CN102549112B - 用于从天然存在的油脂的复杂混合物生产生物石脑油的方法 - Google Patents
用于从天然存在的油脂的复杂混合物生产生物石脑油的方法 Download PDFInfo
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- CN102549112B CN102549112B CN201080042894.0A CN201080042894A CN102549112B CN 102549112 B CN102549112 B CN 102549112B CN 201080042894 A CN201080042894 A CN 201080042894A CN 102549112 B CN102549112 B CN 102549112B
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- grease
- steam
- soap
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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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- 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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
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- 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
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- 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
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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
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- C11B3/12—Refining fats or fatty oils by distillation
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- C—CHEMISTRY; METALLURGY
- 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
- C11B3/00—Refining fats or fatty oils
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- C11B3/14—Refining fats or fatty oils by distillation with the use of indifferent gases or vapours, e.g. steam
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- 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
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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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Abstract
用于从天然存在的油脂的复杂混合物制造生物石脑油以及任选地制造生物丙烷的方法,其中-使所述复杂混合物经历精炼处理以除去大部分的非甘油三酸酯和非脂肪酸组分,从而得到精炼的油脂;-通过加氢脱氧将所述精炼的油脂转化为作为生物石脑油的直链或基本直链的链烷烃;-或从所述精炼的油脂得到脂肪酸,将所述脂肪酸通过该游离脂肪酸的加氢脱氧或脱羧基转化为作为生物石脑油的直链或基本直链的链烷烃;-或从所述精炼的油脂得到脂肪酸皂,将所述脂肪酸皂通过该皂的脱羧基转化为作为生物石脑油的直链或基本直链的链烷烃。
Description
技术领域
本发明涉及由天然存在的油脂(fats&oils)的复杂混合物在联合生物精炼(integrated bio-refinery)中生产生物石脑油。原油的有限供应和日益增加的成本以及对降低基于化石的二氧化碳排放的需求已经促使寻求用于生产烃产品例如生物石脑油和生物柴油的替代方法。所述生物石脑油可用作常规蒸汽裂化的原料。由来自活生物体的有机物质构成,生物质是世界上主要的可再生能源。
背景技术
由于数十年的经验和在现有实践上的连续改进,油脂的工业化学是成熟的技术。天然油脂主要由甘油三酸酯和一定程度的游离脂肪酸(FFA)组成。许多不同类型的甘油三酸酯在自然界中由植物或动物来源产生。发现油脂中的脂肪酸是对甘油进行酯化的(三酰基甘油)。所述酰基是在通常与甘油进行酯化的末端处具有羧基的长链(C12-C22)烃。油脂通过化学组成和其脂肪酸部分的结构表征。所述脂肪酸部分可为饱和的或含有一个或多个双键。油脂的整体性质通常以“皂化值”、“碘值”、“未皂化值”进行说明。所述“皂化值”(表示为一摩尔氢氧化钾所皂化的脂肪的克数)是平均分子量的指示和因此是链长的指示。所述“碘值”(表示为在与一氯化碘的反应中被脂肪消耗的碘的重量百分数)是不饱和度的指示。
油脂的一些典型来源和各自的脂肪酸组成在表1中举例给出。
此时存在可利用的其它潜在原料,即捕集器(trap)和污水(sewage)脂膏(grease)以及其FFA可超过50%的其它非常高游离脂肪酸的脂膏。
油脂的主要来源是棕榈和棕榈仁、大豆、油菜籽、向日葵、椰子、玉米、动物脂肪、乳脂。
在不久的将来将变成可利用甘油三酸酯的潜在新的来源,即由麻风树属(Jatropha)提取的那些和由微藻类(microalgue)产生的那些。这些微藻类可积聚基于干重多于30重量%的类脂(lipid),并且它们可在露天水池(open basin)中利用大气CO2或者在密闭的光生物反应器中培养。在后一情形中,所需的CO2可来源于俘获并且注入到所述光生物反应器中的化石烃的使用。化石CO2的主要来源是发电站、用于精炼厂的锅炉、用于在精炼厂和蒸汽裂化器中使烃物流达到高温或者在烃转化中提供反应热的蒸汽裂化器炉。特别地,蒸汽裂化炉产生大量CO2。为了提高这些炉的废气中的CO2浓度,可以使用例如富氧燃烧(oxycombustion)、化学循环(looping)或者CO2吸收的技术。在富氧燃烧中,从空气中提取氧气并且将该纯氧用于燃烧烃燃料以得到仅含水和CO2的物流,从而容许容易地将CO2浓缩用于储存或再利用。在化学循环中,固体材料充当从再氧化区到燃烧区的氧转移剂,在再氧化区中经还原的固体用空气再氧化成氧化的固体,在燃烧区中烃燃料借助于氧化的固体燃烧并且因此得自燃烧区的流出物仅含水和CO2。CO2的吸收可借助于贫溶剂进行,所述贫溶剂在压力下和典型地在低温下高度优先吸收CO2,并且当减压和/或加热时将释放所述CO2。和是可商购获得的用于除去和浓缩CO2的技术。CO2的其它来源为来自如下的副产物:碳水化合物发酵为乙醇或其它醇,以及从由生物质制造的合成气除去过量CO2或煤气化。
US 2007/0175795报导了使烃和甘油三酸酯接触以形成混合物,和使该混合物在固定床反应器中与加氢处理催化剂在足以制得包含柴油沸程烃的反应产物的条件下接触。实施例展现了这样的混合物的加氢处理提高了所得烃混合物的浊点和倾点。
US 2004/0230085报导了制造生物来源的烃组分的方法,其特征在于所述方法包括至少两个步骤,第一个步骤是加氢脱氧步骤和第二个步骤是异构化步骤。所得产物具有低的凝固点和高的十六烷值,并且可作为柴油或作为溶剂使用。
US 2007/0135669报导了支化饱和烃的制造,其特征在于使包含不饱和脂肪酸或者与C1-C5醇的脂肪酸酯、或者其混合物的原料经历骨架异构化步骤以及之后的脱氧步骤。结果展现了可获得非常好的浊点。
US 2007/0039240报导了使牛脂裂化成柴油燃料的方法,包括:使牛脂在裂化容器中在260-371℃的温度下在环境压力下并且在没有催化剂的存在下热裂化,以得到部分裂化的烃。
US 4554397报导了制造烯烃的方法,包括使羧酸或羧酸酯与催化剂在200-400℃的温度下接触,其中所述催化剂同时包含镍和至少一种选自锡、锗和铅的金属。
已经发现了由所有种类的天然甘油三酸酯或脂肪酸在联合生物精炼中制造生物石脑油的方法。在所述方法中,将粗油脂物理或化学地精炼以除去基本上所有的非甘油三酸酯组分和非游离脂肪酸。
在寻求用于石脑油裂化器的替代原材料方面,使用生物原料是可能的方案。不过,使用这种类型的原料可导致腐蚀问题和过度结垢,这是因为由该生物原料中的氧原子形成含氧化合物。而且,现有蒸汽裂化器并未设计成除去由这些生物原料的蒸汽裂化产生的高的量的碳氧化合物。根据本发明,这样的问题可通过在将该生物原料注入蒸汽裂化器之前对其进行加氢脱氧/脱羧基(脱羰基)而解决。由于该加氢脱氧/脱羧基(脱羰基),降低了由于在该蒸汽裂化器中产生CO和CO2以及痕量低分子量含氧化合物(醛和酸)而引起的消极影响。
另一个优点当然是在蒸汽裂化器中生物单体的产生。
发明内容
在第一实施方式中,本发明的主题是用于从天然存在的油脂的复杂混合物制造生物石脑油的方法,其中
-使所述复杂混合物经历精炼处理以除去大部分的非甘油三酸酯和非脂肪酸组分,从而得到精炼的油;
-通过加氢脱氧将所述精炼的油脂转化为作为生物石脑油的直链或基本直链的链烷烃;
-或从所述精炼的油脂得到脂肪酸,通过所述脂肪酸的加氢脱氧或脱羧基将所述脂肪酸转化为作为生物石脑油的直链或基本直链的链烷烃
-或从所述精炼的油脂得到脂肪酸皂,通过所述脂肪酸皂的脱羧基将所述脂肪酸皂转化为作为生物石脑油的直链或基本直链的链烷烃。
在实施方式2中,本发明依据实施方式1,其中天然存在的油脂的所述复杂混合物选自植物油和动物脂肪,优选非食用油、高度饱和的油、废食物油、植物油精炼的副产物、以及其混合物。
在实施方式3中,本发明依据实施方式1或2,其中通过油脂的物理精炼得到所述脂肪酸,所述物理精炼包括蒸汽蒸馏或真空蒸馏
或者通过所述油脂的甘油三酸酯的水解获得所述脂肪酸
或者通过皂的酸化得到所述脂肪酸。
在实施方式4中,本发明依据实施方式1或2,其中所述脂肪酸皂如下获得:通过油脂的皂化
或者通过化学精炼,包括存在于所述油脂中的游离脂肪酸的中和
或者从所述油脂的水解得到的脂肪酸的中和。
在实施方式5中,本发明依据实施方式1-3的任一项,其中通过在氢气和至少一种催化剂存在下的加氢脱氧,将所述精炼的油脂转化为作为生物石脑油的直链或基本直链的链烷烃、以及生物丙烷,所述至少一种催化剂可选自:Ni、Mo、Co或者混合物如NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相并且优选地负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上。
在实施方式6中,本发明依据实施方式5,其中在200-500℃的温度下、在1MPa-10MPa(10-100巴)的压力下以及使用100-2000Nl/l的氢气与原料比率实施所述加氢脱氧。
在实施方式7中,本发明依据实施方式1-4的任一项,其中通过如下将所述精炼的油转化为作为生物石脑油的直链或基本直链的链烷烃:将所述油脂水解为甘油和脂肪酸、除去所述甘油,或者将油脂物理精炼(包括蒸汽蒸馏或真空蒸馏),或者进行皂的酸化;和将所述脂肪酸加氢脱氧或脱羧基;所述加氢脱氧或脱羧基在氢气和至少一种催化剂的存在下进行,所述至少一种催化剂可选自:Ni、Mo、Co或者混合物如NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相并且优选地负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上;或者负载在高表面积碳、氧化镁、氧化锌、尖晶石(Mg2Al2O4,ZnAl2O4)、钙钛矿(BaTiO3,ZnTiO3)、硅酸钙(如硬硅钙石)、氧化铝、二氧化硅或者二氧化硅-氧化铝、或者其混合物上的第10族(Ni、Pt和Pd)和第11族(Cu和Ag)的金属或合金混合物。
在实施方式8中,本发明依据实施方式1-4的任一项,其中通过如下将所述精炼的油转化为作为生物石脑油的直链或基本直链的链烷烃:将所述油脂水解为甘油和脂肪酸、除去所述甘油,或者将油脂物理精炼(包括蒸汽蒸馏或真空蒸馏),或者进行皂的酸化;和在如下物质上实施所述脂肪酸的脱羧基:碱性氧化物,如碱金属氧化物、碱土金属氧化物、镧系元素氧化物、氧化锌、尖晶石(Mg2Al2O4,ZnAl2O4)、钙钛矿(BaTiO3,ZnTiO3)、硅酸钙(如硬硅钙石),其作为本体(bulk)材料或者分散在中性或碱性载体上;碱性沸石(如通过交换或者浸渍得到的碱金属或碱土金属低的二氧化硅/氧化铝沸石)。
在实施方式9中,本发明依据实施方式7和8,其中在200-500℃的温度下、在1MPa-10MPa(10-100巴)的压力下以及使用100-2000Nl/l的氢气与原料比率实施所述加氢脱氧;或者其中在100-550℃的温度下、在0.1MPa-10MPa(1-100巴)的压力下以及使用0-2000Nl/l的氢气与原料比率实施所述脱羧基。
在实施方式10中,本发明依据实施方式4,其中在100-550℃下、在0.1MPa-10MPa的压力下以及在水的存在下,实施所述皂的脱羧基。
在实施方式11中,本发明依据实施方式4和10,其中采用每摩尔皂至少1摩尔水的水与原料比率实施所述皂的脱羧基。
在实施方式12中,本发明为如在实施方式1-11的任一项的方法中得到的生物石脑油作为蒸汽裂化器的直接原料以得到包括生物乙烯、生物丙烯、生物丁二烯、生物异戊二烯、生物环戊二烯和生物戊间二烯、生物苯、生物甲苯、生物二甲苯和生物汽油的裂化产物的用途,所述生物石脑油以其本身使用、或者在通过实施方式5的方法生产时与生物丙烷一起使用、或者在与选自LPG、石脑油和瓦斯油(gasoil)的至少一种常规原料共混的情况下使用,
其中在蒸汽裂化方法中,将所述烃原料与蒸汽以0.3-0.45kg蒸汽/kg烃原料的比率混合。
在实施方式13中,本发明是实施方式12的方法,其中将所述烃原料与蒸汽以0.3-0.4kg蒸汽/kg烃原料的比率混合。
在实施方式14中,本发明是如实施方式12或13中限定的用于蒸汽裂化原料的方法,其中将混合物加热到750-950℃的温度且停留时间为0.05-0.5秒。
在实施方式15中,本发明是如实施方式12-14任一项中限定的用于蒸汽裂化原料的方法,其中将该混合物加热到750-950℃的温度且停留时间为0.05-0.15秒。
在实施方式16中,本发明是在实施方式1-11任一项的方法中得到的生物石脑油用于蒸汽裂化以获得至少3的由生物石脑油的裂化得到的乙烯与甲烷重量比的用途。
“生物石脑油”指的是由可再生来源通过这些可再生来源的加氢处理生产的石脑油。它是主要由链烷烃组成且可用于蒸汽裂化以生产轻质烯烃、二烯烃和芳族化合物的烃组合物。该生物石脑油的分子量为具有8-24个碳、优选10-18个碳的烃的范围。
“基本直链的链烷烃”指的是由至少90%重量的直链链烷烃组成的链烷烃组合物。
所述天然存在的油脂的复杂混合物可选自植物油和动物脂肪,优选高度饱和的非食用油、废食物油、植物油精炼的副产物、及其混合物。本说明书中已经在之前提到了这些油脂的具体实例。
所述精炼的油(最终仍含有一些游离脂肪酸)可通过在氢气和至少一种加氢脱氧催化剂存在下的加氢脱氧转化为作为生物石脑油的直链或基本直链的链烷烃、以及生物丙烷。所述加氢脱氧催化剂可选自:Ni、Mo、Co或者混合物如NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相并且优选地负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上;或者负载在高表面积碳、氧化镁、氧化锌、尖晶石(Mg2Al2O4,ZnAl2O4)、钙钛矿(BaTiO3,ZnTiO3)、硅酸钙(如硬硅钙石)、氧化铝、二氧化硅、或者其混合物上的第10族(Ni、Pt或Pd)或第11族(Cu或Ag)的金属或合金混合物。优选的是,用于该催化活性相的载体呈现低的酸度,优选中性或者碱性,以避免导致支化的链烷烃和裂化的加氢异构化反应。所述油脂的加氢脱氧可在200-500℃、优选280-400℃的温度下,在1MPa-10MPa(10-100巴)例如6MPa的压力下以及使用100-2000但是优选350-1500例如600Nl H2/l油的氢气与精炼的油的比率实施。
还可通过如下将所述精炼的油转化为作为生物石脑油的直链或基本直链的链烷烃:经由(i)将所述油脂水解为甘油和脂肪酸,除去所述甘油,经由(ii)油脂的物理精炼(蒸汽/真空蒸馏)或者经由脂肪酸皂的酸化而生产脂肪酸,随后将所述脂肪酸加氢脱氧或脱羧基(或脱羰基);所述加氢脱氧在氢气和至少一种加氢脱氧或脱羧基催化剂的存在下进行。所述加氢脱氧或脱羧基催化剂可选自:Ni、Mo、Co或者混合物如NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相并且优选地负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上;或者负载在高表面积碳、氧化镁、氧化锌、尖晶石(Mg2Al2O4,ZnAl2O4)、钙钛矿(BaTiO3,ZnTiO3)、硅酸钙(如硬硅钙石)、氧化铝、二氧化硅或者二氧化硅-氧化铝、或者其混合物上的第10族(Ni、Pt或Pd)或第11族(Cu或Ag)的金属或合金混合物。优选的是,用于该催化活性相的载体呈现低的酸度,优选中性或者碱性,以避免导致支化的链烷烃和裂化的加氢异构化反应。可在蒸汽的存在下如下实施水解(分裂(splitting)):在15-75巴下且在50-300℃下热实施;或者以催化方式实施,例如采用碱性催化剂(如MgO、CaO、ZnO、尖晶石(Mg2Al2O4,ZnAl2O4)、钙钛矿(BaTiO3,ZnTiO3)、硅酸钙(如硬硅钙石)或碱性氧化铝)或采用酸性催化剂(如硫酸)。Sonntag(Sonntag,N.,J.Am.Oil.Chem.Soc.,56,p.729,1979)和Bailey’s Industrial Oil and Fat Products,ed.F.Shahidi,2005,John Wiley&Sons已经公布了关于油脂分裂的详细信息。在Colgate-Emery法中,经加热的液体类脂在立式管式反应器的底部引入。经加热的水在顶部进入。由于所述油脂在压力下上升穿过下降的水,因此建立了在油中的高水溶性连续区域,在其中发生水解。从该塔收取流出物,其中从一个出口收取脂肪酸和从另一出口收取含水甘油物流。少量无机酸例如硫酸或磺酸或一些金属氧化物例如锌或镁氧化物的存在加速分裂反应。这些金属氧化物是真正的催化剂且它们还有助于乳液的形成。
所述脂肪酸的加氢脱氧可在200-500℃(优选280-400℃)的温度下、在1MPa-10MPa(10-100巴)例如6MPa的压力下以及使用100-2000Nl H2/l油(例如600Nl H2/l油)的氢气与精炼的油的比率实施。所述脂肪酸的脱羧基可在100-550℃下、在不存在或存在氢气的情况下、在0.01MPa-10MPa的压力下实施。
也可通过脂肪酸皂的热脱羧基将所述精炼的油转化为作为生物石脑油的直链或基本直链的链烷烃。这些皂在化学精炼期间如下获得:通过中和将游离脂肪酸转化为皂;通过由油脂的水解得到的脂肪酸的中和;或者通过将甘油三酸酯完全皂化为甘油和皂。皂为对应脂肪酸的金属盐。
本发明还涉及在上述方法中得到的生物石脑油作为蒸汽裂化器的直接原料以得到包括生物乙烯、生物丙烯、生物丁二烯、生物异戊二烯、生物(二)环戊二烯、生物戊间二烯、生物苯、生物甲苯、生物二甲苯和生物汽油的裂化产物的用途,所述生物石脑油以其本身使用、或者当通过上述方法生产时与生物丙烷一起使用、或者在与选自LPG、石脑油和瓦斯油的至少一种常规原料共混的情况下使用。
此外,本发明涉及用于蒸汽裂化如以上定义的原料的方法,其中将所述原料与蒸汽混合,具有至少0.2kg蒸汽/kg原料的蒸汽/原料比率。将该混合物输送通过加热的炉管(coil),该炉管具有至少700℃的炉管出口温度和至少1.2巴绝对压力的炉管出口压力。
具体实施方式
在提炼(rendering)、压榨(crushing)或者溶剂提取之后得到的所有粗(raw)油脂不可避免地含有可变量的非甘油三酸酯组分,例如游离脂肪酸、甘油单酸酯和甘油二酸酯、磷脂、甾醇、生育酚、生育三烯酚烃、颜料(棉酚、叶绿素)、维生素(类胡萝卜素)、甾醇糖苷、糖脂、蛋白质片段、痕量的农药和痕量的金属、以及树脂质的和粘质的(mucilaginous)材料。非甘油酯的量随着油来源、提取工艺、季节和地理来源而变化。将所述非甘油三酸酯组分(其妨碍进一步的加工且造成油的变暗、起泡、冒烟、沉淀和逐渐出现臭味(off-flavour))除去是精炼方法的目标。
精炼预处理
精炼方法的选择
图1说明了精炼预处理,其中,将粗油通过物理的或化学的各种路线加工为精炼漂白除臭(RBD)的油。物理精炼和碱/化学精炼的不同之处主要在于除去游离脂肪酸的方式。
在化学精炼中,在用碱溶液(通常为NaOH)中和期间将FFA、大部分的磷脂和其它杂质除去。
在物理精炼中,所述FFA在除臭期间通过蒸馏除去,并且所述磷脂和其它杂质必须在蒸汽蒸馏油脂之前除去。
目前,通过个体(individual)粗油脂的特性确定选择的精炼方法:
(1)通常物理精炼的油脂;
(2)可物理或化学精炼的油脂;和
(3)仅能化学精炼的油脂。
下表2总结了各种处理的优点和缺点:
表2
物理精炼
通过汽提,所述物理精炼可除去FFA以及不能皂化物和其它杂质,从而消除皂脚的产生并将中性油的损失保持为最低限度。然而,仍然需要粗油脂的脱胶预处理以除去如下的那些杂质:当加热到蒸汽蒸馏需要的温度时,所述杂质变暗或者以其它方式造成品质差的产物。脱胶方法对于物理精炼是至关要紧的,但对于化学精炼是任选的。其由如下组成:用水、盐溶液、酶、苛性钠、或者稀酸(例如磷酸、柠檬酸或马来酸)处理粗油以除去磷脂、蜡、助氧化剂(pro-oxidant)和其它杂质。所述脱胶方法将所述磷脂转化为水合胶(hydrated gum),所述水合胶不溶于油并且容易通过沉降、过滤或离心作用作为淤渣(sludge)分离。脱胶之后,磷必须低于30ppm。因此漂白或干法脱胶可进一步将该水平降低到小于5ppm并除去所有痕量的铁和铜。为了实现这些结果,通常采用酸或者酶脱胶方法。
各种工业脱胶方法具有不同的目标。待脱胶的油脂在胶含量和胶性质方面宽泛地变化,并且最终,可利用的胶处理设施、什么设备是需要和/或可利用的、以及辅助物的成本也影响最合适的脱胶方法的选择。类脂手册(Thelipid handbook,edited by Frank D.Gunstone,John L.Harwood,Albert J.Dijkstra.3rd ed.,chapter 3.4)详细地论述了这些方面。下面简要描述市场上应用的四种主要脱胶方法。
水脱胶方法的主要目的为生产在运输和存储期间不沉积残渣(residue)的油,并控制粗油的磷含量正好低于200ppm。该方法包括将活蒸汽(live steam)加入粗油中一段短的时间。水适当的量通常为油的磷脂含量的约75%。太少的水产生暗的粘性的胶和混浊的油,而太多的水造成经由水解的过度的油损失。水脱胶的油仍然含有磷脂(80-200ppm);采用该方法仅将能水合的磷脂除去。不能水合的磷脂(其为磷脂酸的钙和镁盐和磷脂酰乙醇胺)在水脱胶之后保留在油中。
酸脱胶方法导致比水脱胶低的残留磷含量,并且因此如果干法脱胶和物理精炼是随后的精炼步骤,则酸脱胶方法是好的替代。可认为酸脱胶方法是水脱胶方法的变型,因为它使用了水和酸的组合。采用酸脱胶可将所述不能水合的磷脂调节为能水合的形式。使用磷酸和柠檬酸,因为它们是食品级的、足够强且它们结合二价金属离子。为了达到对于好品质的物理精炼油所要求的低于5ppm的磷值,已经开发了若干种酸脱胶方法。
酸精炼与酸脱胶不同之处在于,通过碱的添加将所释放的磷脂(脱胶用酸的作用未导致磷脂的完全水合)中和,以使得它们为能水合的。
在干法脱胶方法中,将油用酸处理(原理是强酸从弱酸的盐中置换弱酸)以使金属离子/磷脂络合物分解,然后与漂白土混合。然后通过过滤将含有所述脱胶用酸、磷脂、颜料和其它杂质的所述土除去。已经水或酸脱胶的种子油也可干法脱胶以保证对于蒸汽蒸馏的低磷油。少于0.2%的FFA的增加应当是预期的,但是最终磷含量必须降低到小于5ppm。该方法构成了对于棕榈油、月桂油、低芥酸菜子油和低磷脂动物脂肪(例如牛脂或猪油)的主要处理。干法脱胶方法允许粗油在仅仅两步中被完全精炼:干法脱胶和物理精炼。
在酶脱胶方法中,磷脂酶A1(最新开发的脱胶酶)将磷脂变为溶血磷脂和游离脂肪酸。该方法具有三个重要的步骤:
(1)用缓冲剂调节pH;
(2)在存储罐中酶反应;和
(3)从油分离淤渣。
待通过这种方式酶脱胶的油可为粗油或经过水脱胶的。
类脂手册(The lipid handbook,edited by Frank D.Gunstone,John L.Harwood,Albert J.Dijkstra.3rd ed.)描述了该脱胶方法的许多变型和细节。
漂白的目的是提供脱色的油以及将其纯化为进一步的加工作准备。使所有充分精炼的油经历某一漂白处理。精炼的油含有溶解或作为胶态悬浮体的痕量的许多种不希望的杂质。所述漂白处理不仅仅是增加光穿过油的透射,且常常被称为“吸附清洁”。所述漂白处理常常是所述油遇到的首次过滤,因此,它保证了皂、残余磷脂、痕量金属和一些氧化产物的除去,而且它催化胡萝卜素的分解,并且吸附剂还催化过氧化物的分解。例如皂、胶和助氧化剂金属的这些妨碍过滤的非颜料材料使加氢催化剂中毒、使油变暗且影响成品油(finished oil)香味(flavour)。另一个功能是除去过氧化物和次生的氧化产物。漂白处理的关键参数为程序、吸附剂类型和剂量、温度、时间、湿度和过滤,如类脂手册(The lipid handbook,edited by Frank D.Gunstone,John L.Harwood,Albert J.Dijkstra.3rd ed.,chapter 3.7)中所示。用于食用油脂的三种最常见类型的接触漂白方法为间歇式大气法、间歇式真空法和连续式真空法。已经使用或者提出使用化学试剂,但是实际上所有食用油脱色和纯化采用吸附白土、合成无定形二氧化硅和活性炭完成。
在最后的主要加工步骤之前,出于两个理由,可将漂白的油加氢。一个理由是将天然存在的油脂转化为具有对于功能性(functionality)所需要的一致性(consistency)和操作特性(handling characteristic)的物理形式。加氢的第二个理由是增加氧化和热稳定性。该步骤在于油脂分子改性,而不是其它描述的方法中的纯化。
将氢气直接加入以在催化剂(主要为镍)的存在下与不饱和的油反应。该方法极大地影响许多食用油产品的期望的稳定性和性质。所述加氢方法容易控制且能够在任意点停止。油脂熔点的逐渐升高是优点之一。如果通过加氢将双键完全消除,则产物在室温下是硬脆的固体。起酥油(shortening)和人造黄油(margarine)是典型的实例。取决于使用的条件、起始油和异构化或饱和程度,采用加氢方法可生产宽范围的油脂产品。
为了采用物理精炼得到好品质的油脂,有利的是在汽提之前具有低于5ppm的磷含量。
将脱胶-漂白的油进行真空提馏(vacuum strip)。该工艺包括在碱路线以及物理精炼之后应用的除臭过程。除臭(期间可除去FFA的最后的主要加工步骤)是在升高的温度(180-240℃)下的真空-蒸汽蒸馏过程(1-2毫巴的剩余压力),在此期间,将FFA和微量水平的有气味(odoriferous)材料(主要由氧化引起)除去以得到温和(bland)且没有气味(odorless)的油。为了使不期望的高沸点组分挥发,施加高真空和使用蒸汽稀释,使得沸腾温度可最低化。所述除臭利用了臭味和异味(off-odor)物质与甘油三酸酯之间挥发性的不同。
有气味的物质、FFA、醛、酮、过氧化物、醇和其它有机化合物集中在除臭器馏出物中。这些物质的有效除去取决于它们的蒸气压,对于给定的组成,这些物质的有效除去是温度的函数并随着温度而提高。
通常作为精炼方法的最后阶段,除臭对于总体的精炼油品质和馏出物组成具有重要的影响。其主要目的是给予温和的味道和气味、低FFA含量、高氧化稳定性和浅且稳定的颜色。由于需要相当高的温度以除去不期望的组分,因此不希望的副反应为双键的异构化、聚合、内部酯化、以及维生素和抗氧化剂的降解。引入在除臭器中能够达到非常低操作压力的新干冷凝(将蒸汽冷凝为冰)真空体系(接近0.1kPa)。这种进步容许除臭温度的降低而不以消极的方式影响提馏效率。为了最小化油在高温下的时间,除臭器可在双重温度下运行,以在(在适中的温度下)除臭与在高温下热漂白和最终提馏所需要的停留时间之间达到最佳的折衷。
除臭器馏出物是从食用油的蒸汽蒸馏收集的材料。来自物理精炼的油的所述馏出物主要由具有低水平的不能皂化组分的FFA组成。通过应用产生富集的FFA馏分(cut)的双重冷凝体系,可将FFA的浓度从典型的80%改进到最高达98%。可将所述馏出物用作工业脂肪酸的来源或者与用于烧蒸汽锅炉的燃料油混合。
由于在汽提之前精炼的油中较高的残留FFA含量,物理精炼是优选的。
化学精炼
当应用于粗油时,它包括脱胶(除去磷脂)、中和(除去游离脂肪酸)、漂白(脱色)和除臭(图1)。
脱胶包括例如加入水以使存在的任何胶水合,之后离心分离。不能水合的胶通过如下除去:首先,使用磷酸或柠檬酸将它们转化为能水合的形式,之后加入水并离心。也可使用酸脱胶(参见上面的描述)。
之后的步骤是中和,其中,将含水的碱(典型地苛性钠或碳酸钠)喷射到已经预热到约75-95℃的油中。所述碱与所述油中的游离脂肪酸反应,以形成皂,通过沉降或离心将所述皂分离。含水碱强度、混合时间、混合能量、温度和过量苛性碱的量的选择都对使得所述化学精炼方法高效率地和有效地运行有重要的影响。在中和之后,可结合干燥步骤以保证所加入的水的完全除去。所述皂可以其本身使用或者可使用硫酸水解(酸化)为相应的FFA。
对经过中和的油漂白,以除去有色物质(例如类胡萝卜素)和其它次要成分,例如氧化降解产物或痕量的金属。漂白使用活性漂白土(典型地在90-130℃的范围内处理10-60分钟)。所述土在真空下吸入到油中并通过过滤除去。
将经过漂白的油在低压下蒸汽蒸馏以除去包括不期望气味和香味的挥发性杂质。取决于油的性质、量、所用设备的类型,称为除臭的该方法在180-270℃的温度范围发生并可持续15分钟到5小时。
从精炼的油得到生物石脑油
将油脂转化为可用于蒸汽裂化以产生轻质烯烃、二烯烃和芳族化合物的石脑油类烃和LPG存在三种选择。这些总结在表3中。
表3
第一种选择在于加氢脱氧,其从所述油脂除去氧原子。这可在甘油三酸酯(以其本身的形式)、含有FFA的甘油三酸酯上或者在仅FFA上进行。油脂的加氢脱氧已经在1989年被报导(W.H.Craig和D.W.Soveran,“Production ofhydrocarbons with relatively high cetane rating”,US 4992605,以及Gusmao J,Brodzki D,Djéga-Mariadassou G,Frety R.,“Utilization of vegetable oils as analternative source for diesel-type fuel:Hydrocracking on reduced Ni/SiO2andsulphided Ni-Mo/γ-Al2O3”,Cat.Today 1989(5)533),其中使用了常规的CoMo或NiMo经硫化催化剂。这些催化剂在加氢脱硫中是公知的且已知还催化加氢脱氧(E.Furimsky,Applied Catalysis A,General,199,pages 147-190,2000)。
油脂的加氢脱氧优选在含有固体催化剂的连续固定床反应器、连续搅拌罐反应器或淤浆型反应器中进行,所述固体催化剂可选自:Ni、Mo、Co或者混合物如NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相并且优选地负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上。优选的是,用于所述催化活性相的载体呈现出低的酸度,优选中性或者碱性,以避免在升高的温度和压力下在氢气的存在下导致支化的链烷烃和裂化的加氢异构化反应。温度为200-500℃、压力为1MPa-10MPa(10-100巴)且氢气与油原料的比率为100-2000Nm3/m3液体。为了最佳性能和稳定连续的运行,优选的是催化剂的活性金属组分为硫化物形式。为此,优选的是存在痕量的能分解的硫化合物或故意向原料中加入痕量的能分解的硫化合物,以使金属硫化物保持处于其硫化物状态。例如,这些硫化合物可为H2S、COS、CS2、硫醇(例如,甲基硫化物)、硫醚(例如,二甲硫醚)、二硫化物(例如,二甲基二硫醚)、噻吩类和四氢噻吩类化合物。
在加氢脱氧条件下,发生若干种反应。最容易的是在烷基链中的双键的加氢。更困难的反应是从C-O键除去氧原子。脂肪酸的羧基和甘油部分的羟基都加氢脱氧。这导致直链链烷烃(由脂肪酸产生)和丙烷(由甘油产生)的产生。取决于条件(催化剂、温度、氢气等),还可将羧基分解为CO/CO2(脱羧基)且所述CO/CO2本身又可进一步加氢成为甲烷。这些加氢脱氧反应消耗许多氢气。
作为实例,给出如下方程式:三油酸甘油酯加氢脱氧:
[C18H33O]3C3H5O3+15H2→3C18H38+C3H8+6H2O
脂肪酸的加氢脱氧:
R-CH2-CH2-COOH+3H2→R-CH2-CH2-CH3+2H2O
取决于可用氢气的量、催化剂和运行条件,可发生中间物CO/CO2的进一步加氢:
CO+3H2→CH4+H2O
CO2+4H2→CH4+2H2O
第二种选择在于脂肪酸的脱羧基或脱羰基。这些脂肪酸可从油脂通过物理精炼(包括蒸汽/真空蒸馏)、通过甘油三酸酯的(蒸汽)分裂或通过使用酸的皂的分裂(酸化)获得。在1982年已经报导了在气相中在Pd/SiO2和Ni/Al2O3催化剂上进行羧酸的脱羧基(W.F.Maier,Chemische Berichte,115,pages808-812,1982)。在2005年已经报道了使用过渡金属催化剂的高选择性的脱羧基(I.Kubickova,Catalysis Today,106,pages 197-200,2005and M.Snare,Industrial Engineering,Chemistry Research,45,p.5708-5715,2006)。基于巴的催化剂呈现出对于脱羧基最高的选择性。使用碱性催化剂如MgO、ZnO和混合碱性氧化物,在催化条件下,也可将羧酸脱羧基(A.Zhang*,Q.Ma,K.Wang,X.Liu,P.Shuler,Y.Tang,“Naphthenic acid removal from crude oilthrough catalytic decarboxylation on magnesium oxide”,Applied Catalysis A:General 303,p.103,2006;A.More,John R.Schlup,and Keith L.Hohn“Preliminary Investigations of the Catalytic Deoxygenation of Fatty Acids”,AIChe,The 2006annual meeting,San Francisco and B.Kitiyanan,C.Ung-jinda,V.Meeyoo,“Catalytic deoxygenation of oleic acid over ceria-zirconia catalysts”,AIChe The 2008annual meeting)。
可发生下列反应:
脱羧基:
R-CH2-CH2-COOH→R-CH2-CH3+CO2
脱羰基:
R-CH2-CH2-COOH→R-CH=CH2+CO+H2O
优选在间歇型罐式反应器、连续固定床型反应器、连续搅拌罐反应器或淤浆型反应器中在固体催化剂存在下进行脱羧基。所述催化剂可选自:Ni、Mo、Co或者混合物如NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相并且优选地负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上;或者负载在高表面积碳、氧化镁、氧化锌、尖晶石(Mg2Al2O4,ZnAl2O4)、钙钛矿(BaTiO3,ZnTiO3)、硅酸钙(如硬硅钙石)、氧化铝、二氧化硅、二氧化硅-氧化铝、或者其混合物上的第10族(Ni、Pt和Pd)或第11族(Cu和Ag)的金属或合金混合物。优选的是,用于该催化活性相的载体呈现出低的酸度,优选中性或者碱性,以避免导致支化的链烷烃和裂化的加氢异构化反应。脱羧基也可在如下物质上实施:碱性氧化物,如碱金属氧化物、碱土金属氧化物、镧系元素氧化物、氧化锌、尖晶石(Mg2Al2O4,ZnAl2O4)、钙钛矿(BaTiO3,ZnTiO3)、硅酸钙(如硬硅钙石),其作为本体材料或者分散在中性或碱性载体上;碱性沸石(如通过交换或者浸渍得到的碱金属或碱土金属低的二氧化硅/氧化铝沸石)。
虽然,所述脱羧基反应不需要氢气,但是优选的是所述脱羧基在氢气存在下进行,所述氢气经由加氢反应,通过从催化剂表面除去牢固吸附的不饱和物质(例如当脱羰基是优势反应途径时),稳定催化活性。氢气的存在还可对存在于脂肪酸的酰基部分中的双键进行加氢,以从脱羧基方法得到链烷烃反应产品。可在100-550℃下、在存在或不存在氢气的情况下、在0.01-10Mpa的压力下实施脂肪酸的脱羧基。氢气与原料的比率为0-2000Nl/l。
在脱羧基条件下可发生的其它反应为:
R-CH=CH2+H2→R-CH2-CH3
脂肪酸的加氢脱氧:
R-CH2-CH2-COOH+3H2→R-CH2-CH2-CH3+2H2O
取决于可用氢气的量、催化剂和运行条件,可发生中间物CO/CO2的进一步加氢:
CO+3H2→CH4+H2O
CO2+4H2→CH4+2H2O
从油脂获得生物石脑油的第三种选择是通过脂肪酸皂的热脱羧基。所述皂可如下得到:从油脂的化学精炼,通过中和,产生精炼的甘油三酸酯和皂;通过在油脂的(蒸汽)分裂后得到的脂肪酸的中和;或通过油脂使用碱性氧化物或碱性氢氧化物的直接皂化,产生皂和甘油。
已经通过脂肪酸在热的压缩水中借助于碱金属氢氧化物的分解而实施了脱羧基,导致产生烷烃和CO2(M.Watanabe,Energy Conversion andManagement,47,p.3344,2006)。早在1947年就报导了通过蒸馏分解桐油的钙皂(C.C,Chang,S.W,Wan,“China’s Motor Fuels from Tung Oil”,Ind.Eng.Chem,39(12),p.1543,1947;Hsu,H.L.,Osburn,J.O.,Grove,C.S.,“Pyrolysisof the calcium salts of fatty acids”,Ind.Eng.Chem.42(10),p.2141,1950;Craveiro,A.A.;Matos,F.J.A.;Alencar,J.W.;Silveira E.R.Energia:FontesAlternativas 3,p.44,1981;A.Demirbas,“Diesel fuel from vegetable oil viatransesterification and soap pyrolysis”,Energy Sources 249,p.835,2002)。
优选的皂是由碱金属、碱土金属、镧系元素、锌或铝阳离子构成的那些。皂的热脱羧基可通过加热直到熔化的皂开始分解为相应的链烷烃或烯烃和相应的金属碳酸盐或金属氧化物/氢氧化物和CO2实施。不希望受制于任何理论,相信发生了下列的总反应:
[R-CH2-CH2-COO-]xMx++x H2O→x R-CH2-CH3+M[HCO3]x
M[HCO3]x←→M[OH]x+CO2
优选的是在液态、超临界或蒸气水的存在下实施皂的热分解。
蒸汽裂化
蒸汽裂化器是复杂的工业设备,其可分成三个主要的区(每一个区具有若干类型的具有非常特定功能的设备):(i)热区,其包括:热解或裂化炉、骤冷交换器和骤冷环、热分离序列(train)的柱子,(ii)压缩区,其包括:裂化气压缩机、纯化和分离柱、干燥器,和(iii)冷区,其包括:冷箱、脱甲烷塔、冷分离序列的分馏柱、C2和C3转化器、汽油加氢稳定化反应器。烃裂化在直接火力加热器(炉)中的管式反应器中进行。可使用各种管尺寸和结构,例如盘管(coiled tube)、U-管或直管设计。管径为1-4英寸。每一个炉由其中将废热回收的对流区和其中发生热解的辐射区组成。将原料-蒸汽混合物在对流区中预热至约530-650℃,或者将原料在对流区中预热并且随后在其流到辐射区之前与稀释蒸汽混合,在所述辐射区中,取决于原料类型和期望的裂化苛刻度(severity),在750-950℃的温度和0.05-0.5秒的停留时间下发生热解。在一个有利的实施方案中,停留时间为0.05-0.15秒。蒸汽/原料(蒸汽/[烃原料])重量比为0.2-1.0kg/kg,优先为0.3-0.5kg/kg。在一个有利的实施方案中,蒸汽/原料重量比为0.2-0.45并且优选0.3-0.4。对于蒸汽裂化炉,所述苛刻度可通过如下调节:温度、停留时间、总压力和烃的分压。一般而言,乙烯产率随着温度而增加,同时丙烯产率降低。在高温下,丙烯裂化并且因此有助于更大的乙烯产率。由此获得的在苛刻度方面的升高导致选择率的适度降低以及C3=/C2=比率的显著降低。因此,高苛刻度操作有利于乙烯,而低苛刻度操作有利于丙烯生产。在炉管中原料的停留时间以及温度应一起考虑。焦炭形成速率将决定最大可接受的苛刻度。较低的操作压力导致较容易的轻质烯烃形成和减少的焦炭形成。通过如下实现可能的最低压力:(i)在裂化气压缩机的抽吸下,将炉管的输出压力保持为尽可能接近大气压,(ii)通过用蒸汽稀释降低烃的压力(这对于减缓焦炭形成具有显著影响)。蒸汽/原料比必须保持在足以限制焦炭形成的水平。
来自热解炉的流出物包含未反应的原料、期望的烯烃(主要是乙烯和丙烯)、氢气、甲烷、C4混合物(主要是异丁烯和丁二烯)、热解汽油(C6-C8范围的芳族化合物)、乙烷、丙烷、二烯烃(乙炔、甲基乙炔、丙二烯),和在燃油的温度范围内沸腾的较重质烃。通过在平行的输送管线热交换器(TLE)中产生高压蒸汽而使该裂化气迅速骤冷至338-510℃以停止热解反应,使连串(consecutive)反应最少化和回收该气体中的显热(sensible heat)。在基于气态原料的设备中,该经TLE骤冷的气流向前流至直接水骤冷塔,在该水骤冷塔中,该气体进一步用再循环的冷水冷却。在基于液体原料的设备中,预分馏器在该水骤冷塔之前以使燃油级分从裂化气冷凝和分离。在这两种设备中,裂化气中的重质汽油和稀释蒸汽的主要部分在该水骤冷塔中在35-40℃冷凝。该水骤冷气体随后在4或5个阶段中压缩至约25-35巴。在压缩阶段之间,除去冷凝的水和轻质汽油,并且将该裂化气用苛性碱(caustic)溶液、或者用再生的胺溶液之后用苛性碱溶液洗涤,以除去酸性气体(CO2、H2S和SO2)。将压缩的裂化气用干燥剂干燥并且用丙烯和乙烯制冷剂冷却至深冷(cryogenic)温度用于后续产物分馏:前端脱甲烷化、前端脱丙烷化或前端脱乙烷化。
在前端脱甲烷化配置中,首先通过脱甲烷塔在约30巴下使尾气(CO、H2和CH4)从C2+组分中分离。底部产物流动去脱乙烷化,所述脱乙烷化的顶部产物在乙炔加氢单元中处理并且在C2分离柱(splitting column)中进一步分馏。所述脱乙烷化的底部产物去脱丙烷化,所述脱丙烷化的顶部产物在甲基乙炔/丙二烯加氢单元中处理并且在C3分离柱中进一步分馏。脱丙烷塔的底部产物去脱丁烷化,在所述脱丁烷中,将C4从热解汽油级分分离。在该分离顺序中,将加氢所需的H2从外部加入C2和C3物流中。所需的H2典型地从所述尾气通过该残留CO的甲烷化回收并且最终进一步在变压吸附单元中浓缩。
前端脱丙烷化配置典型地用于基于气态原料的蒸汽裂化器。在该配置中,在第三压缩阶段的末尾除去酸性气体后,通过脱丙烷化使C3和更轻的组分从C4+分离。脱丙烷塔C3-塔顶物通过第四阶段压缩至约30-35巴。该C3-馏分中的乙炔和/或二烯烃用仍然存在于该物流中的H2催化加氢。加氢后,将该轻质气体物流脱甲烷化、脱乙烷化和进行C2分离。脱乙烷化的底部产物可最终进行C3分离。在替代配置中,C3-塔顶物首先脱乙烷化并且C2-如上所述处理,而C3在C3乙炔/二烯烃加氢单元中处理并且进行C3分离。使C4+脱丙烷塔塔底物脱丁烷化,以使C4从热解汽油分离。
存在两种形式的前端脱乙烷化分离顺序。到第三压缩阶段,该产物分离顺序与前端脱甲烷化以及前端脱丙烷化分离顺序相同。气体首先在约27巴脱乙烷化以使C2-组分从C3+组分分离。顶部C2-物流流动至催化加氢单元,在所述催化加氢单元中该物流中的乙炔选择性加氢。使该加氢的物流冷冻(chill)至深冷温度并且在约9-10巴的低压下脱甲烷化以剥离(strip off)尾气。将C2底部物流分离以产生顶部乙烯产物和用于再循环的乙烷底部物流。平行地,来自前端脱乙烷塔的C3+底部物流在脱丙烷塔中进行进一步产物分离,所述脱丙烷塔的顶部产物在甲基乙炔/丙二烯加氢单元中处理并且在C3分离柱中进一步分馏。脱丙烷塔的底部产物去脱丁烷化,在所述脱丁烷化中C4从热解汽油级分分离。在前端脱乙烷化分离配置的更新近的形式中,裂化气在三个压缩阶段后苛性碱洗涤、预冷冻并且然后在约16-18巴顶部压力下脱乙烷化。净的(net)顶部物流(C2-)在下一阶段中在约35-37巴下进一步压缩,之后其送至催化转化器以便用仍然含于该物流中的氢气将乙炔加氢。加氢后,将该物流冷冻并且脱甲烷化以将尾气从C2底部物流剥离。C2在9-10巴压力下操作的低压柱中分离,而不是在高压C2分离器(splitter)(其使用丙烯制冷剂来冷凝该柱的回流液)中通常使用的19-24巴下分离。对于低压C2分离器分离方案,将塔顶物冷却和压缩系统集成到热泵、开放循环的乙烯制冷回路中。该乙烯产物变成乙烯制冷再循环系统的排出(purged)物流。
将该C2分离器的乙烷底部产物再循环回至蒸汽裂化。丙烷也可再裂化,这取决于其市场价值。再循环蒸汽裂化在两个或更多个专用热解炉中完成,以确保在再循环炉之一在除焦的同时设备继续运行。
上述配置存在许多其它变型,特别是以将不期望的乙炔/二烯烃从乙烯和丙烯馏分除去的方式。
图2到图4中呈现了各种实施方式。
在第一实施方式(图2)中,油脂通过真空蒸馏或蒸汽蒸馏(10)物理地精炼以收取作为顶部产物的混合脂肪酸(12)和作为底部产物的甘油三酸酯(11)。可将油脂(最后仍然含有游离脂肪酸)(21)或物理精炼的甘油三酸酯(20)送到加氢脱氧段,在该加氢脱氧段中将它们转化为生物石脑油(31)和生物丙烷(30)。将该生物石脑油(41)和生物丙烷(43)送去蒸汽裂化(50)或者将其与化石LPG、石脑油或瓦斯油(40)共混并且因此将该共混物蒸汽裂化(50)。将蒸汽裂化的产物冷却、压缩、分馏(fractionation)和纯化(51)。这导致作为主要组分的轻质烯烃(乙烯、丙烯和丁烯)、二烯烃(丁二烯、异戊二烯、(二)环戊二烯和戊间二烯)、芳族化合物(苯、甲苯和混合二甲苯)和汽油。
在第二实施方式(图3)中,油脂通过真空蒸馏或蒸汽蒸馏(10)物理地精炼以收取作为顶部产物的混合脂肪酸(12)和作为底部产物的甘油三酸酯(11)。任选地,可将油脂水解(21)以产生混合脂肪酸(22)和甘油(23)。所述混合脂肪酸的品质可通过酰基部分中的双键的加氢进一步改善,或者在水解之前,可将所述油脂加氢以除去残留双键并随后送到(21)水解步骤。可将所述混合脂肪酸送去(30)加氢脱氧段,在该加氢脱氧段中将它们转化为生物石脑油(36),或者替代地可将它们送到脱羧基段(31),在该羧基段(31)中将它们转化为生物石脑油(35)。将该生物石脑油(41)送去蒸汽裂化(50)或者将其与化石LPG、石脑油或瓦斯油(40)共混并且因此将该共混物蒸汽裂化(50)。将蒸汽裂化的产物冷却、压缩、分馏和纯化(51)。这导致作为主要组分的轻质烯烃(乙烯、丙烯和丁烯)、二烯烃(丁二烯、异戊二烯、(二)环戊二烯和戊间二烯)、芳族化合物(苯、甲苯和混合二甲苯)和汽油。
在第三实施方式(图4)中,将油脂皂化(21)以收取皂(22)和甘油(23)。任选地,可将油脂水解(21)以产生混合脂肪酸(22)和甘油(23)。替代地,可在粗油脂(24)的化学精炼步骤期间通过中和步骤得到皂(25)。皂的又一来源(30)是经由脂肪酸的中和,所述脂肪酸通过产生脂肪酸(28)和甘油(27)的油脂的(蒸汽)分裂(26)得到。皂的品质可通过酰基部分中的双键的加氢进一步改善,或者在皂化或水解之前,可将所述油脂加氢以除去残留双键并随后送到皂化(21)或水解(26)步骤。所述皂可送到(31)脱羧基段,在所述脱羧基段中将它们转化为生物石脑油(35)和金属碳酸盐或CO2(36)。该生物石脑油(41)送去蒸汽裂化(50)或者将其与化石LPG、石脑油或瓦斯油(40)共混并且因此将该共混物蒸汽裂化(50)。将蒸汽裂化的产物冷却、压缩、分馏和纯化(51)。这导致作为主要组分的轻质烯烃(乙烯、丙烯和丁烯)、二烯烃(丁二烯、异戊二烯、(二)环戊二烯和戊间二烯)、芳族化合物(苯、甲苯和混合二甲苯)和汽油。
实施例
实施例1
在下列条件下评价甘油三酸酯原料的加氢脱氧:
在等温反应器中,装载10ml由负载在氧化铝上的钼和镍组成的加氢处理催化剂(从Albemarle获得的KF848),将所述催化剂干燥且在标准条件下用掺杂有DMDS的直馏瓦斯油预硫化。在下面的条件下进行油菜籽油的加氢脱氧:
LHSV=1h-1
入口温度=320℃
出口压力=60巴
H2/油比率=630Nl/l
原料=掺杂有1重量%DMDS的油菜籽油
表4显示了油菜籽油的典型组成。
在大气压力下通过分离器(气体/液体)分离气体和液体流出物。将气体送到μ-GC分析仪并且将液体送到取样器。质量平衡为约99%且所有产物重量是对于100g处理的原料计算的。
表4油菜籽油的典型组成
总的液体流出物是两相的且需要分离步骤。通过GC-MS分析有机相。完整的分析报道在表5中。
液体流出物由94.4重量%的n-链烷烃组成,但是它由99.94重量%的令人感兴趣的(interesting)组分组成,所述组分可以送到石脑油裂化器。
表5:烃相的材料平衡和完整GC分析
94.4重量%的烃相由作为用于蒸汽裂化器的高品质生物石脑油原料的n-链烷烃组成。在烃相中发现大约0.059重量%的残留含氧化合物。这对应于112wppm的O原子。考虑到甘油三酸酯原料中的氧含量,其占了10.86重量%(或108600wppmO原子),这导致了99.89%的加氢脱氧转化率。
实施例2
将n-链烷烃和常规石脑油在不同的苛刻度条件下蒸汽裂化。表6给出了结果。从结果中明显看出,相比于化石石脑油,这样得到的生物石脑油是用于蒸汽裂化的更好原料。
可得到明显更高的乙烯和丙烯产率,然而甲烷的产生和热解汽油的产生减少了至少约20%。HVC(高价值化学物=H2+乙烯+丙烯+丁二烯+苯)的最终产率高于70重量%。乙烯/甲烷重量比始终高于3。
表6
P/E是丙烯/乙烯的比率
COT炉管出口温度
S/HC是蒸汽/烃的比率
Claims (23)
1.用于从天然存在的油脂的复杂混合物即粗油脂制造生物石脑油和任选地制造生物丙烷的方法,其中
(a)使所述粗油脂经历包括脱胶和漂白的精炼预处理以除去大部分的非甘油三酸酯和非脂肪酸组分,从而得到精炼的油脂;和
(b1)将所述精炼的油脂通过真空蒸馏或蒸汽蒸馏物理地精炼以收取作为顶部产物的混合脂肪酸和作为底部产物的甘油三酸酯,和
(c1)将物理精炼的甘油三酸酯送到加氢脱氧段,在该加氢脱氧段中将它们转化为生物石脑油和生物丙烷;或者
(c2)将所述混合脂肪酸送去加氢脱氧段,在该加氢脱氧段中将它们转化为生物石脑油,或者将所述混合脂肪酸送到脱羧基段,在该羧基段中将它们转化为生物石脑油;或者
(b2)将所述精炼的油脂皂化以收取皂和甘油,或者在粗油脂的化学精炼步骤期间通过中和步骤得到皂,或者经由通过精炼的油脂的蒸汽分裂/水解获得的脂肪酸的中和得到皂,所述蒸汽分裂/水解产生脂肪酸和甘油;和将所述皂送到脱羧基段,在所述脱羧基段中将它们转化为生物石脑油。
2.用于从天然存在的油脂的复杂混合物即粗油脂制造生物石脑油和任选地制造生物丙烷的方法,其中
(a)使所述粗油脂经历包括脱胶和漂白的精炼预处理以除去大部分的非甘油三酸酯和非脂肪酸组分,从而得到精炼的油脂,所述精炼预处理在于包括以下步骤的物理精炼:脱胶-漂白和蒸汽精炼-除臭,所述蒸汽精炼也产生游离脂肪酸,或者所述精炼预处理在于包括以下步骤的化学精炼:脱胶-产生能够被分裂成游离脂肪酸的皂的中和-漂白和除臭;和
(b1)将所述精炼的油脂通过真空蒸馏或蒸汽蒸馏物理地精炼以收取作为顶部产物的混合脂肪酸和作为底部产物的甘油三酸酯,和
(c1)将最后仍然含有游离脂肪酸的所述精炼的油脂或者将物理精炼的甘油三酸酯送到加氢脱氧段,在该加氢脱氧段中将它们转化为生物石脑油和生物丙烷;或者
(c2)将所述混合脂肪酸送去加氢脱氧段,在该加氢脱氧段中将它们转化为生物石脑油,或者将所述混合脂肪酸送到脱羧基段,在该羧基段中将它们转化为生物石脑油;或者
(b2)将所述精炼的油脂皂化以收取皂和甘油,或者在粗油脂的化学精炼步骤期间通过中和步骤得到皂,或者经由通过精炼的油脂的蒸汽分裂/水解获得的脂肪酸的中和得到皂,所述蒸汽分裂/水解产生脂肪酸和甘油;和将所述皂送到脱羧基段,在所述脱羧基段中将它们转化为生物石脑油。
3.权利要求1或2的方法,其中天然存在的油脂的所述复杂混合物选自植物油和动物脂肪。
4.权利要求1的方法,其中步骤(a)的精炼预处理在于包括以下步骤的物理精炼:脱胶-漂白和蒸汽精炼-除臭,所述蒸汽精炼也产生游离脂肪酸,或者步骤(a)的精炼预处理在于包括以下步骤的化学精炼:脱胶-产生能够被分裂成游离脂肪酸的皂的中和-漂白和除臭。
5.权利要求1或2的方法,其中还通过皂的酸化得到脂肪酸。
6.权利要求1或2的方法,其中还将所述精炼的油脂水解以产生混合脂肪酸和甘油。
7.权利要求1或2的方法,其中通过酰基部分中的双键的加氢进一步改善所述混合脂肪酸的品质,或者在水解之前,将所述油脂加氢以除去残留双键并随后送到水解步骤。
8.权利要求1或2的方法,其中通过酰基部分中的双键的加氢进一步改善所述皂的品质,或者在皂化或水解之前,将所述油脂加氢以除去残留双键并随后送到皂化或水解步骤。
9.权利要求1或2的方法,其中在步骤(c1)中,所述加氢脱氧在氢气和至少一种催化剂存在下进行,所述至少一种催化剂选自:Ni、Mo、Co、NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相。
10.权利要求9的方法,其中在200-500℃的温度下、在1MPa-10MPa(10-100巴)的压力下以及使用100-2000Nl/l的氢气与原料比率实施所述加氢脱氧。
11.权利要求9的方法,其中所述催化相负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上。
12.权利要求1或2的方法,其中在步骤(c2)中,所述加氢脱氧或脱羧基在氢气和至少一种催化剂的存在下进行,所述至少一种催化剂选自:Ni、Mo、Co、NiW、NiMo、CoMo、NiCoW、NiCoMo、NiMoW和CoMoW的氧化物或硫化物,其作为催化相;或者负载在高表面积碳、氧化镁、氧化锌、尖晶石、钙钛矿、硅酸钙、氧化铝、二氧化硅、二氧化硅-氧化铝、或者其混合物上的第10族和第11族的金属或合金混合物。
13.权利要求12的方法,其中所述催化相负载在高表面积的碳、氧化铝、二氧化硅、二氧化钛或氧化锆上。
14.权利要求1或2的方法,其中在步骤(c2)中,在如下物质上实施所述脂肪酸的所述脱羧基:碱性氧化物,其作为本体材料,或者分散在中性或碱性载体上;碱性沸石。
15.权利要求14的方法,其中碱性氧化物选自碱金属氧化物、碱土金属氧化物、镧系元素氧化物、氧化锌、尖晶石、钙钛矿、硅酸钙,和碱性沸石选自通过交换或者浸渍得到的碱金属或碱土金属低的二氧化硅/氧化铝沸石。
16.权利要求1或2的方法,其中在200-500℃的温度下、在1MPa-10MPa(10-100巴)的压力下以及使用100-2000Nl/l的氢气与原料比率实施所述加氢脱氧;或者其中在100-550℃的温度下、在0.1MPa-10MPa(1-100巴)的压力下以及使用0-2000Nl/l的氢气与原料比率实施所述脱羧基。
17.权利要求1或2的方法,其中在100-550℃下、在0.1MPa-10MPa的压力下以及在水的存在下,实施所述皂的脱羧基。
18.权利要求1或2的方法,其中采用每摩尔皂至少1摩尔水的水与原料比率实施所述皂的脱羧基。
19.在权利要求1-18任一项的方法中得到的生物石脑油作为蒸汽裂化器的直接原料以得到包括生物乙烯、生物丙烯、生物丁二烯、生物异戊二烯、生物环戊二烯和生物戊间二烯、生物苯、生物甲苯、生物二甲苯和生物汽油的裂化产物的用途,所述生物石脑油以其本身使用、或者在制造时与生物丙烷一起使用、或在与选自LPG、石脑油和瓦斯油的至少一种常规原料共混的情况下使用,
其中在蒸汽裂化方法中,将所述烃原料与蒸汽以0.3-0.45kg蒸汽/kg烃原料的比率混合。
20.权利要求19的用途,其中将所述烃原料与蒸汽以0.3-0.4kg蒸汽每kg烃原料的比率混合。
21.权利要求19或20中定义的用于蒸汽裂化原料的用途,其中将混合物加热到750-950℃的温度且停留时间为0.05-0.5秒。
22.权利要求19-20任一项中定义的用于蒸汽裂化原料的用途,其中将混合物加热到750-950℃的温度且停留时间为0.05-0.15秒。
23.在权利要求1-18任一项的方法中得到的生物石脑油用于蒸汽裂化以获得至少3的由生物石脑油的裂化产生的乙烯与甲烷的重量比的用途。
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EP09166485A EP2290035A1 (en) | 2009-07-27 | 2009-07-27 | A process for the production of bio-naptha from complex mixtures of natural occurring fats and oils |
PCT/EP2010/060028 WO2011012439A1 (en) | 2009-07-27 | 2010-07-13 | A process for the production of bio-naphtha from complex mixtures of natural occurring fats & oils |
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US (3) | US8648224B2 (zh) |
EP (3) | EP2290035A1 (zh) |
KR (1) | KR101424897B1 (zh) |
CN (1) | CN102549112B (zh) |
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CA2767208C (en) | 2015-09-22 |
EP2459679A1 (en) | 2012-06-06 |
CN102549112A (zh) | 2012-07-04 |
US8975459B2 (en) | 2015-03-10 |
US8648224B2 (en) | 2014-02-11 |
US20140155665A1 (en) | 2014-06-05 |
EP2290035A1 (en) | 2011-03-02 |
KR20120032540A (ko) | 2012-04-05 |
US20120157728A1 (en) | 2012-06-21 |
US20150141715A1 (en) | 2015-05-21 |
EP3059295A1 (en) | 2016-08-24 |
CA2767208A1 (en) | 2011-02-03 |
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