CN101238198A - 掺杂金属的混合金属氧化物、其制备方法及其作为催化剂组合物的应用 - Google Patents
掺杂金属的混合金属氧化物、其制备方法及其作为催化剂组合物的应用 Download PDFInfo
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- CN101238198A CN101238198A CNA2006800198779A CN200680019877A CN101238198A CN 101238198 A CN101238198 A CN 101238198A CN A2006800198779 A CNA2006800198779 A CN A2006800198779A CN 200680019877 A CN200680019877 A CN 200680019877A CN 101238198 A CN101238198 A CN 101238198A
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229910003455 mixed metal oxide Inorganic materials 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000000499 gel Substances 0.000 claims description 40
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000011109 contamination Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000007599 discharging Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 239000000945 filler Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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Abstract
混合的金属氧化物组合物包括(i)占总含量90－99.9wt％的至少两种形成凝胶的金属，所述金属选自Ti、Zr、Ce、La、Al、Cr、P和Fe；和(ii)含量为0.1－10wt％的金属掺杂物，所述金属参杂物选自W、Pt、Pd、Rh、V、Mo、Co、Ni、Mn以及它们的混合物，所有重量百分比均以氧化物计算并基于组合物的总重量，所述的组合物通过以下步骤获得(a)向包括所述形成凝胶的金属的水溶性三价或四价盐的水溶液中加入碱，由此形成凝胶；(b)将金属掺杂物加入所述凝胶中，获得掺杂的凝胶，和(c)任意地煅烧所述掺杂的凝胶。该组合物适合于在FCC工艺中用作添加剂或者催化剂组分。
Description
本发明涉及一种掺杂金属的混合金属氧化物组合物及其在催化工艺，例如流化催化裂化(FCC)中的应用。
EP-A 0554968(W.R.Grace和Co.)涉及一种包括含有30-50wt％的MgO、30-50wt％的Al2O3和5-30wt％的La2O3的共沉淀三元氧化物的组合物。该组合物在流化催化裂化工艺中用于钝化金属和控制FCC装置再生器的SOx排放。
US6,028,023公开了一种由MgO和Al2O3制备水滑石类化合物的方法。这些化合物通过下述步骤制备：(a)制备包括含镁化合物和含铝化合物的反应混合物，由此形成水滑石类化合物或非水滑石类化合物，随后进行煅烧和再水合。将获得的化合物用于FCC工艺中降低SOx的排放。
上述组合物的缺点在于：当它们与含沸石的FCC催化剂结合时，它们对沸石的水热稳定性具有负面的影响。
本发明的目的是提供一种组合物，该组合物适用于FCC工艺中降低再生器的SOx排放并生产贫硫燃料，同时所述组合物对沸石的水热稳定性具有最小的影响。
本发明涉及一种混合的金属氧化物组合物，包括(i)占总含量90-99.9wt％的至少两种形成凝胶的金属，所述金属选自Ti、Zr、Ce、La、Al、Cr、P和Fe，和(ii)含量为0.1-10wt％的金属掺杂物，所述金属掺杂物选自W、Pt、Pd、Rh、V、Mo、Co、Ni、Mn以及它们的混合物，所有重量百分比均以氧化物计并基于组合物的总重量，所述的组合物通过以下步骤获得：
(a)向包括所述形成凝胶的金属的水溶性三价或四价盐的水溶液中加入碱，由此形成凝胶；
(b)将金属掺杂物加入所述凝胶中，获得掺杂的凝胶；以及
(c)任选地煅烧该掺杂的凝胶。
步骤(a)
本发明的混合金属氧化物组合物通过以下方法获得，该方法包括第一步骤：向三价或四价水溶性盐形式的至少两种形成凝胶的金属的水溶液中添加碱。适当的碱包括氢氧化钠、氢氧化铵和氢氧化钾。氢氧化铵是优选的碱，因为它在产物中不会留下碱金属。所获得的凝胶含有至少两种形成凝胶的金属。
所述至少两种形成凝胶的金属选自Ti、Zr、Ce、La、Al、Cr、P和Fe。存在于水溶液的这些金属的合适盐是Ti(IV)、Zr(IV)、Ce(IV)、La(III)、Al(III)、Cr(III)、Fe(III)和含磷的盐。这种盐的例子是这些金属的硝酸盐和氯化物盐，W、Mo和V的铵盐以及金属的硫酸盐，例如硫酸氧锆。
步骤b)
在配制凝胶期间或之后，将金属掺杂物加入步骤a)所形成的凝胶中。金属掺杂物选自W、Pt、Pd、Rh、V、Mo、Co、Ni、Mn以及它们的混合物。掺杂物优选以水溶性盐的形式加入凝胶中。
可以任选地将凝胶老化、干燥和/或成型以形成颗粒，可以在任选的成型步骤期间或在任选的老化、干燥和/或成型步骤之后将金属掺杂物加入。
如果在形成凝胶之后但是在任选的干燥步骤之前加入掺杂物，则优选在凝胶的高速剪切混合期间加入，以改善掺杂物在凝胶中的分散性。如果在干燥或者成型步骤之后加入掺杂物，则优选通过用含有掺杂物的溶液浸渍干燥和/或成型的凝胶的形式将其加入。
适当的老化条件包括温度为20-300℃，优选为50-160℃；以及自生压力。优选进行老化0.5-6小时，更优选0.5-24小时，最优选1-6小时。
适当的干燥方法包括喷雾干燥、快速干燥、快速煅烧和空气干燥。
适当的成型方法包括喷雾干燥(成型与干燥相结合的方法)、挤出、球化和制粒。
步骤c)
掺杂的凝胶可以或不进行老化、干燥和/或成型，可以在200-1000℃，更优选400-800℃，最优选350-600℃范围内的温度下煅烧。优选实施煅烧0.5-6小时，优选1-4小时。所有商业型煅烧炉都可以使用，例如固定床或旋转式煅烧炉。可以在各种气氛下实施煅烧，所述气氛例如空气、氧气、惰性气体(例如N2)、蒸汽或它们的混合物。
本发明的混合金属氧化物包括至少两种形成凝胶的金属，以氧化物计算并基于干燥固体物的重量，其总含量为90-99.9wt％，优选95-99wt％。所述形成凝胶的金属优选在组合物中以大约等摩尔的量存在。以氧化物计算并基于干燥固体物的重量，该组合物中所存在的掺杂物的量为0.1-10wt％，优选1-5wt wt％。
作为制备方法的结果，本发明的组合物含有形成凝胶的金属和高度分散的金属掺杂物，这意味着组合物中的金属氧化物比以离散的金属氧化物颗粒形式的组合更加密切地混合。
氧化的组合物的应用
本发明的混合金属氧化物可以适用于或作为以下方法的催化剂或催化剂添加剂或吸附剂，所述方法包括烃转化、净化或合成方法，特别是石油炼制工业和费-托方法。适合使用这些组合物的方法的例子是催化裂化、加氢、脱氢、加氢裂化、加氢处理(加氢脱氮、加氢脱硫、加氢脱金属)、聚合反应、水汽重整、碱催化的反应、气-液转化(例如费-托转化)、以及减少来自FCC装置的再生器的SOx和NOx排放。本发明的混合金属氧化物还可以用于生物转化方法。
特别地，该组合物非常适用于减少SOx排放以及生产低S和N含量的燃料(如汽油和柴油)的FCC工艺。
可以以所述方式将本发明的混合金属氧化物加入FCC装置中，或者它可以引入FCC催化剂中，从而获得如下组合物，该组合物除了本发明的混合金属氧化物组合物之外，还包括传统的FCC催化剂组分，例如基质或填料(例如，粘土如高岭土、氧化钛、氧化锆、氧化铝、氧化硅、氧化硅-氧化铝、斑脱土等)和分子筛材料(例如，沸石Y、USY、REY、RE-USY、沸石-β、ZSM-5等)。因此，本发明还涉及含有本发明的混合金属氧化物组合物、基质或填料、以及分子筛的催化剂颗粒。
实施例
实施例1
通过将氢氧化铵加入含有等摩尔量的硝酸铈和硫酸氧锆的水溶液中形成沉淀。形成凝胶。将凝胶分成两部分：将第一部分在65℃下老化8小时，另一部分在室温下陈化2小时。
在高速剪切混合条件下，将5wt％偏钨酸铵(以氧化物计并基于全部固体含量)加入两种凝胶部分。将凝胶部分稀释至固体含量为30wt％，然后喷雾干燥以形成微球粒。
将获得的物质与常规FCC催化剂混合并在MAT装置中试验。结果显示，与使用FCC催化剂本身相比，SOx排放和汽油中的硫含量降低。
实施例2
重复实施例1，除了用8wt％的偏钒酸铵替代5wt％的偏钨酸铵。
实施例3
重复实施例1，除了用10wt％的氯化铑替代5wt％的偏钨酸盐。
实施例4
通过将氢氧化钠加入含有等摩尔量的硝酸铈和氯化钛的水合溶液中形成沉淀。形成凝胶。将凝胶在65℃下老化2小时。
在高剪切混合条件下，将2wt％偏钨酸铵(以金属氧化物计并基于全部固体含量)加入凝胶。将凝胶部分稀释至固体含量为30wt％，然后喷雾干燥以形成微球粒。在500℃下煅烧微球粒2小时。
将获得的微球粒与常规的FCC催化剂混合并在MAT装置中试验。结果显示，与使用FCC催化剂本身相比，SOx排放和汽油中的硫含量降低。
实施例5
重复实施例4，除了使用硝酸铁(III)替代氯化钛，偏钨酸铵的加入量为4wt％。
实施例6
重复实施例5，除了由等摩尔量的硝酸铈、硫酸氧锆、和铁(III)硝酸盐形成沉淀。
实施例7
通过将氢氧化钠加入含有等摩尔量的硝酸铈和氯化钛的水溶液中形成沉淀。形成凝胶。将凝胶部分稀释至固体含量为30wt％，然后喷雾干燥以形成微球粒。
然后用氢氯铂酸(2wt％Pt)溶液浸渍微球粒，随后快速干燥并在500℃下煅烧2小时。将获得的组合物与常规FCC催化剂混合并在MAT装置中试验。结果显示，与使用FCC催化剂本身相比，汽油中的S含量降低。
Claims (6)
1.混合金属氧化物组合物，其包括(i)占总含量90-99.9wt％的至少两种形成凝胶的金属，所述金属选自Ti、Zr、Ce、La、Al、Cr、P和Fe；和(ii)含量为0.1-10wt％的金属掺杂物，所述金属掺杂物选自W、Pt、Pd、Rh、V、Mo、Co、Ni、Mn以及它们的混合物，所有重量百分比均以氧化物计算并基于组合物的总重量，所述的组合物通过以下步骤获得：
(a)向包括所述形成凝胶的金属的水溶性三价或四价盐的水溶液中加入碱，由此形成凝胶；
(b)将金属掺杂物加入所述凝胶中，获得掺杂的凝胶；和
(c)任选地煅烧该掺杂的凝胶。
2.根据权利要求1所述的混合金属氧化物组合物，其中，以氧化物计算并基于组合物的总重量，所述至少两种形成凝胶的金属的含量为95-99wt％。
3.根据权利要求1或2所述的混合金属氧化物组合物，其中，以氧化物计算并基于组合物的总重量，所述金属掺杂物的含量为1-5wt％。
4.根据前述权利要求中任一项所述的混合金属氧化物组合物，其中，在高速剪切混合条件下，将金属掺杂物加入凝胶中。
5.催化剂颗粒，其包括前述权利要求中任一项所述的混合金属氧化物组合物、基质或填充材料和分子筛。
6.权利要求1-4中任一项所述的混合金属氧化物或权利要求5所述的催化剂颗粒在流化催化裂化工艺中的应用。
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| US20030186805A1 (en) * | 2002-03-28 | 2003-10-02 | Vanderspurt Thomas Henry | Ceria-based mixed-metal oxide structure, including method of making and use |
| DE10329626A1 (de) * | 2003-06-25 | 2005-01-20 | Itn Nanovation Gmbh | Mischmetalloxide und ihre Verwendung in CO2-Sensoren |
| EP1706202A2 (en) * | 2003-12-09 | 2006-10-04 | Albemarle Netherlands B.V. | Process for the preparation of an oxidic catalyst composition comprising a divalent and a trivalent metal |
-
2006
- 2006-06-02 EP EP06777269A patent/EP1904607A1/en not_active Ceased
- 2006-06-02 WO PCT/EP2006/062898 patent/WO2006131507A1/en active Application Filing
- 2006-06-02 CN CNA2006800198779A patent/CN101238198A/zh active Pending
- 2006-06-02 US US11/915,708 patent/US20090269266A1/en not_active Abandoned
- 2006-06-02 JP JP2008514124A patent/JP2008545610A/ja active Pending
- 2006-06-02 CA CA002610183A patent/CA2610183A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153456A (zh) * | 2010-10-11 | 2013-06-12 | 埃克森美孚化学专利公司 | 用于制备苯酚的方法 |
| CN104549342A (zh) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | 合成气制低碳烯烃铁催化剂及其制备方法 |
| CN106190232A (zh) * | 2016-07-02 | 2016-12-07 | 成都育芽科技有限公司 | 一种石油加氢精制生产丙烯裂解原料的方法 |
| CN106190232B (zh) * | 2016-07-02 | 2018-05-08 | 东营联合石化有限责任公司 | 一种石油加氢精制生产丙烯裂解原料的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2610183A1 (en) | 2006-12-14 |
| JP2008545610A (ja) | 2008-12-18 |
| EP1904607A1 (en) | 2008-04-02 |
| WO2006131507A1 (en) | 2006-12-14 |
| US20090269266A1 (en) | 2009-10-29 |
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