CN101061229B - 将生物质转化为羧酸和醇类的方法和系统 - Google Patents
将生物质转化为羧酸和醇类的方法和系统 Download PDFInfo
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Abstract
本发明包括用于将生物质转化为羧酸和/或伯醇的方法、工艺和设备。该系统包括:预处理/发酵子系统,可用于从生物质如木质纤维素生物质产生含羧酸盐的发酵肉汤。该系统还包括脱水子系统,可用于从发酵肉汤除去过量的水,产生浓缩的产物。该系统还包括酸产生子系统:可用于产生混合羧酸产物。该系统还包括氢化子系统,可用于产生醇混合物,如含伯醇的混合物。还提供了操作这种系统或其它系统以获得羧酸或醇的混合物的方法。
Description
技术领域
本发明涉及生物质转化为有用物质如羧酸和伯醇的方法,该方法包括联合的预处理,发酵,脱水和处理工艺。更具体地,本发明涉及应用于木质纤维素生物质的方法。
背景技术
大量生物质,特别是木质纤维素生物质在农业和工业加工过程中仍未能得到利用或有效利用。这种生物质的处置经常存在困难或者成本较高。因此,用这种生物质来生产有用的化学品的方法是颇有价值的。
有机酸是重要的商业化学品。历史上有机酸是由动物脂肪或植物油来源制备,或者由基本上是非水性体系的石油来源制备。近年来,有机酸被确定为通过发酵从生物质制备的最吸引人的产品。醇类也是可以通过生物质发酵制备的重要工业化学品。然而,从完全发酵的产物中提取有机酸和醇类并非容易,并且在能量、水和反应物化学品利用方面效率常常不高。
发明概述
本发明提供了将生物质转化为羧酸和/或伯醇的方法、工艺和设备。
根据一个实施方式,本发明提供了转化生物质的系统。该系统包括预处理/发酵的子系统,可用于用石灰或生石灰以及空气对生物质进行预处理,产生处理的生物质,并用接种物(inoculum)使处理的生物质发酵,产生含羧酸盐的发酵肉汤。该系统还包括脱水子系统,可用于从发酵肉汤除去过量的水,产生浓缩的产物。最后,该系统包括酸产生(acid springing)子系统,可用来将浓缩的产物与低分子量叔胺或氨混合,从该羧酸盐产生低分子量的叔胺或氨的羧酸盐产物,用高分子量叔胺替代低分子量叔胺或氨的羧酸盐产物中的低分子量叔胺或氨,形成高分子量的叔胺的羧酸盐产物,热断裂高分子量叔胺的羧酸盐产物中的胺-羧酸根键,产生混合的羧酸产物。
在更具体的实施方式中,所述系统还包括氢化子系统,可用于将混合的羧酸产物与高分子量醇混合,形成酯,用氢化催化剂将该酯转化醇的混合物,将该醇混合物与高分子量醇分离。
根据另一个实施方式,本发明提供一种制得发酵产物的方法。该方法包括:用石灰或生石灰、水、接种物和空气处理生物质堆,产生发酵肉汤;用高分子量羧酸对该发酵肉汤进行酸化,产生酸化的发酵肉汤;在汽提塔中汽提发酵肉汤,产生汽提的发酵肉汤;在蒸发器中浓缩该汽提的发酵肉汤,产生浓缩的产物;将该浓缩的产物与低分子量叔胺或氨和二氧化碳混合,产生低分子量的叔胺或氨的羧酸盐;用高分子量叔胺交换低分子量叔胺或氨羧酸盐,产生高分子量的叔胺的羧酸盐;加热该高分子量叔胺羧酸盐至能足以断裂酸/胺键的温度,产生游离羧酸产物;和回收游离羧酸产物。
在更具体的实施方式中,所述方法还包括:将羧酸产物与高分子量醇混合,形成酯;对酯进行氢化,形成醇产物;分离高分子量醇与醇产物;并回收醇产物。
附图简述
结合附图,参照下面的详细描述能更好理解本发明,附图中:
图1所示是根据本发明实施方式的预处理和发酵系统;
图2所示是根据本发明实施方式的脱水系统;
图3所示是根据本发明实施方式的酸产生系统;
图4所示是本发明实施方式的氢化系统。
发明详述
本发明涉及用于生物质转化,特别是木质纤维素生物质转化为羧酸和醇类特别是伯醇的的系统、方法和设备。
下面参见图1,该图提供预处理和过滤系统10,该系统中,生物质堆12可以与石灰或生石灰(碳酸钙或氧化钙)和二氧化碳(未示出)混合,并堆积在深坑14的顶部,深坑内填充有砂砾16。深坑14还可以衬有衬料18。生物质堆12可以包含任何种类的生物质。在选定的实施方式中,生物质堆可包含木质纤维素生物质,如加工后的甘蔗或高粱秆或玉米秸叶。多孔排水管20可以埋在砂砾16中。生物质堆12上可盖上盖子22,防止下雨和碎片落入,特别是系统10是在户外时。泵24可以将水34从深坑14循环到生物质堆12的顶部。当水34循环通过堆12时,它流过热交换器26,热交换器可调节温度。冷却水或热源28也可以循环通过热交换器26。
在集中了生物质堆12后的近1个月期间,用鼓风机30将空气38吹入通过生物质堆12。为除去空气中的二氧化碳,可以将空气鼓泡通过石灰水浆液32。也可以送入富氧空气28。在生物质堆12中石灰加上空气28的综合作用能从生物质中除去木质素,使该生物质更能被消化。此外,石灰除去了半纤维素中的乙酰基,这也有助于可消化性。石灰被消耗后,pH值下降到接近中性,此时可加入混合培养的接种物。
接种物可源自任何来源,但在许多实施方式中,源自粪土壤(soil)。源自在海洋性环境中富含有机物的土壤的有机体表现出能特别适用于本发明的实施方式。这些有机体可以在高盐环境中繁殖。例如,接种物可包含耐盐的微生物。
接种后,有机体消化生物质并将其转化羧酸。在生物质堆12内这些酸与碳酸钙或氧化钙反应,生成羧酸钙盐或其它钙盐,这些盐能溶解在循环通过该堆的水中。这种水溶液称作发酵肉汤36,可以被收集并进行进一步处理。
参见图2,发酵肉汤36可以在脱水系统40中脱水。将发酵肉汤26泵送通过热交换器42,对肉汤进行预热。然后,预热后的发酵肉汤36用高分子量羧酸46(如己酸、戊酸、庚酸)进行酸化。将酸化的发酵肉汤36送入汽提塔44,在该汽提塔内,蒸汽80汽提出溶解的二氧化碳,这是不可冷凝的气体,这些气体会影响蒸发器58的操作并使碳酸钙在热交换器56上结垢。汽提塔44优选在1大气压或更高压力下操作,这样可以使排出的蒸汽86能用于该工艺中其它地方的加热。此外,如果热交换器42被溶解的碳酸钙弄污,汽提塔44中压力下降,会降低从热交换器42排出的蒸汽温度,并可能减少结污。然而,如果汽提塔44在减压下操作,可能需要真空泵(未示出),从发酵肉汤36中除去不可冷凝的气体。
然后,可以将蒸汽-汽提和酸化后的发酵肉汤36送入混合器48,通过从储槽78添加石灰50,将混合器中的pH升高到约11-12,这可以使浮渣54沉淀。然后在固体分离器52内除去浮渣54。这种脱气、脱浮渣的发酵肉汤36可以在热交换器56中进一步加热,之后进入蒸发器58。压缩机60可以从蒸发器58的低压室蒸发水。在蒸发器58的高压室中释放的冷凝热可提供在低压室进行蒸发所需的热量。推动该蒸发过程所需要的能量可由发动机提供。
在图2所示的实施方式中,可以使用一个合并循环的发动机,这样可以提高能量效率。燃气轮机88可向压缩机60提供轴功率。燃气轮机可使用燃料74。来自燃气轮机88的废气72可被导向锅炉62,锅炉产生高压蒸汽,驱动蒸汽涡轮机64。热交换器66能够将从蒸汽涡轮机64排出的低压蒸汽冷凝。冷却水76可用来促进这种冷却。来自蒸发器58的高压部分的蒸馏水82可以在热交换器56和42中冷凝,并返回预处理/发酵系统10。浓缩的产物68可以在热交换器56和42中冷却,并送入酸产生系统90。液体涡轮机70能从蒸发器58排出的高压液体取回一些功(work)。
泵84可以位于该系统的不同位置,以促进流体流动。
参见图3,浓缩的产物68然后可送入酸产生系统90。在混合器92中,来自脱水系统40的浓缩的产物68可与二氧化碳94和低分子量叔胺96如三乙胺混合。该羧酸盐与低分子量叔胺96反应,形成可溶的盐。钙与二氧化碳94反应,形成不溶解的碳酸钙98,可以用固体分离器100回收碳酸钙。然后,碳酸钙98可以用蒸馏水洗涤,除去粘附的产物和在容器102汽提的蒸汽,确保从碳酸钙98中除去所有低分子量叔胺96。然后将碳酸钙98送入预处理/发酵系统10,用作缓冲剂,或者送入石灰窑(未示出),转变为石灰。
水溶液104含有溶解的低分子量叔胺羧酸盐。然后,该溶液在热交换器106中预热,并送入蒸发器108,在此处采用与脱水系统40相同的蒸气-压缩技术,除去大部分的水。具体地,涡轮机130向压缩机132提供能量。将蒸发器108排出的废流体送入塔134,在该塔内与石灰136和蒸汽138混合,向混合器92提供另一个产物流,并向预处理/发酵系统10提供水140。
然后,低分子量叔胺羧酸盐的浓溶液104被送入塔110,该塔中可加入高分子量叔胺112如三辛胺或三乙醇胺。可以取代低分子量叔胺96,并将其从塔110的顶部排出,同时高分子量叔胺羧酸盐的溶液104可从塔110的底部排出。
然后高分子量叔胺羧酸盐溶液104可以在热交换器114中预热,并送入塔116。在塔116内,温度可高至足以断裂化学键,使更挥发的羧酸146从塔116顶部排出。低挥发性的高分子量叔胺112可从塔的底部排出,并可循环到塔110。
采用固体分离器118,可以除去高分子量叔胺112中的任何盐120。回收的盐120可以用挥发性溶剂122,例如三乙胺洗涤,除去该分离器118中的高分子量叔胺112。在蒸馏塔124内,将溶剂122与回收的高分子量叔胺分离。然后,盐120在汽提器126中进行蒸汽汽提,除去挥发性溶剂122,形成固体144。
系统90可包括各种热交换器140,用来循环过程热量。不同的流体可通过这些热交换器,如冷却水142、蒸汽148和燃料150。在一种热交换器140中,来自脱水系统40的蒸汽86用作热源,然后收集在冷凝器152中,该冷凝器中二氧化碳154与水156分离,返回发酵/预处理系统10。
泵158还可以位于该系统的不同位置,以促进流体流动。
参见图4,来自酸产生系统90的混合羧酸146被送入氢化系统170。将混合酸146置于塔172中,与高分子量醇174如庚醇混合。羧酸146与醇174反应,形成酯176和水178。在塔172中分离水178,并送入热交换器180,然后返回塔172,或用于系统10、40、90或170的其它地方。酯176可送入氢化反应器182,该反应器包含合适的氢化催化剂,如Raney镍。在反应器182中,通入氢200,使酯176转化为醇。使用固体分离器186将固体与醇184分离。将醇混合物184送入塔188,从该塔底部回收高分子量醇174,从顶部回收醇产物。醇产物190可以是伯醇。
系统170可包括各种热交换器192,用来循环过程热量。各种流体通过这些热交换器,如冷却水194和蒸汽196。泵198也可以在该系统的不同位置,以促进流体流动。
本领域已知的回收羧酸,但没有产生醇的另一种系统可用来替代图4中的氢化系统。
参见图5,系统300可包括预处理/发酵系统10、脱水系统40、酸产生系统90和任选的氢化系统170作为子系统302。系统300在不同子系统302中重新使用过程热量、水、石灰、二氧化碳和其它物质。
在另一个未明确示出的实施方式中,在酸产生系统90可以使用氨替代低分子量叔胺96。此外,如果供氨更容易,则羧酸钙、二氧化碳和氨之间的反应可以在进入脱水系统40之前进行。这种实施方式中,氨羧酸盐的水溶液,而不是羧酸钙的水溶液在脱水系统40中蒸发。这会有助于防止在热交换器或系统40中结垢,因为铵盐结垢的可能性小于钙盐。氨而且是价廉的,放出的氨可转向预处理/发酵系统10,用作氮源。但是,氨可能与羧酸反应形成酰胺,这不是所需的副产物。
本发明的实施方式包括上述系统操作中涉及的所有过程。参见图6,本发明提供了制备羧酸和醇类的联合方法。该方法包括在步骤400用石灰或生石灰、水34、接种物和空气处理生物质堆12,产生发酵肉汤36。在步骤410,可以用高分子量羧酸46对发酵肉汤36进行酸化,然后,在步骤420,在汽提塔44中进行汽提。在步骤430,产物在蒸发器58中浓缩,产生浓缩的产物68。浓缩的产物68可以与二氧化碳94和低分子量叔胺96在步骤440进行混合,形成低分子量叔胺羧酸盐。在步骤450,在塔110中用高分子量叔胺112交换这种羧酸盐。在步骤460,在塔116中加热高分子量叔胺羧酸盐至高到足以断裂酸与胺的键的温度。该步骤产生羧酸146,可以在步骤470进行回收。在某些实施方式中,在步骤480,羧酸146与高分子量醇174混合,形成酯176。在步骤490,酯176可以在室182中氢化,形成醇产物190。在步骤500,高分子量醇174和醇产物190可以在塔188中进行分离。醇产物190可以是伯醇。
另一个实施方式中,氨可用来替代低分子量叔胺96。在步骤400之后立刻加入氨。
在2000年3月28日颁发的美国专利6,043,392,在1999年11月16日颁发的美国专利5,986,133,在2002年11月12日颁发的美国专利6,478,965,2002年5月28日颁发的美国专利6,395,926,1999年10月5日颁发的5,962,307和2004年5月21日公开的WO04/041995以及它们的美国和外国同族申请以及专利中也描述能用于本发明的各种方法、系统和设备。上述所有专利和申请参考结合于本文。
Claims (21)
1.一种用于转化生物质的系统,该系统包括:
预处理/发酵子系统,其用于:
用石灰或生石灰以及空气对生物质进行预处理,产生处理的生物质;
用接种物使所述处理的生物质发酵,产生含羧酸盐的发酵肉汤;
脱水子系统,其用于:
用高分子量羧酸酸化该发酵肉汤,形成酸化的发酵肉汤;
汽提该酸化的发酵肉汤,产生汽提的发酵肉汤;和
从所述汽提的发酵肉汤除去过量的水,产生浓缩的产物;
酸产生子系统,其用于:
将所述浓缩的产物与低分子量叔胺或氨混合,从羧酸盐产生低分子量的叔胺或氨的羧酸盐产物;
用高分子量叔胺替代所述低分子量叔胺或氨的羧酸盐产物中的低分子量叔胺或氨,形成高分子量的叔胺的羧酸盐产物;
热断裂所述高分子量叔胺的羧酸盐产物中的胺-羧酸根键,产生混合的羧酸产物。
2.如权利要求1所述的系统,该系统还包括氢化子系统,其用于:
将所述混合的羧酸产物与高分子量醇混合,形成酯;
用氢化催化剂使所述酯转化为醇混合物;
将所述醇混合物与所述高分子量醇分离。
3.如权利要求1所述的系统,其特征在于,所述生物质包括木质纤维素生物质。
4.如权利要求1所述的系统,其特征在于,所述预处理/发酵子系统还包括:
深坑,其具有:
衬料;
放在衬料上的砂砾;和
多孔排水管,其埋入所述砂砾中;
生物质堆,其位于所述深坑的顶部;
盖子,其盖在所述生物质堆上面;和
泵,其用于将水从所述深坑循环到所述生物质堆的顶部。
5.如权利要求4所述的系统,其特征在于,所述预处理/发酵子系统还包括:
鼓风机,其用于将空气循环通过所述生物质堆;
石灰水浆液,其用于除去来自空气的二氧化碳。
6.如权利要求1所述的系统,其特征在于,所述接种物包含耐盐的微生物。
7.如权利要求1所述的系统,其特征在于,所述脱水子系统还包括:
加入到发酵肉汤中的高分子量羧酸,产生酸化的发酵肉汤;
蒸发器,其用于浓缩所述酸化的发酵肉汤。
8.如权利要求7所述的系统,其特征在于,所述高分子量羧酸包括己酸、戊酸或庚酸。
9.如权利要求1所述的系统,其特征在于,所述酸产生子系统还包括:
混合器,其用于混合所述浓缩的产物与所述低分子量叔胺或氨以及二氧化碳;
塔,其用于用高分子量叔胺交换所述低分子量叔胺或氨的羧酸盐产物中的低分子量叔胺或氨;
塔,其用于热断裂所述高分子量叔胺的羧酸盐产物中的胺-羧酸根键,产生混合的羧酸产物。
10.如权利要求1所述的系统,其特征在于,所述低分子量叔胺包括三乙胺。
11.如权利要求1所述的系统,其特征在于,所述高分子量叔胺包括三辛胺或三乙醇胺。
12.如权利要求2所述的系统,其特征在于,所述氢化子系统还包括:
塔,其用于使所述混合的羧酸产物与高分子量醇混合,形成酯;
氢化反应器,其用于用氢化催化剂将所述酯转化为醇混合物;
塔,其用于分离所述醇混合物与所述高分子量醇。
13.如权利要求2所述的系统,其特征在于,所述高分子量醇包括庚醇。
14.如权利要求2所述的系统,其特征在于,所述醇混合物主要包含伯醇。
15.如权利要求1所述的系统,该系统还包括用于在至少一个子系统内循环过程热量或者将过程热量从一个子系统循环到另一个子系统的系统。
16.如权利要求1所述的系统,该系统还包括用于在至少一个子系统内循环水或者将水从一个子系统循环到另一个子系统的系统。
17.如权利要求1所述的系统,该系统还包括用于在至少一个子系统内循环石灰或生石灰或者将石灰或生石灰从一个子系统循环到另一个子系统的系统。
18.一种制得发酵产物的方法,该方法包括:
用石灰或生石灰、水、接种物和空气处理生物质堆,产生发酵肉汤;
用高分子量羧酸对所述发酵肉汤进行酸化,产生酸化的发酵肉汤;
在汽提塔中汽提所述发酵肉汤,产生汽提的发酵肉汤;
在蒸发器中浓缩所述汽提的发酵肉汤,产生浓缩的产物;
将所述浓缩的产物与低分子量叔胺或氨以及二氧化碳混合,产生低分子量叔胺或氨的羧酸盐;
用高分子量叔胺交换所述低分子量的叔胺或氨的羧酸盐,产生高分子量叔胺羧酸盐;
加热所述高分子量叔胺羧酸盐至足以断裂酸/胺键的温度,产生游离羧酸产物;
回收所述游离羧酸产物。
19.如权利要求18所述的方法,该方法还包括:
将所述羧酸产物与高分子量醇混合,形成酯;
氢化所述酯,形成醇产物;
分离所述高分子量醇与所述醇产物;
回收所述醇产物。
20.如权利要求18所述的方法,其特征在于,所述生物质包括木质纤维素生物质。
21.如权利要求20所述的方法,其特征在于,所述醇产物主要包含伯醇。
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JPH10275110A (ja) | 1997-03-27 | 1998-10-13 | Internatl Business Mach Corp <Ibm> | ディスクドライブ装置及びその制御方法 |
US5986133A (en) | 1997-06-30 | 1999-11-16 | The Texas A&M University System | Recovery of fermentation salts from dilute aqueous solutions |
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CN1938257A (zh) * | 2004-01-29 | 2007-03-28 | 齐凯姆公司 | 有机酸的回收 |
CN101061229B (zh) * | 2004-06-16 | 2012-06-13 | 得克萨斯A&M大学系统 | 将生物质转化为羧酸和醇类的方法和系统 |
WO2008070561A1 (en) * | 2006-12-01 | 2008-06-12 | The Texas A & M University System | A method of biomass conversion into mixed alcohols |
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2008
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AU2005262467A1 (en) | 2006-01-19 |
AU2005262467B2 (en) | 2010-08-19 |
BRPI0512229A (pt) | 2008-02-19 |
AU2010241346A1 (en) | 2010-12-02 |
US8283141B2 (en) | 2012-10-09 |
EP1774010A2 (en) | 2007-04-18 |
EP2261365A2 (en) | 2010-12-15 |
WO2006007406A3 (en) | 2006-12-28 |
US8124386B2 (en) | 2012-02-28 |
JP2008503213A (ja) | 2008-02-07 |
US20120034663A1 (en) | 2012-02-09 |
US20110039315A1 (en) | 2011-02-17 |
JP4866845B2 (ja) | 2012-02-01 |
AU2010241346B2 (en) | 2013-09-26 |
EP2261365A3 (en) | 2012-02-29 |
CN101061229A (zh) | 2007-10-24 |
US7820417B2 (en) | 2010-10-26 |
US20090325251A1 (en) | 2009-12-31 |
WO2006007406A2 (en) | 2006-01-19 |
CA2569822A1 (en) | 2006-01-19 |
HK1114642A1 (en) | 2008-11-07 |
US20060024801A1 (en) | 2006-02-02 |
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