CN100575331C - 一种生产乙醇的方法 - Google Patents
一种生产乙醇的方法 Download PDFInfo
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- CN100575331C CN100575331C CN200510099551A CN200510099551A CN100575331C CN 100575331 C CN100575331 C CN 100575331C CN 200510099551 A CN200510099551 A CN 200510099551A CN 200510099551 A CN200510099551 A CN 200510099551A CN 100575331 C CN100575331 C CN 100575331C
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- Prior art keywords
- fermentation
- ethanol
- acid
- acetic acid
- acetate
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Abstract
一种生产乙醇的方法,它包括生物化学和合成转化的结合从而高收率生产乙醇,同时生产很有价值的联产品。乙酸中间体从碳水化合物如玉米中使用酶研磨和发酵步骤制得,接着使用酯化和氢化反应方法把乙酸转化成乙醇。联产品可以包括玉米油和含有发酵中生产得到的生物质的高蛋白动物饲料。
Description
发明领域
本申请是申请日为2000年3月10日、申请号为00804895.9、发明名称为“一种生产乙醇的方法”的发明专利申请的分案申请。
本发明涉及一种从大量来源中的任何一种碳水化合物源转化成用作燃料或化学用途的乙醇的方法。与现有技术比较,本发明使用发酵或化学转化的组合极大地增加从碳水化合物源获得乙醇的收率。此外还可以生产用于动物饲料的很有价值联产品。
发明的背景技术
乙醇是人类饮料和食品中所用的主要化学物质,可作为工业化学物质和作为燃料或燃料组份如为了减少从汽车中的排放而重新配制的汽油。本发明主要涉及用作化学物质或燃料的乙醇的生产。
现有好几种传统乙醇生产方法都以碳水化合物发酵为基础。在最典型的方法中,把来自谷类的碳水化合物水解得到其组份糖并且用酵母发酵产生乙醇。在该方法中,通过酵母的代谢可以从碳水化合物部分中能够生成二氧化碳。在酵母代谢中生成二氧化碳是固有的。由酵母产生二氧化碳限制了酵母生产乙醇的收率最大为约52重量%。因为二氧化碳的价值较低并且通常损失到大气中,给环境造成负担,所以这是对乙醇经济生产的最大限制。
另外,酵母对使用糖而不是葡萄糖的能力受到限制。当葡萄糖是从来自谷类的淀粉水解生成的主要糖类时,它却不是通常碳水化合物源所生产的唯一糖类。对生物质有效转化成乙醇的问题现已进行了大量研究。来自农业的废物如玉米杆、稻草、肥料等形式的生物质和生物质作物如换季草或白杨树甚至城市废物如报纸都能够被转化成乙醇。但是这些方法的主要限制是由生物质处理成发酵培养基产生的水解产物的复杂性。该水解产物一般包括葡萄糖,但也包括大量的其他糖如木糖,这是酵母所不能代谢的。这是对酵母为基础的乙醇方法收率的又一个潜在的限制。
研究已经指出如果来自于生物质的水解产物大多数不是糖时,与使用酵母相比使用除酵母外的生物体消耗得会更多。例子包括发酵单胞菌属的细菌和大肠杆菌细菌,它们经基因工程可使用木糖。由此增加了能够转化成乙醇的底物糖的潜在范围。有一类被建议生产乙醇的生物体,一般是梭状牙胞杆菌属。这些嗜热生物通常产生醋酸和乙醇。但是,人们相信这些生物体能产生有限收率的乙醇。在有关乙醇发酵的文献中人们一般认为这种收率的限定是由所有推荐生产乙醇的生物体包括嗜热生物生产乙醇所用的称之为Embden-Myerhof路径的生化路径所决定。
以用生物体联产CO2为基础从糖生产乙醇收率的固有问题没有丝毫进展。
生产乙醇的工业方法的重要部分是生产有价值的主要用于动物饲料或食品的联产品。在玉米干燥研磨方法中,联产品包括蒸馏器中的干燥谷类和可溶物〔DDG、DDGS〕。在玉米的湿法研磨方法中,联产品包括胚、谷蛋白粉和纤维。这些联产品在动物饲料业有巨大市场。但是从很大程度上说,这两种方法中原始谷类的成分即油、蛋白和纤维部分都是经过加工而在组合物中没有改变的,而碳水化合物部分都大量转化成乙醇。所以这些联产品的量是取决于组合物本身的植物成分。
把碳水化合物工业发酵生产的除乙醇外还有其他化学物质。主要例子是乳酸和醋酸。醋酸是以醋形式的一种食物的主要成分并且也是主要工业化学物质。食用醋自可饮用的乙醇一般通过醋杆菌属的作用即使用空气中的氧把乙醇氧化成醋酸而生产。
醋酸的主要工业用途是作为溶剂、合成其他化学物质如醋酸乙烯酯和生产醋酸纤维素的中间体。人们已经提出醋酸主要的新用途如生产醋酸镁钙(CMA)用作道路防冻剂来替代氯化钠(NaCl)。CMA与氯化钠相比因为它腐蚀性很小并且是可生物降解的,所以对环境的影响大大下降。
研究者建议把碳水化合物发酵来生产工业级醋酸。但是,目前由于主要涉及从稀释的发酵液中回收醋酸的经济因素而没有用发酵生产。醋酸一般在大约5%或更低的低浓度在作为发酵液的水中生成。因为醋酸比水熔点高,必须蒸馏全部水,即大约95%的发酵液来回收醋酸或者必须使用其他更复杂的方法来回收醋酸。
有关醋酸生产的领域使用称作产醋酸菌,这是一类能够使用独特生化路径从糖中以100%碳的转化率产生醋酸的细菌。例如用热醋梭菌(Clostridiumthermoaceticum)把一摩尔葡萄糖转化成三摩尔醋酸。这些细菌在内部将CO2转化为醋酸。这些细菌称之为同型发酵微生物或同型产醋酸菌。它们不能把任何碳水化合物转化成二氧化碳而只能生成醋酸。同型产醋酸菌的例子在Drake,H.L.(编辑),Acetogenesis,Chapman & Hall,1994中公开,本文将其全部引用为参考文献。此外,这些同型发酵的生物体一般把各种的糖包括葡萄糖、木糖、果糖、乳糖等转化为醋酸。这样它们特别适合于来自生物质的复合水解产物发酵。但是,这类研究没有克服醋酸发酵方法的经济局限,使其与天然气为基础的途径相竞争。
所以,当今从煤炭、汽油或天然气中制备工业醋酸。主要方法是把天然气转化成甲醇并且接着用一氧化碳羰基化甲醇直接得到醋酸。US 3,769,329中描述了该方法。
就天然气方法而言,现已提出从醋酸通过该方法中生成的醋酸的酯合成或者相关改良并接着氢化该酯来生产乙醇。US 4,454,358和US 4,497,967中公开了从合成气生产醋酸的方法,然后将醋酸酯化并氢化生成乙醇,在本文中将其全文引用为参考文献。氢化酯来生产醇是大家所熟知的。这些方法中没有一个是以把碳水化合物转化成乙醇为基础的。
有另外一类公知的发酵,是使用同型发酵乳酸菌以100%碳的收率转化碳水化合物的特性。例如这些细菌能够把一摩尔的葡萄糖转化成两摩尔的乳酸。与此相关的是乳酸也可以用作该同型发酵产醋酸菌以100%碳收率发酵得到醋酸的底物。例如用蚁酸醋酸梭菌能够把两摩尔乳酸转化成三摩尔醋酸。在本发明之前,没有人知道设计一种从碳水化合物高收率生产乙醇的方法,这就是本发明的主要目的。
发明概述
按照本发明的一个实施方案,通过把发酵和化学转化结合可以较高的碳收率把碳水化合物转化成乙醇,这样克服了把碳水化合物转化成乙醇的已知方法的主要局限。本发明把几个化学和生物化学步骤结合成为具有多种优点的新方法中。本发明的基本方法包括三个步骤:
1.用同型醋酸发酵法(或者同型乳酸发酵和随后同型醋酸发酵)把广泛的碳水化合物以很高的碳收率(约>90%)转化成醋酸,
2.回收、酸化(如果需要的话)和转化醋酸为酯(优选使用循环的乙醇产品转化为乙酯),并且
3.氢化酯,生成乙醇和再生酯的醇部分。
该方法的基本效果是把碳水化合物以很高的碳收率转化为乙醇。从碳水化合物中没有生产出二氧化碳作该方法的副产物。
本发明的其他益处是生产出高价值的副产物,这是因为把植物蛋白转化成了细菌的单一细胞蛋白。把植物蛋白转化成单一细胞细菌蛋白增加了蛋白的浓度,重建了蛋白,例如就其必需氨基酸而言使其成为使用价值更高的动物饲料组合物,并且例如潜在地提供了牛奶生产的方面的其他益处。
纤维部分的转化和谷类的纤维素和木聚糖部分对乙醇的总产率都起作用。
当生产单一细胞蛋白和使用纤维素是本发明的其他重要益处时,仅仅收率因素就有很大改善并且能够在玉米湿研磨方法结合其自身实施,而没有生产单一细胞蛋白或使用纤维素纤维。
本发明优于现有技术的状态的优点还包括下列一种或多种:
1.与已知的乙醇生产方法相比来自原料的产物收率非常高并且具有明显经济效益,
2.该方法没有从碳水化合物产生二氧化碳,具有利于环境的优点,即,可回收来源非常有效的转化为乙醇。
3.对乙醇的生产有特有的广泛的底物范围,即,广泛的潜在生物质来源和其组份糖类,并且
4.价值很高的副产物,如单一细胞蛋白;植物蛋白的重构,高效生产。
在本发明的一个实施方案中,提供了一种收率很高的生产乙醇的方法。该方法包括把含有碳水化合物源的培养基发酵成醋酸盐、醋酸或其混合物。醋酸盐、醋酸或其混合物可以用化学方法转化为乙醇。优选把碳水化合物源中的至少60%左右,更优选至少80%左右并且更优选在至少90%左右的碳转化成乙醇。基本上在碳水化合物源中没有碳转化成二氧化碳。但是,如果在方法中由蒸汽转换随后生产了氢,在当时那个阶段也会产生二氧化碳。优选发酵培养基含有至少20%左右的氮并且以优选至少大约10%生物质产物的重量得到可用作动物饲料的生物质副产物。该碳水化合物源包括任意适当的来源如玉米、小麦、生物质、木材、废纸、肥料、干酪乳皮、废糖蜜、糖用甜菜根或糖用的甘蔗。如果使用了农业产品如玉米,把玉米研磨生产出回收的产物玉米和玉米油。该碳水化合物源例如玉米在发酵前被酶水解。优选用同型发酵微生物进行。该发酵是使用产醋酸菌如梭状芽胞杆菌属的微生物如热醋梭菌(Clostridium thermoaceticum)或蚁酸醋酸梭菌(Clostridium.formicoaceticum)菌种对发酵液再同型醋酸发酵。
在本发明的一个实施方案中,发酵包括把碳水化合物源通过发酵转化成乳酸、乳酸盐或其混合物并且接着通过发酵把乳酸、乳酸盐或其混合物转化为醋酸、醋酸盐或其混合物。乳酸发酵是使用乳杆菌属的微生物完成的同型乳酸发酵。另外一种选择是,在初始发酵中使用两歧细菌可把碳水化合物源转化为乳酸、乳酸盐、醋酸、醋酸盐或其混合物。通常,碳水化合物源的一摩尔葡萄糖最初转化成大约两摩尔的乳酸盐并且把该乳酸盐转化为三摩尔醋酸盐。
在与发酵结合中所形成的醋酸可以是醋酸盐形式,这取决于发酵培养基中的pH指。醋酸盐能够被酸化成醋酸。例如,醋酸盐与碳酸和胺反应形成醋酸钙和醋酸的胺络合物。该胺络合物可以回收并热分解再生胺并形成醋酸。碳酸钙能够回收再利用。把醋酸酯化和氢化形成醇。另外一种方法,把醋酸直接氢化形成乙醇。酯化优选用反应蒸馏来实现。
在本发明的另外一个技术方案中,用二氧化碳酸化醋酸盐来生成醋酸和碳酸钙并且酯化成可回收用的醋酸酯。该方法最好在低或接近大气压下进行。为了维持发酵液的pH,最好向发酵液中循环碳酸钙。酯优选是挥发性酯。如本文所使用的,术语“挥发性酯”指得是能够蒸馏回收的酯,并且该酯应当比回收的水更具挥发性。酯化中所用的醇优选是甲醇、乙醇或其混合物。该酯优选蒸馏如通过反应蒸馏回收,接着将其转化为乙醇。
反应蒸馏是在反应柱中通过酸化、酯化和回收酯来完成的。把混有乙醇的醋酸盐稀释水溶液装入该柱反应部分的顶部。把二氧化碳气体导入该柱反应部分的底部。二氧化碳与醋酸盐和乙醇在反应区反应形成碳酸钙和乙酸乙酯。例如通过蒸发含有过量乙醇和水的混合物和含有乙酸乙酯、水和乙醇的共沸物来浓缩乙酸乙酯。例如通过加入水由此引起富含乙酸乙酯部分和富含水和乙醇部分的相分离来把该共沸混合物从过量的乙醇和水中分离出来。该乙醇和水能够被返回反应区并且碳酸钙能够循环至发酵液中用来调节pH。
在本发明的一个实施方案中,能够从碳水化合物源生产出乙醇,并且基本上没有碳和碳水化合物源转化为二氧化碳。
在本发明的又一个实施方案中,从碳水化合物源生产乙醇,其中把碳水化合物源中至少60%、优选70%,更优选80%、更优选95%和最优选95%的碳转化为乙醇。
在本发明的其他实施方案中,从羧酸盐的稀释溶液中回收酯。用二氧化碳酸化羧酸盐来生成相应的羧酸和碳酸钙,同时用醇酯化形成酯。回收该酯。该酯优选是挥发性酯并且醇是甲醇、乙醇或其混合物。通过蒸馏法如反应蒸馏法回收该酯。把该酯转化成乙醇。酸化、酯化和回收能够在反应柱中进行。首先,把混有醇的羧酸盐稀释水溶液导入该柱的反应部位的顶部。把二氧化碳气体导入该柱反应部分的底部。二氧化碳和羧酸盐与醇反应形成碳酸钙和羧酸盐的挥发性酯。通过蒸发含有过量醇和水的混合物和由酯、水和醇组成的共沸物来浓缩该酯。例如通过加入水并由此引起富含酯部分和富含水和醇部分的相分离来把该共沸混合物与过量的醇和水中分离。该过量的醇和水能够被返回到反应区。
按照本发明的实施方案,把碳水化合物源和天然气转化成了容易输送的液体产物。通过发酵把碳水化合物源转化成了醋酸、醋酸盐或其混合物。该醋酸、醋酸盐或其混合物又被转化成乙酸乙酯。使用从天然气源获得的氢至少把部分乙酸乙酯转化成了乙醇。然后把所生成的乙醇和/或乙酸乙酯输送到距生产地遥远的地方。碳水化合物源和天然气源最好在一定距离内,使生产可运送液体产品经济上合理,并且遥远的位置是足够之远以致于把碳水化合物源和天然气源运送到遥远的加工处是经济上不合理的。所述的经济上合理的距离优选是小于500英里左右而经济上不合理的距离是大于1000英里左右。例如,碳水化合物源和天然气源位于加勒比海岛如特立尼达而遥远的位置就是海湾海岸如得克萨斯海湾海岸。另外一方面,碳水化合物源和天然气源可位于澳大利亚和/或新西兰而遥远的位置就可是在亚洲,如日本、台湾、韩国或中国。
在本发明另外一个实施方案中,碳水化合物源中至少80%的碳被转化为乙醇。该方法包括把碳水化合物源酶水解成糖和氨基酸。通过同型乳酸发酵把碳水化合物、糖和氨基酸(来自原始来源或其他来源)转化成乳酸、乳酸盐或其混合物。通过同型醋酸发酵把乳酸、乳酸盐或其混合物转化成醋酸、醋酸盐或其混合物。把发酵液的pH用碱维持在大约6到大约8的范围。从发酵液中可回收用作动物饲料的生物质副产品。用二氧化碳酸化醋酸盐来生产醋酸和碳酸钙而同时用醇把醋酸酯化成挥发性酯。用反应蒸馏法回收挥发性酯。氢可以用任何一种方法如蒸汽转化天然气来生产。氢化醋酸酯形成乙醇。
附图简述
图1是本发明方法中一个实施方案的方块图。
图2详细说明了葡萄糖转化成乳酸盐的代谢途径。
图3详细说明了葡萄糖转化成醋酸盐的代谢途径。
图4详细说明了反应蒸馏法的一个实施方案。
本发明的详细描述
本发明的乙醇生产方法的一个实施方案使用了酶研磨、间接发酵和化学合成的组合来生产高价值产品的盐。图1是该方法的方块流程图。玉米10被研磨20,提取油30,然后用酶44把剩余的物质用酶法转化成可发酵糖和氨基酸。通过两步发酵50生产醋酸和细菌生物质60。第一步骤使用乳酸菌如lactobacillus casei把可发酵的糖转化成乳酸。第二步发酵使用厌氧细菌如蚁酸醋酸梭菌把从第一步发酵中得到的乳酸和剩余糖转化成醋酸而没有任何二氧化碳副产品。这种发酵步骤的结合使得醋酸的收率较高,并共同生产细菌生物质60,这种细菌生物质符合美国FDA对直接食用的微生物的要求。使用化学合成步骤(酯化+氢化)80把所得到的醋酸转化成乙醇70。来自发酵的细菌生物质60是可以直接使用的或者可加工成高蛋白动物饲料浓缩物,其称之为单一细胞蛋白(SCP)60。
主要步骤的总化学反应如下:
酶处理:(1/n)淀粉+H2O ->右旋糖
发酵1:右旋糖 ->2乳酸
发酵2:2乳酸 ->3醋酸
酯化:3醋酸+3乙醇 ->3乙酸乙酯+3H2O
蒸汽转化:1.5甲烷+3H2O ->1.5CO2+6H2
氢化:3乙酸乙酯+6H2 ->6乙醇
总计:(1/n)淀粉+1.5甲烷+H2O ->3乙醇+1.5CO2
其中n是在淀粉分子中右旋糖单位的数值。上述方程式表示了淀粉是玉米中可发酵糖的唯一来源。但是,本发明的乙醇方法使用了酶研磨方法,它也使玉米的纤维素和半纤维素部分成为可发酵的部分。该酶研磨方法比传统湿法研磨使来自定量玉米的可发酵糖的量增加了大约20%。
本发明乙醇方法的高产率的另外一个原因是由该方法所产生的二氧化碳的量和来源。在本发明的乙醇方法中,对每摩尔乙醇来说,仅生产了0.5摩尔的二氧化碳。相比较而言,传统发酵途径每摩尔乙醇要生产1摩尔的二氧化碳。而且,本发明的乙醇方法使用了不昂贵的甲烷而不是右旋糖作二氧化碳的碳源。从不昂贵的原料中产生较低的二氧化碳使得该方法更经济。
适当发酵底物的制备
现有技术中有多种熟知方法来提供适合乳酸或醋酸发酵的发酵培养基。这些培养基是能够使培养基中氮的含量最小化并且由此使得单一细胞蛋白含量最小化的培养基。另一方面,也有试图增加原料中氮使用的方法。
为了本发明的目的,可以使用任何适当的培养基制备方法。
仅作为说明的例子,人们可考虑使用玉米作原料。正如在研磨技术领域中技术人员所公知的那样,在玉米研磨中通常使用好几步预处理步骤,如清洗、为油的生产除去胚等。
通常使用酶处理来把玉米转化成适合于在下步发酵中用细菌发酵的培养基,尽管也可以使用酸水解。把磨碎的玉米与水混合形成浆,然后加热灭菌。可以使用连续灭菌器,它能够把玉米浆加热到120-140℃并提供1到5分钟的停留时间。优选设计保留管以提供湍流(Re>4000)带有最小的死角,从而有好的灭菌效果,而没有出现过量的carmelization。
加热灭菌也开始液化过程。在液化的过程中,淀粉颗粒膨胀和浆液粘度急剧上升。通过解聚淀粉分子,一种称作糖化的方法使用热稳定的α-淀粉酶来限制粘度的上升。α-淀粉酶是水解淀粉分子中1,4键的酶。因为它随机攻击淀粉分子内部的键而被分为胞内酶。在pH5.5-7.0在小于10分钟停留时间把淀粉水解10-15%就实现了粘度的足够下降。
优选用葡糖淀粉酶来完成淀粉分子的水解。因为葡糖淀粉酶只攻击淀粉分子的末端,所以它是一种胞外酶。该酶水解1,4和1,6键,所以几乎能够实现淀粉的完全水解。葡糖淀粉酶的理想条件通常是58-62C,pH4.4-5.0和24-48小时的停留时间。因为该酶也催化非发酵多糖的形成-方法称作返原和退减作用,所以较长的停留时间一般也不利。
除了使用玉米的淀粉部分外,在本发明中最好使用其他主要部分,包括半纤维素、纤维素以及蛋白。在目前的乙醇方法中一般这是做不到的。本发明的较高收率和广泛的发酵所用底物的使用能力都提高了与目前方法相反的这些所加步骤的价值,这些将被说明。
半纤维素的水解能够用好几种方法进行。已知对酸水解进行了许多研究,但是酶水解也是大家所熟知的。半纤维素的完全酶水解需要酶的混合物。用α-L-阿拉伯糖呋喃糖苷酶和α-葡糖醛酸糖苷酶从木糖骨架中除去悬置的阿拉伯糖和葡糖醛酸。用内切-b-1,4-木聚糖酶和b-木糖苷酶水解该木糖骨架。
纤维素的使用是有价值的。已知有好几种方法把纤维素水解成可发酵的糖。例如,通过内切-b-葡聚糖酶、外切-b-葡聚糖酶和b-葡糖苷酶,这三种纤维素酶的协同作用水解纤维素。所述的内切-b-葡聚糖酶是胞内酶,它能够随意水解纤维素分子内部中的1,4-键。外切-b-葡聚糖酶能够从纤维素链的非还原末端除去纤维二糖单位(b连接的葡萄糖的二糖)。b-葡糖苷酶能够把纤维二糖单位水解成两个葡萄糖分子。三种酶一起工作,它们就能够把纤维素转化成葡萄糖单体。本发明中所用的乳酸细菌能够直接使用纤维二糖,其降低了水解的原料抑制,这也是本发明的一个特征。
在过去10-20年中已经有许多有关半纤维素和纤维素酶的研究。要求这些酶能够把木材生物质材料有效转化成可发酵的糖,然后将其用作传统方法中乙醇和其他发酵产品的发酵原料。生物质材料如草、木材、纸和作物残余物是比以淀粉为基础的材料如玉米淀粉便宜很多。
在称之为同时糖化和发酵(SSF)的设计中通过把糖化与发酵方法并用实现了酶消耗的下降。通过把葡萄糖转化成乙醇或其他所需发酵产物来避免纤维素酶的产物抑制。十年来用淀粉酶的乙醇工业已经使用了SSF的基本原理。研究也表明这种构思对半纤维素和纤维素的酶系统起作用。该方法也可以用于本发明。它是优选的方法,这是因为与消耗大量葡萄糖部分的酵母发酵相比,本发明中所用的发酵使用了水解中所生成的多种类型的糖并且进一步促进了水解。
除了使用含有半纤维素和纤维素的纤维部分外,本发明最好使用蛋白部分。
蛋白酶是用来把玉米蛋白水解成较小的肽和氨基酸。这些氨基酸和肽对发酵细菌来说是主要氮源。水解蛋白需要加速发酵的氮的同化。US4,771,001说明用蛋白酶增加乳酸发酵的蛋白使用。该专利也说明了在干酪乳皮情况下使用不同原料。为了本发明的目的,蛋白用来提供如图所示的来自玉米或者来自其他蛋白源的发酵并将其混入培养基中。可以使用任何产生乳酸或醋酸发酵的适当发酵培养基并且不抑制发酵的蛋白源。
在最普通的实施方案中,本发明不取决于具体碳水化合物或蛋白源,但可以使用任何适当的原料源。
发酵
本发明发酵部分的总目的是把可发酵的碳水化合物和氨基酸转化成醋酸和单一细胞细菌蛋白。在优选的实施方案中,使用两步发酵方法。第一步使用同型发酵的乳酸菌把大量可发酵的糖转化成乳酸和单一细胞蛋白。第二步使用同型发酵的产生醋酸的细菌把乳酸和剩余的碳水化合物转化成醋酸。
乳酸发酵步骤使用同型发酵的乳酸细菌如干酪因子乳芽孢杆菌把可发酵的糖转化成乳酸。乳酸菌是革兰氏阳性菌、无孢子形成、兼性厌氧菌。在大多数温血动物包括人的口腔和肠道中发现这些细菌。没有一种是致病性的并且大多数都被美国FDA批准作为用于动物饲料的直接饲喂微生物的活的生物体。在人消耗的多数酸奶中也存在活的培养物。
如图2所示,乳酸是同型发酵菌株的唯一代谢产物。使用常规的Embden-Meyerhof糖解通道把葡萄糖代谢成丙酮酸盐。在单一DNA偶合步骤中把丙酮酸盐转化成乳酸。大多数乳酸菌是嗜温性的,最佳生长温度是35到45℃。细胞生长对pH是敏感的,最佳的pH是大约6.0。产物抑制在乳酸含量大约4wt%时开始影响细胞生长和酸的生成的动力学。对生长的完全抑制出现在大约7wt%而酸生成的完全抑制出现在大约10-12wt%。
发酵的进料是很稀的仅有大约5wt%的可发酵糖的碳水化合物。单一阶段连续搅拌的罐式反应器(CSTR)型发酵器是适合于这种步骤的。但是,也可以使用任何适合的生物反应器,包括间歇、分批进料、细胞循环和多步骤的CSTR。在进料中低浓度的碳水化合物将限制对细胞生长和酸生成的动力学的产物抑制作用,这样用大约18-24小时的停留时间的90+%的转化右旋糖是可能的。大多数高发酵菌株很容易代谢一定范围的底物糖。有利的是把乳酸发酵与随后的醋酸发酵以使用全部糖的方式结合。
相对于许多工业乳酸发酵,本发明可以以发酵是碳水化合物限制而不是氮限制的方式操作。这样通过保持与状态有关的生长中的大多数发酵使得生物质的生产最大化并确保足够的氮可用于生长。对与发酵有关的任何生长来说,生物质的收率通常是大约所生产的每摩尔ATP10.5g。由于乳酸发酵产生了每摩尔葡萄糖净2摩尔ATP,所以生物质的收率将大约是2(10.5/180)=0.12g/每克葡萄糖。按照化学计算,剩余的0.88g葡萄糖被转化成0.88g乳酸。
作为单一细胞蛋白的生物质有效生产是本发明的重要部分。相对于历史上单一细胞蛋白的生产,使用厌氧的同型发酵性发酵是非常有益的。这是因为生物体的所有能量生产来自于所需代谢物或者是乳酸或者醋酸的生成。这就是说,正如厌氧发酵的情况,没有浪费的副产物二氧化碳。此外,因为没有生成二氧化碳,发酵产热也是最小的。所以,对于生成有价值的单一细胞蛋白或乳酸和醋酸来说,使用含在原料碳水化合物中能量也是最大的。除了浪费二氧化碳质量,传统的酵母发酵也需要除热。
用离心法澄清第一步发酵中的发酵液。浓缩液含有乳酸菌并将其送往单一细胞蛋白回收。所产生的单一细胞蛋白的量是与由提供给培养基中发酵的水解蛋白形式的氮如氨基酸和肽的量有关。这是能够有很小量的范围,但不是零,因为乳酸菌需要一些复合氮源如1%到大约15%单一细胞蛋白的总收率,它基于总氮加培养基中的碳水化合物。在很大范围内可控制单一细胞蛋白生产是本发明的一个特征。用任何适当方法如喷雾干燥加工单一细胞蛋白能够生成畅销的产品。
本发明的其他重要特征是生产质量提高的作为动物饲料成分的单一细胞蛋白。从乳酸发酵中来的单一细胞蛋白具有这些特征。它具有大约70%的高蛋白浓度,这取决于发酵用的生物体菌株和具体条件。它具有很好的氨基酸分布。即,它含有高百分比的称作基本氨基酸,这些氨基酸例如包括赖氨酸、蛋氨酸、异亮氨酸、色氨酸和苏氨酸。相对于大约1%的总玉米仁的玉米蛋白来说,这些氨基酸在乳酸菌中的总百分比大约是10.5%。该玉米蛋白组合物取决于被认为的玉米部分。例如玉米谷蛋白粉具有大约7.5%的基本氨基酸,但玉米谷蛋白饲料具有大约2.5%的基本氨基酸。这种提高的氨基酸组合物是直接与作为动物饲料成分的蛋白量有关的。
在优选的实施方案中,本发明能够高效和高质量地生产单一细胞蛋白。
把从第一步发酵的发酵液中分离乳酸菌的浓缩物添加到第二个发酵器中,在此用产醋酸的细菌把乳酸盐转化成醋酸盐。在许多自然环境中乳酸盐都是优选的产醋酸细菌的底物。乳酸盐底物的发酵率和收率都是非常高的,如从乳酸盐得到超过98%的醋酸盐。
没有完全除去乳酸菌一般也是可以容许的,因为醋酸发酵通常使用嗜热性菌株并且第二步发酵是在较高温度下进行的。由于乳酸菌在这些较高温度下一般不能生长,所以用嗜温性乳酸菌的醋酸发酵的污染通常不是问题。在第一步发酵器中也希望接近完全的转化葡萄糖,所以乳酸菌偶尔通过离心泄漏到第二步发酵器中不会有碳水化合物源。
从十九世纪三十年代起人们已经知道并研究过产醋酸的细菌。Drake,H.L.(编辑),Acetogenesis,Chapman & Hall,1994就对该领域一个很好的综述。产醋酸细菌包括梭状牙胞杆菌属、醋杆菌属、消化球菌属和其他人们较少知道的菌种。这些细菌的生长环境是:污水管、多种废物处理厂的厌氧菌蒸煮器、天然沉积物、白蚁内脏、反刍动物、非反刍动物包括人的肠道。致病性是很小的。所有这些微生物都是严格的厌氧性的,也就是说与氧接触通常对该微生物是致命的。梭状牙胞杆菌属是芽胞的前体。芽胞对许多处理形成芽胞细菌建立的无菌技术和特殊步骤都拮抗。醋杆菌属和消化球菌属不是芽胞的前体。
图3为大多数产醋酸细菌所用的代谢途径的简图。该生物体使用正常的Embden-Meyerhof糖解途径把葡萄糖代谢成丙酮酸盐。乳酸也被代谢最初将其转化回丙酮酸。使用常规氧化途径该生物体把丙酮酸盐制成醋酸和二氧化碳。产醋酸细菌的主要区别特征是在氧化步骤中所产生的二氧化碳不释放到环境。取而代之的是,产醋酸细菌有一个会固定二氧化碳并生成另外摩尔的醋酸的代谢途径。
新的产醋酸途径提供了微生物的三种功能:
1.象所有的厌氧菌,需要末端电子受体而不是氧来平衡代谢的氧化还原反应。在这种情况,二氧化碳的还原起了电子丧失的作用。
2.从该途径生成了细胞能量(即ATP)。把一摩尔葡萄糖转化成两摩尔醋酸和两摩尔二氧化碳的代谢途径从所消耗的每摩尔葡萄糖产生四个ATP。产醋酸途径的加入从二氧化碳中产生了其他醋酸并增加了ATP的收率到每摩尔葡萄糖4-6个ATP。额外的ATP不是直接从底物磷酰化得到的而是在其他方法如电子转移链并从位于细胞膜上的离子泵制得的。从第二来源所生产的ATP的精确量随着菌株与菌株的不同而变化并且也取决于细胞环境。
3.使用细胞组成途径把二氧化碳转化成生长所需的细胞碳,即使在常规碳源如葡萄糖不能获得时。
一些产醋酸菌会产生除醋酸外的其他有机酸如甲酸、丙酸、琥珀酸等。所述的这些有机物是异型发酵的,这与仅生成醋酸的同型发酵性生物体相反。在本发明中异型发酵途径显示本发明潜在收率下降,适当菌株的选择和引起这些其他有机酸形成的因素解释将会把影响降到最小。
到目前为止,当前大多数工作已经使用梭状牙胞杆菌属菌株。这些菌株中的大多数是嗜热性的,最佳的生长温度大约是60℃。现已进行了好几个动力学研究来检查pH和醋酸盐含量对细胞生长和酸生成的作用。(Yang,S.T.,Tang,I.C.,Okos,M.R.,“用蚁酸醋酸梭菌的乳酸盐的同型醋酸发酵的动力学和数学模型”,生物技术和生物工程,第32卷,第797-802页,1988,Wang,D.I.,Fleishchaker,R.J.,;Wang,G.Y.,“用发酵生成醋酸的新途径”,系列生物化学工程AIChE论文集:可更新的来源,第181期,第74卷,第105-110页,1978;以及Tang,I.C.,Yang,S.T.,Okos,M.R.,“用乳链球菌和Clostridium formicoacetium共培养从乳清乳糖生成醋酸”,应用微生物学和生物技术,第28卷,第138-143页,1988,本文将这些文献全文引用为参考文献)。这些生物体对低pH敏感并且在比乳酸菌非常低的浓度出现产物抑制。最佳的pH是7左右并且在每批发酵中最大的醋酸盐耐量大约仅为30g/l。
一个阶段或两个阶段的CSTR发酵器的设计一般适合于第二发酵步骤。但是,也可以使用任何适当的生物反应器,包括间歇、批量进料、细胞循环和多步骤的CSTR。相对于第一步发酵步骤,醋酸发酵是受氮限制而不是受碳水化合物限制。从乳酸生产醋酸的收率大约85%的理论值。
在一个实施方案中,为本发明第二部分的化学转化制备第二发酵步骤的发酵液。例如,用离心机和微过滤器结合澄清发酵液。离心机除去了大量生物质并通过降低它的负载来减小下游微滤器的体积。把微滤器的渗透液送到毫微过滤设备中。微过滤器对毫微过滤设备来说起到提前过滤的作用。毫微过滤设备除去了分子量在大约300以上的蛋白、没有被转化的糖等。毫微过滤设备除去了醋酸盐发酵液中的大量杂质并产生了能被送往下游步骤并产生白色渗透水溶液。
把从离心机、微过滤器和毫微过滤器的浓缩液加工来回收用于单一细胞蛋白的有效成分或者循环到一个发酵步骤。另一方面,可以把它们以任何可接受的方式如堆肥化处理或焚烧来清除掉。
尽管本发明优选的实施方案使用了两步发酵步骤和单一细胞蛋白的生产,但是在大多数情况下这是不需要的。可以提供只醋酸发酵的适当培养基。尽管不能生产单一细胞蛋白,但是从碳水化合物源的增长收率也将提供本发明的重要优点。
此外为了达到本发明的优点,必需使用原料的半纤维素或纤维素部分。一个例子是把本发明与玉米湿法研磨结合使用,其中培养基将是几乎纯的淀粉和研磨所产生的玉米浸泡水。本发明相对于现有技术还将增加乙醇收率75%,提供巨大的经济效益。
所以,发酵步骤的主要特征是把任何来源的碳水化合物转化成醋酸。
酸化和酯化
在本发明的下一个步骤中,发酵中所产生的醋酸或醋酸盐转化成醋酸酯,优选甲酯或乙酯并且更优选乙酯。作为本发明部分的把醋酸或醋酸盐转化成酯的适当方法是可以接受的。
醋酸是一种pKa=4.76的弱有机酸酸。如果在接近于中性pH(即pH=7.0)进行发酵,发酵产物将实际上大多是醋酸盐而不是醋酸。在发酵中,任何适当的碱都能够用来中和发酵液。优选的中和剂是氢氧化钙,它能够由氧化钙(石灰)或该方法的后面步骤中循环的碳酸钙(CaCO3)提供。其他中和剂也能够使用如氢氧化钠或氢氧化铵,正如发酵生物体所需的条件测定的。但是,甚至醋酸盐是抑制剂并且在发酵液中醋酸盐的最大浓度通常是限定到大约5%。
这样,从溶液如发酵液中回收醋酸盐有两个问题。醋酸盐通常必须转化成酸并且酸必须从稀释的水溶液中除去。此外,理想地是回收用于中和发酵液的碱来降低成本并避免潜在的环境影响。
最典型的途径是随后酸化这些盐来生成醋酸然后接着回收醋酸。即使在盐转化成酸的稀溶液后,还需要从水中回收产物。许多不同工艺途径已经被提出来回收这种稀溶液。因为醋酸的沸点比水高,如果使用简单的蒸馏法,大量的水大约95%的发酵液必须从醋酸中蒸馏出来以回收酸。另外,一些更复杂的方法可以用来回收醋酸,通常与溶剂提取相结合。但是这类研究,即酸化接着从稀释的溶液中回收没有克服醋酸发酵方法的经济局限使其与合成气为基础的途径竞争。所以,所有的工业醋酸通常从来自煤炭、汽油或天然气中的合成气制得。
人们已经提出许多方法来酸化醋酸盐溶液。一种方法是把醋酸盐与强酸如硫酸反应形成醋酸(HAc)和硫酸钙(CaSO4)。硫酸钙沉淀并且容易从醋酸溶液中分离。但是,这种方法需要消耗酸和碱并且产生副产物废盐,这将成为环境的负担。另外一种方法是双电极电解,把盐分解成酸和碱(对Ca盐来说这种方法不能很好地工作,但在这种情况人们可以取代成Na)。从盐生成稀醋酸的其他方法都是大家所公知的。
人们已经提出羧酸盐与胺和二氧化碳反应并生成碳酸钙沉淀和形成能够被提取并且热再生的酸胺络合物,如US 4,405,717中所述,在本文将其全文引用为参考文献。
US 4,282,323中公开了以多种方式用二氧化碳酸化醋酸盐的方法,本文将其全文引用为参考文献。在所引用的专利中,用溶剂分离相来除去已形成的醋酸。
醋酸形成乙酸乙酯的酯化是大家所熟知的反应:
酯化一般是在液相中进行的。反应平衡系数是4.0并且几乎不依赖于温度。反应的酸催化剂包括:强布朗斯台德酸如硫酸和甲磺酸,酸性离子交换树脂、沸石和许多其他物质,包括二氧化碳溶于水所形成的碳酸。反应速度会受到催化剂的类型和浓度、反应温度以及离开平衡的程度的影响。
为了避免分离酸化和酯化的步骤还存在另外的其他途径。羧酸盐可以直接与醇如乙醇反应直接生成酯。可以插入中间步骤把Ca盐转化成铵盐。在该步骤中稀释的醋酸钙与氨水和二氧化碳反应形成醋酸铵和沉淀的碳酸钙。然后如US 2,565,487中所述可以把醋酸的铵盐直接酯化,其中把US 2,565,487的全文引用为参考文献。
优选的方法
优选的方法是把化学和相变化结合成新的有效方法,其直接生产醋酸的挥发性酯并从发酵液中把该酯蒸馏除去。
三部分是:
1)在低的或接近于大气压下用二氧化碳酸化发酵液生成醋酸和沉淀的碳酸钙,碳酸钙能够作为碱直接循环到发酵中;
2)用醇如甲醇或乙醇同时酯化所形成的醋酸形成挥发性酯,并且
3)反应蒸馏把酸化和酯化平衡推向高转化方面。
由于酯化是一种平衡反应,通过连续除去一种或多种产物驱使反应向右移动能够实现高转化。类似于Chronopol为丙交酯合成所开发的(见US5,750,732,本文将其全文引用为参考文献)和由Eastman化学为乙酸甲酯的生产所开发的(见US 4,939,294和4,435,595和Agreda,V.H.,Partin,L.R.,Heise,W.H.,“由反应蒸馏得到的高纯度乙酸甲酯”,化学工程进展,第40-46页,1990年2月,将其全文引用为参考文献)反应蒸馏是经济的有吸引力的方法。在本文把全文引用为参考文献的US 5,599976公开了在连续反应蒸馏方法中把非常稀的醋酸转化为酯。Xu和Chaung(Xu,Z.P.,Chuang,K.T.,“在离子交换催化剂上醋酸酯化的动力学研究”,Can,J.Chem.Eng.,第493-500页,第74卷,1996)揭示了从稀释的溶液中生产醋酸酯的反应蒸馏是从非常稀的溶液中除去醋酸的优选方法,这正如本发明所使用的。在这种意义上,在蒸馏柱中醋酸是与酯化醇相反的方式流动。在本发明中,乙酸乙酯比醋酸挥发性更大,所以从液体混合物中蒸除乙酸乙酯并且把酯化反应推向右边,这样能够在单一容器中实现高转化。这里所提到的方法超出了这些实施例,在这些实施例中是把酸化与反应蒸馏酯化同时结合的。所引用的方法全部都是从醋酸(或Chronopol情况中的乳酸)开始而不是从盐开始。
在优选途径中反应蒸馏方法的最后效果是从没有蒸发形成大量蒸汽的水的稀释溶液中除去醋酸。
此外,使用二氧化碳作为带有碳酸钙沉淀的优选酸化剂使得发酵的中和剂循环而没有消耗化学物质。也能够在发酵中直接使用碳酸钙或通过煅烧首先把碳酸钙转化为氧化钙。
图4中表示反应蒸馏方法80a。
反应部分:把原料,一种醋酸钙410(Ca(Ac)2)的稀水414稀释溶液(5%)与乙醇418混合并加载到柱422的反应部分424的顶部。在柱422的中心部分的反应区424同时发生二氧化碳420与醋酸钙410和乙醇418的反应,伴随着形成碳酸钙428和乙酸乙酯432。
CO2(g)+H2O->H2CO3
Ca(Ac)2+H2CO3->CaCO3(s)+2HAc
2HAc+2EtOH->2EtAc
在反应混合物中最具挥发性的组份是乙酸乙酯/水/乙醇共沸物436。共沸物的组成是82.6%乙酸乙酯、9%水和8.4%乙醇并且正常的沸点是70.2℃。通过同时蒸发一些EtOH和水从反应混合物中除去共沸物436。在汽提部分后,该反应区的底部产物是含有悬浮的碳酸钙的水和乙醇溶液。
分离部分:在上部分离区450,也通过汽化从反应混合物中将乙醇和水与共沸物分离。把乙醇水混合物454循环到反应区424中并且塔顶产物是共沸混合物436。从塔顶的冷凝液中分离出二氧化碳将其循环用于补充二氧化碳的柱。通过加水破坏共沸混合物,这将引起相分离,从而使富含水和乙醇相反应蒸馏柱返回到适当点(没有显示)。
汽提部分:由于在反应部分用过量的乙醇有利于向酯化反应进行,所以汽提部分458把过量的乙醇返回到反应区。在汽提部分458中,从柱422中放出的含有碳酸钙的水蒸气中除去乙醇并通过简单的液/固分离462如离心法或过滤将其分离成用于循环的固体碱466和水470。
反应蒸馏方法的最后效果是从稀释溶液中回收醋酸,由此在顶部产生相对浓缩的产物蒸汽而没有汽化水形成大量蒸汽。这三段的组合降低了能量的消耗。产物酯的同时去除使得酯化反应的平衡移动并在短时间内有较高的转化。
在蒸馏体系中处理沉淀是不普通的。但是,在这种情况下在体相中出现沉淀反应并不是因为在加热转移表面的溶液浓缩,一种普通型的污垢物。在玉米干法研磨的乙醇工业中乙醇啤酒蒸馏釜通常用具有简单结构和大开口的塔盘处理装载在汽提部分中的固体。另一种选择是,在其他结构如带有普通蒸汽歧管的一系列搅拌罐中也能够操作反应部分来促进柱反应部分。
这种对乙酸乙酯方法的低成本、低能量、整体酸化、酯化和纯化的连续开发潜在地实现了由再生的来源工业规模化经济性生产的大量化学物,目前这些大量化学物都是由非再生来源生产的。
使用再生来源的一个最大优点是减少了二氧化碳的产生替代了化石原料。用国内再生原料替代进口石油对美国经济是有益的。使用农业物品生产化学物质和液体燃料而没有补贴对农业部来说就产品需求和稳定市场和减少美国政府补贴开支方面是有重要意义的。
氢化
本发明的第三主要步骤是把醋酸酯通过氢化转化成两倍的醇。氢化酯生产醇是公知的反应。
US 2,782,243、US 4,113,662、US 4,454,358和US 4,497,967公开了氢化醋酸酯生成乙醇的方法,本文将这些美国专利的全文引用为参考文献。
在具体情况下,或者在液相或者在气相中进行氢化。任何适当的氢化方法都可以使用。这种反应也是一个平衡反应。通过使用氢气的部分高压使反应向右边进行。通常反应条件是150-250℃和500-3000psi,取决于所要求的转化率和选择性。通过任何适当的氢化催化剂如亚铬酸铜、镍、阮内镍、钌和铂催化该反应。因为亚铬酸铜、镍或阮内镍催化剂不被水抑制,所以优选它们作为氢化的催化剂。在液相方法中,醇如乙醇是很好的溶剂。
在气相方法中,汽化乙酸乙酯进料并加入含有过量氢气的氢化反应器。在通过该床后,冷却蒸气并闪蒸到低压分离鼓中。富含氢的气相可以循环于反应器。蒸馏液相除去残余的水和没有反应的乙酸乙酯。所述的水不是由氢化化学反应生成的;它的来源是存在于上游反应蒸馏柱的回流液储器的液-液平衡含量。
可以需要其他蒸馏柱作为最终精炼步骤,这取决于酯化和氢化单元的副产品性质和数量。
优选的酯是乙酸乙酯,因为它避免了第二种化合物导入该方法,必须将其从产物蒸汽中纯化出去。
水的反汽提器收集了酸化、酯化和氢化单元中的水蒸气。水是汽提溶剂回收的蒸汽,然后把该水送入最后处理并排放或循环到发酵部分。
用于本发明的氢气有许多潜在来源。可以使用任何适当的氢气源,这种氢气源能够为氢化反应产生足够纯度的氢气并且将不会使催化剂中毒。生产氢气的原料包括能够电解产生氢气的水。也能够使用许多化石和可再生的有机原料。如果使用化石原料,如来自天然气的甲烷,伴随着氢气会生产出一些二氧化碳。但是如果使用可再生的原料,然后二氧化碳的生产将会对环境是无作用的。例如,以分子水平含有碳和氢的原料能够用来生产氢。木材小片、木屑、城市废物、循环纸、来自浆和纸工业的废物、来自动物和/或作物生产的农业固体废物都是可再生原料的例子,它们都能够用来生产氢,例如使用汽化技术。
把甲烷蒸汽转化生成氢是公知的方法。如图1所示,在蒸汽转化器94中把天然气90和水92反应形成氢气96和二氧化碳98。生产氢气的其他方法(部分氧化碳氢化合物、部分氧化煤、电解水等)也能够使用。,例如在空气分离厂的栅栏线操作中可以获得纯氧气的地方,部分氧化方法的经济上是可行的。在获得电源不昂贵的地方,电解是可行的。
相对于乙醇生产的现有技术而言,本发明的其他优点是方法中的热平衡。在本发明中,如果就地通过蒸汽转化制得氢气,由于酯的氢化反应是一个较高的放热过程,所以在综合厂在高温下可以得到过多的热量。因此,总方法是很高能量效率的。此外,没有任何碳水化合物原料浪费,因为必须消耗冷却水的二氧化碳。
本发明的其他优点是能够把天然气通过氢气高效转化为液体产品如乙醇。这种特征能够在这样的情况下使用,即任何碳水化合物源位于靠近天然气生产源或管道容易输送的地方。这能够使在遥远的地理位置如生产天然气和糖甘蔗或其他碳水化合物作物的岛使用天然气来高效生产容易输送的液体化学物质或燃料。例如,使用本发明方法的工厂能够位于特立尼达岛,在那里天然气和碳水化合物源能够以经济的吸引人的价格获得。该工厂能够生产液体形式的几乎纯的乙醇,可运送到能够经济使用的遥远的地方如德克萨斯海湾海岸。乙醇能够用作燃料或进一步加工的原料。例如,把乙醇转化成乙烯并通过现存的乙烯管道系统出售。另外一种选择是,在工厂内循环使用乙醇生产乙酸乙酯。换句话说,工厂能够生产含有几乎是全部乙酸乙酯、几乎全部是乙醇或二者任意结合的液体产品。因为天然气和碳水化合物源相互位置相对较近,所以这些原料能够转化成以经济的方式容易运送到遥远地方的高价值的液体产品。
碳水化合物源和天然气源优选相互位于500英里内,更优选在300英里内并且更优选在200英里内。可运送的液体产品位于遥远的地方,在那里经济地运送碳水化合物和天然气是不可行的,例如距产地800英里以外,特别是1000英里以外,更特别是1500英里以外。应当考虑更容易地把碳水化合物源运送到天然气源。也应当考虑随着原料价格、可运送的液体产品的价格和运送成本的不同具有经济优势的具体距离也变化。正如本领域技术人员所预见的那样,许多因素都影响着运送成本,这些因素包括地理障碍如山区、水体等并且不仅仅取决于距离。作为进一步的例子,在澳大利亚和/或新西兰发现天然气和碳水化合物源。位于这些岛国的工厂能够生产乙醇和/或乙酸乙酯运送到亚洲,具体是日本、台湾、韩国和中国。
在详细描述本发明的各种实施方案的同时,那些实施方案的修饰和改良的出现对本领域技术人员来说是显而易见的。但是,应当清楚地理解这类修饰和改良都是在本发明的精神和范围内。
Claims (7)
1.一种把碳水化合物源和天然气源转化成容易输送的液体产物的方法,它包括下列步骤:
(a)通过发酵把所述碳水化合物源转化成醋酸、醋酸盐或其混合物;
(b)把该醋酸、醋酸盐或其混合物转化成乙酸乙酯;
(c)用从所述天然气源中获得的氢将至少部分所述乙酸乙酯转化成乙醇;并且
(d)把所述乙醇或乙酸乙酯转送到不同于生产地的其他地方。
2.按照权利要求1所述的方法,其中所述的碳水化合物源和所述的天然气源相互位于300英里之内,并且其中运送所述的乙醇或乙酸乙酯的遥远的位置是指位于距生产地大于800英里的位置。
3.按照权利要求1所述的方法,其中所述的碳水化合物源和所述的天然气源相互位于500英里之内,并且其中运送所述的乙醇或乙酸乙酯的遥远的位置是指位于距生产地大于1,000英里的位置。
4.按照权利要求2所述的方法,其中所述的碳水化合物源和所述的天然气源位于一个或多个加勒比海群岛并且所述的遥远的位置是位于海湾海岸。
5.按照权利要求2所述的方法,其中所述的碳水化合物源和所述的天然气源在澳大利亚、新西兰或者二者都有并且所述的遥远的位置是指在日本、台湾、韩国或中国。
6.按照权利要求1所述的方法,其中所述的发酵包括第一步发酵中生成乳酸、乳酸盐或其混合物并且在第二步发酵中生成醋酸、醋酸盐或其混合物。
7.按照权利要求1所述的方法,其中氢是从所述的天然气通过蒸汽转化得到。
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