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    • 3. 发明授权
    • Processes for the preparation of 2-chloro-1,1,1,2,3,3,3-heptafluoropropane, hexafluoropropene and 1,1,1,2,3,3,3-heptafluoropropane
    • 制备2-氯-1,1,1,2,3,3,3-七氟丙烷,六氟丙烯和1,1,1,2,3,3,3-七氟丙烷的方法
    • US07129383B2
    • 2006-10-31
    • US10523223
    • 2003-08-21
    • Mario J. NappaVelliyur Nott Mallikarjuna RaoH. David RosenfeldSekhar SubramoneyMunirpallam A. SubramanianAllen C. Sievert
    • Mario J. NappaVelliyur Nott Mallikarjuna RaoH. David RosenfeldSekhar SubramoneyMunirpallam A. SubramanianAllen C. Sievert
    • C07C17/00C07C17/266C07C17/10
    • C07C19/08B01J23/26B01J23/866B01J35/002B01J37/0236B01J37/03B01J37/26C07C17/206C07C17/21C07C17/23C07C17/25C07C19/10C07C21/18
    • A process for the preparation of 2-chloro-1,1,1,3,3,3-heptafluoropropane is disclosed which involves (a) contacting a mixture comprising hydrogen fluoride, chlorine, and at least one starting material selected from the group consisting of halopropenes of the formula CX3CCI═CX2 and halopropanes of the formula the CX3CCIYCX3, wherein each X is independently F or Cl, and Y is H, Cl or F (provided that the number of X and Y which are F totals no more than six) with a chlorofluorination catalyst in a reaction zone to produce a product mixture comprising CF3CCIFCF3, HCI, HF. and underfluorinated halogenated hydrocarbon intermediates. The process is characterized by said chlorofluorination catalyst comprising at least one chromium-containing component selected from (i) a crystalline alpha-chromium oxide where at least 0.05 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by nickel, trivalent cobalt or both nickel and trivalent cobalt, provided that no more than 2 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by nickel and that the total amount of chromium atoms in the alpha-chromium oxide lattice that are replaced by nickel and trivalent cobalt is no more than 6 atom %, and (ii) a fluorinated crystalline oxide of (i). Also disclosed is a process for the manufacture of a mixture of HFC-227ea and hexafluoropropene by reacting a starting mixture comprising CFC-217ba and hydrogen in the vapor phase at an elevated temperature, optionally in the presence of a hydrogenation catalyst. This process involves preparing the CFC-217ba by the process described above.
    • 公开了一种制备2-氯-1,1,1,3,3,3-七氟丙烷的方法,其涉及(a)使包含氟化氢,氯和至少一种起始原料的混合物接触,所述起始材料选自 的式CX3CCI-CX2的卤代丙烯和式CX3CCIYCX3的卤代丙烷,其中每个X独立地为F或Cl,Y为H,Cl或F(条件是总计X不超过6的X和Y的数目 )与反应区中的氯氟化催化剂反应以产生包含CF 3 CClF 3,HCl,HF的产物混合物。 和不完全氟化的卤代烃中间体。 该方法的特征在于所述氯氟化催化剂包含至少一种含铬组分,其选自(i)α-氧化铬晶格中至少0.05原子%的铬原子被镍取代的结晶α-氧化铬,三价 钴或镍和三价钴,条件是α-铬氧化物晶格中不超过2原子%的铬原子被镍代替,并且α-氧化铬晶格中的铬原子的总量被 镍和三价钴不超过6原子%,和(ii)(i)的氟化结晶氧化物。 还公开了通过在升高的温度下,任选地在氢化催化剂存在下,使包含CFC-217ba和氢的起始混合物在气相中反应制备HFC-227ea和六氟丙烯的混合物的方法。 该方法包括通过上述方法制备CFC-217ba。
    • 6. 发明授权
    • Process for purifying hydrofluoropropanes
    • 氢氟丙烷的纯化方法
    • US07161049B2
    • 2007-01-09
    • US10734946
    • 2003-12-11
    • Velliyur Nott Mallikarjuna RaoAllen C. Sievert
    • Velliyur Nott Mallikarjuna RaoAllen C. Sievert
    • C07C17/38
    • C07C17/354C07C17/04C07C17/206C07C17/23C07C17/395C07C19/08
    • A process is disclosed for purifying a hydrofluoropropane of undesirable C2–C4 olefinic and C1–C4 saturated chlorinated impurities, comprising the steps of: contacting a first mixture of hydrofluoropropane, olefinic impurity and saturated chlorinated impurity with hydrogen and hydrogen fluoride concurrently in the presence of a bifunctional catalyst, for example an alloy of gold and palladium supported on carbon, capable of catalyzing hydrogenation and fluorination. During the contacting step, olefinic impurity is converted to saturated hydrogenated derivative and/or saturated hydrofluorinated derivative, and saturated chlorinated impurity is converted to a saturated hydrodechlorinated derivative and/or saturated fluorinated derivative. The hydrofluoropropane thus formed is substantially free of both the olefinic and saturated chlorinated impurities and may be used as obtained or subject to further purification steps such as distillation to remove the process derivatives (e.g., hydrogenation, hydrodechlorination and hydrofluorination derivatives) from the hydrofluoropropane.
    • 公开了一种纯化不期望的C 2 -C 4 -C 4烯烃和C 1 -C 4烷基的氢氟烷的方法, 饱和氯化杂质,包括以下步骤:在双功能催化剂,例如负载在碳上的金和钯的合金的同时,将氢氟丙烷,烯属杂质和饱和氯化杂质的第一混合物与氢气和氟化氢同时接触, 催化氢化和氟化。 在接触步骤中,烯烃杂质转化为饱和氢化衍生物和/或饱和氢氟化衍生物,饱和氯化杂质转化为饱和加氢脱氯衍生物和/或饱和氟化衍生物。 如此形成的氢氟烷基本上不含烯烃和饱和氯化杂质,并且可以获得使用或经过进一步的纯化步骤如蒸馏以从氢氟丙烷中除去工艺衍生物(例如氢化,加氢脱氯和氢氟化衍生物)。
    • 7. 发明授权
    • Cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalyst precursors
    • 钴取代的氧化铬组合物,它们的制备及其作为催化剂和催化剂前体的用途
    • US07217678B2
    • 2007-05-15
    • US10523228
    • 2003-08-21
    • Velliyur Nott Mallikarjuna RaoH. David RosenfeldAllen C. SievertShekhar SubramoneyMunirpallam Appadorai Subramanian
    • Velliyur Nott Mallikarjuna RaoH. David RosenfeldAllen C. SievertShekhar SubramoneyMunirpallam Appadorai Subramanian
    • B01J27/06B01J23/00
    • C07C17/21B01J23/864B01J35/002B01J35/1014B01J37/0236B01J37/03C07C17/00C07C17/08C07C17/10C07C17/20C07C17/206C07C17/23C07C17/25C07C17/358C07C17/37C07C21/18C07C21/04C07C19/08C07C21/06C07C19/12C07C19/10
    • A crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt (Co+3) atoms is disclosed. Also disclosed is a chromium-containing catalyst composition comprising as a chromium-containing component the crystalline cobalt-substituted alpha-chromium oxide; and a method for preparing a composition comprising the crystalline cobalt-substituted alpha-chromium oxide. The method involves (a) co-precipitating a solid by adding ammonium hydroxide to an aqueous solution of a soluble cobalt salt and a soluble trivalent chromium salt that contains at least three moles of nitrate per mole of chromium in the solution and has a cobalt concentration of from about 0.05 mole % to about 6 mole % of the total concentration of cobalt and chromium in the solution; and after at least three moles E of ammonium per mole of chromium in the solution has been added to the solution, (b) collecting the co-precipitated solid formed in (a); (c) drying the collected solid; and (d) calcining the dried solid. Also disclosed is a chromium-containing catalyst composition comprising a chromium-containing component prepared by treating the crystalline cobalt-substituted alpha-chromium oxide with a fluorinating agent; and a process for changing the fluorine distribution (i.e., content and/or arrangement) in a hydrocarbon or halogenated hydrocarbon in the presence of a catalyst. The process involves using as the catalyst a composition comprising the crystalline cobalt-substituted alpha-chromium oxide and/or the treated cobalt-substituted alpha-chromium oxide.
    • 公开了一种结晶α-Cr氧化物,其中α-Cr氧化物晶格中约0.05原子%至约6原子%的铬原子被三价钴(Co + O 3+)原子所取代。 还公开了含铬催化剂组合物,其包含结晶钴取代的α-氧化铬作为含铬组分; 以及制备包含结晶钴取代的α-氧化铬的组合物的方法。 该方法包括(a)通过向可溶性钴盐和可溶性三价铬盐的水溶液中加入氢氧化铵共沉淀固体,该溶液在溶液中每摩尔铬含有至少三摩尔硝酸盐,并且具有钴浓度 为溶液中钴和铬的总浓度的约0.05摩尔%至约6摩尔% 并且在溶液中每摩尔铬至少三摩尔E之后的铵加入到溶液中,(b)收集(a)中形成的共沉淀固体; (c)干燥收集的固体; 和(d)煅烧干燥的固体。 还公开了一种含铬催化剂组合物,其包含通过用氟化剂处理结晶钴取代的α-氧化铬制备的含铬组分; 以及在催化剂存在下改变烃或卤代烃中的氟分布(即含量和/或排列)的方法。 该方法包括使用包含结晶钴取代的α-氧化铬和/或经处理的钴取代的α-氧化铬的组合物作为催化剂。