CN103189487A - 来自单一原料的燃料和基础油调合料 - Google Patents
来自单一原料的燃料和基础油调合料 Download PDFInfo
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- CN103189487A CN103189487A CN2011800524209A CN201180052420A CN103189487A CN 103189487 A CN103189487 A CN 103189487A CN 2011800524209 A CN2011800524209 A CN 2011800524209A CN 201180052420 A CN201180052420 A CN 201180052420A CN 103189487 A CN103189487 A CN 103189487A
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- China
- Prior art keywords
- oil blending
- carbon atom
- base oil
- acyl group
- atom chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002199 base oil Substances 0.000 title claims description 27
- 239000000295 fuel oil Substances 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000002283 diesel fuel Substances 0.000 claims abstract description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 15
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 125000001924 fatty-acyl group Chemical group 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- 150000001721 carbon Chemical group 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000006317 isomerization reaction Methods 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical group [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 4
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
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- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
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- 150000002190 fatty acyls Chemical class 0.000 description 17
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- 239000000446 fuel Substances 0.000 description 13
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- 229930195733 hydrocarbon Natural products 0.000 description 11
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- 229930195729 fatty acid Natural products 0.000 description 10
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 7
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
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- 150000002148 esters Chemical class 0.000 description 4
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- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000014698 Brassica juncea var multisecta Nutrition 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 240000000385 Brassica napus var. napus Species 0.000 description 1
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 1
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- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000221089 Jatropha Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- -1 fatty acid ester Chemical class 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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- 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
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- 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
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
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- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/02—Pretreatment
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
- C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/14—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by isomerisation
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- 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
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- C10G2300/10—Feedstock materials
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- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
一种包括如下步骤的方法：提供包含以下的脂肪酰类物质混合物：(i)至少30wt.%的C10-C16酰基碳原子链含量，其中至少80%的C10-C16酰基碳原子链是饱和的；和(ii)至少20wt.%的C18-C22酰基碳原子链含量，其中至少50%的酰基C18-C22碳原子链含有至少一个烯烃；使至少一些所述混合物低聚以获得包含C36+低聚物的第二混合物；将所述第二混合物进行加氢处理以获得一定量的柴油调合料和C36+烷烃；以及将至少一些所述柴油调合料与C36+烷烃分离。
Description
技术领域
本发明总体上涉及由生物质-衍生的组合物制备运输燃料和基础油调合料的方法。
背景技术
由生物质生产的运输燃料和基础油调合料具有日益引起关注，这是因为它们衍生自可再生资源并且可以提供类似石油-衍生产品的受人关注的替代品和/或补充品。由生物质生产燃料和基础油调合料的常规方法通常使用需要双重反应器（和有关设备）的单独的燃料和基础油组列(trains)并且燃料的生产典型地需要加氢异构化步骤。
将植物油或其它脂肪酸衍生物转化为运输燃料的常规途径尤其可包括酯交换、催化加氢处理、加氢裂化、无氢催化裂化和热裂解。
可以使甘油三酯进行酯交换以产生脂肪酸烷基酯，最常见的是脂肪酸甲基酯(FAME)。常规FAME主要由C18+饱和脂肪酸的甲基酯组成。然而常规FAME的差的低温性能限制了其在较冷气候条件区域中的较广泛使用。通常，需要将至少一个双键引入到FAME分子中以改善其低温性能。然而，衍生自不饱和脂肪酸的FAME分子促成燃料的差的氧化稳定性和沉积物形成。
可以将甘油三酯进行加氢处理以常规地产生正构C18+链烷烃产物。然而，正构C18+链烷烃产物的差的低温性能限制了可在夏季时间调合在常规柴油中的产物的量并且阻止其在冬季时间期间的使用。还可以将正构C18+链烷属产物异构化为C18+异链烷烃产物以便使倾点降低。
需要开发将生物质-衍生的组合物有效加工（通常同时地）成具有改善的低温性能的较宽范围的润滑剂和燃料类型的方法，其中可以在降低的资金设备要求和在降低的氢耗情况下生产所述润滑剂和燃料。
发明概述
在一个实施方案中，本发明涉及包括以下步骤的方法：
提供包含以下的脂肪酰类物质混合物：(i)至少30wt.%的C10-C16酰基碳原子链含量，其中至少80%的C10-C16酰基碳原子链是饱和的；和(ii)至少20wt.%的C18-C22酰基碳原子链含量，其中至少50%的酰基C18-C22碳原子链含有至少一个烯烃；使至少一些所述混合物低聚以获得包含C36+低聚物的第二混合物；将所述第二混合物进行加氢处理以获得一定量的柴油调合料和C36+烷烃；以及将至少一些所述柴油调合料与C36+烷烃分离。
前面所述相当广泛地概括了本发明的特征以便可以更好的理解以下本发明的详述。下文中将对形成本发明权利要求书主题的本发明的另外特征和优点进行描述。
附图简要描述
为了更完整地理解本发明以及其优点，现在结合所附的附图对以下描述进行评述，其中：
图1描述了本发明一个实施方案的工艺流程图。
详述
在整个说明书中将使用下列术语，且除非有其他说明，下列术语将具有下列含义。
术语“生物衍生油”是指任何含有甘油三酯的油，该油至少部分衍生自生物来源例如但不限于作物、蔬菜、微藻、动物和它们的组合。这样的油还可以包含游离脂肪酸。所述生物来源在下文称作“生物质”。对于使用微藻作为甘油三酯来源的更多优点，参见R.Baum，“Microalgae are Possible Source of Biodiesel Fuel，”Chem.&Eng.News,72,28-29(1994)。
术语“脂肪酰类物质(fatty acyl)”是指用于描述脂肪酸、它们的缀合物和衍生物（包括酯）以及它们的组合的通称。脂肪酰类物质包括衍生自脂肪酸与醇的反应的酯。这些酯可以包括脂肪酸烷基酯，例如脂肪酸甲基酯，和甘油的脂肪酸酯，例如甘油单酯、二酯和三酯。在甘油三酯中，使甘油的三个羟基酯化。
术语“脂肪酸”是指一类具有4-24个碳原子的具有以下通式的有机酸：
其中R通常是饱和(烷基)烃链或者单或多不饱和(烯基或烯属)烃链。
术语“酰基碳原子链”表示-C(=O)R基团，其中R如上所定义。因此，例如，具有以下结构的月桂酸可以描述为具有C12酰基碳原子链。
术语“甘油三酯”是指具有以下分子结构的一类分子：
其中x、y和z可以相同或不同，并且其中x、y和z所定义的分支中的一个或多个可具有不饱和区域。
术语“低聚”是指相同或类似分子（即“单体”）的加成反应而形成更大的分子。例如，不饱和脂肪酸能够通过它们结构中的双键反应或结合。当两种这种物质结合而形成更大的分子时，将制得的物质称作“二聚体”。当例如上述脂肪酸组分含有多个不饱和区域时，可形成由三个或更多单体构成的低聚物（例如“三聚体”）。
术语“加氢加工”是指其中使烃系物质与氢气(通常在压力下)以及与催化剂(加氢加工可以是非催化的)反应的加工。这样的过程包括、但不限于加氢脱氧（对于含氧物质）、加氢处理、加氢裂化、加氢异构化和加氢脱腊。这样的过程的实例描述在美国专利No.6,630,066和美国专利No.6,841,063中。本发明的实施方案利用这样的加氢加工使脂肪酰类物质转化为链烷烃。术语“加氢处理”和“加氢处理”在本文中可互换使用。
术语“加氢异构化”是指其中通过使用氢和催化剂使正构链烷烃至少部分转化为异链烷烃的方法。异构化脱蜡催化剂是用于这类方法的代表性催化剂（参见美国专利No.5,300,210；美国专利No.5,158,665；和美国专利No.4,859,312）。
术语“运输燃料”是指适用于车辆消耗的烃系燃料。这样的燃料包括、但不限于柴油、汽油、喷气燃料等。
术语柴油是指沸点为350°F-700°F(177℃-371℃)的烃。
术语“基础油”是指运动粘度在100℃下为1.5-74.9mm2/s的烃流体。其是可以将其它油或物质加入到其中以产生润滑剂的烃流体。美国石油学会(API Publication Number1509,Appendix E)通常将基础油分在五种一般级别中的一种：I类基础油含有<90%饱和物和/或>0.03%硫并且具有≥80和<120的粘度指数；II类基础油含有≥90%饱和物和≤0.03%硫并且具有≥80和<120的粘度指数；III类基础油含有≥90%饱和物和≤0.03%硫并且具有≥120的粘度指数；IV类基础油是聚α-烯烃；V类基础油包括不包括在I、II、III或IV类内的所有其它基础油。
术语“浊点”是指当在规定条件下冷却首先出现最小可观测的烃晶体簇时的液体温度（参见ASTM D2500）。
术语“Cn”是指烃分子或含烃分子或碎片(例如烷基或烯基)，其中“n”表示所述碎片或分子中碳原子的数目，而与线性或支化无关。术语“C36+”是指分子或碎片中具有36或更多个碳原子的烃或含烃分子或碎片。
1.组成：在一个实施方案中，本发明涉及提供包含以下的脂肪酰类物质混合物：至少30wt.%的C10-C16酰基碳原子链含量，其中至少80%的C10-C16酰基碳原子链是饱和的；和至少20wt.%的C18-C22酰基碳原子链含量，其中至少50%的酰基C18-C22碳原子链含有至少一个双键。
在第一子实施方案中，脂肪酰类物质混合物具有至少40wt.%的C10-C16酰基碳原子链含量；在第二子实施方案中，至少50wt.%的C10-C16酰基碳原子链含量；在第三子实施方案中，至少60wt.%的C10-C16酰基碳原子链含量；在第四子实施方案中，至少70wt.%的C10-C16酰基碳原子链含量；在第五子实施方案中，不大于80wt.%的C10-C16酰基碳原子链含量。
在第六子实施方案中，脂肪酰类物质混合物具有至少30%的C18-C22酰基碳原子链含量；在第七子实施方案中，至少40wt.%的C18-C22酰基碳原子链含量；在第八子实施方案中，至少50wt.%的C18-C22酰基碳原子链含量；在第九子实施方案中，至少60wt.%的C18-C22酰基碳原子链含量；在第十子实施方案中，不大于70wt.%的C18-C22酰基碳原子链含量。
在一个实施方案中，脂肪酰类物质混合物是生物衍生油，该生物衍生油源于选自作物、蔬菜、微藻、动物源和它们的组合的生物质源。本领域技术人员可认识到，通常脂肪酰类化合物的任何生物源可用作可以由其获得生物衍生油的生物质。还可理解的是，一些这类来源更为经济并且更易于区域性培植，以及未由其得到食品的那些来源可以受到额外关注。示例性的生物衍生油源包括、但不限于低芥酸菜籽、蓖麻、大豆、油菜籽、棕榈、椰子、花生、麻风树（jatropha）、黄色油脂、藻类和它们的组合以满足组成目标。在一个实施方案中，脂肪酰类物质混合物是其中脂肪酸基团具有两种或三种不同的链长度以满足组成目标的甘油三酯。在另一个实施方案中，脂肪酰类物质混合物是满足组成目标的甘油三酯的共混物。在又一个实施方案中，脂肪酰类物质混合物衍生自甘油三酯的至少部分的水解以满足组成目标。
脂肪/油的水解或断裂(splitting)产生脂肪酸和甘油可通过以下多种方法实现：在无催化剂情况下的高压水解，在具有催化剂情况下的中等压力高压釜水解，在具有催化剂情况下的环境压力Twitchell处理，和酶水解。关于脂肪/油的水解的更多内容参见N.O.V.Sonntag,“Fat Splitting,”J.Am.Oil Chem.Soc.,56(II),729A-732A,(1979);N.O.V.Sonntag,“New Developments in the Fatty Acid Industry,”J.Am.Oil Chem.Soc.,56(II),861A-864A,(1979);V.J.Muckerheide,Industrial Production of Fatty Acids:Fatty Acids;Their Chemistry,Properties,Production and Uses,Part4,第2版,IntersciencePublishers,2679-2702(1967)；和M.W.Linfield等的“Enzymatic FatHydrolysis and Synthesis,”J.Am.Oil Chem.Soc.,61,191-195(1984)。
2.方法：现参照图1，本发明的一个实施方案涉及包括以下步骤的方法：（步骤101）提供包含以下的脂肪酰类物质混合物：(i)至少30wt.%的C10-C16酰基碳原子链含量，其中至少80%的C10-C16酰基碳原子链是饱和的；和(ii)至少20wt.%的C18-C22酰基碳原子链含量，其中至少50%的酰基C18-C22碳原子链含有至少一个双键；（步骤102）使至少一些所述混合物低聚以获得包含C36+低聚物的第二混合物；（步骤103）将所述第二混合物进行加氢处理以获得一定量的柴油调合料和C36+烷烃；以及（步骤104）将至少一些所述柴油调合料与C36+烷烃分离。
在一些这样的上述方法实施方案中，具有提供满足组成目标的脂肪酰类物质混合物的子步骤。这类步骤通常与章节1中所述的所述混合物的形成一致。
在一些这样的上述方法实施方案中，具有低聚子步骤。不意欲受理论束缚，认为上述低聚通过在具有不饱和区预的脂肪酸组分之间的加成偶合反应而进行。这样的低聚可通过热、催化、和/或化学方法实现。示例性的催化剂包括SiO2-Al2O3、沸石和粘土，例如斑脱土和蒙脱石。在一些这样的上述方法实施方案中，低聚的混合物包含低聚物组分，其中所述混合物的低聚物组分包含至少约50wt.%的二聚体（二聚）物质（即由不饱和脂肪酸组分的二聚产生的二聚物）。通常，在不存在加入的氢气的情况下，在300°F-700°F(140℃-371℃)的温度下，以0.5-10h-1的液时空速，和在使得进料处于液相的压力下，于粘土催化剂上实施低聚。低聚可以在存在加入的氢气下进行，条件是不存在加氢金属催化剂。用于使不饱和脂肪酸低聚的方法是本领域熟知的（参见例如美国专利No.2,793,219；2,793,220；3,422,124；3,632,822；和4,776,983）。
在一些这样的上述实施方案中，具有分离子步骤。加氢处理从脂肪酸除去氧以主要产生正构链烷烃产物。加氢处理涉及加氢加工/加氢处理催化剂和含氢环境。在一些这样的实施方案中，活性加氢加工催化剂组分是选自钴-钼(Co-Mo)催化剂、镍-钼(Ni-Mo)催化剂、镍-钨(Ni-W)催化剂、贵金属催化剂和它们的组合的金属或合金。这类物质典型地负载在耐高温氧化物载体（例如氧化铝或SiO2-Al2O3）上。加氢处理条件通常包括290℃-430℃的温度和一般为400磅力/平方英寸表压(psig)-2000psig，典型地为500psig-1500psig的氢气分压。关于加氢加工/加氢处理的综述参见例如Rana等的“A Review of RecentAdvances on Process Technologies for Upgrading of Heavy Oils andResidua,”Fuel,86,1216-1231(2007)。关于将甘油三酯加氢加工获得链烷属产物的方法是本领域熟知的（参见例如美国专利No.4,992,605）。
在常规加工中，将C18+脂肪酸进行加氢处理以产生正构链烷烃产物。衍生自C18+脂肪酸的正构链烷烃产物促成柴油的倾点问题。可使用异构化脱蜡催化剂将衍生自C18+脂肪酸的正构链烷属产物进一步异构化以降低其倾点。相反，本发明的方法不需要后续异构化步骤，这是因为正构链烷烃产物衍生自C10-C16脂肪酰类物质，这较少乃至非常少促成柴油的倾点问题。消除后续异构化步骤还降低成本，这是因为该步骤典型地需要单独的催化剂床和/或单独的反应器。此外，可将本发明的C10-C16柴油调合料调合到柴油总合(pool)中，因为链长度比正构C18+产物更短从而使浊点可足够低以致对所述总合的浊点具有降低的负面影响。通过使C18+脂肪酰类物质低聚，这不仅有助于生产有价值的基础油产品，而且还从柴油调合料除去这些C18+脂肪酰类物质，从而使对倾点和浊点的影响最小化。
在一些这样的上述实施方案中，具有分离子步骤。虽然本领域技术人员将认识到可适宜地使用多种分离技术，但是在一些这样的上述方法实施方案中所述分离步骤包括蒸馏。在一个实施方案中，蒸馏步骤使用蒸馏塔（单元）以将C36+烷烃和柴油调合料分离成单独的馏分。通常，在高沸点馏分中收集C36+烷烃，而在低沸点馏分中收集柴油调合料。在一些特定实施方案中，馏分分歧(fractional bifurcation)出现在340°C附近，在该情形中柴油调合料主要包含在340°C馏分中（沸点低于340°C）而C36+主要包含在340°C+馏分中（沸点高于340°C）。本领域技术人员可认识到在表征高沸点和低沸点馏分时具有一定灵活性，并且可由在多个温度范围的“馏分(cut)”获得产物。
在一个实施方案中，所生产的柴油调合料包含至少70wt.%的C10-C16烷烃；在第二实施方案中，包含至少80wt.%的C10-C16烷烃；在第三实施方案中，包含至少90wt.%的C10-C16烷烃。
柴油调合料的浊点可通过ASTM D2500进行测定。在一个实施方案中，柴油调合料具有小于-10℃的浊点。
在一个实施方案中，这样的上述方法还包括将至少一些所述C36+烷烃进行加氢异构以获得一定量的基础油调合料的步骤。通常，加氢异构化的步骤使用异构化催化剂进行。合适的这类异构化催化剂可包括但不限于在载体例如但还不限于SAPO-11、SM-3、SM-7、SSZ-32、ZSM-23、ZSM-22和类似的这样的载体上的Pt或Pd。在一些或其它实施方案中，加氢异构的步骤涉及包含选自Pt、Pd和它们的组合的金属的异构化催化剂。通常将异构化催化剂负载在选自β或沸石Y分子筛、SiO2、Al2O3、SiO2-Al2O3和它们的组合的酸性载体材料上。在一些这样的实施方案中，在250℃-400℃，和典型地290℃-400℃的温度下进行异构化。操作压力通常为200psig-2000psig，更通常为200psig-1000psig。氢气流量通常为50-5000标准立方英尺/桶(SCF/桶）。其它合适的加氢异构化催化剂公开在美国专利No.5,300,210、美国专利No.5,158,665、和美国专利No.4,859,312中。
[0039]关于上述催化驱动的加氢异构化步骤，在一些实施方案中，本文描述的方法可以通过使产物与催化剂的固定静态床、与固定流化床或者与移动床接触来实施。在一个本发明预期的实施方案中，使用滴流床操作，其中通常在氢气存在下，让这种进料滴流通过静态固定床。这类催化剂的操作说明公开于美国专利No.6,204,426和美国专利No.6,723,889中。
基础油调合料的粘度指数可通过ASTM D2270进行测定。在一个实施方案中，基础油调合料具有大于120的粘度指数；在第二实施方案中，具有大于130的粘度指数；在第三实施方案中，具有大于140的粘度指数。
基础油调合料的倾点可通过ASTM D97进行测定。在一个实施方案中，所生产的基础油调合料具有小于-10℃的倾点。
在一个实施方案中，还可以使基础油调合料经受任选的加氢精制步骤，这通常用于改善颜色、以及氧化和热稳定性。在一个实施方案中，基础油用作润滑基础油调合料。
出于本说明书和所附权利要求的目的，除非另外标明，表达量、百分比或比例的所有数和说明书和权利要求所用的其它数都应理解为在所有情况下用术语“约”做修饰。因此，除非有相反指明，下面说明书和所附权利要求书中的给出的数值参数是近似值，其可以取决于本发明意欲寻求的所需性能而改变。应当注意，如本说明书和所附权利要求中所使用的，单数形式“一”、“一个”和“该”包括复数指代物，除非明确地毫无疑义地限定于一个所指事物。如本文中所使用的，术语“包括”及其语法变化形式旨在是非限制性的，使得述及的所列项目不排除可取代或补充所列项目的其它相似项目。在不会造成不一致的程度下，通过参考将本文中参考的所有引用之处并入本文中。
Claims (11)
1.包括以下步骤的方法：
a)提供包含以下的脂肪酰类物质混合物：
(i)至少30wt.%的C10-C16酰基碳原子链含量，其中至少80%的C10-C16酰基碳原子链是饱和的；和
(ii)至少20wt.%的C18-C22酰基碳原子链含量，其中至少50%的酰基C18-C22碳原子链含有至少一个双键；
b)使至少一些所述混合物低聚以获得包含C36+低聚物的第二混合物；
c)对所述第二混合物进行加氢处理以获得一定量的柴油调合料和C36+烷烃；以及
d)将至少一些所述柴油调合料与C36+烷烃分离。
2.权利要求1的方法，其中所述柴油调合料包含至少70wt.%的C10-C16烷烃。
3.权利要求1的方法，其中所述柴油调合料具有小于-10℃的浊点。
4.权利要求1的方法，其中加氢处理步骤涉及加氢加工催化剂和含氢环境。
5.权利要求4的方法，其中所述加氢加工催化剂选自钴-钼(Co-Mo)催化剂、镍-钼(Ni-Mo)催化剂、镍-钨(Ni-W)催化剂、贵金属催化剂和它们的组合。
6.权利要求1的方法，其中所述分离步骤包括蒸馏。
7.权利要求1的方法，其还包括将对至少一些所述C36+烷烃进行加氢异构化以获得一定量的基础油调合料的步骤。
8.权利要求7的方法，其中所述加氢异构化步骤涉及包含选自Pt、Pd和它们的组合的金属的异构化催化剂。
9.权利要求7的方法，其中所述基础油调合料具有大于120的粘度指数。
10.权利要求7的方法，其中所述基础油调合料具有大于140的粘度指数。
11.权利要求7的方法，其中所述基础油调合料用作润滑基础油调合料。
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| BR112013007134A2 (pt) | 2016-06-14 |
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Application publication date: 20130703 |