CN106458768A - 金属氧化物稳定的氧化锆陶瓷材料 - Google Patents
金属氧化物稳定的氧化锆陶瓷材料 Download PDFInfo
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- CN106458768A CN106458768A CN201580023264.1A CN201580023264A CN106458768A CN 106458768 A CN106458768 A CN 106458768A CN 201580023264 A CN201580023264 A CN 201580023264A CN 106458768 A CN106458768 A CN 106458768A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 108
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims description 82
- 239000002184 metal Substances 0.000 title claims description 81
- 239000011224 oxide ceramic Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 66
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 53
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 46
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 19
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 70
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 42
- 239000012702 metal oxide precursor Substances 0.000 claims description 39
- 229910052726 zirconium Inorganic materials 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 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 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229960004643 cupric oxide Drugs 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
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- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 5
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- 229910052787 antimony Inorganic materials 0.000 claims description 4
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
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- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010937 tungsten Substances 0.000 claims description 3
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001399 aluminium compounds Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 42
- 150000005846 sugar alcohols Chemical class 0.000 abstract description 14
- 150000007524 organic acids Chemical class 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 235000000346 sugar Nutrition 0.000 abstract description 10
- 235000005985 organic acids Nutrition 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 150000008163 sugars Chemical class 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 121
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 239000012071 phase Substances 0.000 description 42
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- 238000002441 X-ray diffraction Methods 0.000 description 34
- 238000001228 spectrum Methods 0.000 description 23
- 238000001354 calcination Methods 0.000 description 22
- 238000006555 catalytic reaction Methods 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
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- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 10
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Classifications
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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
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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Abstract
本公开内容大体上涉及适合于用作催化剂支撑体材料的陶瓷材料、使用这类材料的催化剂以及用于使用它们的方法,例如用于将糖、糖醇、甘油和生物可再生的有机酸转化成有商业价值的化学品和中间体的方法。本发明的一个方面是包含氧化锆和一种或更多种金属氧化物的陶瓷材料,该一种或更多种金属氧化物选自氧化镍、氧化铜、氧化钴、氧化铁和氧化锌,陶瓷材料是至少约50wt.%氧化锆。在某些实施方案中,陶瓷材料大体上无任何粘合剂或另外的稳定剂。
Description
发明背景
发明领域
本公开内容大体涉及陶瓷材料、催化剂和用于使用它们的方法,例如用于将糖、糖醇和甘油转化成有商业价值的化学品和中间体的方法。
技术背景
氧化锆由于其高的物理和化学稳定性以及适度酸性的表面性质而已经在化学催化领域中被用作支撑体材料。尽管如此,氧化锆作为用于非均相催化剂的支撑体材料的用途具有有限的应用,这归因于它相对高的成本和在形成某些形状时的困难。此外,氧化锆尤其易受经历导致表面积和孔体积的损失的相变的影响。这减少了氧化锆的强度和耐久性。为了抵消这些相转变影响,稳定剂用于抑制从优选的正方晶相至较不合意的单斜相的相转变。之前使用的稳定剂包括,例如,氧化硅、氧化钇、氧化镧、氧化钨、氧化镁、氧化钙、氧化铈、氧化铬和氧化锰。
物理和化学稳定性是水相反应中的非均相催化剂的应用中的主要顾虑。传统的基于SiO2或Al2O3的催化剂支撑体当用于水溶液中时倾向于崩解或侵蚀,这通常导致被定位用于长期工业应用的催化剂主体的机械强度的损失。在实验室和工业应用中,非均相催化剂的机械强度通常通过压碎强度来评估,其中增加的压碎强度值一般指示支撑体或载体的改进的机械强度。用氧化铬促进剂材料促进的氧化锆的使用产生了用于挤出和/或用作用于在水性环境中进行的工业应用中的催化剂的载体或支撑体的、具有改善的物理性质的基于氧化锆的支撑体或催化剂。氧化铬促进的氧化锆支撑体或催化材料通常展示没有至水溶液中的浸出,这改进了在各种水相应用中的支撑体/载体或催化剂的机械强度和稳定性。
然而,含铬材料、尤其是含铬(VI)材料的使用由于它们的毒性、腐蚀性和致癌性质而是较不合意的。含锰材料对含铬材料是可行的替换物,但其作为催化材料的用途可能常常被限制于其中产物pH高于6的水相反应。仍存在对于在范围广泛的pH值下的水相应用也是稳定的环境上无毒害的材料的需求。
发明概述
在某些方面中,本发明解决了对适合于水相应用的无铬催化剂或催化剂支撑体的需求。在各个方面,本公开内容提供了氧化锆-金属氧化物材料,其是水热稳定的,适合于在水相还原反应中使用,对低pH稳定,并且可以容易地形成。材料中的金属氧化物在某些方面中可以用作在水相中稳定氧化锆的织构促进剂(textural promoter),以及用作改进催化性能的促进剂,并且甚至自身用作催化活性组分。在某些方面中,材料尤其可用于水相氢化和氢解工艺。
在一个方面中,本公开内容提供了包含氧化锆和金属氧化物的陶瓷材料,其中氧化锆在材料的约50wt.%至约99wt.%的范围内存在;金属氧化物是氧化镍、氧化铜、氧化钴、氧化铁和氧化锌中的一种或更多种;并且金属氧化物在材料的约1wt.%至约50wt.%的范围内存在。催化材料还可以大体上无任何粘合剂、挤出助剂或另外的稳定剂。
在另一方面中,本公开内容提供催化剂,其包含与催化活性材料组合的如本文描述的陶瓷材料(例如,作为催化剂支撑体材料)。在某些实施方案中,催化活性材料可以是催化金属,例如,Ni、Cu、Co、Fe、Ru、Rh、Pd、Ag、Re、Os、Ir、Pt、Au、Sb、La、Bi或其任何组合,例如NiCu、NiBi或NiSb。
在另一方面中,本公开内容提供利用如本文描述的陶瓷材料和催化剂的方法。如下文将描述的,在某些实施方案中,如本文描述的陶瓷材料是足够稳定的以被用于连续水相反应方案中,例如连续搅拌器罐式反应器或固定床反应器中的那些。因此,在一个实施方案中,用于进行催化反应的方法包括使一种或更多种反应物与如本文描述的陶瓷材料或催化剂接触,其中反应物中的至少一种是在水相中。在某些实施方案中,反应在50℃至325℃的范围内的温度下且在约10巴至约250巴的范围内的压力下进行。
特别地,本公开内容提供用于还原反应的方法,所述还原反应例如糖、糖醇和甘油的氢化或氢解。这些还原反应包括使糖、糖醇或甘油与氢气和如本文描述的陶瓷材料或催化剂接触。例如,某些此类方法包括用于通过使糖、糖醇或甘油与氢气和如本文描述的陶瓷材料或催化剂接触而将糖、糖醇或甘油转化成包含较短碳链骨架的多元醇或醇的工艺。
本公开内容还提供使用上述陶瓷材料或催化剂用于有机酸例如在水相中的氢化的方法。例如,某些此类方法包括用于还原有机酸(例如,乳酸、琥珀酸、己二酸、3-羟基丙酸、和/或糖酸)的工艺,该工艺是通过使有机酸与氢气和如本文描述的陶瓷材料或催化剂接触。
在另一方面中,本公开内容还提供用于制备如本文描述的陶瓷材料和催化剂的方法。例如,在一个实施方案中,陶瓷材料通过在不存在任何粘合剂、挤出助剂或另外的稳定剂下挤出氧化锆-金属氧化物前体来制造。在一个实施方案中,陶瓷材料通过在不存在任何粘合剂、挤出助剂或另外的稳定剂下挤出催化活性材料-氧化锆-金属氧化物前体来制造。在另一个实施方案中,催化剂通过将一种或更多种催化活性材料沉积到氧化锆-金属氧化物支撑体材料上来制造。沉积可以包括但不限于浸渍、初湿含浸法(incipient wetnessmethod)、沉淀和物理混合。
本发明的特定实施方案依据以下的某些实施方案的详细描述、实施例和权利要求将变得明显。
附图中若干视图的简述
图1提供包含6.6wt.%、15wt.%和18wt.%镍(作为金属Ni计算的wt.%)的氧化镍稳定的氧化锆陶瓷材料的XRD图谱。XRD在于450℃下煅烧持续3h之后进行。XRD图谱示出,氧化锆的晶体含量主要呈正方晶相。对应于NiO的峰用星号标记。
图2提供包含16wt.%、23wt.%、28wt.%和32wt.%铜(作为金属Cu计算的wt.%)的氧化铜稳定的氧化锆材料的XRD图谱。XRD在于450℃下煅烧持续3h之后进行。XRD图谱示出,氧化锆的晶体含量主要呈无定形相。对应于CuO的峰用星号标记。
图3提供包含6.5wt.%和7.5wt.%铜(作为金属Cu计算的wt.%)的氧化铜稳定的氧化锆材料的XRD图谱。XRD在于550℃下煅烧持续3h之后进行。XRD图谱示出,氧化锆的晶体含量主要呈稳定的正方晶相。没有观察到CuO。
图4提供包含9.9wt.%钴(作为金属Co计算的wt.%)的氧化钴稳定的氧化锆材料的XRD图谱。XRD在于450℃和600℃下煅烧持续3h之后进行。XRD图谱示出,氧化锆的晶体含量主要呈完全稳定的正方晶相。对应于Co3O4的峰用星号标记。
图5提供包含9.9wt.%铁(作为金属Fe计算的wt.%)的氧化铁稳定的氧化锆材料的XRD图谱。XRD在于600℃下煅烧持续3h之后进行。XRD图谱示出,氧化锆的晶体含量主要呈完全稳定的正方晶相。
图6提供包含6wt.%和11wt.%锌(作为金属Zn计算的wt.%)的氧化锌稳定的氧化锆材料的XRD图谱。XRD在于450℃和550℃下煅烧持续3h之后进行。所有材料示出作为氧化锆的晶体含量的完全稳定的正方晶相。没有观察到氧化锌。
图7提供包含10wt.%镍和10wt.%镧(分别作为金属Ni和La计算的wt.%)的三元相氧化锆材料的XRD图谱。XRD在于600℃下煅烧持续3h之后进行。XRD图谱示出,氧化锆的晶体含量主要呈完全稳定的正方晶相。
图8提供常规的氧化锆材料的XRD图谱。XRD在于450℃和550℃下煅烧持续3h之后进行。XRD图谱示出,氧化锆当在450℃下煅烧时主要呈正方晶相并且当在550℃下煅烧时主要呈单斜混合物。
发明详述
在描述所公开的方法和材料之前,应理解,本文描述的方面不限于特定的实施方案、装置、或构造,并且因此当然可以改变。还应理解的是,本文使用的术语仅用于描述特定的方面的目的,并且除非本文中具体地限定,否则不意图是限制性的。
贯穿本说明书,除非上下文另有要求,否则词语“包含(comprise)”和“包括(include)”以及变型(例如,“包含(comprises)”、“包含(comprising)”、“包括(includes)”、“包括(including)”)将被理解为暗示包含所声明的组分、特征、元件或步骤或组分、特征、元件或步骤的组,但是不排除任何其他的整数或步骤或整数或步骤的组。
如本说明书和所附权利要求中所使用的,除非上下文中另有清楚地指定,否则单数形式“一(a)”、“一(an)”和“该(the)”包括复数指示物。范围在本文中可以表示为从“约”一个特定值和/或至“约”另一个特定值。当此种范围被表示时,另一方面包括从该一个特定值和/或至该另一个特定值。类似地,当值通过使用先行词“约”表示为近似值时,将理解的是,该特定值形成另一方面。将进一步理解,每个范围的端点相对于该另一个端点以及独立于该另一个端点都是有效的(significant)。
如本文中使用的术语“接触”包括至少一种物质与另一种物质的物理接触。
本文中的所有百分数、比率和比例都按重量计,除非另有指定。除非有相反地具体陈述,否则组分的重量百分数(重量%,也作为wt%)是基于其中包含该组分的制剂或组合物的总重量(例如,基于活性材料的总量)。所有摩尔%值是基于金属原子的摩尔数。
考虑到本公开内容,本文描述的方法和材料可以由本领域普通技术人员来配置,以满足期望的需求。通常,公开的材料、方法和装置提供用于催化、特别是水相氢解和氢化中的催化的支撑体或载体的改进。例如,在某些方面中,该材料相比基于Cr的材料是对环境较少危害的、是水热稳定的、适合于在连续水相氢解和氢化中使用,并且可以在不存在任何粘合剂和/或挤出助剂下容易地挤出。
本发明的一个实施方案是包含氧化锆(例如ZrO2)和一种或更多种金属氧化物的陶瓷材料。氧化锆以在约50wt.%至约99wt.%的范围内的量存在于陶瓷材料中。陶瓷材料中的金属氧化物以在约1wt.%至约50wt.%的范围内的量存在。金属氧化物是氧化镍(作为金属Ni计算的wt.%)、氧化铜(作为金属Cu计算的wt.%)、氧化钴(作为金属Co计算的wt.%)、氧化铁(作为金属Fe计算的wt.%)和氧化锌(作为金属Zn计算的wt.%))中的一种或更多种。如本领域普通技术人员将理解,氧化锆和金属氧化物合意地大体上一起存在于材料的相同相中(例如,作为混合氧化物MZrOx)。例如,在某些实施方案中,金属氧化物的至少50%、至少70%或甚至至少90%一起与氧化锆存在于材料的相同的相中。
如下文将更详细描述的,本文描述的陶瓷材料可以在催化的领域中是有用的。例如,本文描述的陶瓷材料可以用作催化剂支撑体材料,金属或金属化合物可以布置在该催化剂支撑体材料上。在其它实施方案中,本文描述的陶瓷材料自身可以以其氧化物形式或在通过将金属氧化物的一部分还原成对应金属而活化后被用作催化剂。
在某些实施方案中,金属氧化物以在以下范围内的量(即,基于金属计算)存在:从约1wt.%至约20wt.%、或约1wt.%至约15wt.%、或约1wt.%至约10wt.%、或约1wt.%至约8wt.%、或约1wt.%至约7wt.%、或约3wt.%至约15wt.%、或约3wt.%至约10wt.%、或约3wt.%至约7wt.%、或约5wt.%至约7wt.%、或约5wt.%至约8wt.%、或约5wt.%至约10wt.%、或从约3wt.%至约50wt.%、或从约10wt.%至约50wt.%、或从约15wt.%至约50wt.%、或从约3wt.%至约20wt.%、或从约10wt.%至约20wt.%、或从约15wt.%至约25wt.%。
在某些实施方案中,氧化锆以基于氧化锆的在以下范围内的量存在:从约80wt.%至约99wt.%、从约85wt.%至约99wt.%、从约90wt.%至约99wt.%、从约92wt.%至约99wt.%、从约93wt.%至约99wt.%、从约85wt.%至约97wt.%、从约90wt.%至约97wt.%、从约93wt.%至约97wt.%、从约93wt.%至约95wt.%、从约92wt.%至约95wt.%、从约90wt.%至约95wt.%、从约50wt.%至约97wt.%、从约50wt.%至约90wt.%、从约50wt.%至约85wt.%、从约80wt.%至约97wt.%、从约80wt.%至约90wt.%、或从约75wt.%至约85wt.%。
如上文描述的,金属氧化物可以包括铁、钴、镍、铜或锌的氧化物。如本领域普通技术人员将理解,金属的氧化态可以是可变的,并且金属可以以多种氧化态中的一种或更多种存在于材料内。在某些实施方案中,金属氧化物是氧化铁。氧化铁可以作为铁(II)、铁(III)或其混合物存在。例如,在一个实施方案中,氧化铁作为铁(II)氧化物存在。在另一个实施方案中,氧化铁作为铁(III)氧化物存在。在其它实施方案中,氧化铁作为混合的铁(II,III)氧化物存在。
在某些实施方案中(例如,当金属氧化物是氧化铁时),氧化铁以基于金属Fe的在以下范围内的量存在:从约1wt.%至约30wt.%、约1wt.%至约20wt.%、或约1wt.%至约15wt.%、或约1wt.%至约12wt.%、或约1wt.%至约10wt.%、或约1wt.%至约8wt.%、或约1wt.%至约7wt.%、或约1wt.%至约3wt.%、或约3wt.%至约15wt.%、或约3wt.%至约10wt.%、或约3wt.%至约7wt.%、或约5wt.%至约7wt.%、或约5wt.%至约8wt.%、或约5wt.%至约10wt.%。在某些实施方案中,氧化铁以在陶瓷材料的从约5wt.%至约30wt.%的范围内的量存在。
在某些实施方案中,金属氧化物是氧化钴。氧化钴可以作为钴(II)、钴(III)或其混合物存在。例如,在一个实施方案中,氧化钴作为钴(II)氧化物存在。在另一个实施方案中,氧化钴作为钴(III)氧化物存在。在其它实施方案中,氧化钴作为混合的钴(II,III)氧化物存在。
在某些实施方案中(例如,当金属氧化物是氧化钴时),氧化钴以基于金属Co的在以下范围内的量存在:从约1wt.%至约25wt.%、或约1wt.%至约15wt.%、或约1wt.%至约12wt.%、或约1wt.%至约10wt.%、或约1wt.%至约8wt.%、或约1wt.%至约7wt.%、或约1wt.%至约3wt.%、或约3wt.%至约15wt.%、或约3wt.%至约10wt.%、或约3wt.%至约7wt.%、或约5wt.%至约7wt.%、或约5wt.%至约8wt.%、或约5wt.%至约10wt.%。在某些实施方案中,氧化钴以在催化材料的从约5wt.%至约25wt.%的范围内的量存在。
在某些实施方案中,金属氧化物是氧化镍。例如,在一个实施方案中,氧化镍作为镍(II)氧化物存在。
在某些实施方案中(例如,当金属氧化物是氧化镍时),氧化镍以基于金属Ni的在以下范围内的量存在:从约1wt.%至约40wt.%、或约1wt.%至约30wt.%、或约1wt.%至约20wt.%、或约1wt.%至约15wt.%、或约1wt.%至约12wt.%、或约1wt.%至约10wt.%、或约1wt.%至约8wt.%、或约1wt.%至约7wt.%、或约1wt.%至约3wt.%、或约3wt.%至约15wt.%、或约3wt.%至约10wt.%、或约3wt.%至约7wt.%、或约5wt.%至约7wt.%、或约5wt.%至约8wt.%、或约5wt.%至约10wt.%、或约5wt.%至约20wt.%、或约5wt.%至约30wt.%。在某些实施方案中,氧化镍以在催化材料的从约5wt.%至约20wt.%的范围内的量存在。
在某些实施方案中,金属氧化物是氧化铜。氧化铜可以作为铜(I)、铜(II)或其混合物存在。例如,在一个实施方案中,氧化铜作为铜(I)氧化物存在。在另一个实施方案中,氧化铜作为铜(II)氧化物存在。在其它实施方案中,氧化铜作为混合的铜(I,II)氧化物存在。
在某些实施方案中(例如,当金属氧化物是氧化铜时),氧化铜以基于金属Cu的在以下范围内的量存在:从约1wt.%至约40wt.%、或约1wt.%至约35wt.%、或约1wt.%至约30wt.%、或约1wt.%至约25wt.%、或约1wt.%至约20wt.%、或约1wt.%至约15wt.%、或约1wt.%至约10wt.%、或约1wt.%至约8wt.%、或约1wt.%至约7wt.%、或约1wt.%至约3wt.%、或约3wt.%至约15wt.%、或约3wt.%至约10wt.%、或约3wt.%至约7wt.%、或约5wt.%至约7wt.%、或约5wt.%至约8wt.%、或约5wt.%至约10wt.%、或约15wt.%至约35wt.%、或约20wt.%至约35wt.%、或约25wt.%至约35wt.%、或约10wt.%至约35wt.%、或约10wt.%至约25wt.%。在某些实施方案中,氧化铜以在催化材料的从约5wt.%至约35wt.%的范围内的量存在。
在某些实施方案中,金属氧化物是氧化锌。例如,在一个实施方案中,氧化锌作为锌(II)氧化物存在。
在某些实施方案中(例如,当金属氧化物是氧化锌时),氧化锌以基于金属Zn的在以下范围内的量存在:从约1wt.%至约25wt.%、或约1wt.%至约20wt.%、或约1wt.%至约15wt.%、或约1wt.%至约12wt.%、或约1wt.%至约10wt.%、或约1wt.%至约8wt.%、或约1wt.%至约7wt.%、或约1wt.%至约3wt.%、或约3wt.%至约15wt.%、或约3wt.%至约10wt.%、或约3wt.%至约7wt.%、或约5wt.%至约7wt.%、或约5wt.%至约8wt.%、或约5wt.%至约10wt.%。在某些实施方案中,氧化锌以在催化材料的从约5wt.%至约25wt.%的范围内的量存在。
不意图被理论所约束,本发明人相信,金属氧化物用于稳定氧化锆免于经历从优选的正方晶相或无定形相至较不合意的单斜相的不合意的相变。因此,氧化锆与金属氧化物的比率对于陶瓷材料的性能可以是重要的。
在如本文描述的催化材料和方法的某些实施方案中,陶瓷材料的至少约70wt.%是氧化锆和一种或更多种金属氧化物。例如,在如本文描述的材料和方法的某些实施方案中,陶瓷材料的至少约80wt.%、至少约90wt.%、至少约95wt.%、至少约99wt.%、至少约99.5wt.%、或甚至至少约99.9wt.%是氧化锆和一种或更多种金属氧化物。
本文描述的陶瓷材料可以在没有铬下制造,但仍提供稳定在正方晶相或无定形相的氧化锆,从而提供更加环境友好的材料。因此,在如本文描述的材料和方法的某些实施方案中,材料大体上无铬。
在如本文描述的材料和方法的某些实施方案中,材料大体上无锰及其氧化物。
在本文描述的陶瓷材料的某些实施方案中,可以包含其它的金属氧化物(即,不同于镍、铜、钴、铁和锌的氧化物)。另外的不可还原的金属氧化物可以包括,例如,钇、镧、铈、铌、钨、钼、钛、钙、镁、硼、锡、锑的氧化物及其混合物。如本领域普通技术人员将理解,这类其它的金属氧化物可以用于向陶瓷材料提供另外的合意的性质,例如,调谐催化材料的酸度/碱度,或改进本文使用的金属氧化物的分散,或改进可还原性,改进织构性质。其它可还原的金属氧化物还可以用作用于催化金属的前体,在下文更加详细地描述。适合于用作催化金属前体的可还原金属氧化物包括,例如钯、铂、铱、铼、银和钌。在其中陶瓷材料包含一种或更多种另外的金属氧化物的实施方案中,另外的金属氧化物可以以基于金属的至多约15wt.%、例如至多约12wt.%、至多约10wt.%、至多约8wt.%、至多约7wt.%、至多约3wt.%、至多约1wt.%、或至多约0.05wt.%的量存在。在某些实施方案中,另外的金属以在以下范围内的量存在:从约0.05wt.%至约12wt.%、或约0.05wt.%至约10wt.%、或约0.05wt.%至约8wt.%、或约0.05wt.%至约7wt.%、或约3wt.%至约15wt.%、或约3wt.%至约10wt.%、或约3wt.%至约7wt.%、或约5wt.%至约7wt.%、或约5wt.%至约8wt.%、或约5wt.%至约10wt.%、或约10wt.%至约15wt.%。
在如本文描述的催化材料和方法的某些实施方案中,陶瓷材料的至少约70wt.%是氧化锆和一种或更多种金属氧化物(即,包括上述一种或更多种另外的金属氧化物)。例如,在如本文描述的材料和方法的某些实施方案中,陶瓷材料的至少约80wt.%、至少约90wt.%、至少约95wt.%、至少约99wt.%、至少约99.5wt.%、或甚至至少约99.9wt.%是氧化锆和一种或更多种金属氧化物(即,包括一种或更多种上述另外的金属氧化物)。
在某些实施方案中,如本文描述的陶瓷材料包含以下(或在一个实施方案中,基本上由以下组成):以在约50wt.%至约99wt.%的范围内的量(基于ZrO2计算)的氧化锆;以基于金属的在约1wt.%至约50wt.%的范围内的量的氧化镍、氧化铜、氧化钴、氧化铁和氧化锌中的一种或更多种;以及任选的以至多约15wt.%的量的一种或更多种另外的金属氧化物。例如,在特定的实施方案中,如本文描述的陶瓷材料包含以下(或在一个实施方案中,基本上由以下组成):以在约70wt.%至约99wt.%的范围内的量的氧化锆;以基于金属的在约1wt.%至约30wt.%的范围内的量的氧化镍、氧化铜、氧化钴、氧化铁和氧化锌中的一种或更多种;以及任选的以基于金属的至多约15wt.%的量的一种或更多种另外的金属氧化物。在另一个特定的实施方案中,如本文描述的陶瓷材料包含以下(或在一个实施方案中,基本上由以下组成):以基于氧化锆的在约75wt.%至约99wt.%的范围内的量的氧化锆;以基于金属的在约1wt.%至约25wt.%的范围内的量的氧化镍、氧化铜、氧化钴、氧化铁和氧化锌中的一种或更多种;以及任选的以基于金属的至多约15wt.%的量的一种或更多种另外的金属氧化物。例如,在特定的实施方案中,如本文描述的陶瓷材料包含以下(或在一个实施方案中,基本上由以下组成):以基于氧化锆的在约80wt.%至约99wt.%的范围内的量的氧化锆;以基于金属的在约1wt.%至约20wt.%的范围内的量的氧化镍、氧化铜、氧化钴、氧化铁和氧化锌中的一种或更多种;以及任选的以基于金属的至多约15wt.%的量的一种或更多种另外的金属氧化物。在另一个特定的实施方案中,如本文描述的陶瓷材料包含以下(或在一个实施方案中,基本上由以下组成):以基于氧化锆的在约85wt.%至约99wt.%的范围内的量的氧化锆;以基于金属的在约1wt.%至约12wt.%的范围内的量的氧化镍、氧化铜、氧化钴、氧化铁和氧化锌中的一种或更多种;以及任选的以基于金属的至多约10wt.%的量的一种或更多种另外的金属氧化物。在某些这类实施方案中,陶瓷材料包含以下(或在一个实施方案中,基本上由以下组成):以基于氧化锆的在约90wt.%至约99wt.%的范围内的量的氧化锆;以基于金属的在约1wt.%至约8wt.%的范围内的量的金属氧化物;任选的以基于金属的至多约5wt.%的量的一种或更多种另外的金属氧化物。
如将在下文更详细地描述的,陶瓷材料可以经由本领域普通技术人员熟悉的许多不同技术来制造。陶瓷材料可以以多种晶形制造,例如如通过众所周知的粉末X射线衍射(XRD)技术和设备确定的单斜相、正方晶相、立方相和/或无定形相中的一种或更多种(例如,参见“Introduction to X-ray Powder Diffraction,”R.Jenkins和R.L Snyder,Chemical Analysis,第138卷,John Wiley&Sons,New York,1996)。然而,在某些有利的实施方案中,在如本文描述的陶瓷材料中的氧化锆主要(例如,大于约50%、大于约70%、大于约80%、大于约90%、或甚至大于约95%)呈具有正方几何结构或无定形相的相或其组合,并且具有相对较少量(例如,小于约50%、小于约30%、小于约20%、小于约10%、或甚至小于约5%)的呈单斜相的氧化锆,以便保持期望的机械强度和物理性质,以待用作催化材料。
如本文描述的陶瓷材料可以以任何合适的形式提供。例如,在各种实施方案中,如本文描述的陶瓷材料可以例如使用如下文描述的挤出法被形成为球体、小球、圆柱体(中空的或其他形式的)、对称的或不对称的三-四叶体(tri-quadrulobe)。本领域普通技术人员将理解,陶瓷材料可以以多种其他形式提供。
本文描述的陶瓷材料可以取决于例如用于制造它们所使用的方法和期望的最终用途而被提供有多种不同的孔体积。例如,在某些实施方案中,如本文描述的陶瓷材料具有在约0.1cm3/g至约0.6cm3/g、或约0.2cm3/g至约0.5cm3/g、或约0.3cm3/g至约0.5cm3/g、或约0.4cm3/g至约0.6cm3/g、或约0.1cm3/g至约1cm3/g的范围内的孔体积。在各种实施方案中,如本文描述的陶瓷材料具有约0.1cm3/g、或约0.2cm3/g、或约0.3cm3/g、或约0.4cm3/g、或约0.5cm3/g、或约0.6cm3/g的孔体积。在特定的实施方案中,陶瓷材料具有在约0.2cm3/g至约0.5cm3/g的范围内的孔体积。在其他特定的实施方案中,陶瓷材料具有在约0.2cm3/g至约0.4cm3/g的范围内的孔体积。
类似地,本文描述的陶瓷材料可以取决于例如用于制造它们所使用的方法和期望的最终用途而被提供有多种不同的表面积。例如,在某些实施方案中,如本文描述的陶瓷材料的表面积在约10m2/g至约400m2/g的范围内。表面积使用布鲁厄-埃米特-特勒(BET)表面积方法来测量。在某些实施方案中,如本文描述的陶瓷材料具有在从约10m2/g至约400m2/g、或约50m2/g至约400m2/g、或约70m2/g至约400m2/g、或约100m2/g至约400m2/g、或约200m2/g至约400m2/g、或约300m2/g至约400m2/g、或约10m2/g至约300m2/g、或约50m2/g至约300m2/g、或约70m2/g至约300m2/g、或约100m2/g至约300m2/g、或约200m2/g至约300m2/g、或约10m2/g至约200m2/g、或约50m2/g至约200m2/g、或约70m2/g至约200m2/g、或约100m2/g至约200m2/g的范围内的表面积。在一个实施方案中,如本文描述的陶瓷材料具有约25m2/g至约250m2/g的表面积。在另一个实施方案中,如本文描述的陶瓷材料具有约50m2/g至约150m2/g的表面积。在另一个实施方案中,如本文描述的陶瓷材料具有约30m2/g至约120m2/g的表面积。
本文描述的陶瓷材料可以取决于例如用于制造它们所使用的方法和期望的最终用途而被提供有多种不同的压碎强度。例如,在某些实施方案中,如本文描述的陶瓷材料具有在约45N/cm(即,~1lb/mm)至约450N/cm(即,~10.0lb/mm)的范围内的压碎强度。例如,在某些实施方案中,如本文描述的陶瓷材料取决于它的用途而具有至少45N/cm(即,~1lb/mm)、或至少67N/cm(即,~1.5lb/mm)、或至少90N/cm(即,~2lb/mm)、或至少134N/cm(即,~3lb/mm)、或至少178N/cm(即,~4lb/mm)的压碎强度。在各种实施方案中,如本文描述的陶瓷材料具有在约45N/cm至约178N/cm、或约45N/cm至约134N/cm、或约45N/cm至约90N/cm、或约45N/cm至约67N/cm、或约67N/cm至约178N/cm、或约67N/cm至约134N/cm、或约67N/cm至约90N/cm、约90N/cm至约178N/cm、或约90N/cm至约134N/cm的范围内的压碎强度。材料的压碎强度使用用于挤出的催化剂和催化剂载体颗粒的径向压碎强度的标准测试方法(StandardTest Method for Radial Crush Strength of Extruded Catalyst and CatalystCarrier Particles)ASTM D6175-03(2008)来测量。
如下文将进一步详细地描述的,如本文描述的某些陶瓷材料可以例如在不使用任何粘合剂、挤出助剂或另外的稳定剂的情况下使用挤出法来制备。因此,在某些实施方案中,如本文描述的陶瓷材料大体上无任何粘合剂。在其他实施方案中,如本文描述的陶瓷材料大体上无任何挤出助剂。例如,在一个特定的实施方案中,如本文描述的陶瓷材料大体上无任何粘合剂和任何挤出助剂。此外,因为金属氧化物可以稳定氧化锆,所以在某些实施方案中,如本文描述的陶瓷材料可以大体上无另外的稳定剂。在某些实施方案中,如本文描述的陶瓷材料大体上无任何粘合剂、挤出助剂或另外的稳定剂。例如,在某些实施方案中,如本文描述的陶瓷材料大体上无二氧化硅、铝化合物、硅-铝化合物(silica aluminacompound)、石墨和炭黑。在所有此类实施方案中,陶瓷材料可以作为挤出物被提供。
本文描述的陶瓷材料可以使用多种技术来制造。例如,在一个实施方案中,共沉淀技术被用于制造如本文描述的陶瓷材料。锆化合物和一种或更多种金属氧化物前体化合物可以在水溶液中组合并且用碱共沉淀以使氧化锆-金属氧化物前体共沉淀。可选择地,锆化合物可以首先被沉淀并且然后金属氧化物前体化合物可以与沉淀的氧化锆前体混合以形成氧化锆-金属氧化物前体。金属氧化物前体还可以经由众所周知的浸渍技术来添加(例如,以相对低的水平,例如,当该金属氧化物前体将被用作催化剂金属前体时)。然后,氧化锆-金属氧化物前体可以根据众所周知的工艺来干燥、成形并且煅烧以形成最终的陶瓷材料。
多种含锆化合物可以用作起始材料。例如,锆化合物可以选自由以下组成的组:卤化锆或卤氧化锆(zirconyl halide)、硝酸锆或硝酸氧锆、有机酸锆或有机酸氧锆(zirconyl organic acid)、及其组合。具体的化合物包括例如ZrCl4、ZrOCl2、Zr(NO3)2·5H2O、ZrO(NO3)2和ZrO(CH3COO)2。当然,如本领域普通技术人员将理解的,可以使用其他锆化合物;本文描述的工艺不限于本文具体确定的化合物。在溶液中,锆可以呈氧锆基(ZrO2+)或锆离子(Zr4+或Zr2+)的形式,其可以通过使相应的盐溶解于水中来获得。
各种各样的含金属的化合物可以被用作金属氧化物前体。金属化合物可以例如呈类似于上文关于锆化合物描述的那些的卤化物、硝酸盐或有机酸盐的形式。例如,对于铁的金属氧化物前体化合物可以是Fe(NO3)3。其它的金属氧化物前体在下文关于实施例来描述,并且将对本领域普通技术人员是明显的。在其它的实施方案中(例如,当金属氧化物前体化合物与沉淀的氧化锆前体组合时),金属氧化物前体化合物可以作为金属氧化物本身被提供。
类似地,任选的另外的(例如,钇、镧、铈、铌、钨、钼、钛、钙、镁、硼、锡、锑、银、铼、钌、钯、铑和铱的)金属氧化物可以通过将相应的盐包括在待沉淀的溶液中、通过浸渍或通过使金属氧化物前体(例如,金属氧化物本身)与沉淀的材料混合来并入氧化锆-金属氧化物前体中。盐可以例如呈类似于上文关于锆起始材料和金属氧化物前体化合物描述的那些的卤化物、硝酸盐或有机酸盐的形式。例如,镧可以作为硝酸镧六水合物来引入。其它的金属氧化物前体在下文关于实施例来描述,并且将对本领域普通技术人员是明显的。
在用于制造如本文描述的陶瓷材料的共沉淀方法中,锆化合物和金属氧化物前体化合物与任何其他另外的金属氧化物前体一起溶解于水溶液中。然后添加碱(例如,氨、氢氧化铵、碳酸钠或氢氧化钠)以在约6至约10的范围内的pH下沉淀氧化锆-金属氧化物前体。在某些实例中,碱是25wt.%NaOH,并且最终沉淀的pH在约7和约10之间。最终沉淀的pH在约8和约9之间。本领域普通技术人员将取决于起始材料、期望的最终产物和所使用的特定程序来选择适当的条件。
在沉淀之后,氧化锆-金属氧化物前体沉淀物可以被过滤或以其他方式从液体分离。可以使用多种方法和/或装置,包括使用滤纸和真空泵,以及离心分离、其他真空机构和/或正压装置。任选地,如果在工艺中所使用的任何进料材料包含不合意的元素或化合物例如氯化物或钠,那么可以洗涤氧化锆-金属氧化物前体。通常,如果不期望的元素或其他污染物存在于进料材料中,那么一次至十次洗涤或甚至更多次洗涤可以是合意的。
然后,氧化锆-金属氧化物前体可以使用如将对本领域普通技术人员明显的多种技术和条件来干燥。氧化锆-金属氧化物前体的干燥(例如,当作为实体块例如滤饼被提供时)可以通过使其分开(例如,破坏)成较小的量来辅助。滤饼的分开(例如,破坏)可以是手动的或自动的。氧化锆-金属氧化物前体可以在环境条件(例如,室温和环境压力)下或在范围至多约120℃的适度温度下干燥。在一个实施方案中,取决于所使用的干燥设备,锆-金属氧化物前体在范围为在40℃和90℃之间的温度下干燥持续约20分钟至20小时。在一个实施方案中,干燥氧化锆-金属氧化物前体,直到达到了在约60wt.%至约70wt.%范围内的烧失量(LOI)。如本文所使用的,LOI可以理解为材料在480℃下灼烧两小时的重量损失百分数。在其他实施方案中,氧化锆-金属氧化物前体或经沉淀的锆前体被干燥直到达到了约64wt.%至约68wt.%、或约65wt.%至68wt.%的LOI。如本领域普通技术人员将理解的,氧化锆-金属氧化物前体可以被干燥至对于后续形成步骤合意的水平。在某些实施方案中,可能合意的是,使氧化锆-金属氧化物前体有一点湿润以辅助形成。
在被干燥至合适水平之后,氧化锆-金属氧化物前体可以使用本领域普通技术人员熟悉的任何形成方法被形成为适合于催化剂支撑体/载体的任何形状。例如,在用于制造如本文描述的陶瓷材料的方法的特定实施方案中,干燥的氧化锆-金属氧化物前体通过经由合适的模具被挤出来形成。挤出法是本领域中众所周知的。例如,可以使用本领域中已知的螺杆挤出机、压力挤出机(press extruder)或任何其他挤出设备和/或方法。可选择地,氧化锆-金属氧化物前体可以通过压制、压片、制粒(pelleting)、粒化(granulating)或甚至喷雾干燥来形成;本领域普通技术人员将调整氧化锆-金属氧化物前体的湿度以适合于所使用的特定形成工艺。任选地,挤出的或以其他方式形成的氧化锆-金属氧化物前体可以在被形成之后被进一步干燥(例如,在适度温度下,例如,至多约120℃,例如,持续适度的时间段,例如,通常约1小时至5小时)。
为了将挤出的或以其他方式形成的氧化锆-金属氧化物前体转化成陶瓷材料,氧化锆-金属氧化物前体可以被煅烧。例如,在用于制造如本文描述的陶瓷材料的方法的某些实施方案中,挤出的或以其他方式形成的氧化锆-金属氧化物前体在约300℃至约1000℃的范围内的温度下是陶瓷的,或在另一个实施方案中,在约400℃至约700℃的范围内的温度下是陶瓷的。在用于制造如本文描述的陶瓷材料的方法的各种实施方案中,挤出的或以其他方式形成的氧化锆-金属氧化物前体在约300℃至约1000℃、或约400℃至约700℃、或约500℃至约600℃、或约400℃至约500℃、或约400℃至约600℃、或约500℃至约700℃、或约600℃至约700℃的范围内的温度下被煅烧。煅烧可以持续例如约2小时至约12小时、或约3小时至约5小时的范围内的时间,例如约3小时、约4小时、约5小时、或约6小时。在用于制造如本文描述的陶瓷材料的方法的某些实施方案中,挤出的或以其他方式形成的氧化锆-金属氧化物前体在约600℃下是陶瓷的。如在本领域中常规的,多种加热程序可以用于煅烧中。例如,在某些实施方案中,缓慢的温度斜坡(temperature ramp)可以用于避免材料的热冲击。在一个特定的实施方案中,挤出的或以其他方式形成的如本文描述的氧化锆-金属氧化物前体可以在以1℃/分钟的速率加热至600℃的情况下被煅烧,在该600℃的温度下煅烧继续持续约3小时。基于本文描述的实施例,本领域普通技术人员可以确定合适的煅烧条件以提供期望的陶瓷材料。
用于制造陶瓷材料的某些特定方法在下文的实施例中被描述;本领域普通技术人员可以改变这些方法以适合制造本文中一般描述的陶瓷材料。
如本文描述的陶瓷材料可以与一种或更多种催化活性材料组合提供以形成催化剂。因此,本发明的另一方面是本文描述的用作催化剂支撑体材料的陶瓷材料,其中催化活性材料布置在其上。催化活性材料可以是,例如,催化金属。在某些实施方案中,催化剂包括如本文描述的陶瓷材料,以及选自由以下组成的组的一种或更多种催化金属:Ni、Cu、Co、Fe、Ru、Rh、Pd、Ag、Re、Os、Ir、Pt、Au、Sb、La、Bi或其任何组合。在某些实施方案中,催化金属是镍、铜和锑中的一种或更多种。例如,催化金属可以是NiCu、NiBi或NiSb。当然,本领域普通技术人员将理解,催化剂支撑体材料与其他催化剂例如钯、铂、铑和钌一起可以是有用的。催化金属可以经由浸渍、镀涂或沉积,或经由陶瓷材料的金属氧化物的一部分的还原(例如,在原位)来提供。
本文描述的陶瓷材料和催化剂在某些实施方案中可以呈现出高的水热和机械稳定性,并且因此对于在还原反应例如水相氢化或氢解反应中的有利使用可以是合适地耐久的,该还原反应包括糖、糖醇或甘油的还原。因此,本发明的另外的方面涉及本文描述的陶瓷材料和催化剂的各种用途。例如,本发明的一个实施方案是进行催化反应的方法,该方法包括使一种或更多种反应物与如本文描述的催化剂接触,其中反应物中的至少一种是在水相中。在某些实施方案中,此类反应可以在相对高的温度(例如,在50℃至325℃的范围内,或在约90℃至约275℃的范围内)下,和/或在相对高的压力(例如,在约10巴至约250巴的范围内,或在约50巴至约200巴的范围内)下进行。在某些实施方案中,至少一种反应物是以总压力的至少约20%、至少约50%、或甚至至少约90%的分压提供的气体(例如,氢气)。
如上文描述的,在某些实施方案中,本文描述的陶瓷材料和催化剂可以在多种pH值下是稳定的。因此,本文描述的方法可以在包括酸性pH值的多种pH值下进行。例如,在一个实施方案中,如本文描述的反应被进行,使得反应混合物的pH(在工艺期间的某时刻)在约2至约10的范围内、例如在约2至约6或约2.5至约5的范围内。该工艺可以被进行,使得陶瓷材料或催化剂在这类pH值下与反应混合物接触持续至少约1分钟、至少约2分钟、至少约10分钟、或甚至至少约30分钟。
本文描述的陶瓷材料和催化剂在使糖、糖醇或甘油催化氢化或氢解成例如有商业价值的化学产品和中间体中可以是特别有用的,该有商业价值的化学产品和中间体包括但不限于,包含较短的碳链骨架的多元醇或醇例如丙二醇(propylene glycol)(1,2-丙二醇)、甘醇(1,2-乙二醇)、甘油、亚丙基二醇(1,3-丙二醇)、甲醇、乙醇、丙醇和丁二醇类。如本文中使用的,除非另有限定,否则术语多元醇是指含有多于一个羟基的任何多羟基醇。如广义地定义的,术语多元醇可以涵盖上文描述的反应物和/或产物两者。
在如本文描述的催化方法的一个实施方案中,使糖、糖醇或甘油与氢气源和如本文描述的陶瓷材料或催化剂接触。如本领域普通技术人员将理解,氢气源可以是氢气。
本文描述的陶瓷材料和催化剂在将有机酸催化氢化成有商业价值的化学产品和中间体中也可以是有用的。示例性有机酸包括但不限于,乙酸、甲酸、丙酸、丁酸、己酸、羟基乙酸、乳酸、3-羟基丙酸、羟基丁酸、羟基环戊酸(hydroxycyclopentanoic acid)、水杨酸、扁桃酸、苯甲酸、脂肪酸和糖酸类。除非另外指示,否则如本文中使用的术语糖酸(类)是指含有一个或更多个羧酸部分的任何单糖。实例包括但不限于,甘油酸、木糖酸、葡糖酸、抗坏血酸、酒石酸、粘酸、糖二酸(saccharic acid)、葡糖醛酸和半乳糖醛酸。有机酸还可以包括多元羧酸化合物,例如酒石酸、柠檬酸、苹果酸、草酸、琥珀酸、己二酸、丙二酸、半乳糖二酸、1,2-环戊烷二羧酸、马来酸、富马酸、衣康酸、邻苯二甲酸、对苯二甲酸、苯基丙二酸、羟基邻苯二甲酸、二羟基富马酸、丙三羧酸、苯-1,3,5-三羧酸、异柠檬酸、粘酸和葡萄糖二酸。在本公开内容的一个实施方案中,有机酸选自乳酸、琥珀酸、己二酸和各种糖酸类。因此,如本文描述的催化方法的一个实施方案包括使有机酸和氢气与如本文描述的催化剂(例如,与作为催化金属的Ni、Cu、Co、Fe、Ru、Rh、Pd、Ag、Re、Os、Ir、Pt、Au、Sb、La、Bi或其任何组合)接触。接触可以在如上文描述的相对高的温度和/或压力下进行。本文描述的催化剂可以通过任何合适的方法来制造。例如,催化活性材料(例如,催化金属)可以使用常规方法来布置在如本文描述的催化剂支撑体材料上,例如,通过在其上沉积催化活性材料。沉积可以包括但不限于,浸渍、初湿含浸法、沉淀和物理混合。可选择地,催化活性材料可以在形成催化剂的任何阶段被提供(例如,作为催化活性材料或作为对于在后面的步骤中转化成催化活性材料的、催化活性材料的某种前体)。
实施例
以下的实施例被提供以例证本发明的实施方案并且不被意图构成对它们的在所附权利要求中被界定的范围的限制。
实施例1:镍稳定的氧化锆材料
镍稳定的氧化锆材料通过使用氢氧化钠溶液使硝酸镍(Ni(NO3)2)和硝酸氧锆(ZrO(NO3)2)前体溶液共沉淀来制备。对于典型的制备,以下表1的样品6作为实例,将550g硝酸镍溶液(基于金属的13.8wt.%镍)与1665g硝酸氧锆溶液(等效于20wt.%氧化锆)预混合,并且用25wt.%NaOH溶液沉淀。沉淀在剧烈搅拌下在室温下在从6-10、通常8-9的范围内的恒定pH下进行。沉淀物被老化过夜(约16h)并且用过量的去离子水洗涤,直到最终的过滤的水的电导率小于0.4mS/cm。沉淀物被相应地干燥并且得到的材料使用螺旋式挤出机(augerextruder)来挤出。挤出物在110℃下干燥持续3h,随后在从400℃-650℃范围内的温度下煅烧持续2-5h。
表1列出六种配制品,样品1-6的物理性质。如通过XRF全分析(XRF bulkanalysis)所分析的,基于金属的镍含量从6.6wt.%至大约18wt.%变化。所有挤出物呈现出良好的压碎强度(高于1.9lb/mm)和0.15mL/g至0.22mL/g的孔体积。布鲁厄-埃米特-特勒表面积(BET S.A.)随着煅烧温度、沉淀pH和老化时间的变化而从约50m2/g至约120m2/g变化。
表1.氧化镍稳定的氧化锆挤出物的性质
1作为金属Ni计算的Ni的重量百分数。
图1示出选定的镍稳定的氧化锆材料(样品1、样品4和样品6)的XRD图谱。在450℃下煅烧持续3h之后,镍稳定的氧化锆材料在较高镍含量的材料中主要呈现出正方晶相氧化锆图谱以及NiO峰(用星号标记)。
实施例2:铜稳定的氧化锆材料
铜稳定的氧化锆材料通过使用氢氧化钠溶液使硝酸铜和硝酸氧锆前体溶液共沉淀来制备。对于典型的制备,样品10作为实例,将467g硝酸铜(Cu(NO3)2)溶液(基于金属的15.5wt.%Cu)与1169g硝酸氧锆溶液(等效于20wt.%ZrO2)预混合,并且用25wt.%NaOH溶液沉淀。沉淀在剧烈搅拌下在室温下在从6-10、通常8-9的范围内的恒定pH下进行。沉淀物被老化过夜(约16h)并且用过量的去离子水洗涤,直到最终的过滤的水的电导率小于0.4mS/cm。将饼干燥,并且得到的干燥材料使用螺旋式挤出机来挤出。挤出物在110℃下干燥持续3h,随后在从400℃-600℃范围内的温度下煅烧持续2-5h。
表2列出配制品中的六种以及相关的物理性质。如通过XRF全分析所分析的,基于金属的Cu含量从6.5wt.%至大约32wt.%变化。所有挤出物示出高于2.3lb/mm的良好的压碎强度和0.2mL/g至0.5mL/g的孔体积。对于得到的材料,布鲁厄-埃米特-特勒表面积(BETS.A.)由于煅烧温度和沉淀pH的变化而从约50m2/g至约200m2/g变化。
表2.铜稳定的氧化锆挤出物的性质
1作为金属Cu计算的Cu的重量百分数。
图2提供在450℃下煅烧的铜稳定的氧化锆材料(样品9-12)的XRD图谱。氧化锆呈无定形相的形式。在28%和32%的较高的铜负载下,还观察到CuO峰(用星号标记)。图3提供在550℃下煅烧的铜稳定的氧化锆材料(样品7和样品8)的XRD图谱。氧化锆的完全稳定的正方晶相在具有6.5%和7.5%Cu含量(作为金属Cu计算)的铜稳定的氧化锆中是明显的。
实施例3:钴稳定的氧化锆材料
钴稳定的氧化锆材料通过使用氢氧化钠溶液使硝酸钴六水合物和硝酸氧锆混合的前体溶液沉淀来制备。对于典型的制备(即,样品13和样品14的配制品),将120g Co(NO3)2·6H2O与1040g硝酸氧锆溶液(20wt.%ZrO2)预混合,并且用25wt.%NaOH溶液沉淀。沉淀在剧烈搅拌下在室温下在从6-10、通常8-9的范围内的恒定pH下进行。沉淀物被老化过夜(约16h)并且用过量的去离子水洗涤,直到最终的过滤的水的电导率小于0.4mS/cm。然后,将饼合适地干燥。得到的干燥材料使用螺旋式挤出机来挤出。如此形成的挤出物在110℃下干燥持续3h,随后在从400℃-600℃的范围内的温度下煅烧持续2-5h。
表3列出两种这类配制品(样品13和样品14)以及其物理性质。如通过XRF全分析所分析的,基于金属的钴含量是约10wt.%。挤出物呈现出高于1.2lb/mm的良好的压碎强度和约0.4g/mL的孔体积。明显取决于煅烧温度、沉淀pH和老化时间,布鲁厄-埃米特-特勒表面积(BET S.A.)从约32m2/g至约90m2/g变化。
表3.钴稳定的氧化锆挤出物的性质
1作为金属Co计算的Co的重量百分数。
图4提供在450℃和600℃下煅烧的钴稳定的氧化锆材料的XRD图谱。氧化锆呈完全或部分稳定的正方晶相的形式。除了氧化锆峰之外,还检测到氧化钴(Co3O4)。氧化钴颗粒的量随着煅烧温度从450℃至600℃而增长。由于氧化锆晶格中氧化钴的降低的浓度,稳定的正方晶相氧化锆相的一部分在600℃下煅烧的材料(样品13)中恢复至单斜氧化锆。
实施例4.铁稳定的氧化锆材料
铁稳定的氧化锆材料通过使用25wt.%氢氧化钠溶液使硝酸铁九水合物和硝酸氧锆混合的前体溶液沉淀来制备。对于典型的制备(即,样品15的制备),将147g Fe(NO3)3·9H2O与885g硝酸氧锆溶液(20wt.%ZrO2)预混合,并且用25wt.%NaOH溶液沉淀。沉淀在剧烈搅拌下在室温下在从6-10、通常8-9的范围内的恒定pH下进行。沉淀物被老化过夜(约16h)并且用过量的去离子水洗涤,直到最终的过滤的水的电导率小于0.4mS/cm。然后,将饼合适地干燥。得到的干燥材料使用螺旋式挤出机来挤出。如此形成的挤出物在110℃下干燥持续3h,随后在从400℃-600℃的范围内的温度下煅烧持续2-5h。
表4列出用于铁稳定的氧化锆的配制品中的一种以及其物理性质。如通过XRF全分析所分析的,基于金属的Fe含量是约9.9wt.%。挤出物是相对弱的,具有大约0.6lb/mm的压碎强度。布鲁厄-埃米特-特勒表面积(BET S.A.)是148m2/g,并且孔体积是约0.5g/mL。
表4.铁稳定的氧化锆挤出物的性质
1作为金属Fe计算的Fe的重量百分数
图5示出在600℃下煅烧的铁稳定的氧化锆材料的XRD图谱。氧化锆呈完全稳定的正方晶相的形式。
实施例5:锌稳定的氧化锆材料
锌稳定的氧化锆材料通过使用氢氧化钠溶液使硝酸锌六水合物和硝酸氧锆混合的前体溶液沉淀来制备。对于典型的制备,将60.5g Zn(NO3)2·6H2O与1052g硝酸氧锆溶液(20wt.%ZrO2)预混合,并且用25wt.%NaOH溶液沉淀。沉淀在剧烈搅拌下在室温下在从6-10、通常8-9的范围内的恒定pH下进行。沉淀物被老化过夜(约16h)并且用过量的去离子水洗涤,直到最终的过滤的水的电导率小于0.4mS/cm。然后,将饼合适地干燥。得到的干燥材料使用螺旋式挤出机来挤出。如此形成的挤出物在110℃下干燥持续3h,随后在从400℃-600℃的范围内的温度下煅烧持续2-5h。
表5列出关于锌稳定的氧化锆的三种配制品以及其物理性质。如通过XRF全分析所分析的,基于金属的Zn含量从6%至11%变化。对于在550℃下煅烧的样品,挤出物是坚固的,具有高于2lb/mm的压碎强度。通过将煅烧温度降低至450℃,表面积明显地从40m2/g增加至110m2/g。取决于组成、煅烧概况、沉淀pH和老化时间,得到的材料的孔体积是约0.2-0.4g/mL。
表5.锌稳定的氧化锆挤出物的性质
1作为金属Zn计算的Zn的重量百分数
图6提供表5的Zn稳定的氧化锆材料的XRD图谱。材料分别在450℃和550℃下煅烧持续3h。在所有材料上看到稳定的正方晶相。没有观察到分离的氧化锌。
实施例6:三元氧化锆陶瓷
可以容易地应用上文描述的方式来制备三元材料。例如,镍/镧稳定的氧化锆材料通过使用氢氧化钠溶液使硝酸镍溶液(基于金属的13.8wt.%镍)、硝酸镧六水合物和硝酸氧锆混合的前体溶液沉淀来制备。在该制备中,将85g La(NO3)3·6H2O和205g硝酸镍溶液与1031g硝酸氧锆溶液(20wt.%ZrO2)预混合,并且用25wt.%NaOH溶液沉淀。沉淀在剧烈搅拌下在室温下在从6-10、通常8-9的范围内的恒定pH下进行。沉淀物被老化过夜(约16h)并且用过量的去离子水洗涤,直到最终的过滤的水的电导率小于0.4mS/cm。然后,将饼合适地干燥。得到的干燥材料使用螺旋式挤出机来挤出。如此形成的挤出物在110℃下干燥持续3h,随后在从400℃-600℃的范围内的温度下煅烧持续2-5h。
表6列出关于三元氧化锆材料的两种配制品以及相关的物理性质。挤出物是坚固的,具有高于2.0lb/mm的良好的压碎强度和显著的表面积。
表6.镍/镧稳定的氧化锆挤出物的性质
1基于金属计算的组成的重量百分数
图7提供处于稳定的正方晶相的三元氧化锆陶瓷(样品19)的XRD图谱。该材料在600℃下煅烧持续3h。
实施例7:与氧化锆的比较实验
纯的氧化锆通过使用相同的沉淀方式来制备,以便与金属氧化物稳定的氧化锆做比较。在450℃和550℃下煅烧的ZrO2挤出物的性质在表7中示出。材料示出非常弱的压碎强度并且在指压之后变成粉末。磨耗大于40%。如本文所使用的,磨耗(attrition)被定义为细粒经由磨损(abrasion)的损失,磨损是颗粒彼此或与容器壁的耗损(wearing)、碾磨或摩擦。测试如在据此通过引用并入本文的ASTM D4058中描述的进行,或可选择地通过将5-10克材料在封闭的30mL塑料容器中剧烈地/均匀地手动摇动持续5分钟并且通过筛过16目筛网测量细粒的损失来进行,例如,如在据此通过引用并入本文的Pure&Appl.Chem.,第63卷,第9期,1227-1246(1991)中描述的。通过上文在不存在任何粘合剂和挤出助剂下的方法制备的纯的ZrO2挤出物不适合于用作成形的载体。
表7.ZrO2挤出物的性质
图8提供在变化的煅烧温度下以相同的方式制备的氧化锆的XRD图谱。图8中的XRD图谱示出,在纯的氧化锆材料上的增加的煅烧温度下,从正方氧化锆至正方和单斜混合物的混合物的相变。
实施例8:甘油氢解
在该实施例中,铜稳定的氧化锆样品9、样品10和样品11被直接用作用于在水相溶液中的甘油氢解的催化剂。
进料(100mL)包含具有6.8的初始pH的约40wt.%甘油。催化剂首先被设置尺寸为10-14筛目尺寸。约6.5g-7.0g催化剂被装载到反应器篮中,并且在0.5K/min的缓慢的加热缓变率(heating ramp rate)和2000h-1的氢气GHSV下在220℃下在原位还原持续2小时。测试在100巴氢气压力下在220℃下进行持续6h。产物在测试期间每一小时至2h被取样。还在相同的测试条件下针对甘油氢解研究T4466,商业CuCr催化剂。该催化剂在0.5K/min的缓慢的加热缓变率和2000h-1的氢气GHSV下在185℃下还原持续2h。
还在完全相同的条件下针对甘油氢解研究钴稳定的氧化锆样品14。钴稳定的氧化锆样品在5K/min的加热缓变率和1000h-1的氢气GHSV下在480℃下还原持续2h。
表8中总结了测试结果。用过的催化剂的表征被总结在表9中。所有铜稳定的氧化锆材料示出比钴稳定的氧化锆和T4466(商业CuCr催化剂)明显更高的活性。样品10具有最高的活性,其中转化率高于80%。通过甘油氢解至丙二醇(PG)的选择性在铜稳定的氧化锆催化剂上是高于85%。T4466示出至1,2PG的99%选择性。然而,转化率仅仅是约12%。在6h反应之后的水相产物(aqueous product)的ICP分析表明,对于铜稳定的氧化锆样品,即使产物pH低到2.8,也没有Cu浸出到溶液中。相反,在钴稳定的氧化锆样品和T4466上,检测到20ppm Co并且检测到2ppm Cu。
在用过的铜稳定的氧化锆样品中观察到孔体积和表面积的减小。所有的用过的样品保持良好的压碎强度。
表8.在被研究的催化剂上关于甘油氢解的测试结果的概述。该测试在分批反应器中在100巴氢气压力下在220℃下进行持续6h。进料是100mL的40wt.%甘油水溶液。
表9.关于甘油氢解的用过的铜稳定的氧化锆的表征。还列出T4466(商业CuCr催化剂)以用于比较。
1基于金属计算的组成的重量百分数
注:T4466是片剂,并且被设置尺寸为10-14目,呈不规则形状。
实施例9:糖氢化
糖氢化成糖醇是重要的工业过程。该过程在水相中进行。因此,在升高的温度和压力下在水相中的催化剂稳定性是高度合意的,尤其是对于固定床连续工艺。
关于木糖氢化来研究镍稳定的氧化锆(样品4)和镍/镧稳定的氧化锆(样品19)。关于木糖氢化还研究钯促进的镍稳定的氧化锆(编号4),以便增强催化活性。Pd促进的NiZrOx-编号4通过常规的初湿含浸法来制备。将期望量的硝酸钯水合物(Pd:39wt.%)首先溶解于水中并且滴到NiZrOx-编号4中,随后在110℃下干燥持续2h并且在450℃下煅烧持续2h。测试在具有1英寸的O.D.的固定床反应器中进行。30mL的每种催化剂被装载到具有SiC(40-60目)的1:1体积稀释的反应器中。所有的催化剂在3K/min的加热缓变率下在具有1000h-1的GHSV的纯氢气的流动下在450℃下活化持续4小时。进料包含食品级的木糖(Danisco USAInc),并且通过稀释的碳酸钠来调节pH,之后泵送到反应器中。详细的测试条件在表10中列出。测试在氢气流(氢气/木糖=10,通过摩尔比)下在80巴或120巴的氢气压力下在110℃下进行持续多于200h。所有的催化剂在测试期间示出稳态性能。在80巴的较低的操作压力下,催化剂通过使用8wt.%木糖溶液来评估。在120巴下,木糖浓度增加至20wt.%。所有的催化剂示出超过99.9%的转化率和超过98%的选择性。对于测试9,在Pd(0.2wt.%)促进的镍稳定的氧化锆(编号4)催化剂上,催化剂示出约100%的至木糖醇的选择性。催化剂在该水热条件下是化学上非常稳定的,其中没有明显的浸出。
表10.在镍稳定的氧化锆、镍/镧稳定的氧化锆和钯促进的镍稳定的氧化锆催化剂上的对于木糖氢化的测试条件和平均催化性能。还示出作为用于催化剂的化学稳定性的参考的水相产物中的金属含量。
表11.关于木糖氢化的用过的催化剂的表征
1基于金属计算的组成的重量百分数
用过的催化剂容易从反应器卸载并且保持良好的物理完整性。所有的用过的催化剂示出FCC镍金属和完全稳定的正方氧化锆的特有的XRD峰。用过的催化剂的压碎强度、表面积和孔体积略微减小,其中没有主要的相反影响。
实施例10:糖醇氢解
NiSb催化剂在镍稳定的氧化锆材料(样品1)上形成,该镍稳定的氧化锆材料最初包含基于金属的约6.6wt.%镍。催化剂通过常规的浸渍方法来制造。镍稳定的氧化锆(样品1,50g)浸没在硝酸镍、醋酸锑和柠檬酸的混合溶液中持续1h,并且倾析残余溶液。然后将得到的材料在110℃下干燥持续2h并且在450℃下煅烧持续2h。为了制造混合的前体溶液,将醋酸锑首先在搅拌下溶解于柠檬酸水溶液(柠檬酸/Sb=4,通过摩尔比)中。然后使溶液与硝酸镍溶液(基于金属的13.8wt.%)混合。
木糖醇氢解测试在具有0.5英寸的O.D.的固定床反应器中进行。15mL的催化剂被装载到具有SiC(60-80目)的1:1体积稀释的反应器中。催化剂在3K/min的加热缓变率下在具有1000h-1的GHSV的纯氢气的流动下在450℃下活化持续4小时。进料包含食品级的木糖醇(Danisco USAInc),并且通过稀释的NaOH溶液来适当地调节pH,之后泵送到反应器中。详细的测试条件在表11中列出。测试在氢气流(氢气/木糖醇=10,通过摩尔比)下在120巴的氢气压力下在210℃下进行持续210h。液时空速保持在3h-1。进料中的木糖醇/NaOH比率(摩尔)被控制在约10,这产生在12.4的pH下的混合溶液。催化剂在测试期间示出稳态性能。平均转化率是约89%,其中乙二醇(EG)选择性24.5%,并且1,2-PG选择性37.1%,并且甘油选择性8.8%。没有从氢解(HOS)水相产物中检测到任何组分的浸出。
新鲜的催化剂和用过的催化剂的比较在表12中列出。催化剂保持良好的物理完整性和压碎强度。
表11.在制备在镍稳定的氧化锆(样品1)上的NiSb催化剂上的对于木糖醇氢解的测试条件和平均催化性能
表12.新鲜的催化剂和用过的催化剂用于木糖醇氢解的表征
1基于金属计算的组成的重量百分数
应理解,本文描述的实施例和实施方案仅为了例证性目的。除非被上下文清楚地排除,否则本发明的一方面所公开的全部实施方案可以以任何合适的组合与本发明的其他方面所公开的实施方案组合。将对本领域的技术人员明显的是,可以对本发明作出各种修改和变型而不脱离本发明的范围。因此,意图的是,本发明覆盖本发明的修改和变型,条件是它们在所附权利要求及其等效物的范围内。本文引用的所有出版物、专利和专利申请据此为了所有目的通过引用并入本文。
Claims (15)
1.一种陶瓷材料,包含氧化锆和金属氧化物,其中
所述氧化锆以在所述材料的约50wt.%至约99wt.%的范围内的量存在;
所述金属氧化物是氧化镍、氧化铜、氧化钴、氧化铁和氧化锌中的一种或更多种;并且
所述金属氧化物以基于金属计算的在所述材料的约1wt.%至约50wt.%的范围内的量存在。
2.如权利要求1所述的陶瓷材料,其中
所述氧化锆以在所述材料的约75wt.%至约99wt.%的范围内的量存在;
所述金属氧化物以基于金属计算的在所述材料的约1wt.%至约25wt.%的范围内的量存在;并且
其中所述陶瓷材料任选地包含一种或更多种另外的金属氧化物,所述一种或更多种另外的金属氧化物以基于金属计算的所述材料的至多约20wt.%的量存在。
3.如权利要求1所述的陶瓷材料,大体上无铬。
4.如权利要求1所述的陶瓷材料,大体上无锰。
5.如权利要求1所述的陶瓷材料,大体上无氧化硅、铝化合物、硅-铝化合物、石墨和炭黑。
6.如权利要求1所述的陶瓷材料,其中所述氧化锆主要呈正方晶相、无定形相或两者。
7.如权利要求1所述的陶瓷材料,其中所述陶瓷材料的至少约80wt.%是所述氧化锆和所述金属氧化物。
8.如权利要求1所述的陶瓷材料,其中所述催化剂支撑体材料具有在约0.1cm3/g至约1.0cm3/g的范围内的孔体积;在约10m2/g至约400m2/g的范围内的表面积;以及在约1.0lb/mm至约10lb/mm的范围内的压碎强度。
9.如权利要求1所述的陶瓷材料,其中所述金属氧化物是铁,并且所述铁以基于金属计算的所述材料的约5wt.%至约30wt.%存在。
10.如权利要求1所述的陶瓷材料,其中所述金属氧化物是钴,并且所述钴以基于金属计算的所述材料的约5wt.%至约25wt.%存在。
11.如权利要求1所述的陶瓷材料,其中所述金属氧化物是镍,并且所述镍以基于金属计算的所述材料的约5wt.%至约40wt.%存在。
12.如权利要求1所述的陶瓷材料,其中所述金属氧化物是铜,并且所述铜以基于金属计算的所述材料的约5wt.%至约35wt.%存在。
13.如权利要求1所述的陶瓷材料,其中所述金属氧化物是锌,并且所述锌以基于金属计算的所述材料的约5wt.%至约25wt.%存在。
14.如权利要求1所述的陶瓷材料,还包含一种或更多种另外的金属氧化物,所述一种或更多种另外的金属氧化物选自钇、镧、铈、铌、钨、钼、钛、钙、镁、硼、锡和锑的氧化物。
15.一种用于制造权利要求1所述的陶瓷材料的方法,包括在不存在任何粘合剂、挤出助剂或另外的稳定剂下挤出氧化锆-金属氧化物前体材料。
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- 2015-04-27 CN CN201580023264.1A patent/CN106458768A/zh active Pending
- 2015-04-27 WO PCT/US2015/027701 patent/WO2015167978A1/en active Application Filing
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CN110255614B (zh) * | 2019-06-26 | 2022-03-08 | 西安建筑科技大学 | 一种稳定氧化锆粉体及其制备方法与应用 |
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US20170190643A1 (en) | 2017-07-06 |
EP3137434A1 (en) | 2017-03-08 |
US10065910B2 (en) | 2018-09-04 |
WO2015167978A1 (en) | 2015-11-05 |
US20150314274A1 (en) | 2015-11-05 |
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