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1. 发明授权

US07074973B2 Process for the preparation of 1,1,1,2,2-pentafluoroethane 失效
标题翻译：制备1,1,1,2,2-五氟乙烷的方法
公开(公告)号：US07074973B2
公开(公告)日：2006-07-11
申请号：US10523227
申请日：2003-08-21
申请人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Shekhar Subramoney , Munirpallam A. Subramanian , Allen C. Sievert
发明人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Shekhar Subramoney , Munirpallam A. Subramanian , Allen C. Sievert
IPC分类号： C07C17/00
CPC分类号： C07C17/206 , B01J23/864 , B01J35/002 , B01J37/0236 , B01J37/03 , B01J37/26 , C07C17/21 , Y02P20/582 , C07C19/08
摘要： A process for the preparation of pentafluoroethane is disclosed which involves contacting a mixture comprising hydrogen fluoride and at least one starting material selected from haloethanes of the formula CX3CHX2 and haloethanes of the formula CX2═CX2, where each X is independently selected from the group consisting of F and Cl (provided that no more than four of X are F), with a fluorination catalyst in a reaction zone to produce a product mixture comprising HF, HCl, pentafluoroethane, underfluorinated halogenated hydrocarbon intermediates and less than 0.2 mole percent chloropentafluoroethane based on the total moles of halogenated hydrocarbons in the product mixture. The process is characterized by the fluorination catalyst comprising (i) a crystalline cobalt-substituted 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) and/or (ii) a fluorinated crystalline oxide of (i).
摘要翻译：公开了一种制备五氟乙烷的方法，其涉及将包含氟化氢和至少一种选自式CX 3 CHX 2 2的卤代乙烷的起始物质和式CX 2 -CX 2 X，其中每个X独立地选自F和Cl（条件是不超过四个X为F），与反应区中的氟化催化剂，以产生基于产物混合物中卤代烃总摩尔数的HF，HCl，五氟乙烷，过氟化卤代烃中间体和小于0.2摩尔％氯五氟乙烷的产物混合物。该方法的特征在于氟化催化剂，其包含（i）结晶钴取代的α-氧化铬，其中α-氧化铬晶格中约0.05原子％至约6原子％的铬原子被三价钴（Co （ⅰ））和/或（ⅱ）氟化结晶氧化物。

2. 发明授权

US07129383B2 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 失效
标题翻译：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
公开(公告)号：US07129383B2
公开(公告)日：2006-10-31
申请号：US10523223
申请日：2003-08-21
申请人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Sekhar Subramoney , Munirpallam A. Subramanian , Allen C. Sievert
发明人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Sekhar Subramoney , Munirpallam A. Subramanian , Allen C. Sievert
IPC分类号： C07C17/00 , C07C17/266 , C07C17/10
CPC分类号： C07C19/08 , B01J23/26 , B01J23/866 , B01J35/002 , B01J37/0236 , B01J37/03 , B01J37/26 , C07C17/206 , C07C17/21 , C07C17/23 , C07C17/25 , C07C19/10 , C07C21/18
摘要： 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.
摘要翻译：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。

3. 发明授权

US07217678B2 Cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalyst precursors 有权
标题翻译：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
公开(公告)号：US07217678B2
公开(公告)日：2007-05-15
申请号：US10523228
申请日：2003-08-21
申请人： Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Allen C. Sievert , Shekhar Subramoney , Munirpallam Appadorai Subramanian
发明人： Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Allen C. Sievert , Shekhar Subramoney , Munirpallam Appadorai Subramanian
IPC分类号： B01J27/06 , B01J23/00
CPC分类号： C07C17/21 , B01J23/864 , B01J35/002 , B01J35/1014 , B01J37/0236 , B01J37/03 , C07C17/00 , C07C17/08 , C07C17/10 , C07C17/20 , C07C17/206 , C07C17/23 , C07C17/25 , C07C17/358 , C07C17/37 , C07C21/18 , C07C21/04 , C07C19/08 , C07C21/06 , C07C19/12 , C07C19/10
摘要： 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.
摘要翻译：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。

4. 发明授权

US07504358B2 Nickel-substituted and mixed nickel-and cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalysts precursors 有权
公开(公告)号：US07504358B2
公开(公告)日：2009-03-17
申请号：US10523226
申请日：2003-08-21
申请人： Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Allen C. Sievert , Shekhar Subramoney , Munirpallam Appadorai Subramanian
发明人： Velliyur Nott Mallikarjuna Rao , H. David Rosenfeld , Allen C. Sievert , Shekhar Subramoney , Munirpallam Appadorai Subramanian
IPC分类号： B01J23/00 , C07C19/08 , C07C21/00
CPC分类号： C07C17/37 , B01J23/26 , B01J23/866 , B01J35/0013 , B01J35/002 , B01J35/006 , B01J35/023 , B01J35/1014 , B01J37/0236 , B01J37/03 , C07C17/08 , C07C17/10 , C07C17/206 , C07C17/21 , C07C17/23 , C07C17/25 , C07C17/358 , C07C19/10
摘要： A crystalline alpha-chromium oxide where from about 0.05 atom % to about 2 atom % of the chromium atoms in the alpha-chromium oxide lattice are substituted by nickel atoms, and optionally, additional chromium atoms in the alpha-chromium oxide lattice are substituted by trivalent cobalt atoms (provided that the total amount of the nickel atoms and the trivalent cobalt atoms in the alpha-chromium oxide lattice is no more than 6 atom %) is disclosed. Also disclosed is a chromium-containing catalyst composition comprising as a chromium-containing component the crystalline substituted alpha-chromium oxide; and a method for preparing a composition comprising the crystalline substituted alpha-chromium oxide. The method comprises (a) co-precipitating a solid by adding ammonium hydroxide to an aqueous solution of a soluble divalent nickel salt, a soluble trivalent chromium salt, and optionally, a soluble divalent or trivalent cobalt salt, that contains at least three moles of nitrate per mole of chromium in the solution, has a nickel concentration of from about 0.05 mole % to about 2 mole % of the total of nickel, chromium, and cobalt in the solution, and has a combined concentration of nickel and cobalt of no more than 6 mole % of the total of nickel, chromium, and cobalt in the solution; and after at least three moles of ammonium per mole of chromium 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 said crystalline 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 substituted alpha-chromium oxide and/or the treated substituted alpha-chromium oxide.

5. 发明授权

US07122704B2 Fluoroketone compounds 失效
标题翻译：氟酮化合物
公开(公告)号：US07122704B2
公开(公告)日：2006-10-17
申请号：US10871857
申请日：2004-06-18
申请人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
发明人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
IPC分类号： C07C49/00 , A62C1/00 , G03C1/00
CPC分类号： C07C49/175 , C07C45/58 , C07C49/16
摘要： The present invention relates to new fluoroketone compounds from the groups monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones. These fluoroketone compounds have utility in preventing, controlling and extinguishing fire. These fluoroketone compounds have further utility as additives to reduce or eliminate the flammability of normally flammable working fluids such as refrigerants, foam blowing agents, solvents, aerosol propellants, and sterilants.
摘要翻译：本发明涉及来自单溴全氟酮，一氢溴三氟全氟酮，（全氟烷氧基）一溴全氟酮，（氟烷氧基）一溴全氟酮和一氯三溴全氟酮的新的含氟酮化合物。这些含氟酮化合物可用于预防，控制和扑灭火灾。这些含氟酮化合物具有进一步的作为添加剂的用途，以减少或消除通常可燃的工作流体如致冷剂，泡沫发泡剂，溶剂，气溶胶推进剂和灭菌剂的可燃性。

6. 发明授权

US07087788B2 Fluorosulfone compounds 失效
标题翻译：氟砜化合物
公开(公告)号：US07087788B2
公开(公告)日：2006-08-08
申请号：US10916355
申请日：2004-08-11
申请人： Allen C. Sievert , Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , Paul R. Resnick
发明人： Allen C. Sievert , Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , Paul R. Resnick
IPC分类号： C07C315/00 , C07C317/00
CPC分类号： C07C317/04 , A62D1/00 , A62D1/0057 , A62D3/38
摘要： The present invention relates to new fluorosulfone compounds. These fluorosulfone compounds have utility in preventing, controlling and extinguishing fire.
摘要翻译：本发明涉及新的氟代砜化合物。这些氟砜化合物可用于预防，控制和扑灭火灾。

7. 发明授权

US07343981B2 Methods using fluoroketones for: extinguishing fire; preventing fire, and reducing or eliminating the flammability of a flammable working fluid 失效
标题翻译：使用氟酮的方法：灭火; 防止火灾，并减少或消除易燃工作流体的可燃性
公开(公告)号：US07343981B2
公开(公告)日：2008-03-18
申请号：US10871715
申请日：2004-06-18
申请人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
发明人： Mario J. Nappa , Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
IPC分类号： A62C2/00
CPC分类号： C07C49/175 , C07C45/58 , C07C49/16
摘要： The present invention relates to methods of using at least one fluoroketone selected from monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones for i) extinguishing fire by applying to the fire such a fluoroketone, ii) preventing fire in an air-containing enclosed area containing combustible materials by introducing into the area such a fluoroketone and maintaining the fluoroketone in an amount sufficient to suppress combustion of combustible materials in the enclosed area, and iii) reducing or eliminating the flammability of a flammable working fluid, by mixing between about 0.1 to about 99 percent by weight of such a fluoroketone with the flammable working fluid.
摘要翻译：本发明涉及使用选自一溴全氟酮，一氢溴三氟全氟酮，（全氟烷氧基）一溴全氟酮，（氟代烷氧基）一溴全氟酮，和一氯三氟全氟酮的至少一种氟代酮的方法，用于i）通过向火中施加氟代酮消除火焰，ii）含有可燃性物质的含空气的封闭区域通过将这样的氟代酮引入到这样的区域中并将氟酮保持在足以抑制在封闭区域内的可燃材料的燃烧的量，以及iii）减少或消除易燃工作流体的可燃性，将约0.1至约99重量％的这种氟酮与易燃工作流体混合。

8. 发明授权

US07161049B2 Process for purifying hydrofluoropropanes 失效
标题翻译：氢氟丙烷的纯化方法
公开(公告)号：US07161049B2
公开(公告)日：2007-01-09
申请号：US10734946
申请日：2003-12-11
申请人： Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
发明人： Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
IPC分类号： C07C17/38
CPC分类号： C07C17/354 , C07C17/04 , C07C17/206 , C07C17/23 , C07C17/395 , C07C19/08
摘要： 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.
摘要翻译：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）。

9. 发明授权

US07285691B2 Process for the preparation of 1,1,1,3,3,3-hexafluoropropane and at least one of 1,1,1,2,3,3-hexafluoropropane and 1,1,1,2,3,3,3-heptafluoropropane 有权
公开(公告)号：US07285691B2
公开(公告)日：2007-10-23
申请号：US10572625
申请日：2004-10-13
申请人： Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
发明人： Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
IPC分类号： C07C17/10 , C07C17/00
CPC分类号： C07C17/23 , B01J23/002 , B01J23/26 , B01J27/12 , B01J37/26 , B01J2523/00 , C07C17/21 , C07C19/08 , C07C19/10 , B01J2523/27 , B01J2523/67
摘要： A process is disclosed for the manufacture of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and at least one 1,1,1,2,3,3-hexafluoropropane (HFC-236ea) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The process involves (a) reacting HF, Cl2, and at least one halopropene of the formula CX3CCl=CX2 (where each X is independently F or Cl) to produce a product including both CF3CCl2CF3 and CF3CClFCClF2; (b) reacting CF3CCl2CF3 and CF3CClFCClF2 produced in (a) with hydrogen to produce a product comprising CF3CH2CF3 and at least one compound selected from the group consisting of CHF2CHFCF3, and CF3CHFCF3; and (c) recovering from the product produced in (b), CF3CH2CF3 and at least one compound selected from the group consisting of CHF2CHFCF3 and CF3CHFCF3. In (a), the CF3CCl2CF3 and CF3CClFCClF2 are produced in the presence of a chlorofluorination catalyst including a ZnCr2O4/crystalline α-chromium oxide composition, a ZnCr2O4/crystalline α-chromium oxide composition which has been treated with a fluorinating agent, a zinc halide/α-chromium oxide composition and/or a zinc halide/α-chromium oxide composition which has been treated with a fluorinating agent.

10. 发明授权

US07405334B2 Process for the reduction of acidic contaminates in fluorinated hydrocarbons 失效
标题翻译：降低氟化烃中酸性污染物的方法
公开(公告)号：US07405334B2
公开(公告)日：2008-07-29
申请号：US10444487
申请日：2003-05-23
申请人： Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
发明人： Velliyur Nott Mallikarjuna Rao , Allen C. Sievert
IPC分类号： C07C17/38
CPC分类号： C07C17/38
摘要： The present invention relates to processes for reducing the concentration of acidic impurities HF, HCl, HBr, HI, HNO3 and H2SO4 in fluorinated hydrocarbons. The process involves: (i) contacting the fluorinated hydrocarbon with a phosphorous oxyacid salt, and (ii) recovering the fluorinated hydrocarbon having reduced concentration of, or substantially free of, said acidic contaminant, provided that said fluorinated hydrocarbon is not CF3CH2CF3 or CF3CHFCF3.
摘要翻译：本发明涉及用于降低酸性杂质HF，HCl，HBr，HI，HNO 3和H 2 SO 4的浓度的方法氟化烃。该方法包括：（i）使氟化烃与含磷酸盐接触，和（ii）回收具有降低浓度或基本上不含所述酸性污染物的氟化烃，条件是所述氟化烃不是CF 3 3 CF 3或CF 3 CHFCF 3 3。

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