CN102770548A - 改进的谷粒碾磨方法 - Google Patents
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Abstract
本发明描述了由全谷粒生产乙醇及其他副产品的改进干磨方法，由此通过在有机酸的存在下蒸煮醪而对醪进行热化学处理。有机酸有效地水解碾磨的玉米中的淀粉和半纤维素组分，以由胚乳及核的其他部分得到可发酵糖，然而不会同时产生抑制发酵水平的其他已知的半纤维素物质的酸水解产品，如羟甲基糠醛(HMF)和糠醛。此外，有机酸能够溶解淀粉和更难分解的半纤维素，然而只是使它们部分水解，因此大部分淀粉和半纤维素被水解成低聚物，并且化学不稳定及还原性糖的量保持足够的低以便也不会对发酵成乙醇产生明显的干扰。
Description
本发明涉及一种改进的谷粒碾磨方法，并且尤其是碾磨谷粒的改进方法，并且尤其用于碾磨玉米以生产乙醇及其他增值产品的方法。
近年来对乙醇作为燃料添加剂的需求增加，已经导致乙醇生产的大幅度增长。目前主要是通过湿磨或干磨方法由玉米生产乙醇。湿磨设备属于资本密集型，并且使用大量的工艺用水，但是通过将玉米分级成其胚芽，纤维、蛋白质和淀粉组分能够随乙醇生产出许多增值的副产品，包括高果糖玉米糖浆、玉米面筋粉、玉米面筋饲料、胚芽粉和玉米油，但还包括改性淀粉、麦芽糊精及其他物质。
湿磨乙醇法在常规上涉及五个基本的加工步骤：浸泡、胚芽回收、纤维回收、蛋白质回收和淀粉洗涤与后续发酵。在第一步，将玉米浸泡在弱亚硫酸的溶液中以水合及软化核，用于后续分离/分级，并从胚芽中浸出可溶物(水溶性氨基酸及蛋白质)。浸泡后通过密度和粒度的差异除去胚芽和纤维部分。通过水力旋流器***除去密度比经过浸泡步骤之后剩下的核的固体组分低的胚芽，然后进行紧压并干燥。当希望时，可以从胚芽中压榨和/或溶剂提取玉米油并且然后作为进一步的副产品进行精制。通过筛分除去含有核皮的纤维部分，然后使之与来自浸泡步骤的蒸发浓缩浸泡水接触。然后干燥此混合物以产生玉米面筋饲料副产品。
然后通过离心机和水力旋流器***将剩下的固体分离成一个淀粉部分和一个蛋白质部分。使用面筋增稠离心机浓缩面筋蛋白质部分，通过真空带式过滤并以回转蒸汽列管干燥器或闪蒸干燥器干燥来进一步脱水。最终干产品玉米面筋粉具有一个高蛋白含量，低纤维含量，主要用于非反刍动物和宠物的饲料。对由水力旋流器回收的淀粉进行蒸煮、液化和糖化以产生葡萄糖，然后使葡萄糖经历发酵成为所希望的初级乙醇产品。蒸馏乙醇，使之离开水和残余的水溶性固体。可以将回收的残余固体添加到玉米面筋饲料中，同时可以将发酵中产生的二氧化碳销往饮料行业。
相比之下，干磨加工法比湿磨乙醇法的资本密集程度低得多，原因在于不是将玉米核分级成其基本部分，而是作为整体进行处理，并不要求大量的工艺用水。
然而，与湿磨乙醇法相比，干磨乙醇法也有一定的缺点。对于生产乙醇来说，加工包括核的非淀粉部分在内的整个核的效率低。而且，干磨乙醇方法主要得到一种可销售的但价值相对较低的副产品，其形式为含可溶物的玉米干酒糟及溶解物（distillers'dried grains with solubles）(DDGS)。干磨乙醇方法中的非发酵部分的确含有相当高的含油量，但回收很困难。
简言之，在典型的干磨乙醇方法中，磨碎整个的玉米，用水浆化并添加酶进行蒸煮以产生液化“醪”。向醪中添加酵母和酶，醪同时经历糖化和发酵，在液体部分中产生所需的初级乙醇产品，同时用酵母回收剩下没有发酵的固体作为玉米干酒糟。来自发酵的二氧化碳从蒸汽液体分离器中的肉汤中释出，并从液体部分中回收乙醇用作燃料添加剂。
典型方法的一种变化形式是首先用冷水、热水和/或蒸汽对玉米进行一段时间的处理，将玉米的水分含量从15％提高到22％，以便软化麸/皮和胚芽，并允许它们与核的淀粉质胚乳组织分离。通过研磨/脱胚步骤输送玉米以将核破碎成皮、胚芽和胚乳部分。干燥后，抽吸步骤使皮与胚乳分离，同时使用重力分选台使胚芽部分与胚乳分离。然后磨碎胚乳，并按与典型干磨方法中相同的方式进行加工。虽然浸泡、脱胚、抽吸及密度分离步骤和设备需要额外的资金，但与上述的典型方法相比，干磨方法的这种变化形式仍被认为是有利的，原因在于可以获得玉米油形式的附加的副产品价值(得自胚芽)，以及从皮和油渣饼中获得动物饲料价值。
总之，那么与上述的干磨法相比，湿磨乙醇法可提供附加的副产品可能性，但却要求大量的资本投入和工艺水资源，并且在操作上所涉及的复杂性要大得多。另外，作为湿磨的主要副产品之一的高果糖玉米糖浆已经被一些人认为是促成肥胖的重要原因。干磨法较为简单，需要的资金和水较少，但在副产品方面产生的价值较少，并且就从玉米核的各组成部分中充分获取价值来说通常是低效的。
由谷粒(如玉米)生产燃料添加剂品质的乙醇的改进碾磨方法将具有例如湿磨和干磨法两者所希望的属性，即能够分馏，并且能够从玉米核的所有部分中获取价值，这是湿磨所具有的特征，同时保留干磨加工的简单性和低资本及水资源要求。
总体来说，本发明提供了在干磨乙醇方法中加工谷粒及谷粒产品的改进方法以由此获得更大的价值。因此，虽然下文的说明书是就优选的实施方案（特别是加工玉米）描述这种改进的方法，但本领域技术人员会意识到，这些方法可有利地应用于其他谷粒，如小麦、谷子、大麦、高粱、小黑麦、稻米、苋属植物、荞麦、黑麦、燕麦和藜麦。
本发明通过对典型的干磨方法进行简单的改变而提供所需要的改进，由此通过在有机酸的存在下蒸煮醪而对醪进行热化学处理。这种有机酸有效地水解碾磨的玉米中的淀粉和半纤维素组分这两者，以由胚乳及核的其他部分提供可发酵糖，然而还不会产生抑制发酵水平的其他已知的半纤维素物质的酸水解产品，如羟甲基糠醛(HMF)和糠醛。此外，有机酸(“有机酸”将被理解为既包括单独的酸，也包括有机酸的混合物)能够溶解淀粉和更难分解(recalcitrant)的半纤维素，然而只是使它们部分水解，因此大部分淀粉和半纤维素被水解成低聚物，并且化学不稳定及还原性糖的量保持足够的低，同样不会对发酵成乙醇产生明显的干扰。
图1以一个示例性实施方案描述本发明改进的谷粒碾磨方法。
在本发明优选的实施方案中，对如下的典型干磨方法进行改进，以将诸如醋酸或甲酸(或它们的组合)的有机酸加入到“醪化”步骤当中：将整个的玉米磨碎，用水浆化，用酶处理并蒸煮以形成液化醪，然后用另外的酶处理，发酵并进一步加工以产生燃料级添加剂品质的乙醇及其他产品。一个酸回收步骤是任选的，但优选作为进一步的有限改进***该步骤，以在添加酵母和另外的酶进行醪发酵之前从醪中回收有机酸。
通过引入有机酸，优选以有机酸水溶液的形式与水一起引入有机酸，使玉米的淀粉和半纤维素组分溶解并部分水解，如上文所述。通过由存在于核中(尤其是皮中)的半纤维素形成可发酵的C5糖，可以提高核的总乙醇收率。
此外，因为有机酸并非强酸，所以可以避免HMF(羟甲基糠醛)和糠醛的水平达到倾向于不利地干扰或抑制C5和C6糖后续发酵成乙醇，已知上述两种物质为酸水解半纤维素物质的副产品，而且也都是通过发酵生产生物乙醇中的已知酶活性抑制剂。而且，可保持低量的化学不稳定的游离糖或还原糖，以避开对酵母的化学抑制剂和避免糖的损失。
有机酸也提供另外的可能性，以从存在于玉米核中的蛋白质和油中获得价值。关于从玉米中回收油，从整个的玉米中提取油迄今还是昂贵和低效的，因为油主要存在于胚芽中，因此在作为整体的磨碎的玉米当中存在的浓度低。
下面已经显示，使用中等浓度的有机酸水溶液(例如甲酸的50％水溶液)蒸煮(在90摄氏度和环境压力下)已经添加了淀粉酶的总固体为30％至40％的玉米浆，以使85％的玉米固体溶解到水相里，通过离心或过滤很容易使所述水相与残留的固体分离。这些残留的固体具有的高浓度油足以使现在从整个核的加工中回收玉米油变得经济合算。此外，在按常规方式通过压榨或萃取回收油之后，发现残留的固体具有高蛋白质含量，因为玉米蛋白不被我们发明中的有机酸所溶解。这种高蛋白固体用作动物饲料是所希望的，但与只是非常适合反刍动物的玉米干酒糟相反，由我们的方法所提供的残留固体在优选的实施方案中适合用在供诸如家禽和生猪之类的非反刍动物的饲料中。
通过参考图1更全面地说明和理解本发明，其中在优选的实施方案中示出了改进的干磨乙醇方法10。实施方案10仅旨在为示例性的，本领域技术人员很容易意识到，在不偏离由下文之后的权利要求更具体限定的本发明的适当范围的情况下，可以对实施方案10进行多种修改和变动，并且也可以使本发明的使用与各种现有或已知的干磨法相适应。
现在再看图1，如图所示，在碾磨步骤14中碾磨或磨碎整个的玉米12。可以通过任何已知的方法进行碾磨，例如通过使用Fitz碾磨机、Beall脱胚机或Satake脱胚机。碾磨步骤14产生磨碎的玉米流16，该玉米流为包括胚芽、胚乳、皮和细粒在内的非均质混合物。细粒主要是淀粉，并且皮主要是纤维性物质。
用水18使磨碎的玉米流16浆化，并在醪化步骤20中蒸煮成醪，此步骤在有机酸22(或者是新供给的有机酸，或者主要是从任选的酸回收步骤28中产生的有机酸，其中根据需要供给新的补充酸)的存在下进行，并且添加酶24以有助于玉米的可发酵组分的液化。通常使磨碎的玉米流16与一定体积的水18合并，该一定体积的水18的重量为要醪化的玉米重量的两到三倍，水18通常在典型的干磨方法中以发酵逆流、蒸发冷凝水或玉米浸泡液的形式供给。有机酸22优选为醋酸或甲酸，优选与一些水18一起作为中等浓度至较高浓度的酸水溶液供给。优选的浓度范围是50重量百分比至70重量百分比，而更优选酸溶液较接近50％的酸。
优选将玉米、水和酸混合物在70与90摄氏度之间的温度下(更优选在88至90摄氏度的温度下)保持大约30分钟，此后添加α-淀粉酶(以料流24表示)，并将温度升高到105至110摄氏度持续5至15分钟，以有助于主要是胚乳和皮中的淀粉和半纤维素物质的液化。添加酶与加热相结合使淀粉分解成麦芽低聚糖，如在典型的干磨法中那样。然而有机酸另外水解(热化学处理)以前只当作价值较低的玉米干酒糟副产品的皮中的半纤维素，并提供C5糖，这增加到出自醪化步骤20的醪流26的可发酵含量中。
然后醪26前往任选的酸回收步骤28，其中如所希望的回收有机酸并优选再循环以提供至少一部分酸流22。酸回收步骤28可采取多种形式，这取决于例如所用的有机酸及其在醪流26中的浓度。在这方面，已知甲酸与水形成浓度大致在50重量百分比的共沸物，而醋酸不会，因此可根据使用的情况按希望采用共沸蒸馏或常规蒸馏。无论如何，如果认为酸回收重要的话，本领域技术人员应当能够针对步骤28很好地选择经济合算的酸回收技术。
使酸回收步骤28之后的醪30的温度降低到60与75度之间，并在步骤31中添加葡糖淀粉酶(显示为料流32)，以进一步由玉米核的淀粉质胚乳产生葡萄糖，同时将温度保持在60与75度之间达1到48小时的一段时间。
然后在发酵步骤36中添加葡糖淀粉酶及发酵微生物来对所得到的发酵培养基34进行发酵，该微生物可以是例如酵母(如酿酒酵母)、细菌或真菌，这种发酵通常在30至40摄氏度的温度下发生。可以采用制造商建议的典型的葡糖淀粉酶添加量，例如每克淀粉大致为0.22个单位。也可以添加其他酶，包括半纤维素酶、蛋白酶、纤维素酶、和阿魏酸酯酶。
发酵导致产生二氧化碳产物流38、乙醇和各种不可发酵的固体及残留物，包括酵母、面筋蛋白、胚芽和纤维。在允许二氧化碳作为料流38从发酵液中释出之后，使乙醇和剩下的固体进(附注标号40)到蒸馏步骤42，由此回收来自发酵的粗乙醇流44，以在用作燃料添加剂之前进行进一步的清洁和纯化(未显示)。
来自发酵步骤36剩下的水和固体例如在离心步骤46中经受液/固分离，得到含有含油胚芽及其他固体的固体部分48和稀糟部分50，优选在步骤52中通过蒸发对后者进行浓缩，用于将其掺入到高蛋白饲料产品54当中。固体部分48中相当多的油含量作为粗玉米油副产品流56被提取出来，以借助于油回收步骤58进一步精制(未显示)。
油回收步骤58可采用提取固体部分48中的油价值的任何常规技术，包括例如化学萃取、压榨萃取、液压萃取、二氧化碳辅助萃取和超临界流体萃取。压榨萃取是优选的。在采用超临界流体萃取的情况下，优选的超临界流体是二氧化碳，可以有或没有诸如丙烷和/或乙醇的共溶剂。超临界流体萃取的合适方法例如在授予Christianson等人的美国专利4,495,207中给出，该专利通过引用结合在此。
然后如上所述将剩下的高蛋白固体60与来自蒸发步骤52的浓料流62合并以生产高蛋白饲料产品54。
Claims (6)
1.一种改进的谷粒碾磨方法，包括通过发酵生产乙醇，包括：
将一种全谷粒磨碎；
将该磨碎的全谷粒与水形成一种浆料；
向该浆料中添加一种或多种酶和一种或多种有机酸，同时加热以液化该磨碎的全谷粒的可发酵组分并产生一种醪；
向该醪中添加一种酶以形成用于生产乙醇的发酵培养基；并且
在酵母和一种或多种添加酶的存在下对该发酵培养基进行发酵。
2.如权利要求1所述的方法，其中以醋酸、甲酸或醋酸与甲酸组合的水溶液的形式添加该一种或多种有机酸。
3.如权利要求2所述的方法，其中该有机酸水溶液为50重量百分比或更多的酸。
4.如权利要求3所述的方法，其中该酸水溶液为在水中50至70重量百分比的酸。
5.如权利要求1-4中任一项所述的方法，进一步包括酸回收及再循环步骤，用于在形成该发酵培养基前从该醪中回收酸并进行再循环。
6.一种碾磨全谷粒以便通过发酵生产乙醇的改进的干磨方法，包括：
磨碎一种全谷粒；
将该磨碎的全谷粒在重量为磨碎的全谷粒的两到三倍的水中形成一种浆料；
向该浆料中添加醋酸或甲酸或这两者的50重量百分比以及更多的水溶液，同时保持该浆料的温度在70摄氏度到90摄氏度；
添加α-淀粉酶并将该浆料的温度升高到105至110摄氏度持续5至15分钟；
降低所得醪的温度或者使所得醪的温度冷却到摄氏60度与75度之间；
向该醪中添加葡糖淀粉酶，同时保持温度在60与75摄氏度之间持续1至48小时；
添加葡糖淀粉酶、半纤维素酶、蛋白酶、纤维素酶和阿魏酸酯酶中的一种或多种及酵母对所得到的发酵培养基进行发酵以生产乙醇；并且
回收所述乙醇。
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| WO2011097065A3 (en) | 2011-11-17 |
| CA2788329A1 (en) | 2011-08-11 |
| EP2531605A4 (en) | 2014-03-19 |
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| WO2011097070A2 (en) | 2011-08-11 |
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| EP2531528A4 (en) | 2014-04-02 |
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| RU2012134274A (ru) | 2014-03-10 |
| CN102822203A (zh) | 2012-12-12 |
| AU2011213271B2 (en) | 2014-05-22 |
| EP2531605A2 (en) | 2012-12-12 |
| AU2011213271A1 (en) | 2012-08-09 |
| JP2013518972A (ja) | 2013-05-23 |
| CA2788329C (en) | 2017-08-01 |
| KR20120120394A (ko) | 2012-11-01 |
| BR112012019121A2 (pt) | 2016-06-28 |
| MX2012008944A (es) | 2012-11-30 |
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