CN101506335A - 从废物中生产燃料的方法 - Google Patents

从废物中生产燃料的方法 Download PDF

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CN101506335A
CN101506335A CNA2007800318031A CN200780031803A CN101506335A CN 101506335 A CN101506335 A CN 101506335A CN A2007800318031 A CNA2007800318031 A CN A2007800318031A CN 200780031803 A CN200780031803 A CN 200780031803A CN 101506335 A CN101506335 A CN 101506335A
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贡特尔·H·基斯
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Abstract

本发明涉及一种对所有种类废物材料的处理和利用的方法，其中所述废物材料被分批地压缩形成紧密的小包并穿过温度处理区域，生产合成气，在随后的反应中将所述合成气转化成烃分子。

Description

从废物中生产燃料的方法
技术领域
本发明涉及一种首先用废物制成合成气，再将合成气转化成烃的方法。所生成的烃可以用作燃料。
背景技术
在过去的几年中，油价持续上涨，即使在此期间油价部分回落，但从长远观点来看，还会呈现出高的油价，以至于将来燃料生产的替代方法将变得具有更大的价值。
最著名的燃料生产的替代方法是费托合成，费托(Fischer-Tropsch)工艺是用于将合成气(CO/H2)转化成液态烃的工业规模的方法，弗朗茨·费希尔和他的同事汉斯·托晋希(Tropsch)在1925年以前在鲁尔河畔米尔海姆研制出液态烃，鲁尔化学公司(Ruhrchemie AG)从1934年起将此工艺应用在工业规模上。CO/H2的混合物在铁或者钴催化剂的作用下化合反应形成石蜡、烯烃和酒精。
费托合成反应(聚合)的化学机理主要是生成长链，仅有少量的支链(也就是，本质上是直的)的烃分子。在混合产物中发现有不同的链长，对于燃料的生产，C5-C20的链长范围具有特殊的价值。可以通过选择催化剂(掺有促进剂的钴或铁)和合成条件(尤其是温度，合成气组分，气压)来调整链长。然后将初步的费托合成产物进行化学处理得到更高的燃料产量和质量(例如碳氢化合物分裂，异构，也就是原油处理方法)。
由于形成仅有少量支链的烃分子的化学合成机理，该产物尤其适合用作具有高十六烷值和极其低含量的硫和芳香烃的高质量的柴油燃料。至于不同链长的烃的混合产物可以进一步根据蒸气压、蒸馏曲线尤其通过应用高度发展的原油精炼方法量身定做，这些合成生产的柴油具有特别是低污染从而对环境有益的优点。
同时，南非是唯一采用费托反应满足大部分燃料需要的国家，从煤中生产出用于合成的合成气。
在德国，柯伦(choren)公司研制出首先利用碳-V工艺从生物质中生产合成气，然后借助于费托工艺生产燃料(所谓的阳光柴油(SunDiesel))的方法。所述碳-V工艺具有三步气体处理工艺，其具有如下部分工艺：低温气体处理，高温气体处理和吸热燃料流气体处理。
在第一个工艺步骤中通过不断地在400-500℃之间的温度下与空气或氧气部分氧化(碳化)，使得生物质(水含量为15-20％)碳化，也就是分解成含焦油气体(挥发组分)和固态碳(生物焦炭(biocoke))。
在第二个工艺步骤中，在燃烧室中在易燃材料的灰烬熔融点将含焦油气体按亚化学计量与空气和/或氧气再氧化形成热气化介质。
在第三个工艺步骤中，将碾磨成粉状燃料的生物焦炭排入热气化介质中，粉状燃料和气化介质因此在气化反应堆中进行吸热反应以形成合成原气体。经过相应的条件如用于产生气流、蒸汽和热量的可燃气体或者合成气后，再借助于费托工艺使用这合成原气体产生阳光柴油。这个工艺的缺点在于在几个步骤中发生气化而且必须将生物焦炭碾碎。另外，这个方法不适合于所有类型废物的气化。
发明内容
本发明的目的是提供一种使废物气化和后续合成燃料，尽可能完全利用废物的方法。
通过具有权利要求1的特征的方法实现此目的，在权利要求10中指出了使用该方法的一个可能的用途。从属权利要求因此形成了有益的发展。
本发明提供了一种对所有种类废物材料的处理和利用的方法，其中所述废物材料经过分区域地温度冲击和热分离或者材料转化，并且生成的固体残留物转化成高温熔化物，所述废物材料被分批地压缩形成紧密的小包并穿过具有至少一个低温区域和至少一个高温区域的温度处理区域，在所述温度处理区域从废弃处理材料中生产合成气，在温度升高的趋势下，生产出的所述合成气经过一透气床和一合成气稳定区域，所述合成气位于所述透气床的上方，之后被从所述稳定区域导出，在随后的反应中将所述合成气转化成烃分子。反应产物优选为燃料，尤其是柴油燃料。
该方法的一个主要优点在于根据本发明的方法不必进行在前的复杂分离仅利用现在的所有类型的废物材料，即处理过的、未处理过的、包含污染物和有毒物质的废物和生物废物(biowaste)。在现有技术方面，已知的一种方法为热选(Thermoselect)方法，并且在欧洲专利EP1187891B1、EP1252264B1、EP1377358B1、EP0790291B1或者EP0726307B1中作为实例进行了更详细的描述。这些欧洲专利的全部内容包含于此。
在本方法中，生产出的合成气的至少70％、优选地100％用于反应转化成烃。合成气中没有利用的部分因此有利地用于满足废弃处理方法的内部能量需要。这就保证了该方法的中和的能量平衡。此外，该方法还具有一个主要的优势，保证了准发射自由过程。
在一个更优选的实施例中，将合成气反应生成烃的过程中生成的气态、液态和/或固态的副产物返回到生产合成气的高温区域，从而实现费托合成而不产生更多的需要随后处理的废物。
在一个更优选的实施例中，费托合成的副产物用于满足废弃处理方法的内部能量需要。
为了实现好的产量，在200-350℃的温度范围和10-30bar的气压下根据下述的通用的反应方程式反应是有利的：
nCO+(2n+1)H2→CnH2n+2+nH2O。
该反应在现有技术中作为费托工艺是已知的，在这个方面可参考最佳的方法条件，这些条件为本领域人员熟知并且在现有技术中已提到，如气压，温度和催化剂系统。
另外，如果控制该方法使烃具有平均5-20个碳原子并且尽可能是无支链的，是很有利的。通常，通过费托合成也能够合成长链烃，但是例如石蜡的长链烃具有太高的融点，以至于不能用作液态燃料。然而具有平均5-20个碳原子的烃非常适合用作合成柴油燃料。
因为通过气化方法获得的用于费托工艺的合成气具有相对不利的一氧化碳与氢的体积比，如果在聚合反应之前一氧化碳与氢的体积比在变换反应中向有利于氢气方向移动。本领域技术人员同样地从现有技术中知道该变换反应，可以参考优化的反应条件和所使用的催化剂。
在一个更优选的实施例中，一氧化碳与氢的体积比在变换反应中调节为至少1:1.5，优选地，至少1:2。
另外，本发明说明了上述方法的用途。根据本发明，该方法可以用于燃料的合成，优选地，用于柴油燃料的合成。
下面通过实例，对本发明的方法做进一步的详细描述，而本发明并不局限于该方法所使用的参数。
具体实施方式
根据本发明，参考具有两条生产线、且每条生产线具有15t/h废物产量的热选设备对该方法进行详细的描述，也就是总共有30t/h的废物产量。每千克废物产生12MJ的平均废物产热值是运作的基础。在该设备连续运作的情况下，可以获得体积组分为38％的CO、38％的H2和14％的CO2的大约30000Nm3/h的合成气。根据费托工艺实现燃料生产。为了设置一个有利于费托反应的CO/H2比例，在变换反应中将一部分CO转化生成H2，将这里产生的CO2分离出来。
CO+H2O→H2+CO2
在变换反应中将38％的CO中的13％的CO转化，也就是变换反应后，获得25％的CO和51％的H2，然后将它们用于费托合成。增加了氢气含量并且将CO与H2的比例调到有利费托反应的合成气被聚合成柴油燃料。
25％CO+51％H2＝>＂Diesel＂
所使用的合成气的60％在燃料生产的所有步骤中产出，这与文献资料中的值非常接近，文献资料中指出在实验室条件下优化方法为75％。CO和氢气的具体容积重量是计算物质平衡的基础。方程式如下所述：
21000m3/h(0.25×1.258kg/m3+0.51×0.089kg/m3)＝7557kg/h
在合成柴油的平均密度为0.83kg/l的情况下，能生产出质量为78001/h的柴油，因此具有2条生产线的热选设备一小时可生产出7800升。

Claims (11)

1、一种对所有种类废物材料的处理和利用的方法，其中所述废物材料经过分区域地温度冲击和热分离或者材料转化，并且生成的固体残留物转化成高温熔化物，所述废物材料被分批地压缩形成紧密的小包并穿过具有至少一个低温区域和至少一个高温区域的温度处理区域，在所述温度处理区域从废弃处理材料中生产合成气，在温度升高的趋势下，生产出的所述合成气经过一透气床和一合成气稳定区域，所述合成气位于所述透气床的上方，之后被从所述稳定区域导出，其特征在于：
在随后的反应中将所述合成气转化成烃分子。
2、根据权利要求1所述的方法，其特征在于生产出的所述合成气的至少70％、优选地80％、特别优选地100％用于反应生成烃。
3、根据前述权利要求所述的方法，其特征在于中未用于反应的合成气的部份用于满足所述处理方法的内部能量需要。
4、根据前述任一权利要求所述的方法，其特征在于将从所述反应中生成的气态、液态和/或固态的副产物返回到生产所述合成气的所述至少一个高温区域。
5、根据权利要求4所述的方法，其特征在于返回的所述副产物用于满足所述处理方法的内部能量需要。
6、根据前述任一权利要求所述的方法，其特征在于，所述反应在200-350℃的温度范围根据通用的反应方程式进行：
nCO+(2n+1)H2→CnH2n+2+nH2O。
7、根据前述任一权利要求所述的方法，其特征在于所述烃具有平均5-20个碳原子。
8、根据前述权利要求所述的方法，其特征在于在反应前，所述合成气中一氧化碳与氢气的体积比在变换反应中向有利于氢气的方向移动。
9、根据前述权利要求8所述的方法，其特征在于，在所述变换反应后，一氧化碳与氢气的体积比至少是1:1.5，优选地至少是1:2。
10、一种根据前述任一权利要求所述方法的用途，用于燃料的合成。
11、根据权利要求10所述的用途，其特征在于所述燃料是柴油燃料。
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