CN102300958A - 无机物含量减少的生物油及其制备方法 - Google Patents
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Abstract
本发明公开了将生物质材料转化为稳定生物油的方法。该方法包括将生物质转化为含金属化合物悬浮颗粒的热解油,和去除至少一部分悬浮的金属化合物,得到稳定的生物油。
Description
发明背景
1.发明领域
本发明一般涉及无机物含量低的生物油,更具体说涉及制备这类生物油的方法。
2.相关领域描述
根据其来源,生物质(biomass)可含有显著量的通常称为灰份的无机物,。在学术文献中业已描述了在多产转变前对生物质进行洗涤处理的实验。这些实验证明,生物质中存在的无机物影响到生物质转变过程的转化产率和产物混合。
生物质转化过程通常产生气体、液体和固体产物。液体产物包含水相和油相,油相一般称为生物油。通常假设生物质中存在的无机物最终位于生物质转化产物的水相中。已知生物油不稳定,通常是由于生物油氧含量高之故。目前尚没有注意到生物油中污染的无机物有可能成为生物油不稳定的起作用因素。
美国专利6,022,419(授予Torget等)公开了酸水解木质纤维素的多步骤方法。其第一步,设计任选地溶解大多数易溶组分,如一些木质素、萃取物和蛋白质。对于此任选步骤,采用了100-160℃温度范围、pH=1-5的热水介质。不分离萃取物与生物质。
美国专利6,419,788(授予Wingerson)描述了分离木质纤维素生物质的纤维素与其它成分的方法。所述方法关注点是除去木质素。萃取物与木质素一起取出,残留下半纤维素。该方法目的是产生没有木质素的相对清洁的纤维素。
美国已公开的专利申请2008/029233(授予Wingerson)描述了分离木质纤维素生物质的纤维素纤维与其它成分的逆流(countercurrent)方法。第一次洗涤液包括水,或用于半纤维素水解的无机酸与水的溶液。
这些现有技术方法包括在基本上没有木质素的纤维素产品生产环境中除去萃取物。为了产生生物油,需要留下进料中的木质素,因为它含有生物质中存在的重要能量组分。
因此,特别需要最大程度减少生物油中无机物含量的方法,以及用这种方法产生的生物油。
发明概述
本发明通过提供将生物质材料转变为稳定的生物油的方法而解决了这些问题,所述方法包括步骤:(i)将生物质材料的至少一部分转化为含悬浮金属化合物颗粒的热解油;和(ii)去除该热解油中至少一部分悬浮的金属化合物,得到金属含量减少的生物油。
在一优选实施方案中,先对所述生物质进料进行脱矿物质步骤再转变为热解油,以减少后面要除去的悬浮金属化合物的含量。
本发明的另一方面包括用本发明方法得到的稳定生物油。
发明详述
生物质,特别是木质纤维素生物质,蕴含着丰富的能源。需要将生物质转变为可用于内燃发动机能源的液体燃料。目前可利用的将生物质转变为液体燃料的主要途径是通过发酵变成乙醇和热解。发酵的缺点在于需要从木质素中分离出纤维素,使之接触纤维素酶。另外,发酵反应本身费时,需要大量水,从而使该方法成本很高。
热解可产生气体、液体和固体反应产物。液体反应产物包括水相和油相。油相一般称为生物油,已知其稳定性差。稳定性差通常是由于生物油的氧含量高所致。业已证明,例如,水解处理生物油可降低氧含量,导致稳定性显著改善。
木质纤维素生物质材料包含一定量的无机材料。这些无机材料一般称为“灰份”,因为这些材料见于生物质燃烧后的灰份中。灰份的主要成分一般是钠、钾、钙和硅。钾通常是灰份的主要组分。事实上,“钾”的名称来自钾碱(potash)一词,是16世纪的荷兰语,表示在锅里燃烧木头产生的灰份。
已知灰份所含的许多成分在热解生物质转变中具有催化性能。这些成分的存在将减少可代偿烃的产量,增加木炭产量。业已建议先除去生物质中的灰份再高温分解,可提高生物油产量。
假设性质为无机物的灰份应积聚在液体反应产物的水相中。现已发现,生物质中存在的大量灰份在热解反应期间进入生物油中。由于该事实,可以假定在热解反应期间,无机物灰份被烧结成疏水颗粒。硅可能起一定作用,因为已知在燃烧条件下它会熔合灰份。假设在较低的热解温度下,存在的硅对形成疏水颗粒也有贡献。进一步假设,生物油的某些成分,如聚羧酸可螯合存在于灰份中的金属化合物。这种鳌合物可溶于生物油。
生物油中存在的小颗粒灰份可导致生物油化学上不稳定,因为这些小颗粒有催化作用。本发明的一个重要方面内容是通过去除生物油中的悬浮灰份颗粒来提高生物油的稳定性。
总的说来,本发明提供将生物质材料转变为生物油的方法,所述方法包括步骤(i)将生物质材料的至少一部分转变成含有悬浮金属化合物颗粒的热解油;和(ii)除去热解油中至少一部分悬浮的金属化合物,得到金属含量减少的生物油。
应理解,本文所用的术语“热解油”所描述的物质是该技术领域通常称作的“生物油”。术语热解油用于描述热解反应的直接(immediate)产品,以区分于通过本发明方法得到的、业已除去了至少一部分悬浮金属化合物后的生物油。
在一优选实施方式中,在催化剂存在下加热生物质材料,进行将至少一部分生物质材料转化为热解油的步骤。存在催化剂能使该反应在较低的温度下进行,同时仍能得到高转化产率。但是,采用催化剂可能会增加热解油中的金属化合物颗粒数量,因为催化剂材料可能因磨损而丢失,金属可能因产物转化而从催化剂中析出变成酸性。
换言之,采用催化剂可能提高热解油的质量,因为该反应能在较低温度下进行。但该效应被存在于热解油中的金属化合物悬浮颗粒的催化作用所抵消,导致热解油不稳定。本发明方法因此特别适合涉及采用催化剂材料的生物质转化方法。
应当明白,存在于热解油中的金属化合物至少一部分来源于生物质材料本身。在催化过程中,存在于热解油中的金属化合物的至少一部分也可能来源于催化剂。
在将至少一部分生物质转变为热解油的步骤前进行去除生物质中的无机物步骤具有优点。去除无机物步骤提高了转化步骤期间对催化组合物的控制力,因为可最大程度减少存在于生物质中的固有材料对总体催化性能的作用。去除无机物的步骤也可减少转化反应产生的热解油的金属化合物含量,从而有利于后续去除步骤。
转化步骤前的无机物去除步骤,通常包括在允许从生物质中萃取无机物的条件下,使生物质接触溶剂,然后分离溶剂与生物质。用于该无机去除步骤的优选溶剂是水性溶剂,因为其成本低而且安全,对生物质材料中存在的无机物具有高溶解度。通过在该水性溶剂中加入酸或碱可进一步提高无机物的溶解度。
无机物去除步骤包括用水性溶剂浸泡生物质材料,通过机械作用,如捏挤或压榨除去水性溶剂。可重复该步骤一次至数次,以提高预处理步骤的总体效应。
无机物去除步骤可在升高温度下进行,以提高无机物的溶解度,提高水性溶剂扩散进出所有生物质材料的速率。合适的温度范围为20-120℃,优选60-120℃。但是应小心以避免半纤维素水解,特别是在水性溶剂中存在酸时,因为这类水解会导致生物质材料损失。
热解油中悬浮颗粒的粒径可能有相当大的不同,因为其由该方法操作者不能直接控制的多种因素所决定,例如生物质材料的来源,生物质材料的金属(例如但不限于硅)含量等等。悬浮颗粒的平均粒径通常为1nm-100微米,优选10微米到100微米。
可采用任何类型的液体/固体分离技术去除热解油中的悬浮金属化合物。合适技术的例子包括离心、过滤(包括加压过滤)和萃取。虽然蒸馏对去除液体中的固体极为有效,但一般不适合,因为它要求加热热解油可能产生不良副反应,特别是存在悬浮金属化合物时。然而,在低得多的温度下真空蒸馏可能适合用作分离技术。
适当分离技术的选择取决于悬浮金属化合物颗粒的平均粒径。较大的颗粒,例如,1微米到100微米的颗粒可通过过滤或离心除去。亚微米范围的小颗粒可通过超滤、离心或萃取除去。
存在于生物油中的金属可能溶于生物油的组分中。例如,存在于生物油中的络合羧酸可起螯合剂的作用。被螯合的金属一般不能通过过滤或离心除去,但可通过萃取或(真空)蒸馏除去。
本发明的另一方面内容是用本发明方法得到的稳定生物油。稳定的生物油的特征是金属含量低于2%重量,优选低于1%重量,更优选低于0.5%重量。不同于通过现有技术方法得到的生物油材料,本发明方法得到的稳定生物油可长时间贮存。这种性质经济上十分重要,因为可允许这种生物油长距离运输,也可将季节性生物质农作物的加工整合入非季节性农作物加工中,例如粗制油的精制。
在整个能量供应网中采用生物质经济上的一个重要障碍是生物质材料的运输成本高,这是由于固体生物质材料的密度低和笨重。因此需要在靠近生物质收获的地方将生物质转化为更易管理的运输和贮存形式。液体产品符合这些要求,因为液体的密度高,可用泵输送,可通过管道或油罐车方便地运输。
现有技术方法所用的生物油不符合这些经济上的要求,因为它们稳定性差,禁止长时间贮存或远距离运输。需要提高现有技术的生物油等级使它们适合贮存和运输。这类提高等级(如水解处理)要求精密复杂的设备来抵御高压,因而昂贵不适合长距离供应网。
本发明的生物油克服了这些问题,因为可用较简单的设备低成本地生产这种生物油。
因此,本发明的一个重要方面内容是提供将生物质的能量载体从收获点运输到精炼地点的方法,所述的方法包括步骤(i)在收获点收获生物质材料;(ii)在生物质转化地点将生物质材料转化为稳定的生物油;和(iii)将稳定的生物油运送到精炼地点。
生物质转化地点优选距离收获地点500英里内。生物质转化地点更优选距收获地点100英里内。合适的方法是用本发明的方法制备稳定的生物油。
Claims (21)
1.一种将生物质材料转化为稳定生物油的方法,所述的方法包括步骤(i)将至少一部分生物质材料转化为含有悬浮的金属化合物颗粒的热解油;和(ii)去除热解油中至少一部分悬浮金属化合物,得到金属含量减少的生物油。
2.如权利要求1所述的方法,其特征在于,步骤(i)包括在催化剂存在下,加热所述生物质材料,和/或所述生物质材料产生的生物质热解蒸汽。
3.如权利要求1或2所述的方法,其特征在于,所述金属化合物至少一部分来源于生物质材料。
4.如权利要求2所述的方法,其特征和在于,所述金属化合物至少一部分来源于催化剂。
5.如前述权利要求任一项所述的方法,其特征在于,步骤(i)先于无机物去除步骤。
6.如权利要求5所述的方法,其特征在于,所述无机物去除步骤包括在环境温度或更高温度、在环境压力或更高压力下,使所述生物质材料与水性溶剂或溶液接触。
7.如权利要求6所述的方法,其特征在于,所述水性溶剂或溶液包括酸或碱。
8.如权利要求6所述的方法,其特征在于,所述无机物去除步骤包括用水性溶剂浸泡生物质材料,通过机械作用除去生物质材料中的水性溶剂。
9.如前述权利要求任一项所述的方法,其特征在于,存在的至少一部分金属化合物为粒径范围为1纳米至100微米的悬浮颗粒形式。
10.如权利要求9所述的方法,其特征在于,所述悬浮颗粒的平均粒径为10-100微米。
11.如前述权利要求任一项所述的方法,其特征在于,所述的热解油还包含被热解油的一种或多种成分螯合的金属。
12.如前述权利要求任一项所述的方法,其特征在于,步骤(ii)包括离心。
13.如前述权利要求任一项所述的方法,其特征在于,步骤(ii)包括过滤。
14.如前述权利要求任一项所述的方法,其特征在于,步骤(ii)包括萃取。
15.如前述权利要求任一项所述的方法,其特征在于,步骤(ii)包括减压蒸馏。
16.由权利要求1-15任一项所述的方法得到的稳定生物油。
17.如权利要求16所述的稳定生物油,其特征在于,其金属含量低于2重量%,优选低于1重量%,更优选低于0.5重量%。
18.一种将以生物质为基础的能量载体从收获地点运送到精炼地点的方法,所述的方法包括步骤(i)在收获地点收获生物质材料;(ii)在生物质转化地点将生物质材料转化为稳定的生物油;和(iii)将稳定的生物油运送到精练地点。
19.如权利要求18所述的方法,其特征在于,生物质转化地点距离收获地点500英里内。
20.如权利要求19所述的方法,其特征在于,生物质转化地点距离收获地点100英里内。
21.如权利要求18-20任一项所述的方法,其特征在于,采用权利要求1-15任一项所述的方法制备稳定的生物油。
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US9193924B2 (en) * | 2011-06-16 | 2015-11-24 | Uop Llc | Methods and apparatuses for forming low-metal biomass-derived pyrolysis oil |
US9109177B2 (en) | 2011-12-12 | 2015-08-18 | Ensyn Renewables, Inc. | Systems and methods for renewable fuel |
US10633606B2 (en) | 2012-12-10 | 2020-04-28 | Ensyn Renewables, Inc. | Systems and methods for renewable fuel |
US9611197B1 (en) | 2013-03-15 | 2017-04-04 | Inaeris Technologies, Llc | Method of removing undesirable solid components from a renewable or non-renewable feed and apparatus used in same |
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US5115084A (en) | 1989-07-19 | 1992-05-19 | Biocarbons Corporation | Method for controlling oil reservoir permeability using biomass oil |
US6022419A (en) | 1996-09-30 | 2000-02-08 | Midwest Research Institute | Hydrolysis and fractionation of lignocellulosic biomass |
US6048374A (en) | 1997-08-18 | 2000-04-11 | Green; Alex E. S. | Process and device for pyrolysis of feedstock |
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US7503981B2 (en) * | 2004-12-02 | 2009-03-17 | The Trustees Of Dartmouth College | Removal of minerals from cellulosic biomass |
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