CN102906229B - 使用生物质制备运输燃料或润滑油基础油的方法 - Google Patents
使用生物质制备运输燃料或润滑油基础油的方法 Download PDFInfo
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- CN102906229B CN102906229B CN201180024203.9A CN201180024203A CN102906229B CN 102906229 B CN102906229 B CN 102906229B CN 201180024203 A CN201180024203 A CN 201180024203A CN 102906229 B CN102906229 B CN 102906229B
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- ketone
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- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
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- 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
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- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 16
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
- C10G3/52—Hydrogen in a special composition or from a special source
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Abstract
本发明涉及使用源自生物质的挥发性脂肪酸(VFA)来经济地制备对应于汽油燃料或润滑油基础油的链烷烃化合物的方法。所述方法包括以下步骤:通过生物质发酵制备C2-C4挥发性脂肪酸;将挥发性脂肪酸酮基化,以制备C3-C7酮的混合物;使所制得的酮经过醇醛缩合以制得C6-C60酮;以及通过加氢脱氧将C6-C60酮转化为C6-C60链烷烃。醇醛缩合和加氢脱氧可在低温下依次进行或在单一步骤中同时进行。当使用通过如下方式制得的催化剂体系时,其中:该催化剂体系要么是通过将具有缩合、氢化和加氢脱氧功能中的一种或多种功能的材料进行物理混合而制得的,要么是通过使用粘合剂使所述材料成形而制得的,或者是通过使用所述材料来形成双床催化剂体系而形成的,则可以以经济的方法直接制得汽油燃料或高品质的润滑油基础油。
Description
技术领域
本发明涉及使用源自生物质的挥发性脂肪酸(VFA)来经济地制备对应于汽油燃料或润滑油基础油的链烷烃化合物的方法。更具体而言,本发明涉及通过如下方式以高收率制备支链的非极性链烷烃运输燃料或润滑油基础油,所述方式为:对来自生物源的原材料进行发酵,从而获得挥发性脂肪酸,通过催化反应将所述挥发性脂肪酸转化为酮的混合物,并将所述的酮的混合物单独或依次地进行醇醛缩合、氢化和加氢脱氧。
背景技术
矿物燃料或石油基燃料已经构成了能量生产和运输的基础。近年来,由于成本增加、短缺威胁和供应的中断,生物燃料尤其被认为是石油基燃料的替代性燃料。
生物燃料通常被认为是源自生物质的任何燃料。术语生物质通常用于植物基来源,例如玉米、大豆、亚麻籽、甘蔗和棕榈油,但是该术语通常可以延伸至在碳循环中发挥一定作用的任何现存的生物机体、或是它们的新陈代谢副产物。
关于由生物质制备生物质能的研究基本上已经进入了可取代运输用燃油(汽油和柴油)的替代燃料的研究阶段。作为汽油的替代物,已研制出由甘蔗、玉米等发酵而制备的生物乙醇,并已市场化。类似地,作为柴油的替代物,已研制出通过对棕榈油、大豆油等植物油进行处理而制得的诸如FAME、HBD等生物柴油,并已市场化。
然而,在现有技术中,将植物和植物油等可食用的植物用作制备生物乙醇和生物柴油的原材料存在着伦理道德方面的问题。另外,原材料的供应并不容易,并且由于原材料成本的快速升高,其经济性也迅速降低。为了试图解决这些问题,人们已经积极开始进行对不可食用的植物用作原材料的研究,但是尚未发现明确的解决方案。
在近年来关于由生物质制备运输燃料的研究中,如下研究受到广泛关注,该项研究为这样一种方法,该方法包括:通过各种预处理步骤从木质生物质获得C6糖/多元醇,使用Pt-Re/C催化剂由C6糖/多元醇制备醇、有机酸、环状呋喃等的混合物,并通过各种化学反应路径由该混合物制备油馏分,例如汽油、芳香烃和柴油[Science 322(2008)417]。然而,由于该方法的收率低、预处理成本高、氢气用量大、反应路径复杂等原因,该方法仍需较长时间才能应用于实际工业化生产过程中。
可通过简单的发酵,以高收率由各种原材料(包括木质生物质、海藻和有机废物)获得挥发性脂肪酸(VFA),关于由这些挥发性脂肪酸制备运输用油的研究正在进行中。概括而言,由通过发酵获得的混合脂肪酸或混合酮来制备混合醇的方法是已知的。另外,已知这样一种方法,该方法包括通过醇脱水制备混合烯烃,以及将该烯烃进行低聚以制备汽油和柴油馏分。
美国专利文献US 5,874,263公开了可通过对生物质进行厌氧发酵来制备挥发性脂肪酸或它们的金属盐。具体而言,可通过在厌氧条件下用熟石灰对生物质加以预处理,并提高初始挥发性脂肪酸水平,从而提高由发酵获得的挥发性脂肪酸以及它们的钙盐的产率。
制备挥发性脂肪酸、或者利用由发酵制得的挥发性脂肪酸的金属盐来制备酮混合物的方法如下所述。美国专利文献US 5,969,189公开了通过热解按照上述方式制备的挥发性脂肪酸的钙盐以形成碳酸钙,并由挥发性脂肪酸制备酮混合物的方法。美国专利文献US 6,043,392公开了这样的方法,该方法包括:用胺取代由厌氧发酵制得的挥发性脂肪酸的金属盐,以制备羧酸胺,使该羧酸胺热解,从而制备挥发性脂肪酸,并制备副产物醛、醇和乳酸。
由通过上述方法制得的挥发性脂肪酸直接制备运输燃料的方法如下所述。美国专利文献US 7,351,559公开了通过以下方式来制备可用作燃料的乙醇的方法:将生物质发酵以制备乙酸和乙酸盐,随后使其酯化为乙酸乙酯,然后进行氢化。美国专利文献US 20080280338公开了通过以下方式来制备可用作运输燃料的液体燃料的方法:由源自挥发性脂肪酸的醇和甲烷制备乙炔,并将乙炔转化为乙烯,随后进行低聚化。美国专利文献US 20090239279公开了通过以下方式来提高液体燃料制备效率的方法:将由生物质获得的烃和裂解油(而非上述的醇和甲烷)混合,并使该混合物进行低聚化。
然而,在通过低聚化获得具有支链的燃料的过程中,存在如下缺点:由于焦炭的产生,催化剂快速失活,因此应使用设备和操作成本高的流化床反应器。
另外,传统的生物燃料(例如,生物乙醇和生物柴油)因其物理性能不同于石油类燃料的物理性能,因而仅可替代一部分石油类汽油和柴油。然而,如果由生物来源制得的运输燃料或润滑油基础油的品质相当于或高于传统石油类运输燃料或润滑油基础油的品质,并且可以替代所有的传统石油类燃料,则其技术价值会更高。
另外,存在对如下方法进行研究的需求,该方法通过对来自于自然来源的挥发性脂肪酸进行催化反应,并且将所述催化反应的产物单独或依次地进行醇醛缩合、氢化和加氢脱氧,从而能够以高收率制备支链的非极性链烷烃运输燃料或润滑油基础油。
发明内容
技术问题
因此,本发明人已经进行了研究以克服现有技术中存在的上述问题,并且已认识到,如果研究出由能源价值低且会造成环境污染的生物废物来制备挥发性脂肪酸、并且由该挥发性脂肪酸有效地制备运输燃料或润滑油基础油的替代方法,则可使经济效益最大化,并且有益于环境改善,从而达成如下所述的本发明。
因此,本发明的一个目的在于提供一种由来自于生物来源的材料制备烃的方法,该烃可用作运输燃料和润滑油基础油。更具体而言,本发明的一个目的在于提供一种通过如下方式以高收率制备支链的非极性链烷烃运输燃料或润滑油基础油的方法:对来自于生物来源的原材料经发酵而获得的挥发性脂肪酸进行催化反应,使催化反应产物单独或依次地进行醇醛缩合、氢化和加氢脱氧。
本发明的目的不限于上述目的,本领域技术人员将通过如下描述而清楚地理解本发明的其它目的。
技术方案
为了克服上述问题,本发明提出了一种通过以下方式来制备支链的非极性链烷烃运输燃料或润滑油基础油的方法:将来自于生物来源的原材料经发酵所获得的挥发性脂肪酸通过催化反应而转化为酮的混合物,并在催化剂的存在下,将该酮的混合物单独或依次地进行醇醛缩合和加氢脱氧。
为了达成上述目的,本发明提供了一种制备运输燃料或润滑油基础油的方法,该方法包括以下步骤:
A)通过生物质的发酵来制备C2-C7挥发性脂肪酸或它们的盐;
B)由步骤A)中的挥发性脂肪酸或它们的盐制备C3-C13酮的混合物;以及
C)在氢化催化剂的存在下,将步骤B)中的酮的混合物转化成对应于运输燃料或润滑油基础油的链烷烃。
根据本发明的一个实施方案,为了制备运输燃料或润滑油基础油,步骤C)包括以下步骤:
i)使所述的酮的混合物进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
ii)使所述羟基酮脱水以形成烯酮(enones);
iii)用氢气使烯酮饱和以形成酮;以及
iv)通过加氢脱氧使所形成的酮转化为支链的非极性链烷烃。
根据本发明的一个实施方案,所述方法在步骤ii)和iii)之间还可以包括以下步骤:
iii-a)使烯酮与酮反应,以形成具有加长的碳链长度的羟基烯酮;以及
iii-b)使所述羟基烯酮脱水。
根据本发明的一个实施方案,所述方法在步骤ii)和iii)之间还可以包括以下步骤:
iii-c)用氢气使烯酮饱和;
iii-d)使酮的混合物进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
iii-e)使羟基酮脱水以形成具有加长的碳链长度的烯酮;以及
iii-f)用氢气使步骤iii-e)中的烯酮饱和。
根据本发明的一个实施方案,所述方法在步骤C)之后,还可以包括将所制得的链烷烃进行骨架异构化的步骤D)。
有益效果
根据本发明,可由源自各种生物质的挥发性脂肪酸制备酮的混合物,然后可由酮的混合物制备支链的非极性链烷烃化合物,该化合物可用作运输油或润滑油基础油。因此,由不基于石油的全新来源获得运输油或润滑油基础油成为可能。
与现有技术不同的是,由于可将各种生物质用作原材料,因此本发明具有以下优点:可以保证存在大量的原材料,并且可以显著提高经济效益。
根据本发明制备的支链的非极性链烷烃化合物可以用作具有高的氧化稳定性和高的低温稳定性的高质量燃料,这是由于它们不含去活性物质(包括硫、氮和芳香化合物),并且其以链烷烃为基础。不同于传统的生物燃油,本发明的链烷烃化合物可用作运输燃料或润滑油基础油,而没有掺混方面的限制。
特别是,在制备润滑油基础油的过程中,通常会进行异构化反应以提高润滑油基础油的低温稳定性,但是在本发明的制备润滑油基础油的反应中,并不需要进行异构化反应。
另外,当使用通过如下方式制得的催化剂体系时,其中:该催化剂体系要么是通过将本发明中所披露的具有缩合、氢化和加氢脱氧功能中的一种或多种功能的材料进行物理混合而制得的,要么是通过使用粘合剂使所述材料成形而制得的,或者是通过使用所述材料来形成双床催化剂体系而形成的,则可通过将由各种方法获得的酮的混合物单独或依次地进行醇醛缩合、氢化和加氢脱氧而以高产量制备链烷烃。
附图说明
图1为示出了根据本发明实施方案的总反应路径的示意图。
最佳实施方式
以下,将结合附图进一步详细描述本发明的技术原理。
如上所述,根据本发明制备运输燃料或润滑油基础油的方法包括以下步骤:通过使生物质发酵来制备C2-C7挥发性脂肪酸;将挥发性脂肪酸酮基化来制备C3-C13酮的混合物;以及在氢化催化剂的存在下将所制得的酮转化为链烷烃。在一个实施方案中,将酮转化为链烷烃的步骤可通过加氢脱氧来进行。通过加氢脱氧作用由酮的混合物直接制得的链烷烃可为C3-C13直链链烷烃。可通过异构化反应将所述直链链烷烃转化为支链链烷烃。
在另一个实施方案中,将酮转化为链烷烃的步骤可包括以下步骤:通过醇醛缩合将所制得的酮转化为具有加长的碳链长度的酮;并且通过加氢脱氧作用将转化后的酮转化为链烷烃。根据该实施方案制备的链烷烃可以为C6-C60支链链烷烃。将酮转化为链烷烃的步骤可在单催化剂体系或单反应器中进行,并且可通过单独的连续过程来进行醇醛缩合和加氢脱氧反应。
以下将详细描述上述实施方案。
在本发明中,将由生物质发酵制得的C2-C4挥发性脂肪酸及其混合物用作原材料。另外,也可将与其对应的合成材料用作原材料。
图1为示出了根据本发明的总反应路径的示意图。从图1中可看出,本发明涉及使用源自生物质的挥发性脂肪酸(VFA)来制备对应于汽油燃料或润滑油基础油的链烷烃化合物(特别是支链链烷烃化合物)的方法。可想到由生物来源的脂肪来制备醛、酮和醇,并使所得的产物进行醇醛缩合。然而,当将源自非挥发性脂肪(非挥发性脂肪不是挥发性脂肪酸)的醛、酮和醇用作原材料时,将存在这样的问题,即原材料的供应受到限制,并且由于原材料中的烃链长度较长,因此为了制备润滑油基础油,就需要进行异构化步骤。另外,由于将具有高烯烃含量的脂肪用作原材料,鉴于烯烃在醇醛缩合步骤中的影响,所以将产生不期望的脂环烃化合物。另外,由于醇醛缩合和加氢脱氧的反应彼此不同,因此不可能在单一步骤或单反应器中进行连串反应以制备润滑油基础油。
可通过对传统生物质材料进行发酵来制备源自生物质的挥发性脂肪酸。用于本发明的挥发性脂肪酸(VFA)为C2-C7的水溶性羧酸或其混合物,并且具有(例如)如下结构:
在本发明的一个实施方案中,通过酮基化作用将脂肪酸转化为C3-C7酮的混合物。同时,也可通过对发酵过程中制得的挥发性脂肪酸盐进行热解而直接获得酮的混合物。例如,下面的反应方案1中示出了该酮基化反应:
[反应方案1]
可使用本领域已知工艺将羧酸转化为酮。例如,该转化所用的催化剂可包括二氧化钛、或者二氧化锆或二氧化铈,其担载于氧化铝上。反应区域中的温度可以为200℃至600℃。酮基化反应可以在较宽的压力范围内进行,优选为1psi-200psi。通过上述方法制备的混合酮具有以下结构:
所制得的酮混合物是直链的,并且可使其进行醇醛缩合以形成具有更大碳数目的酮。如果不进行醇醛缩合,可使直链酮的混合物进行加氢脱氧以制备直链链烷烃。根据(例如)如下反应方案2进行醇醛缩合:
[反应方案2]
优选在氢气气氛中进行本发明的醇醛缩合反应。在这种情况下,如下所述,平衡反应可由生成烯酮转变为支链酮,从而可以加快作为速控步骤的醇醛缩合反应的速率。
将由上述缩合反应获得的氢化酮进行脱水,以脱去水分子并形成双键。因此,脱水反应获得烯酮化合物。该脱水反应路径为(例如)如下所示:
[反应方案3]
可在低温下将烯酮化合物中的双键氢化,从而可通过如下方式将烯酮化合物转化为支链酮:
[反应方案4]
可通过如下的加氢脱氧作用将上述支链酮化合物转化为支链链烷烃化合物:
[反应方案5]
由此,根据上述反应方案2至5,可由C3-C 13酮的混合物选择性地制备C3-C60的直链或支链链烷烃,并且在制得的链烷烃中,C6-C14的支链的非极性链烷烃可直接用作运输燃料,而没有掺混方面的限制。
如果对直链酮化合物进行加氢脱氧反应,则主要制得直链链烷烃。可通过异构化将直链链烷烃转化为支链链烷烃。在本领域已知的条件下进行异构化反应。
在根据本发明的方法中,用于由直链酮的混合物制备具有支链的运输燃料的路径可总结如下:
[反应方案6]
在本发明的一个实施方案中,制备运输燃料或润滑油基础油的方法包括以下步骤:
i)将酮的混合物进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
ii)使所述羟基酮脱水,以形成烯酮;
iii)用氢气使烯酮饱和以形成酮;以及
iv)通过加氢脱氧使步骤iii)中所形成的酮转化为支链的非极性链烷烃。
在本发明中,已证实反应方案6中的反应①至④可在单独的反应器或在两个或更多个反应器中进行,但是优选在一个反应器中进行。由反应②制得的烯酮不稳定,因此在低温下容易发生酮基化。因此,反应③的速率高于其它反应的速率。如果反应③快速进行并且烯酮浓度降低,则反应②加速,并且基于相同的原因,醇醛缩合①(平衡反应)加速。由于在此反应条件下反应④容易进行,因此在一个反应器中一步进行醇醛缩合和加氢脱氧反应时,转化速率会高于单独进行这些反应时的转化速率。
另外,当使用通过如下方式制得的催化剂体系时,其中:该催化剂体系要么是通过将具有缩合、氢化和加氢脱氧功能中的一种或多种功能的材料进行物理混合而制得的,要么是通过使用粘合剂使所述材料成形而制得的,或者是通过使用所述材料来形成双床催化剂体系而形成的,则可显著提高支链的非极性链烷烃的收率。
具有缩合功能的催化剂可以为任何具有酸或碱官能度的物质。其例子包括:CeZrOx、CuZrOx、碳铝镁石、氧化铌、氧化铝、二氧化硅、二氧化硅-氧化铝、氧化锆、二氧化钛或它们的混合氧化物、或分子筛(包括沸石)。
作为可用于氢化的催化剂,可使用任何具有氢化功能的材料。具体而言,其可包括选自第VIII族金属、第VI族金属或其混合物中的金属成分。优选地,该金属成分可选自由Pd、Pt、Rh、Ru、Ni、Cu、V、Fe、Co、Mo、W、NiMo、CoMo、NiW和CoW组成的组。
具有加氢脱氧功能的催化剂优选为同时具有氢化功能和脱氧功能的催化剂,并且可通过将具有氢化功能的金属成分担载于具有酸或碱官能度的材料上而制备得到。
同时,可在单催化剂体系或单反应器中,在80℃至500℃的温度以及1-200巴的氢气压力下进行步骤i)至v)。优选地,可在氢气气氛中,在100℃至400℃的温度以及5-50巴的压力下进行这些步骤。单反应器中的WHSV为0至5/小时,优选为0至2/小时,更优选为0至1/小时,并且最优选为大于零至0.6/小时。
在偏离上述条件的其他条件下,可能导致反应不完全。例如,在比上述条件更低的温度、更低的压力和更短的停留时间下,转化率可降低;而在比上述条件更高的温度、更高的压力和更长的停留时间下,高沸点烃可显著增加。
根据与上述反应相同的原理进行制备润滑油基础油的反应,但是是通过经醇醛缩合使碳链长度变长的反应来进行的。可通过如下所述的两种方法来实现通过醇醛缩合而增加碳链长度。
在一种方法中,将源自挥发性脂肪酸的酮另外进行醇醛缩合,得到碳链长度经醇醛缩合而加长的烯酮状态。
具体而言,根据本发明的一个实施方案,制备运输燃料或润滑油基础油的方法包括以下步骤:
i)使酮的混合物进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
ii)使所述羟基酮脱水而形成烯酮;
iii-1)使所述烯酮与酮反应,以形成具有加长的碳链长度的羟基烯酮;
iv)使羟基烯酮进行脱水和氢化,以形成具有加长的碳链长度的酮;以及
v)通过加氢脱氧将所制得的酮转化为支链的非极性链烷烃。
根据本发明的另一实施方案,制备运输燃料或润滑油基础油的方法包括以下步骤:
i)使酮的混合物进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
ii)使所述羟基酮脱水以形成烯酮;
iii-a)使所述烯酮与酮反应,以形成具有加长的碳链长度的羟基烯酮;
iii-b)使所述羟基烯酮脱水;
iv)使已脱水的烯酮进行氢化,以形成具有加长的碳链长度的酮;以及
v)通过加氢脱氧将所形成的酮转化为支链的非极性链烷烃。
在另一种方法中,还将已被稳定化的酮(烯酮)与源自挥发性脂肪酸的酮进行醇醛缩合。
具体而言,根据本发明的一个实施方案,制备运输燃料或润滑油基础油的方法包括以下步骤:
i)使酮的混合物进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
ii)使所述羟基酮脱水,以形成烯酮;
iii)使所述烯酮氢化以形成酮,随后通过醇醛缩合增加酮的碳链长度;
iv)使所述酮进行脱水和氢化;以及
v)通过加氢脱氧将所述酮转化为支链的非极性链烷烃。
根据本发明的另一个实施方案,制备运输燃料或润滑油基础油的方法包括以下步骤:
i)使酮的混合物进行醇醛缩合,以制备羟基酮;
ii)使所述羟基酮脱水,以形成烯酮;
iii-c)用氢气使烯酮饱和,以形成酮;
iii-d)使步骤iii-c)中的酮进行醇醛缩合,以形成具有加长的碳链长度的羟基酮;
iii-e)使所述酮脱水,以形成具有加长的碳链长度的烯酮;以及
iv)使步骤iii-e)中的烯酮进行氢化,从而形成具有加长的碳链长度的酮;以及
v)通过加氢脱氧将步骤iv)中的酮转化为支链的非极性链烷烃。
下述反应方案7可解释根据上述实施方案的步骤i)至v)。反应方案7中示出的步骤i)至v)可在催化剂体系或反应器中同时进行,或是可分为醇醛缩合反应和加氢脱氧反应,并且可使用这些反应各自的催化剂和反应器依次进行。
[反应方案7]
当在单反应器中使用单一催化剂同时进行步骤i)至v)时,氢化催化剂可为如上所述的催化剂。换言之,该催化剂可包含选自第VIII族金属、第VI族金属及其混合物的金属成分。优选地,该金属成分可以为Pd、Pt、Rh、Ru、Ni、Cu、V、Fe、Co、Mo、W、或是其中两种或多种的混合物,尤其为NiMo、CoMo、NiW或CoW。另外,催化剂还可包含载体,其可为CuZrOx、碳铝镁石、氧化铌、氧化铝、二氧化硅、碳、二氧化硅-氧化铝、氧化锆或二氧化钛。
同时,可在单一催化剂体系或反应器中,在80℃至500℃的温度以及1-200巴的氢气压力下进行步骤i)至v)。优选地,可在氢气气氛中,在100℃至400℃的温度以及5-50巴的压力下进行这些步骤。另外,单反应器中的WHSV为0至5/小时,优选为0至2/小时,更优选为0至1/小时,并且最优选为0至0.6/小时。
在偏离上述条件的其他条件下,可能导致反应不完全。例如,在比上述条件更低的温度、更低的压力和更短的停留时间下,转化率可降低;而在比上述条件更高的温度、更高的压力和更长的停留时间下,高沸点烃可显著增加。
如上所述,可增加碳链长度以形成C6-C60酮,可对C6-C60酮进行加氢脱氧以制备用作运输燃料或润滑油基础油的C6-C60的支链链烷烃。
如上制备的润滑油基础油可对应于第III类润滑油基础油,并且不需要额外进行异构化,这不同于通常的石油类润滑油基础油。另外,由于该润滑油基础油是由挥发性脂肪酸(而不是非挥发性脂肪)通过醇醛缩聚而制备的,因此该润滑油基础油为纯的、不含环烷烃结构的、支链的非极性链烷烃。特别是,该支链的非极性链烷烃润滑油基础油为不含去活性物质、并且具有非常优异的低温稳定性和氧化稳定性的高质量润滑油基础油。另外,其与现有的润滑油添加剂可相容。
本发明中,在制备直链酮化合物之后的氢化反应中,相对于2摩尔挥发性脂肪酸而言,仅需要3摩尔的氢气来制备支链链烷烃运输燃料,因此相比于现有技术,氢气消耗也非常低。另外,由于可使用生物质发酵过程中所产生的氢气,因此本发明的方法在提供氢气方面是相对有利的,并且非常经济。
本发明的实施方式
下文中将结合实施例进一步详细描述本发明。然而,应当理解,本发明的范围不限于这些实施例,并且本发明可以包括本发明范围内的各种方式。
实施例1
使用已知技术[Journal of Molecular Catalysis A:Chemical 227(2005)231-239],由源自生物质的挥发性脂肪酸制备酮的混合物。该酮的混合物的组成在下表1中示出。对于具有表1中所示出的组成的酮的混合物,使用0.2重量%的Pd/Nb2O5催化剂以进行制备支链链烷烃的实验。通过以下方法制备所述0.2重量%的Pd/Nb2O5催化剂:通过初湿法(incipient wetness method)将Pd(NO3)2(10重量%Aldrich)担载于铌酸上,在393K的温度下将担载后的材料干燥3小时,并在空气气氛中于533K的温度下对干燥后的材料进行烘焙。使用高压微反应器进行该反应,并在该实验中使用6g上述制备的0.2重量%的Pd/Nb2O5催化剂。在200sccm的氢气流速下,以0.5℃/分钟的速率将所述催化剂加热至723K,将催化剂在该温度下保持2小时,并将温度降至623K,从而将该催化剂还原。在623K下,当氢气压力调节为50巴并且引入的氢气/原材料的比值调节为5时,通过上升气流法(upflow method)以0.5h-1的WHSV引入酮的混合物。在反应完成后,用GC分析混合酮中的每种酮的转化率,分析结果示于下表2中。
[表1]
碳原子数 | 名称 | 含量(重量%) |
C3 | 二甲基甲酮(DMK) | 60 |
C4 | 甲基乙基酮(MEK) | 20 |
C5 | 甲基丙基甲酮(MPK) | 10 |
C5 | 二乙基甲酮(DEK) | 5 |
C6 | 乙基丙基酮(EPK) | 3 |
C7 | 二丙基甲酮(DPK) | 2 |
[表2]
酮 | 转化率(%) |
二甲基甲酮(DMK) | 95 |
甲基乙基酮(MEK) | 90 |
甲基丙基甲酮(MPK) | 88 |
二乙基甲酮(DEK) | 73 |
乙基丙基酮(EPK) | 85 |
二丙基甲酮(DPK) | 99 |
通过GC-MS、Simdist等对产物加以分析,下表3中示出了产物的组成。
[表3]
产物 | 选择率(%) |
直链链烷烃(<C5) | 4 |
支链链烷烃(C6-C20) | 42 |
支链酮(C6-C14) | 25 |
支链烯烃(C4-C16) | 19 |
醇(C4-C10) | 6 |
芳烃(C7-C8) | 4 |
实施例2
对于具有表1所示组成的酮的混合物,使用Cu/Mg10Al7Ox催化剂进行制备支链链烷烃的实验。通过以下方法制备Cu/Mg10Al7Ox催化剂:以1:10:7的摩尔比混合Cu硝酸盐前体、Mg硝酸盐前体和Al硝酸盐前体,并且使用KOH和K2CO3的混合溶液,在pH为10的条件下将所述混合物共沉淀。在338K的温度下搅拌所制得的饼状物,同时向其中滴加蒸馏水,随后静置2小时,过滤沉淀物并洗涤。在393K的温度下将洗涤后的材料干燥足够长的时间,并在空气环境中于773K的温度下烘焙足够长的时间。为了将催化剂还原,将6g的该催化剂引入高压微反应器中,在氢气流速为200sccm的条件下,在573K的温度下将催化剂原位还原1小时。在与实施例1相同的条件下进行制备支链链烷烃化合物的反应。在反应完成后,用GC分析混合酮中每种酮的转化率,该分析结果示于表4中。
[表4]
酮 | 转化率(%) |
二甲基甲酮(DMK) | 88 |
甲基乙基酮(MEK) | 90 |
甲基丙基甲酮(MPK) | 85 |
二乙基甲酮(DEK) | 78 |
乙基丙基酮(EPK) | 82 |
二丙基甲酮(DPK) | 57 |
通过与实施例1中相同的方式分析产物,分析结果示于下表5中。
[表5]
产物 | 选择率(%) |
直链链烷烃(<C5) | 2 |
支链链烷烃(C6-C20) | 33 |
支链酮(C6-C14) | 35 |
支链烯烃(C4-C16) | 25 |
醇(C4-C10) | 4 |
芳烃(C7-C8) | 1 |
实施例3
对于具有表1中所示组成的酮的混合物,使用0.2重量%的Pd/CeZrOx催化剂来进行制备支链链烷烃的实验。为了制备0.2重量%的Pd/CeZrOx催化剂,通过以下方式制备CeZrOx载体。以1:1的比例将Ce(No3)3·6H2O和ZrO(NO3)2混合,并在用NH4OH将pH值保持为10的同时进行共沉淀65小时。将沉淀物过滤、洗涤并在383K的温度下干燥足够长的时间,随后在723K的温度下烘焙2小时。为了将该催化剂还原,将6g的该催化剂引入高压微反应器中,在该反应器中,在氢气流速为200sccm的条件下,以0.5℃/分钟的速率将催化剂加热至623K并保持该温度2小时,从而将催化剂还原。在与实施例1相同的条件下进行制备支链链烷烃化合物的反应。在反应完成后,用GC分析混合酮中每种酮的转化率,该分析结果示于下表6中。
[表6]
酮 | 转化率(%) |
二甲基甲酮(DMK) | 100 |
甲基乙基酮(MEK) | 95 |
甲基丙基甲酮(MPK) | 92 |
二乙基甲酮(DEK) | 72 |
乙基丙基酮(EPK) | 83 |
二丙基甲酮(DPK) | 75 |
通过与实施例1中相同的方式对产物加以分析,该分析结果示于下表7中。
[表7]
产物 | 选择率(%) |
直链链烷烃(<C5) | 1 |
支链链烷烃(C6-C20) | 25 |
支链酮(C6-C14) | 47 |
支链烯烃(C4-C16) | 26 |
醇(C4-C10) | 痕量 |
芳烃(C7-C8) | 1 |
实施例4
使用已知技术[Journal of Molecular Catalysis A:Chemical 227(2005)231-239],由源自生物质的挥发性脂肪酸制备酮的混合物,该酮的混合物的组成在表1中示出。对于具有表1中所示出的组成的酮的混合物,使用由0.25重量%的Pd/Nb2O5和Ni-Mo/ZrO2组成的双床催化剂进行制备支链链烷烃的实验。通过以下方法制备0.25重量%的Pd/Nb2O5催化剂:通过初湿法将Pd(NO3)2(10重量%Aldrich)担载于铌酸上,在393K的温度下将担载后的材料干燥3小时,并在空气气氛中于533K的温度下对干燥后的材料进行烘焙。Ni-Mo/ZrO2催化剂是通过将约10重量%的钼和约3重量%的Ni担载于ZrO2载体上而制得的。催化剂制备中所用的Mo前体为四水合七钼酸铵(以下称为“AHM”),并且Ni前体为六水合硝酸镍(以下称为“NNH”)。
具体而言,用溶解于蒸馏水中的AHM水溶液浸渍ZrO2载体,在423K的温度下干燥2小时,随后在732K的温度下持续烘焙2小时,从而制备得到Mo/ZrO2。然后将NNH溶于蒸馏水中,将Mo/ZrO2催化剂浸渍于该溶液中,在423K的温度下干燥2小时,随后在732K的温度下持续烘焙2小时,从而制备Ni-Mo/ZrO2催化剂。
使用高压微反应器进行所述反应,并且使用如上制备的两种催化剂进行所述实验,这两种催化剂的用量分别为3g(这两种催化剂的总量为6g)。在氢气流速为200sccm的条件下,以0.5℃/分钟的速率将催化剂加热至723K,将催化剂在该温度下保持2小时,然后将温度降至623K,从而将催化剂还原。在623K的温度下,在氢气压力调节为50巴时,以0.5h-1的WHSV引入酮的混合物。用气相色谱-质谱法分析反应物的转化率和产物选择率,并且下表8中示出了该分析结果。
[表8]
实施例5
对于具有表1中所示组成的酮的混合物,使用6g的下述催化剂来进行制备支链链烷烃的实验,其中该催化剂是通过将3g的0.25重量%的Pd/Nb2O5和3g的Ni-Mo/ZrO2物理混合而制得的。0.25重量%Pd/Nb2O5和Ni-Mo/ZrO2催化剂是通过与实施例4相同的方式制备的。以与实施例4相同的方式进行催化剂的还原以及反应,反应物的转化率和产物选择率如下表9所示。
[表9]
实施例6
对于具有表1所示组成的酮的混合物,使用由0.25重量%的Pd/CeZrOx和Ni-Mo/ZrO2组成的双床催化剂来进行制备支链链烷烃的实验。为了制备0.25重量%的Pd/CeZrOx,通过以下方式制备CeZrOx载体。以1:1的比例混合Ce(No3)36H2O和ZrO(NO3)2,用NH4OH将pH值保持为10,同时进行共沉淀65小时。将沉淀物过滤、洗涤、并在383K的温度下干燥足够长的时间,随后在723K的温度下烘焙2小时。使用高压微反应器进行所述反应,并且使用如上制备的总量为6g的两种催化剂(每种催化剂各3g)进行所述实验。以与实施例4相同的方式将催化剂还原并进行反应,反应物的转化率和产物选择率如下表10所示。
[表10]
实施例7
对于具有表1中所示组成的酮的混合物,使用6g的催化剂来进行制备支链链烷烃的实验,其中该催化剂是通过将3g的0.25重量%的Pd/CeZrOx和3g的Ni-Mo/ZrO2物理混合而制得的。0.25重量%的Pd/CeZrOx和Ni-Mo/ZrO2催化剂是以与实施例6相同的方式制备的。以与实施例4相同的方式将所述催化剂还原并进行反应,反应物的转化率和产物选择率如下表11所示。
[表11]
Claims (17)
1.一种使用生物质制备用于运输燃料或润滑油基础油的链烷烃的方法,该方法包括以下步骤:
A)通过生物质的发酵来制备C2-C7挥发性脂肪酸或它们的盐;
B)由步骤A)中所述的挥发性脂肪酸或它们的盐制备C3-C13酮的混合物;以及
C)在氢化催化剂的存在下将步骤B)中所述的酮的混合物转化成链烷烃,
其中步骤C)包括以下步骤:
i)使所述的酮的混合物进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
ii)使所述羟基酮脱水以形成烯酮;
iii)用氢气使所述烯酮饱和以形成酮;以及
iv)通过加氢脱氧使所形成的酮转化为链烷烃,并且
其中步骤C)在单反应器中进行。
2.权利要求1所述的方法,其中所述方法进一步在步骤ii)和iii)之间包括以下步骤:
iii-a)使所述烯酮与酮反应,以形成具有加长的碳链长度的羟基烯酮;以及
iii-b)使所述羟基烯酮脱水。
3.权利要求1所述的方法,其中所述步骤iii)如下:
iii-c)用氢气使步骤ii)中的所述烯酮饱和以形成酮;
iii-d)使步骤iii-c)中的所述酮进行醇醛缩合,以制备具有加长的碳链长度的羟基酮;
iii-e)使步骤iii-d)中的所述羟基酮脱水以形成具有加长的碳链长度的烯酮;以及
iii-f)使步骤iii-e)中的所述烯酮进行氢化,从而形成具有加长的碳链长度的酮。
4.权利要求1至3中任意一项所述的方法,其中所述链烷烃为C6-C60支链链烷烃。
5.权利要求1至3中任意一项所述的方法,其中用于步骤B)至C)中的一步或多步中的氢气是在步骤A)中制得的。
6.权利要求1至3中任意一项所述的方法,其中用于步骤C)中的所述催化剂具有醇醛缩合、氢化和加氢脱氧功能中的一种或多种功能。
7.权利要求6所述的方法,其中所述催化剂是通过物理混合或使用粘合剂进行成型而获得的催化剂体系。
8.权利要求6所述的方法,其中所述催化剂是具有由不同催化剂形成的双床结构的催化剂体系。
9.权利要求6所述的方法,其中所述催化剂具有醇醛缩合功能并包含酸或碱官能度。
10.权利要求9所述的方法,其中具有醇醛缩合功能的所述催化剂包括选自CeZrOx、CuZrOx、碳铝镁石、氧化铌、氧化铝、二氧化硅、二氧化硅-氧化铝、氧化锆、二氧化钛或它们的混合氧化物、或包括沸石在内的分子筛中的一者。
11.权利要求6所述的方法,其中具有氢化功能的所述催化剂为选自具有氢化功能的第VIII族金属、第VI族金属或它们的混合物的金属成分。
12.权利要求11所述的方法,其中所述金属成分选自由Pd、Pt、Rh、Ru、Ni、Cu、V、Fe、Co、Mo、W、NiMo、CoMo、NiW或CoW组成的组。
13.权利要求6所述的方法,其中具有加氢脱氧功能的所述催化剂同时具有氢化功能和脱氧功能。
14.权利要求13所述的方法,其中具有加氢脱氧功能的所述催化剂是通过将具有氢化功能的金属成分担载于包含酸或碱官能度的材料上而制备的。
15.权利要求6所述的方法,其中步骤C)是在1至200巴的氢气压力以及80℃至500℃的温度下进行的。
16.权利要求1所述的方法,其中所述单反应器中的WHSV被调节为0至5/小时。
17.权利要求16所述的方法,其中所述WHSV被调节为0至2/小时。
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CN111215073B (zh) * | 2018-11-23 | 2024-03-12 | 中国石油化工股份有限公司 | 镍硅复合氧化物、其制备方法、包含该氧化物的催化剂及其应用 |
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US5969189A (en) * | 1997-06-30 | 1999-10-19 | The Texas A&M University System | Thermal conversion of volatile fatty acid salts to ketones |
CN101360809A (zh) * | 2005-12-12 | 2009-02-04 | 耐思特石油公司 | 生产支链烃组分的方法 |
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US8679805B2 (en) | 2014-03-25 |
US20130017590A1 (en) | 2013-01-17 |
MY162616A (en) | 2017-06-30 |
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