锆和酸性氧化锆。
在一些实施方案中,硅、钨、硫酸盐、磷酸盐、铌、铝、钼、钛或锡掺杂的氢氧化锆或氧化锆可以包含另外的掺杂剂,特别地以有助于稳定本体形式。另外的掺杂剂可以包括稀土的氢氧化物或氧化物、或钇的氢氧化物或氧化物,或任何其他尚未提及的过渡金属的氢氧化物或氧化物。这种另外的掺杂剂可以以基于氧化物少于25wt%,更特别地0.1wt%-25wt%的浓度存在。特别地,氢氧化锆或氧化锆的总锆含量基于氧化物将不少于50wt%。在一些实施方案中,本发明的氢氧化锆包含按重量计少于5%的氢氧化铈,更特别地按重量计少于2%的氢氧化铈,甚至更特别地按重量计少于1%的氢氧化铈。在一些实施方案中,氢氧化锆大体上不含铈。
如上所述,氢氧化锆或另外稳定或掺杂的氢氧化锆可以被煅烧成它们相应的氧化物。这些氧化物也表现出酸性特性,但一些也可能示出强碱度。进行该煅烧的温度取决于已经被加入到组合物中的掺杂剂。对于一些掺杂剂,过高的温度将导致该掺杂剂从组合物中损失。例如,对于包含硫酸盐的组合物,煅烧温度应低于650℃,更特别地400℃-650℃。对于包含钨的组合物,煅烧温度应低于850℃,更特别地400℃-800℃。对于其他组合物,煅烧温度可以是400℃-1000℃,更特别地450℃-800℃。
特别地,按照通过XRD测量的,氢氧化锆可以是大体上无定形的。更特别地,氢氧化锆可以具有按照通过激光散射测量的小于100μm,更特别地10μm-50μm的d50粒度。
为了在催化或吸附应用中有用,本文定义的组合物可以包含小于250ppm的Na和/或小于250ppm的K,更特别地小于200ppm,甚至更特别地小于125ppm。在一些实施方案中,Na和/或K的含量可以小于50ppm。
根据本发明的第五方面,提供了包含上文描述的氢氧化锆和/或氧化锆中的任何一种的催化剂、催化剂载体或吸附剂。
根据本发明的另外的方面,提供了用于制备氢氧化锆的工艺,该工艺包括以下步骤:
(a)将锆盐溶解在含水酸(aqueous acid)中,
(b)向所得溶液或溶胶中加入一种或更多种络合剂,所述一种或更多种络合剂是包含以下官能团中的至少一种的有机化合物:胺基团、有机硫酸酯基团、磺酸酯基团、羟基基团、醚基团或羧酸基团,
(c)加热在步骤(b)中形成的溶液或溶胶,
(d)加入硫酸化剂,
(e)加入碱以形成氢氧化锆,以及
(f)任选地加入掺杂剂。
当氢氧化锆,任选地包含掺杂剂,通过该工艺产生时,所得材料具有比先前达到的更高的百分比的介孔。此外,可以实现改进的热稳定性,特别是对于在900℃煅烧的未掺杂的氢氧化锆。未掺杂的氢氧化锆还可以表现出更高的百分比的单斜相。
在一些实施方案中,锆盐可以是碱式碳酸锆或氢氧化锆。在某些实施方案中,碱式碳酸锆(ZBC)是优选的,因为它易于溶解于无机酸中,可商购获得,并且所产生的碳酸根阴离子是不稳定的(fugitive)并因此它们不参与复杂的后续反应。一些可选择的阴离子可能不会对环境有利。在一些实施方案中,含水酸可以是盐酸、硫酸、硝酸或乙酸,特别地,含水酸是硝酸。不希望受任何理论束缚,虽然可以使用其他酸,但认为由硝酸提供的硝酸根离子与水溶液中的锆离子配位得特别好。
特别地,在步骤(a)中,在溶液或溶胶中的锆离子与硝酸根离子的摩尔比可以是1:0.8至1:2,更特别地1:0.8至1:1.5。
在本发明的上下文中,术语络合剂被用于指与锆结合的配体。在一些实施方案中,在步骤(b)中,络合剂可以是羧酸、二羧酸、α-羟基羧酸、氨基酸、有机硫酸酯或多元醇。特别地,络合剂可以是多齿配体,更特别地双齿配体。多元醇可以是多糖,例如淀粉。特别地,络合剂可以是α-羟基羧酸。络合剂通常具有与锆配位的极性基团(即胺基团、有机硫酸酯基团、磺酸酯基团、羟基基团、醚基团或羧酸基团)和一个或更多个烃基团。在一些实施方案中,一个或更多个烃基团可以包含一个或更多个芳族取代基,更特别地一个或更多个苯基取代基。不希望受任何理论束缚,多齿配体与金属离子有效地配位。相同分子内的不同官能团的组合可能有利于与金属离子上的不同配位环境相互作用;提供空间效应和电子效应两者。因此,取决于孔尺寸和孔网络的性质,可以使用具有不同烃基团的络合剂。例如,α-羟基羧酸可以是芳族(例如,苯基)或非芳族α-羟基羧酸,更特别地扁桃酸或二苯乙醇酸或乳酸,甚至更特别地扁桃酸。
特别地,在步骤(a)中,形成的溶液可以被加热。特别地,溶液可以被加热至高于25℃,更特别地至少40℃,甚至更特别地至少50℃的温度,更特别地至50℃-70℃范围内的温度。更特别地,溶液可以被加热至约60℃。
任选地,在步骤(a)中,可以通过加入碱增加溶液的pH(即,部分地中和)。pH的这种增加还可以被描述为游离酸度的降低。特别地,可以在加热溶液之前进行pH增加。更特别地,碱可以是氢氧化钠、碳酸钠、碳酸氢钠、氢氧化铵、碳酸铵、碳酸氢铵、氢氧化钾、碳酸钾和/或碳酸氢钾。
特别地,步骤(b)可以另外包括将水,通常去离子水,加入到加热的溶液中。更特别地,在步骤(b)中,在加入络合剂之后,溶液具有以ZrO2表示的按重量计5%-25%,更特别地以ZrO2表示的按重量计10%-20%,甚至更特别地以ZrO2表示的按重量计12%-16%的当量锆含量。以ZrO2表示的当量锆含量意指,例如,100g的按重量计15%的溶液将具有与15g的ZrO2相同的锆含量。
更特别地,在步骤(c)中,加热可以包括将溶液或溶胶加热至60℃-100℃,更特别地80℃-100℃的温度,持续1-15小时。特别地,加热可以进行持续1-5小时。更特别地,在步骤(c)中,溶液或溶胶的温度可以以0.1℃-1.5℃/min的速率增加。在本发明的上下文中,提及的加热速率包括线性(即恒定)加热速率以及非线性加热速率(例如快的初始加热速率,随后是较慢的加热速率)两者。通常进行该加热步骤以便有助于提供用于介孔粉末制备的最佳聚合物/低聚物尺寸。
特别地,在步骤(d)中,在加入硫酸化剂之前,可以允许溶液或溶胶冷却(cool)或溶液或溶胶可以被冷却(cooled)。更特别地,可以允许溶液或溶胶冷却至或溶液或溶胶可以被冷却至低于40℃,甚至更特别地低于30℃的温度。可能的硫酸化剂是水溶性的硫酸盐、硫酸氢盐、亚硫酸盐、亚硫酸氢盐。特别地,硫酸化剂可以是硫酸。可以加入硫酸化剂使得锆离子与硫酸根离子的摩尔比是从1:0.05至1:1。在步骤(d)中硫酸盐加入之后,该工艺可以包括例如通过过滤从溶液或溶胶中分离固体的步骤。
在步骤(e)中,通过加入碱,溶液或溶胶的pH可以增加至pH>8。碱可以是氢氧化钠、碳酸钠、碳酸氢钠、氢氧化铵、碳酸铵、碳酸氢铵、氢氧化钾、碳酸钾和/或碳酸氢钾。更特别地,在步骤(e)中,碱的加入将形成氢氧化锆沉淀物。溶液或溶胶可以被调节至的pH取决于所用的碱。特别地,碱可以是氢氧化铵或碱金属氢氧化物,更特别地氢氧化钠。对于氢氧化铵,可达到的最大pH通常为约pH 10.5-11。对于碱金属氢氧化物,pH可以被调节至pH 11-13或更高。
步骤(e)可以在溶液或溶胶未被冷冻的任何温度,即从-5℃至95℃,更特别地从10℃至80℃进行。
在一些实施方案中,该工艺可以在步骤(e)之后包括步骤(f)加入掺杂剂。这是本发明的方法的新颖特征,因为掺杂剂在步骤(e)之后加入,而不是在步骤(e)中与氢氧化锆共沉淀。特别地,掺杂剂可以是稳定氧化锆的四方相的任何材料,例如作为表面稳定剂或本体稳定剂(bulk stabiliser)。氧化锆的该相可以提供改进的催化性能。掺杂剂还可以用于增加材料的酸度。更特别地,掺杂剂可以包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种。甚至更特别地,掺杂剂可以包括硫酸盐、硅或钨中的一种或更多种。硫酸盐可以以硫酸、硫酸铵、硫酸钠或其他硫酸盐的形式加入;硅可以以二氧化硅例如含水胶体二氧化硅或硅酸钠的形式加入;并且钨可以以钨酸盐例如钨酸钠或偏钨酸铵的形式加入。步骤(f)可以在步骤(e)之后并且在下文提及的干燥步骤之前的工艺中的任何点处进行。
在一些实施方案中,该工艺可以在步骤(e)之后,并且在步骤(f)之前或之后包括步骤(g)热处理氢氧化锆。热处理可以是水热处理。水热处理可以包括在高压釜中将溶液或溶胶加热至50℃-250℃,更特别地100℃-250℃的温度持续0.5-24小时。
更特别地,在步骤(e)和步骤(g)之间和/或在步骤(g)之后,并且在步骤(f)之前或之后,该工艺可以包括分离,例如通过过滤,和/或洗涤氢氧化锆的步骤。如果需要,可以进行这些步骤以除去氯离子、硫酸根离子、磷酸根离子、硝酸根离子、乙酸根离子、钠离子、钾离子、铵离子和/或有机残留物。对于其中未加入硫酸盐或磷酸盐作为掺杂剂的组合物,硫酸根离子或磷酸根离子的水平可以被降低至按重量计0.3%或更少,更特别地按重量计0.1%或更少。钠离子、钾离子和氯离子的水平可以各自被降低至按重量计0.05%或更少,更特别地各自被降低至按重量计0.01%或更少,甚至更特别地各自被降低至按重量计0.005%或更少。
然后碱金属离子可以通过再浆化(reslurrying)洗涤的氢氧化锆以及加入无机酸的另外的步骤来除去。特别地,无机酸可以是硝酸或硫酸,更特别地硝酸。硝酸浓度可以为按重量计从约10%至60%。通常,将溶液的pH调节至小于9的pH,优选地调节至在pH 6.5-9之间。在任选的另外的过滤步骤之后,该工艺可以包括以下任选的步骤:将沉淀物在水介质中再分散并且将所得分散的浆料或湿饼加热至在100℃和350℃之间,更特别地在100℃至200℃之间。这可以例如是在密封的反应容器例如高压釜中,或在开放的容器中高至100℃。
在一些实施方案中,该工艺可以在步骤(e)之后,或如果进行步骤(f)或步骤(g)则在步骤(f)或步骤(g)之后,包括步骤(h)干燥氢氧化锆。特别地,这可以是通过烘干、喷雾干燥或真空干燥。干燥可以在氧化气氛、惰性气氛(例如N2)或还原气氛中进行。更特别地,氢氧化锆可以在50℃-200℃的温度干燥。如果使用真空,则干燥温度可以是在该范围的较下端。在没有真空的情况下,可能需要在该范围的较上端的温度,例如100℃-150℃。
在一些实施方案中,该工艺可以在步骤(g)之后,或如果不进行步骤(f)和/或步骤(g)则在步骤(e)或步骤(f)之后,包括步骤(h)煅烧氢氧化锆以形成氧化锆。更特别地,煅烧步骤可以在400℃-1100℃,甚至更特别地600℃-850℃的温度进行。煅烧步骤可以进行持续0.5-15小时,更特别地2-8小时,甚至更特别地2-3小时。煅烧步骤可以在任何气体气氛中进行。特别地,煅烧步骤可以在静态空气气氛或流动空气气氛中进行,但是可以使用还原性气氛或中性气氛。在本发明的工艺中,空气气氛通常是优选的,因为这可以有助于除去有机物质。中性气氛通常被定义为既不氧化也不还原在该气氛中的组合物的气氛。这可以通过从气氛中除去空气或除去氧气来完成。中性气氛的另外的实例是氮气氛。此外,煅烧气氛可以是由煤气窑产生的燃烧气体的气氛。在该温度的时间可以取决于正在煅烧的热质量,并且为了一致性,有必要利用在该温度足够的时间来确保固体的所需的结晶度、均匀性、酸度和微观结构的发展。在煅烧之后,氧化锆(其可以被掺杂)然后可以例如通过造粒、制成小球、压片或挤出来形成或压制。这些形成步骤或压制步骤可以任选地包括加入粘合剂。
该方法可以包括解附聚(deagglomerate)或碾磨氢氧化锆或氧化锆的任选的另外的步骤。这可以对于氢氧化锆或氧化锆粉末进行,或对于呈在含水或不含水液体中的浆料(即“湿的”)形式的氢氧化锆或氧化锆进行。该步骤可以使用已知方法来进行,所述已知方法例如筛分(sieving)、过筛(sifting)、相对空气碾磨(opposed air milling)、冲击碾磨、球磨、珠磨及类似的。
本发明还涉及通过上述工艺可获得的组合物,以及关于所得材料的用途的应用,包括但不限于催化剂、催化剂载体或前体、粘合剂、功能性粘合剂、涂层和吸附剂。
将通过参考以下附图进一步描述本发明,这些附图不意图限制所要求保护的本发明的范围,在附图中:
图1示出了比较实施例2和制备实施例2的酸性氢氧化锆的氮吸附等温线,
图2a示出了当以600℃/2小时煅烧时,比较实施例1和2以及制备实施例1和2的酸性氧化锆的NH3-TPD概况,
图2b示出了当以600℃/2小时煅烧时,比较实施例1和2以及制备实施例1和2的酸性氧化锆的CO2-TPD概况,
图3示出了当在110℃干燥时,比较实施例1和2以及制备实施例1-4的酸性氢氧化锆的XRD数据,
图4示出了当以450℃/2小时煅烧时,比较实施例1和2以及制备实施例1和2的酸性氧化锆的XRD数据,
图5示出了TPD-MS数据,该数据示出了作为a)比较实施例1、2和5以及制备实施例1和2的新鲜材料;和b)比较实施例4和8以及制备实施例5、6和7的煅烧之后的掺杂的材料的温度的函数的在41amu处的强度。
图6示出了对于a)来自制备实施例1和2以及比较实施例1、2和5的氢氧化锆材料的新鲜和煅烧的样品;和b)制备实施例5-7以及比较实施例4、5和8的煅烧之后的掺杂的氧化锆,在100℃在真空下记录的吡啶饱和的酸性氧化锆样品的DRIFT光谱。
图7示出了当以700℃/2小时煅烧时,比较实施例3和4以及制备实施例5和8的钨稳定的氧化锆的NH3-TPD概况,
图8示出了当以700℃/2小时煅烧时,比较实施例3和4以及制备实施例5和8的钨稳定的氧化锆的XRD数据,
图9示出了当以850℃/2小时煅烧时,比较实施例7和8以及制备实施例7和10的二氧化硅稳定的氧化锆的NH3-TPD概况,
图10示出了当以850℃/2小时煅烧时,比较实施例7和8以及制备实施例7和10的二氧化硅稳定的氧化锆的XRD数据,
图11示出了当以600℃/2小时煅烧时,比较实施例5和6以及制备实施例6、9、11和12的硫酸盐稳定的氧化锆的NH3-TPD概况,
图12示出了当以600℃/2小时煅烧时,比较实施例5和6以及制备实施例6和9的硫酸盐稳定的氧化锆的XRD数据,以及
图13示出了当在110℃干燥时,比较实施例1和2以及制备实施例1和2的酸性氢氧化锆的TG-DTA概况。
现在将参考以下的实施例来举例描述本发明。
比较实施例1
制备了碱式硫酸锆在去离子水中的浆料,该浆料含有200g ZrO2的当量。逐滴加入28wt%含水氢氧化钠,直至溶液达到pH 13。然后过滤并且洗涤所得沉淀的氢氧化锆。将湿饼在去离子水中再浆化,以得到2000g的浆料,并且将该浆料在1barg水热处理持续1小时,并且然后在110℃干燥。
比较实施例2
根据专利EP 1 984 301B1中描述的方法来制备样品。即,将394.84g的20wt%含水硫酸、18.28g去离子水和966.18g氧氯化锆(20.7wt%ZrO2)混合并且冷却至-2℃。然后逐滴加入10wt%含水氢氧化钠,直至溶液达到pH 8。然后加入28wt%含水氢氧化钠,直至溶液达到pH 13。然后过滤并且洗涤所得沉淀的氢氧化锆。将湿饼在去离子水中再浆化,并且在1barg水热处理持续1小时,并且然后在110℃干燥。
比较实施例3
根据比较实施例1制备样品,除了在水热处理之前向2000g浆料中加入8wt%钨酸钠水溶液,以达到所得氢氧化锆中的基于氧化物15.8wt%WO3的目标。将该浆料用硝酸调节至pH 6.7,并且然后将所得浆料过滤并且用去离子水洗涤。
比较实施例4
根据比较实施例2制备样品,除了在水热处理之前加入328g的8wt%钨酸钠水溶液,以达到所得氢氧化锆中的基于氧化物15.8wt%WO3的目标。然后将该浆料用硝酸调节至pH 6.7,并且然后将所得浆料过滤并且用去离子水洗涤。
比较实施例5
根据比较实施例1制备样品,除了在水热处理之前将390g的湿饼在去离子水中浆化,并且加入127.1g的20wt%含水硫酸,以达到所得氢氧化锆中的基于氧化物10wt%SO3的目标。
比较实施例6
根据比较实施例2制备样品,除了在水热处理之前将977g的湿饼在去离子水中浆化,并且加入180.9g的20wt%含水硫酸,以达到所得氢氧化锆中的基于氧化物10%SO3的目标。
比较实施例7
在水热处理之前,将24.17g的30wt%胶体二氧化硅溶液(Ludox AS-30)加入到1761.22g的根据比较实施例1制备的浆料中。逐滴加入28wt%含水氢氧化钠,直至溶液达到pH 11。然后过滤并且洗涤所得沉淀的混合的氢氧化锆。将湿饼再浆化,并且在1barg水热处理持续5小时,并且然后在110℃干燥。
比较实施例8
根据比较实施例2制备样品,除了在水热处理之前将900g的洗涤的湿饼在去离子水中浆化,并且加入22.6g的30wt%胶体二氧化硅溶液(Ludox AS-30)。
制备实施例1
将537.63g的碱式碳酸锆(含有37.2%ZrO2)溶解在490.81g的稀硝酸中(以达到1.2的NO3/Zr比率的目标)。然后将该溶液加热至60℃。将2.759g的扁桃酸连同390.8g的水一起加入到溶液中。然后将该溶液再次加热至94℃持续2小时。
将所得溶液与465.31g的去离子水混合,并且然后将394.84g的20wt%含水硫酸加入到混合物中。然后用稀氢氧化钠溶液将所得溶液的pH调节至pH 13.0。然后将所得浆料过滤并且洗涤。将湿饼在1barg水热处理持续1小时,并且然后在110℃干燥。
制备实施例2
将537.63g的碱式碳酸锆(含有37.2%ZrO2)溶解在490.81g的稀硝酸中(以达到1.45的NO3/Zr比率的目标)。然后加热该溶液。将2.759g的扁桃酸连同390.8g的水一起加入到溶液中。然后将该溶液加热至94℃。
将所得溶液与564.01g的去离子水混合,并且将394.84g的20wt%含水硫酸加入到混合物中。然后用稀氢氧化钠溶液将所得溶液的pH调节至pH 13.0。然后将所得浆料过滤并且洗涤。然后将湿饼在1barg水热处理持续1小时,并且然后在110℃干燥。
制备实施例3
根据制备实施例1中描述的程序制备样品,但使用更少量的扁桃酸-1.226g。
制备实施例4
根据制备实施例2中描述的程序制备样品,但使用更少量的扁桃酸-1.226g。
制备实施例5
根据制备实施例1制备样品,除了在水热处理之前将1891.2g的浆料与258g的含水钨酸钠混合,以达到所得氢氧化锆中的基于氧化物15.8wt%WO3的目标。然后将浆料用稀硝酸调节至pH 6.7,然后将所得浆料过滤并且用去离子水洗涤。
制备实施例6
根据制备实施例1中描述的程序制备样品,除了在水热处理之后但在干燥之前加入稀硫酸。然后在110℃干燥样品,以得到基于氧化物10wt%的目标SO3含量。
制备实施例7
根据制备实施例1制备氢氧化锆湿饼的样品。在水热处理之前,加入12.46g的30wt%胶体二氧化硅溶液(Ludox AS-30)。然后在110℃干燥样品,以得到基于氧化物3.5%的目标SiO2含量。
制备实施例8
根据制备实施例5中描述的程序制备样品,但使用不同比率的初始试剂,使得NO3/Zr=1.45。
制备实施例9
根据制备实施例6中描述的程序制备样品,但使用不同比率的初始试剂,使得NO3/Zr=1.45。
制备实施例10
根据制备实施例7中描述的程序制备样品,但使用不同比率的初始试剂,使得NO3/Zr=1.45。
制备实施例11
根据制备实施例1中描述的程序制备样品,除了在水热处理之前,用稀硫酸将1812.7g的洗涤的浆料调节至pH 6.5。这得到基于氧化物6.5wt%的所得SO3含量。
制备实施例12
将28g的根据制备实施例1中描述的程序制备的样品与稀硫酸混合。然后将其在110℃进一步干燥持续3小时,以得到基于氧化物10wt%的目标SO3含量。
材料和方法
在各种实施例中制备的样品如制备的那样(as prepared)进行分析,但为了分析目的,样品还在静态空气下在各种温度被煅烧持续2小时。在所有情况下,Na的水平通过液体离子色谱法(Methrom IC 761)确认为小于200ppm。
SO3%含量通过Eltra碳硫分析仪CS800测量。
孔隙率特性
在Micromeritics TriStar 3020分析仪中通过在-196℃的液氮吸附来进行表面积、孔径和总孔体积的测量。在分析之前,样品在90℃在真空下脱气持续30分钟。表面积:使用BET多点测定法测量表面积。总孔体积:在以p/p°=0.9814的脱附期间进行孔体积测量。孔尺寸分布和平均孔径:孔尺寸分布的测定使用BJH方法(脱附分支)按照“平均宽度相对于增量孔体积”在1.7nm至300nm的范围内来完成。基于BJH孔尺寸分布图来估计以%计的介孔+大孔或微孔的部分。
粒度
使用装备有ASVR单元的Microtrac X100通过光散射法测量粒度分布。在分析之前运行标准物以确认结果的有效性。用0.05%Nopcosant K分散剂将ASVR单元自动填充至预设水平,加入约0.100g的干样品,并且然后用设置在40W的内部超声探针处理持续60秒。预循环时间为30秒,并且运行时间设置在50秒。样品被测量3次(通过米氏散射理论),并且获得并报告了平均结果。
热重分析(TGA)
TG-DTA(热重分析-差热分析)实验(样品重量损失(TG)和放热DTA信号(例如结晶温度)的测量)使用Setsys-EVO-DTA仪器进行。将50mg的样品放置在100μl Pt坩埚中,并且在温度范围20℃-1000℃内,以加热速率10℃/min,在20%O2/He气氛(流量-20ml/min)的气氛中加热。使用Data Acquisition Setsys-1750CS Evol软件进行实验运行和数据分析。
X射线衍射(XRD)
基于氧化锆的材料的粉末XRD晶相分析在Bruker D8Advance X射线扩散系统(Diffrac.EVA软件,布拉格-布伦塔诺几何学(Bragg-Brentano geometry),LYNXEYE检测器,从10°至70°的2θ范围内的Cu辐射 每步0.015°,每步的时间0.2s,0.02mm Ni过滤器,外加功率40mV/40mA)上进行。使用TOPAS软件(版本4.2)对于氧化锆样品的衍射图样进行定量相分析。参考材料用于峰鉴别(通过Bruker装载的四方氧化锆/单斜氧化锆)。数据评估包括峰值搜索、手动/自动的背景减除和数据平滑。微晶尺寸测定通过谢勒法(Scherrer method)来完成,K=0.9。
烧失量(loss over ignition)(LOI)
在恒定流动的空气气氛下,使用Vecsrar单元测定烧失量(LOI)。将样品(2g)以3℃/min的速率加热至所需温度(通常1000℃,但对于钨掺杂的样品,这将需要为800℃),并且在该温度保持至少60分钟,并且直至没有观察到重量随时间的变化。
酸度测量(对于预煅烧的样品)
NH3/CO2-程序升温脱附(TPD)-测量使用AMI200仪器进行。在流动氩气(20ml/min)中以20℃/min的升温速率,将0.2g的样品从环境温度加热直到实验的最高温度(未掺杂的样品=600℃;硫酸化的样品=544℃;钨酸化的样品=700℃;二氧化硅掺杂的样品=800℃)。然后将样品在该温度停留持续45min,然后冷却回到100℃。然后将5%NH3/He(或5%CO2/He)在100℃流过样品持续30min(20ml/min)。然后将样品暴露于在100℃的流动的氦气持续1小时,以从系统中除去任何未吸附的NH3/或CO2,并且允许在热导检测器(TCD)上有稳定基线。在流动的氦气(20ml/min)中,从100℃至实验的最高温度以10℃/min进行TPD实验,具有2小时停留时间。基于TCD响应来监测NH3或CO2吸收量。基于脉冲校准(pulsecalibration)进行定量分析,由此将一系列已知体积(527微升)的5%NH3/He或5%CO2/He的脉冲注射至氦气载体流中,并且记录TCD响应。
丙胺吸附/热重分析/质谱分析(TGA-MS)-这通过将样品暴露于丙胺过夜来进行。在装备有Pfeiffer Vacuum ThermoStarTM GSD 301T3质谱仪的Mettler Toledo TGA/DSC2STARe系统上的程序升温脱附之前,在30℃在真空中除去过量的物理吸附的丙胺。然后,在考虑清洁样品的质量变化的情况下,基于200℃-800℃的温度范围内的质量损失来计算酸位点的数量。
异位吡啶吸附-这通过用纯吡啶浸渍样品来进行。在真空烘箱中在30℃过夜除去过量的物理吸附的吡啶。然后在样品装入具有漫反射红外傅里叶变换(DRIFT)光谱的环境室(environmental cell)之前,将样品稀释(10wt%在KBr中)。在测量之前,样品在100℃在真空下经受另外的干燥持续15min,以除去在空气暴露期间物理吸附的任何水分。
结果
测试的结果在以下表1-7中阐述。表示出了以下内容:
表1-酸性氢氧化锆的各种性质
表2-当在600℃煅烧持续2小时时按照通过NH3/CO2-TPD测量的酸性氢氧化锆的表面性质
表3-在450℃煅烧持续2小时的样品的XRD相比率分析
表4-当通过丙胺-TPD测量时,新鲜的和在600℃煅烧持续2小时的酸性氢氧化锆的表面性质
表5-当在700℃煅烧持续2小时时按照通过NH3-TPD测量的钨稳定的氢氧化锆的表面性质
表6-当在850℃煅烧持续2小时时按照通过NH3-TPD测量的硅稳定的氢氧化锆的表面性质
表7-当在600℃煅烧持续2小时时按照通过NH3-TPD测量的硫酸盐稳定的氢氧化锆的表面性质
本发明的工艺路线显示了在高温(900℃)煅烧之后的未掺杂的氢氧化锆和相应的氧化物的改善的热稳定性,保留了良好的孔隙率,其中很大的部分为介孔。煅烧的未掺杂的氢氧化锆材料显示出更多的通过单斜相的影响,这对于材料的特定用途可能是重要的。与测试的基准相比,掺杂的氢氧化物的孔隙率也有改进。对于两种类型的材料(未掺杂的/掺杂的),已经注意到存在酸度(酸位点的强度)的普遍显著增加。
关于酸度:酸位点的浓度,酸位点的强度和类型已经通过丙胺吸附/TGA-MS(图5)和异位吡啶吸附(DFTIR)(图6)进行了确认。图5a中呈现的数据(峰面积)显示出未掺杂的氢氧化锆样品与市售的硫酸化的氧化锆-众所周知的超强酸相比显著更高的酸负载量。并且,丙烯释放(41amu)的温度已经证明了所有样品的强酸度。已经发现,酸强度从样品1和2(比较的,峰中心在约368℃)分别地增加至发明的样品3(352℃)和4(346℃),并且超过标准基准的值(423℃)。所得数据表明,即使没有加入稳定掺杂剂,本发明的材料也是强酸性的,这使得它们在其他众所周知的氧化锆类中是独特的。
吡啶浸渍的样品的DRIFT光谱(图6)证明了测试样品的路易斯酸性质,这是由于在1446cm-1和1604cm-1处存在吸收峰-路易斯酸位点的主要特性。
掺杂的材料(硫酸盐、钨或二氧化硅等)在酸度和孔隙率特性方面显示出类似的趋势。已经注意到了与标准商品等级相比的显著改进(孔隙率增加30%,酸度(通过NH3-TPD测量)增加25%(表5、表6和表7)),这对于催化活性具有积极的影响并且使它们在非均相催化市场上具有竞争力。
表2
条件 | %单斜 | %四方 |
比较实施例2 | 74.82 | 25.18 |
比较实施例1 | 77.45 | 22.55 |
制备实施例1 | 85.61 | 14.39 |
制备实施例2 | 83.68 | 16.32 |
表3
表4
Claims (31)
1.一种氢氧化锆或氧化锆,基于氧化物包含至多30wt%的掺杂剂,所述掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,并且所述氢氧化锆或氧化锆具有酸位点,其中所述酸位点中的大多数是路易斯酸位点。
2.如权利要求1所述的氢氧化锆或氧化锆,具有比布朗斯台德酸位点更多的路易斯酸位点。
3.如权利要求1或权利要求2所述的氢氧化锆,基于氧化物包含少于0.1wt%的掺杂剂,所述掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,其中所述氢氧化锆是多孔的,并且关于具有至多155nm的孔径的孔,孔体积的至少70%由具有按照使用BJH方法测量的3.5nm-155nm的孔径的孔提供。
4.如权利要求3所述的氢氧化锆,其中,关于具有至多155nm的孔径的孔,其孔体积的至少75%由具有按照使用BJH方法测量的3.5nm-155nm的孔径的孔提供。
5.如权利要求1或权利要求2所述的氧化锆,基于氧化物包含少于0.1wt%的掺杂剂,所述掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,所述氧化锆在450℃在空气气氛中煅烧持续2小时之后,具有按照通过XRD测量的至少80wt%的单斜相。
6.如权利要求1或权利要求2所述的氧化锆,基于氧化物包含少于0.1wt%的掺杂剂,所述掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,所述氧化锆在900℃在空气气氛中煅烧持续2小时之后,具有至少15m2/g的表面积。
7.如权利要求6所述的氧化锆,在900℃在空气气氛中煅烧持续2小时之后,具有按照通过N2物理吸附测量的至少0.10cm3/g的总孔体积。
8.如权利要求1或权利要求2所述的氧化锆,基于氧化物包含少于0.1wt%的掺杂剂,所述掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种,所述氧化锆在600℃煅烧持续2小时之后,具有按照通过TPD测量的在400℃-600℃时至少14μmol/g的CO2吸收量。
9.如权利要求1或权利要求2所述的掺杂的氢氧化锆,基于氧化物包含0.1wt%-30wt%的硫酸盐,具有至少375m2/g的表面积。
10.如权利要求9所述的掺杂的氢氧化锆,具有按照通过N2物理吸附测量的至少0.50cm3/g的总孔体积。
11.如权利要求1或权利要求2所述的掺杂的氧化锆,基于氧化物包含0.1wt%-30wt%的硫酸盐,在600℃在空气气氛中煅烧持续2小时之后,具有按照通过TPD测量的至少800μmol/g的NH3吸收量。
12.如权利要求9-11中任一项所述的掺杂的氢氧化锆或掺杂的氧化锆,基于氧化物包含1wt%-12wt%的硫酸盐。
13.如权利要求1或权利要求2所述的掺杂的氢氧化锆,基于氧化物包含0.1wt%-30wt%的氢氧化钨或氧化钨,具有至少400m2/g的表面积。
14.如权利要求13所述的掺杂的氢氧化锆,具有按照通过N2物理吸附测量的至少0.7cm3/g的总孔体积。
15.如权利要求13或权利要求14所述的掺杂的氢氧化锆,基于氧化物包含12wt%-20wt%的氢氧化钨或氧化钨。
16.如权利要求1或权利要求2所述的掺杂的氧化锆,基于氧化物包含0.1wt%-30wt%的氢氧化钨或氧化钨,在700℃在空气气氛中煅烧持续2小时之后,具有按照通过TPD测量的至少420μmol/g的NH3吸收量。
17.如权利要求1或权利要求2所述的掺杂的氧化锆,基于氧化物包含0.1wt%-30wt%的氢氧化硅或氧化硅,其中所述氧化锆在850℃煅烧持续2小时之后,具有按照通过TPD测量的至少330μmol/g的NH3吸收量。
18.如权利要求17所述的掺杂的氧化锆,基于氧化物包含1wt%-10wt%的氢氧化硅或氧化硅。
19.如权利要求1或2所述的掺杂的氢氧化锆或氧化锆,包括选自稀土的氢氧化物或氧化物、钇的氢氧化物或氧化物或另一种过渡金属的氢氧化物或氧化物的另外的掺杂剂中的一种或更多种,使得所述氢氧化锆或氧化锆的总锆含量基于氧化物不少于50wt%。
20.一种用于制备氢氧化锆的工艺,所述工艺包括以下步骤:
(a)将锆盐溶解在含水酸中,
(b)向所得溶液或溶胶中加入一种或更多种络合剂,所述一种或更多种络合剂是包含以下官能团中的至少一种的有机化合物:胺基团、有机硫酸酯基团、磺酸酯基团、羟基基团、醚基团或羧酸基团,
(c)加热在步骤(b)中形成的所述溶液或溶胶,
(d)加入硫酸化剂,以及
(e)加入碱以形成氢氧化锆,以及
(f)任选地加入掺杂剂。
21.如权利要求20所述的工艺,其中所述锆盐是碱式碳酸锆或氢氧化锆。
22.如权利要求20或权利要求21所述的工艺,其中所述含水酸是盐酸、硫酸、硝酸或乙酸。
23.如权利要求22所述的工艺,其中所述含水酸是硝酸。
24.如权利要求20-23中任一项所述的工艺,其中所述络合剂是α-羟基羧酸。
25.如权利要求24所述的工艺,其中所述α-羟基羧酸是扁桃酸。
26.如权利要求20-25中任一项所述的工艺,其中在步骤(c)中,将所述溶液或溶胶加热至60℃-100℃的温度。
27.如权利要求20-26中任一项所述的工艺,其中所述硫酸化剂是硫酸。
28.如权利要求20-27中任一项所述的工艺,其中在步骤(e)中,所述溶液或溶胶的pH增加至pH>8。
29.如权利要求20-28中任一项所述的工艺,其中所述掺杂剂包括硅、硫酸盐、磷酸盐、钨、铌、铝、钼、钛或锡中的一种或更多种。
30.如权利要求29所述的工艺,在步骤(e)之后包括步骤(f)加入一种或更多种掺杂剂。
31.催化剂、催化剂载体或前体、粘合剂、功能性粘合剂、涂层或吸附剂,包含如权利要求1-19中任一项所述的氢氧化锆或氧化锆。
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