CN101678344A - 具有高催化效率的Ir、Ru、Rh、Pd、Pt和Au贵金属羧酸盐化合物 - Google Patents
具有高催化效率的Ir、Ru、Rh、Pd、Pt和Au贵金属羧酸盐化合物 Download PDFInfo
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- 229910052707 ruthenium Inorganic materials 0.000 title claims description 14
- 229910052741 iridium Inorganic materials 0.000 title claims description 10
- 229910052703 rhodium Inorganic materials 0.000 title claims description 9
- 230000003197 catalytic effect Effects 0.000 title claims description 8
- 229910052763 palladium Inorganic materials 0.000 title claims description 7
- 229910052737 gold Inorganic materials 0.000 title claims description 5
- 229910052697 platinum Inorganic materials 0.000 title claims description 5
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 12
- 150000003891 oxalate salts Chemical class 0.000 claims abstract description 11
- 238000004090 dissolution Methods 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 15
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002912 oxalic acid derivatives Chemical class 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 7
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 19
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 8
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000004343 Calcium peroxide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal hydrogencarbonate Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
本发明涉及贵金属羧酸盐化合物的制备方法，其中，在容器内用至少一种金属盐将贵金属消解，将消解物料溶解于羧酸中，并通过草酸盐或草酸盐衍生物将由所述金属盐引入的金属离子从所得溶液中分离出来。
Description
本发明涉及具有高催化效率的Ir、Ru、Rh、Pd、Pt和Au贵金属羧酸盐化合物、及其制备方法。
已知铱、钌及其化合物的一种用途是作为催化剂及催化剂前体。例如，根据专利文献EP 0 616 997 A1和EP 0 786 447 A1，铱催化剂被用于羰基化反应中。其中，述及乙酸铱为适合于该用途的铱化合物。
由已公开而处于异议期的德国专利申请(Auslegeschrift)1 127888得知：可在铂族金属盐的存在下，通过低级羧酸的乙烯酯的再酯化反应来制备高级羧酸的乙烯酯。其中，适合的铂族金属盐的例子为钯和铑的乙酸盐，其是通过将溶解于冰醋酸中的钯和铑的氢氧化物与乙酸酐反应而获得的。
专利文献EP 0 844 251涉及羧酸钌溶液的制备，其通过在羧酸的存在下，采用肼衍生物将钌(IV)氧化物还原而制得。钌氧化物的制备，尤其是钌氧化物的过滤，耗费时间很长。
在专利文献EP 1 046 629中，描述了一种制备乙酸铱的方法，其中，借助碱金属氢氧化物、碱金属碳酸盐或碱金属碳酸氢盐的水溶液，从氯代铱化合物中沉淀出氢氧化铱，将沉淀出的氢氧化铱分离出来并与乙酸、或者与乙酸/乙酸酐混合物反应，从而形成含有乙酸铱的溶液，并将乙酸铱以固体形式从该溶液中分离出来。
Watson描述了乙酸铱的制备(Precious Metals Catalysts Seminar，第83页及其后)，其中将Ir海绵体与过氧化钡一同烧结。随后，将烧结体溶解于乙酸/水混合物中，并通过过滤将其与未反应的金属分离开。随后通过加入硫酸而沉淀出硫酸钡，并通过过滤将其由乙酸铱溶液中分离出来。然后，通过蒸发浓缩乙酸铱溶液。该方法的关键步骤是在除去钡的操作中要注意使反应达到平衡。钡或者硫酸盐出现在最终产品中都是不利的。基于这一原因，为了获得所要的产品，需要进行非常精确的调节。
该方法具有如下不利之处：
难以精确地调节硫酸的含量，并且需要进行分析检验。因此，通常需要反复进行硫酸钡的沉淀和过滤以及相应的分析测试。另一不利之处是硫酸钡的过滤非常困难、且成本高。此外，通过该沉淀路线不能充分地降低其中所含的锶的浓度，因而限制了产品的纯度。
本发明的目的是提供具有高催化效率的Ir、Ru、Rh、Pd、Pt和Au贵金属羧酸盐化合物、及其简单的制备方法。根据该方法制备的贵金属羧酸盐化合物，尤其是乙酸盐化合物，应具有尽可能高的催化效率。优选的是，这些化合物还应具有高纯度，尤其是应具有低的氯、硫、钠和钾含量。
为了实现该目的，将显示出含有贵金属和碱土金属过氧化物的熔体或熔融物料溶解于羧酸中(如果需要的话，可加入水)，随后进行过滤。把碱土金属过氧化物所引入的碱土金属离子以草酸盐或草酸衍生物的盐的形式从滤液中分离出去。羧基基团之间排布有有机基团的草酸盐衍生物具有与草酸盐相同的效果。该方法效率高、且避免了根据Watson的方法所需的耗时的BaSO4沉淀以及硫酸钡过滤的操作。可将纯化的贵金属羧酸盐溶液浓缩，可调节溶液浓度以使其增至所需浓度，或浓缩直至分离出固体。
为此，使用现有工艺的方法，如反应溶液的蒸发、喷雾干燥、或低温沉淀、或加入适当的溶剂。足以令人惊讶的是，当采用使碱土金属以草酸盐或草酸衍生物的盐的形式沉淀出来的方法时，得到的贵金属羧酸盐溶液(尤其是乙酸钌或乙酸铱的乙酸溶液)催化性能极佳。在这样制得的溶液中，草酸和/或草酸盐或相应的衍生物的质量小于或等于贵金属的质量。
优选的是，用过氧化钙或过氧化钡将贵金属消解(aufgeschlossen)。贵金属优选为钌和铱。羧酸盐优选为乙酸盐。相应地，优选将消解后的贵金属的混合物溶解于乙酸水溶液中。根据本发明，在以草酸盐或草酸衍生物的盐的形式沉淀后，碱土金属(尤其是钙、锶或钡)的比率为贵金属的100ppm至10％(以重量计)，尤其为500ppm至0.5％(以重量计)。可通过分步结晶而使钙、锶和钡的含量大幅降低。
实施例1：
将1.5g钌粉末(14.8毫摩尔)和10g过氧化钡(纯度：95.8％；56.5毫摩尔)混合。
将该混合物转移至镍坩埚中，并在850℃下加热15小时。
将150ml由乙酸和水构成的混合物(乙酸与水的比例为2∶1)在200ml的三颈烧瓶内加热至50℃。
将钌粉末与过氧化钡的反应混合物引入该三颈烧瓶中。放热反应使混合物升温至80℃。将该混合物加热至沸点，并在沸点下搅拌3小时。
随后，将所得溶液冷却至室温，并通过膜过滤器进行过滤。用少量乙酸/水混合物(2∶1)洗涤滤饼。
获得了169g溶液，其中Ru含量为0.88％(1.487g Ru，14.7毫摩尔)，Ba含量为4.59％(7.757g Ba，56.5毫摩尔)。
将169g的乙酸钌溶液(1.487g Ru，14.7毫摩尔)转移至200ml的三颈烧瓶内，加入14.264g草酸二水合物(113毫摩尔)并搅拌。在搅拌4小时后，将悬浮液在黑带滤纸上过滤，随后在膜过滤器上过滤。用乙酸/水混合物(2∶1)洗涤滤饼。
获得了230g溶液，其中Ru含量为0.57％(1.311g Ru，13毫摩尔)，Ba含量为0.051％(0.117g，0.85毫摩尔)。草酸盐含量(经离子色谱测定其含量)为0.36％。
实施例2
将1.5g钌粉末(14.8毫摩尔)和10g过氧化钡(纯度：95.8％；56.5毫摩尔)混合。
将该混合物转移至镍坩埚中，并在850℃下加热15小时。
将150ml由乙酸和水构成的混合物(乙酸与水的比例为2∶1)在200ml的三颈烧瓶内加热至50℃。
将钌粉末与过氧化钡的反应混合物引入该三颈烧瓶中。放热反应使混合物升温至76℃。将该混合物加热至沸点，并在沸点下搅拌3小时。随后，将溶液冷却至室温，并通过膜过滤器进行过滤。用少量乙酸洗涤滤饼。
获得了166g溶液，其中Ru含量为0.90％(1.494g Ru，14.8毫摩尔)，Ba含量为4.67％(7.752g Ba，56.4毫摩尔)。
将169g的乙酸钌溶液(1.494g Ru，14.8毫摩尔)转移至200ml的三颈烧瓶内，加入14.264g草酸二水合物(113毫摩尔)并搅拌。在搅拌4小时后，将悬浮液在黑带滤纸上过滤，随后在膜过滤器上过滤。用乙酸洗涤滤饼。
获得了193g溶液，其中Ru含量为0.68％(1.314g Ru，13毫摩尔)，Ba含量为0.0515％(0.1g，0.72毫摩尔)。草酸盐含量(经离子色谱测定其含量)为0.26％。
实施例3
称取5.001g铑粉末和34.622g过氧化钡，并将其装入带有螺旋盖的玻璃瓶中，充分混合10分钟。将该混合物转移至镍坩埚中，随后在马弗炉内于850℃下加热15小时。然后，将坩埚冷却至室温。熔体表面呈黑色，内部均匀且为灰色。将该熔体引入由乙酸和完全去离子水构成的溶液中，并搅拌。其中乙酸和水的体积份之比为2∶1。在该过程中，温度升至24℃。获得了含有黑色颗粒的深绿色液体。再搅拌15分钟，将该混合物加热至58℃，并在该温度下保持5小时。在该过程中，在约5分钟内该悬浮液呈棕色。然后，借助51.453g无水草酸使钡以盐的形式沉淀出来，并且再搅拌一小时，然后使用蓝带滤纸，通过吸滤器滤出黄色液体。在旋转蒸发器中，在75℃下将滤液浓缩。将乙酸铑干燥直至质量恒定，并用研钵将其研磨。干燥后的乙酸铑产量为11.012g。经ICP分析，铑含量为34.43重量％。
实施例4
根据Watson的方法用过氧化钡将铱消解，并将其溶解于乙酸中。以与上述实施例1至3相似的方式，用草酸将Watson方法中的钡沉淀出来，然后过滤。这种羧基铱化合物、尤其是乙酸铱，显示出无与伦比的催化性能。
Claims (17)
1.一种物质，包含：
A)贵金属羧酸盐，其贵金属选自：钌、铂、钯、铑和金，
B)选自草酸、草酸盐、草酸衍生物、以及草酸衍生物的盐中的至少一种化合物。
2.根据权利要求1的物质，其特征在于：所述贵金属羧酸盐为羧酸钌。
3.根据权利要求1或2的物质，其特征在于：该物质还显示出含有碱土金属离子(C)。
4.一种物质，包含：
A)羧酸铱，
B)选自草酸、草酸盐、草酸衍生物、以及草酸衍生物的盐中的至少一种化合物，
C)至少一种碱土金属离子。
5.根据权利要求3或4的物质，其特征在于：所述碱土金属离子(C)为钙、钡或锶。
6.根据权利要求1至5中的一项所述的物质，其特征在于：所述贵金属羧酸盐(A)为贵金属乙酸盐。
7.根据权利要求1至6中的一项所述的物质，其特征在于：该物质显示出含有至少一种另外的羧酸(D)。
8.根据权利要求7的物质，其特征在于：所述另外的羧酸(D)为一元羧酸。
9.根据权利要求8的物质，其特征在于：所述一元羧酸为乙酸。
10.根据权利要求1至9中的一项所述的物质，其特征在于：所述物质显示出含有另外的质子溶剂(E)。
11.根据权利要求10的物质，其特征在于：所述质子溶剂(E)为水或醇。
12.根据权利要求1至11中的一项所述的物质，其特征在于：该物质为乙酸溶液。
13.根据权利要求1至11中的一项所述的物质，其特征在于：所述贵金属羧酸盐(A)作为主要成分存在。
14.一种制备具有高催化效率的贵金属羧酸盐化合物或其溶液的方法，尤其是制备根据权利要求1至12中的一项所述物质的方法，其中，用碱土金属过氧化物将贵金属消解，将所得的消解物料溶解于羧酸、或经质子溶剂稀释的羧酸中，其特征在于：将碱土金属离子以草酸盐或草酸衍生物的盐的形式从所得溶液中分离出来。
15.根据权利要求14的方法，其特征在于：所述贵金属为钌或铱。
16.根据权利要求14或15的方法，其特征在于：所述羧酸为乙酸。
17.根据权利要求14至16中的一项所述的方法，其特征在于：所述贵金属羧酸盐为贵金属乙酸盐。
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| DE102007014914A DE102007014914B4 (de) | 2007-03-26 | 2007-03-26 | Katalytisch hochwirksame Edelmetall-Carboxylat-Verbindungen von Ir, Ru, Rh, Pd, Pt und Au |
| PCT/EP2008/002186 WO2008116585A1 (de) | 2007-03-26 | 2008-03-19 | Katalytisch hochwirksame edelmetall-carboxylat-verbindungen von ir, ru, rh, pd, pt und au |
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| US (3) | US20100113258A1 (zh) |
| EP (1) | EP2125209B1 (zh) |
| JP (1) | JP5383646B2 (zh) |
| KR (1) | KR101332498B1 (zh) |
| CN (1) | CN101678344A (zh) |
| BR (1) | BRPI0809300B1 (zh) |
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| RU (1) | RU2482916C2 (zh) |
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Cited By (4)
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|---|---|---|---|---|
| CN102381957A (zh) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | 乙酸钌的制备方法 |
| CN107922304A (zh) * | 2015-07-28 | 2018-04-17 | 优美科股份公司及两合公司 | “带冰”的双(草酸)合铂酸 |
| CN108409554A (zh) * | 2018-03-28 | 2018-08-17 | 西安瑞鑫科金属材料有限责任公司 | 一种醋酸铱的合成方法 |
| CN115141093A (zh) * | 2022-06-28 | 2022-10-04 | 浙江微通催化新材料有限公司 | 一种醋酸钌的制备方法 |
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| RU2565423C1 (ru) * | 2014-11-06 | 2015-10-20 | Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) | Оксоацетатные соединения платины для изготовления гетерогенных катализаторов |
| CN115536520A (zh) * | 2022-11-02 | 2022-12-30 | 金川集团股份有限公司 | 一种醋酸钌的制备方法 |
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| CN107922304A (zh) * | 2015-07-28 | 2018-04-17 | 优美科股份公司及两合公司 | “带冰”的双(草酸)合铂酸 |
| CN108409554A (zh) * | 2018-03-28 | 2018-08-17 | 西安瑞鑫科金属材料有限责任公司 | 一种醋酸铱的合成方法 |
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| CN115141093A (zh) * | 2022-06-28 | 2022-10-04 | 浙江微通催化新材料有限公司 | 一种醋酸钌的制备方法 |
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| Publication number | Publication date |
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| BRPI0809300B1 (pt) | 2019-04-24 |
| KR20090127284A (ko) | 2009-12-10 |
| US11045795B2 (en) | 2021-06-29 |
| JP5383646B2 (ja) | 2014-01-08 |
| EP2125209A1 (de) | 2009-12-02 |
| DE102007014914A1 (de) | 2008-10-02 |
| US20180147570A1 (en) | 2018-05-31 |
| RU2482916C2 (ru) | 2013-05-27 |
| KR101332498B1 (ko) | 2013-11-26 |
| EP2125209B1 (de) | 2017-09-06 |
| ZA200906692B (en) | 2010-05-26 |
| BRPI0809300A2 (pt) | 2014-10-14 |
| US20100113258A1 (en) | 2010-05-06 |
| DE102007014914B4 (de) | 2013-09-12 |
| JP2010522221A (ja) | 2010-07-01 |
| WO2008116585A1 (de) | 2008-10-02 |
| RU2009139264A (ru) | 2011-05-10 |
| US20140274670A1 (en) | 2014-09-18 |
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