CN103119138A - 一种用于替代在热电厂、工厂和中央供热炉中使用的化石燃料的燃料和可燃性混合物 - Google Patents
一种用于替代在热电厂、工厂和中央供热炉中使用的化石燃料的燃料和可燃性混合物 Download PDFInfo
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Abstract
本发明公开了一种新的可燃性混合物和燃料,其燃烧释放的能量比褐煤大15倍,比焦煤大4-5倍。所述可燃性混合物包括固相和液相,其中固相包括:铝粉;至少一种M1X2,其中M1可以是任何处于+2价的氧化状态的金属,而X可以为任何卤族元素;M2CO3,其中M2可以是任何二价金属;氯化锌氨;以石英砂形式存在的SiO2;和生石灰;其中液相包括:至少一种C1-C6羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺;甲基纤维素;和甲醛,或其工业上接近的溶液——福尔马林;和水。当可燃性混合物被密封在容器中时燃料被制备而成。本发明同样公开了能量生产的方法和本发明所述燃料的应用。
Description
发明描述
本发明涉及一种基于氢气生成的燃料和可燃性混合物,其可以用作热电厂(TEPP)化石燃料的替代物。事实上本发明替换化石燃料可以使有害废气如CO2的排出会减少。不过,本发明具有另外的一个性质:吸附CO2,所述CO2是通过燃烧没有被替换部分的煤炭而产生的。另外,根据本发明,可以大大的减少热电厂在煤炭燃烧过程中副产品粉尘的产生的量。
技术问题
本发明的最初目的是寻找一种用于热电厂的替换燃料,其可以用于替换大部分的产生相同电量的煤炭,同时可以降低煤炭开采和运输到热电厂的费用。本发明的另一个目的关注了一个与热电厂发电相关的主要问题,即由于煤炭不完全燃烧产生的大量温室气体。
上述技术问题在可燃性混合物诞生后得到了解决,所述可燃性混合物包括固相和液相,其被存放在密封的容器内,所述容器的一个隔板将液相和固相分开,在整个过程中,所述与液相接触的隔板逐渐解体且使得液相和固相逐步混合,从而引发化学反应导致氢气的产生并在热电厂的炉内燃烧。
现有技术
据申请人所知,现在还没有一种相似的燃料基于相似的原理能够被用作热电厂的替代燃料。在热电厂中,大量的工作投入到了氢气的产生,包括氢气从炉中排出和存储,或者被在另一个工厂使用且与该热电厂一同产生电能。但是,所有的努力概况起来就是水蒸汽气化的原理,水蒸气被输送到炉中,其中固相和气相发生如下化学反应:
本发明包括所有这些反应,特别依赖这样的事实,水在高温的热电厂炉内与煤炭接触,以确保这些反应一定会发生。但是,以上所提到的这些工艺过程仅仅是本发明包含的工艺过程的一小部分,而本发明允许氢气的产生和使用均在原位(不需要输送和存储)。
另一方面,专利文献US7014838描述了使用生石灰和/或消石灰吸收从热电厂排出的CO2。根据所述专利文献,说明CO2吸收的化学原理的基本化学反应如下:
C+H2O=CO+H2
CO+H2O=CO2+H2
CaO+CO2=CaCO3
总反应:C+2H2O+CaO=CaCO3+2H2
在可燃性混合物的固相中,本发明提供有生石灰作为其成分之一,因此,根据本发明,以上提到的CO2的分离同时也会发生。但是,本发明中的生石灰扮演了多个角色,如,生石灰不仅仅专门用作CO2的吸附,且用作H2的产生和同时参与其他的反应,这些增加了可燃性混合的燃烧性能。
发明内容
在描述本发明的实质内容之前,应当限定一下本发明所使用的一些表达方式的专有含义,除非有其他的特别说明。
根据本发明所述的可燃性混合物,是一种包括固相和液相的混合物。每一相还包括更多的组成部分。所有的组成部分均会在下文中列出。
本发明所述的燃料是存储于密封容器中的可燃性混合物,所述密封容器具有或没有附加的隔离体。容器的特性和位于容器内的可燃性混合物中固相和液相的位置和相互关系稍后将做详细的描述。容器被视为了燃料的一部分,因为,其必须是由可燃性材料制备而成,且根据本发明在炉中扮演了一个燃烧触发器的角色。通过可燃性混合物的反应,产生氢气并在容器内积累。所述容器在炉内燃烧随之启动了氢气的燃烧。如果设置隔离体,其也必须是可燃性材料。所述隔离体通过吸附氢气将其保持在容器内。另一方面,位于炉中的隔离体促进了容器的燃烧,且帮助启动氢气的燃烧,其本身也可被视为燃料的一部分。
因此,本发明公开了一种新的可燃性混合物,其燃烧释放的能量比褐煤大15倍,比焦煤大4-5倍。为了使其成为可能,所述可燃性混合物必须被密封在容器中。所述容器可以包括一个隔板用于阻止其固相和液相直接接触,但是与液相中的酸性成分接触的隔板逐渐分解,从而使得可燃性混合物的液相和固相相接处,其实际上扮演了一个产生氢气化学反应的启动器/触发器的角色。由于容器是密封的,产生的氢气被保存在里面。在本发明的一种实施例中,在容器的内部,隔离体被涂覆且吸附氢气分子,从而防止氢气从密封容器的任何的外泄。然而,在炉中的燃烧阶段,其本身为可燃性材料的隔离体和容器在炉中的氧化气氛中引燃氢气。所述隔离体的实例是焦油胶或相似的材料。所述容器由聚合物材料制备而成,优选聚氯乙烯,因为其具有良好的燃烧性能。
除了可燃性混合物外,本发明还涉及了燃料和燃料在热电厂炉或工业炉或中央加热炉中的应用方法。所述可燃性混合物和在热电厂中的能源产品燃料将被详细的描述。可燃性混合物和燃料在工业炉中的应用可以通过对于本领域技术人员来说是很熟悉的标准方法调整得到。
具体实施方式
所述可燃性混合物,可以作为热电厂的替换燃料用于替换部分需求的煤炭,其包括固相和液相,其中固相包括:
铝粉;至少一种M1X2,其中M1可以是处于+2价的氧化状态氮任何金属,而X可以为任何卤族元素;M2CO3,其中M2可以是任何二价金属;氯化锌氨;以石英砂形式存在的SiO2;和生石灰;
其中液相包括:
至少一种C1-C6羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺;甲基纤维素;和甲醛,或其工业上接近的溶液--福尔马林;和水。所述水需要达到本领域的专业纯净度,因为,所述液相是由精确的化合物的水溶液构成的。因此,水在液相中的比例不言自明的,且在下文不再提及。至于固相和液相在可燃性混合物中的重量百分比,根据本发明,固相在混合物中的百分比在32%w/w到46%w/w之间变化,而液相则在54%w/w到68%w/w之间变化。根据本发明的一种形式,固相在混合物中的百分比在36%w/w到42%w/w之间变化,而液相则在58%w/w到64%w/w之间变化。根据本发明的一个具体实施例,固相在混合物中的百分比为39%w/w,而液相则为61%w/w。
根据以上提到的固相的重量百分比,所述固相中的组成部分分别具有如下重量百分比:
根据本发明的一个方面,所述固相组成部分的重量百分比如下:
然而,为了使用本发明所述燃料作为热电厂中煤炭的替换燃料的需求,以上提到的固相组成部分在固相中具有如下重量百分比:
至于液相及其组成部分,和这些组成部分在液相中的重量百分比如下:
至少一种羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺在10%到27%的区间范围内;
甲基纤维素在20%到40%的区间范围内;甲醛,或其工业上接近的溶液--福尔马林在1%到10%的区间范围内。用水将溶液补足100%是不言自明的。
根据本发明的一种形式,所述液相组成部分的重量百分比如下:
至少一种羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺在5%到22%的区间范围内;
甲基纤维素在25%到35%的区间范围内;
甲醛,或其工业上接近的溶液--福尔马林在3%到7%的区间范围内。同样,用水将溶液补足100%。
然而,根据本发明的一个具体实施例,所述液相使用了如下重量百分比的组成部分:
至少一种羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺为17%;
甲基纤维素为29%;
甲醛,或其工业上接近的溶液--福尔马林为5%。其余为水。
另外,根据本发明的一个方面,以上提到的可燃性混合物,或更加确切的说,以上提到的固相中的M1和M2,从Fe,Cu,Zn中选择。另一方面,根据同样的形式,至少一种羧酸,或至少一种其衍生物从C1-C3羧酸或其衍生物的群组中选择;而甲基纤维素则从由明胶和侵填体制备的群组中选择。
根据本发明,在热电厂中作为煤炭替换物的燃料使用时,M1和M2为Zn,而M1X2则为ZnCl2和ZnBr2对混合物,而这并不能认为是一个限制因素,且缩小本专利权利要求所保护范围和主题的。同样的,在本发明所述燃料的上述使用过程中,甲基纤维素为侵填体,而在液相中,两种羧酸为:C1羧酸—如蚁酸,和C2羧酸—如醋酸。
为了提升燃料的可燃性能,一些添加剂会被加入到可燃性混合物中,如焦炭或乙醇,其中,焦炭被添加到固相中,而乙醇被添加到液相中。
本发明的另一个特征是一种在热电厂中生产能量的方法,包括使用以上提到的燃料替换至少一部分煤炭。本发明所述的燃料可以替代超过50%的所需煤炭。根据本发明,达到60%的所需煤炭能够被替换,通过一些改进甚至能够达到100%,所述改进首先是对热电厂炉制备材料的改进。本段指出的百分比可以是体积百分比或其他百分比。根据其热量值,一千克的所述燃料能够替换15千克的褐煤和4-5千克的焦煤。另外,根据本发明所使用的方法,CO2的排出量将能够减小75%。
本发明的下一个主题是以上提到的燃料作为替换/替代燃料在热电厂中的应用。在使用所述燃料时,可燃性混合物及其确定的组成部分吸附煤炭在热电厂中燃烧产生的有害的排出气体。以上全部用于CO2的吸附。
涂覆于容器内部的隔离体的作用是收集氢气和激发燃烧过程。通过甲基纤维素,所述隔离体阻止了氢气从容器的外泄。甲基纤维素可以是明胶或侵填体或其他工业用甲基纤维素。
本发明可以被应用于任何使用固体燃料的炉子,除了热电厂外,还包括,工业炉和变化功率的中央加热炉,其中炉子最低的工作温度不得低于350℃。
当将本发明所述燃料添加到炉中后,作为燃烧的产物,铝酸钙盐3CaO·Al2O3伴随着三个氢气分子以气泡的形式的产生而形成。石英砂、生石灰和水之间的反应导致了permolite-type水合硅酸钙的形成。Permolite反应需要的硫磺作为杂质存在于煤炭中。密封容器具有从这些反应中收集氢气的作用,且在燃料被添加到炉中的时候扮演着一个“导火线”的角色。正如氢气能够在氧气环境中燃烧一样,氧气也可以在氢气环境中燃烧。如果两份体积的氢气和一份体积的氧气被混合着一起(爆炸气体),则该混合气体在点火时会发生爆炸。相应的,本发明为从石英砂、生石灰、水和硫磺生成permolite-type水合硅酸钙做了准备,所述硫磺是从煤炭中获得的,所述煤炭在燃烧中吸取氧气并阻止了爆炸气体的形成。
铝以高纯铝粉的形式存在于可燃性混合物的固相中。高纯的意思是其含有至少90%以上的铝。根据Blen,铝的比表面积最小为7000cm2/g时,能够达到最佳的结果。在本发明的一种优选形式,散装铝粉单位体积质量应该为0.15kg/dm3。
一千克在燃烧时释放的热量是143146kJ/kg,而本发明所述的燃料在氢气燃烧是释放的能量为95690kJ/kg,即为纯氢气燃烧能量的67%。其可用性来源于氢气已经在燃料中燃烧的事实—换句话说氢气已经在容器内部燃烧,其中在容器内的所述可燃性混合物的组成部分产生一个氢气燃烧需要的氧化气氛。
根据本发明,燃料的燃烧通过四个阶段展开:
a)第一阶段,通过可燃性混合物液相组成部分和固相组成部分反应产生氢气。氢气被保持在燃料内部,因为其不能够从容器渗出。通过所述容器和隔离体,氢气被在容器内引燃,所述容器和隔离体均为可燃性物质。
b)纯氢气在直接接近混合物的区域燃烧,氢气作为热电厂炉内高温(1000℃)的结果从混合物中产生,促使了氢气与可燃性混合物包括的水加速分离。
c)在氢气分离的工艺的末端伴随着混合物内的铝酸盐和其它可燃性硅酸盐组成部分的燃烧。
d)不管燃料以何种方式应用于燃烧工艺中,混合物中不能燃烧的部分,氧化钙或生石灰,当其在热电厂烟囱或其他装置中穿越排出的燃料气体时,又可以通过吸附净化有毒气体。通过这种方法,75%的排出的燃料气体被净化到一个相当的程度,从而使其成为环境可接受的。根据本发明,容器的制作工艺如下:
a)两个相互接触的轧辊具有2mm的宽度,其上面对面的设置有1mm深度的沟槽。也就是说,如果下轧辊具有一个纵向沟槽,则上轧辊上的沟槽也是如此设置,通过电流,其在卷筒上将双层薄板贯通,得到剪裁下来的方形/矩形板,使得氢气容纳在里面。容器内部的尺寸必须比其容置物---容器内的可燃性混合物---大三分之二,为收集由在微粒中的可燃性混合物产生的氢气创造空间。
b)经过一定的时间,更加精确的,几小时后,所述可燃性混合物将产生足够的氢气使得微粒看起来膨大。此时,其就做好了使用的准备,如,燃烧。
当温度高于300℃时,塑料容器燃烧,且统一使得氢气与燃料和其燃烧分离,然而,由水中产生的氧气吸附到了可燃性混合物的组成部分上,整个工艺伴随着permolite-type水合硅酸钙的产生,其防止了爆炸气体的发展。
关于碳酸锌(ZnCO3),无水时其以白色粉末的形式存在,且不能直接溶于水。但是,作为商业产品是以水合形式存在的碳酸锌(2ZnCO3X 3Zn(OH)2)。这正是本发明所使用的碳酸锌的形式。
具有消石灰,Ca(OH)2,的固相的组成部分的主要反应如下:
所述消石灰是由生石灰,CaO,与可燃性混合物中液相中的水接触后产生的,且根据本发明基于如下反应获得氢气。
1.2Al+3Ca(OH)2=3CaOX Al2O3+3H2
2.2Al+Ca(OH)2+6H2O=3Ca(Al(OH)4)2+3H2
3.7ZnBr2+Ca(OH)2+6H2O=7ZnO+7Br2+7H2或14HBr
4.2ZnCO3+3Ca(OH)2+=2ZnO2+2Ca CO3+2CaO+3H2
5.(2ZnCO3X 3Zn(OH)2)+2Ca(OH)2=6ZnO2+Ca CO3+2CaO+5H2
6.2ZnCl2X 2NH4Cl+2Ca(OH)2+2H2O=2ZnO+2NH4OH+2CaO+3H2+2Cl2
应当注意的是,另一部分与水接触的CaO转变成水合石灰---Ca(OH)2+6H2O与乙酸一同启动以上提到的反应2。
另一方面,可燃性混合物的液相的组成部分和Ca(OH)2之间反应的主要化学原理如下,通过此反应产生氢气:
7.2HCOOH+2Ca(OH)2+2H2O=3CaO+2CO2+6H2
8.CH3OH+Ca(OH)2=CaCO3+3H2
9.HCHO+Ca(OH)2+=CaCO3+3H2
当燃料容器燃烧后,将发生以下反应:
10.C+H2O=CO+H2
11.H2O+CO=CO2+H2
12.CaO+CO2=Ca CO3
总反应为:C+2H2O+CaO=Ca CO3+2H2
通常,CaO由Ca(OH)2在加热时丢失水分制备而成,而C是来源于煤炭的碳。因此,根据本发明,氢气不仅在燃料内部产生,而且还通过水蒸气的气化反应而产生。造成通过水蒸气的气化反应产生氢气的原因是来源于燃料中的水,如可燃性混合物和煤炭中的水汽。
煤炭的较低热量值在无烟煤的29310kJ/kg和褐煤的12250kJ/kg之间变化。就热量值而言,替换50%煤炭的量,约1000kg,对于褐煤来说需要1250Nm3的氢气,而对于无烟煤来说需要521Nm3的氢气。换算成质量,对于褐煤来说需要110kg氢气,而对于无烟煤来说需要42.7kg氢气。由此得出,1000kg无烟煤释放的热量相当于500kg无烟煤和110kg氢气,或者,对于第二种情况,500kg褐煤和42.7kg氢气。换句话说,8份质量的本发明所述燃料能够替代接近至少50份质量的煤炭。进一步,假设无烟煤的构成是100%的碳,500kg碳和110kg氢的混合物中的碳/氢比C∶H=1∶1.32。碳和氢的比例是能量和环境评价的关键标志之一。对于天然气此比例为C∶H=1∶4,对于汽油此比例为C∶H=1∶2。在这点上,碳元素的比例越大,对环境的有害影响则越大,因为,有更多的二氧化碳中燃烧中产生。这正是为什么本发明所述的可燃性混合物或燃料提出了一种基于以上提到的反应12的降低环境危害性的方法。
Claims (33)
1.一种可燃性混合物,包括固相和液相,其特征在于,所述固相包括:铝粉;至少一种M1X2,其中M1为任何处于+2价的氧化状态金属,而X为任何卤族元素;M2CO3,其中M2为任何二价金属;氯化锌氨;SiO2;和生石灰;所述液相包括:至少一种C1-C6羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺;甲基纤维素;和甲醛,或其工业上接近的溶液--福尔马林;和水。
2.根据权利要求1所述一种可燃性混合物,其特征在于,固相在混合物中的百分比在32%w/w到46%w/w之间变化,而液相则在54%w/w到68%w/w之间变化。
3.根据权利要求2所述一种可燃性混合物,其特征在于,固相在混合物中的百分比在36%w/w到42%w/w之间变化,而液相则在58%w/w到64%w/w之间变化。
4.根据权利要求2所述一种可燃性混合物,其特征在于,固相在混合物中的百分比为39%w/w,而液相则为61%w/w。
8.根据权利要求1所述一种可燃性混合物,其特征在于,所述液相各个组成部分的重量百分比如下:
至少一种羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺在10%到27%的区间范围内;
甲基纤维素在20%到40%的区间范围内;
甲醛,或其工业上接近的溶液--福尔马林在1%到10%的区间范围内;其余为水。
9.根据权利要求8所述一种可燃性混合物,其特征在于,所述液相各个组成部分的重量百分比如下:
至少一种羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺在15%到22%的区间范围内;
甲基纤维素在25%到35%的区间范围内;
甲醛,或其工业上接近的溶液--福尔马林在3%到7%的区间范围内;其余为水。
10.根据权利要求8所述一种可燃性混合物,其特征在于,所述液相各个组成部
分的重量百分比如下:
至少一种羧酸,或至少一种以上提到的羧酸酐,或至少一种它的酯或酰胺为17%;
甲基纤维素为29%;
甲醛,或其工业上接近的溶液--福尔马林为5%。其余为水。
11.根据以上任何一个权利要求所述大一种可燃性混合物,其特征在于,所述M1和M2,从Fe,Cu,Zn中选择,至少一种羧酸,或至少一种其衍生物从C1-C3羧酸或其衍生物的群组中选择;而甲基纤维素则从由明胶和侵填体制备的群组中选择。
12.根据权利要求11所述一种可燃性混合物,其特征在于,M1和M2为Zn,甲基纤维素为侵填体。
13.根据权利要求1、8-10和11所述一种可燃性混合物,其特征在于,在液相中,两种羧酸为:C1蚁酸,和C2醋酸。
14.根据权利要求1、5-7和11所述一种可燃性混合物,其特征在于,M1X2由ZnCl2和ZnBr2的混合物组成。
15.根据以上任何一个权利要求所述大一种可燃性混合物,其特征在于,所述可燃性混合物中还包括作为添加剂的焦炭和乙醇。
16.一种燃料,其特征在于,包括被密封在容器内的根据以上任何一个权利要求所述的可燃性混合物。
17.根据权利要求16所述的燃料,其特征在于,所述密封容器是由聚合物制备而成的。
18.根据权利要求17述的燃料,其特征在于,所述密封容器是由聚氯乙烯制备而成的。
19.根据权利要求16所述的燃料,其特征在于,所述密封容器包括一个隔板所述隔板将液相和固相分离,且与液相中的酸接触并慢慢解体,使得液相和固相逐渐混合,并在容器内部逐渐产生氢气。
20.根据权利要求16所述的燃料,其特征在于,所述密封容器内部内衬有隔离体。
21.根据权利要求16所述的燃料,其特征在于,所述高温隔离体为焦油基粘结剂。
22.根据权利要求16所述的燃料,其特征在于,所述密封容器的三分之一填充有液相和固相,而其余的三分之二用于容纳产生的氢气。
23.一种热电厂能量生产的方法,其特征在于,根据权利要求16-22的燃料被加入到热电厂炉中。
24.根据权利要求23所述的一种热电厂能量生产的方法,其特征在于,根据权利要求16-22的燃料代替50%的所需煤炭。
25.根据权利要求23所述的一种热电厂能量生产的方法,其特征在于,根据权利要求16-22的燃料代替60%的所需煤炭。
26.根据权利要求23所述的一种热电厂能量生产的方法,其特征在于,根据权利要求16-22的燃料代替70%的所需煤炭。
27.根据权利要求23所述的一种热电厂能量生产的方法,其特征在于,根据权利要求16-22的燃料代替全部所需煤炭。
28.根据权利要求23所述的一种热电厂能量生产的方法,其特征在于,1kg的权利要求16-22所述燃料代替15kg的褐煤,或4-5kg的焦煤。
29.根据权利要求23所述的一种热电厂能量生产的方法,其特征在于,使用权利要求16-22所述燃料,CO2的排放量减少75%。
30.根据权利要求16-22的一种燃料的应用,其特征在于,所述燃料在热电厂中被用作煤炭的替代物。
31.根据权利要求31的一种燃料的应用,其特征在于,所述燃料的特性是其能够吸附热电厂中煤炭的不完全燃烧产生的有害燃料气体。
32.根据权利要求32的一种燃料的应用,其特征在于,所述混合物吸附CO2。
33.根据权利要求16-22中任意一个的一种燃料的应用,其特征在于,所述燃料被用于工业炉和中央加热炉中的能量生产。
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PCT/HR2010/000031 WO2012032363A1 (en) | 2010-09-08 | 2010-09-08 | Fuel and combustible mixture used as a substitute for fossil fuels in thermoelectric power plants, industrial and central heating furnaces |
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US (1) | US20130167761A1 (zh) |
EP (1) | EP2614130B1 (zh) |
JP (1) | JP2013538904A (zh) |
KR (1) | KR20130107294A (zh) |
CN (1) | CN103119138A (zh) |
AP (1) | AP2013006792A0 (zh) |
AU (1) | AU2010360471A1 (zh) |
BR (1) | BR112013005477A2 (zh) |
CA (1) | CA2808790A1 (zh) |
CU (1) | CU20130032A7 (zh) |
EA (1) | EA023454B1 (zh) |
EC (1) | ECSP13012479A (zh) |
ES (1) | ES2542601T3 (zh) |
MA (1) | MA34594B1 (zh) |
ME (1) | ME02168B (zh) |
MX (1) | MX2013002540A (zh) |
PL (1) | PL2614130T3 (zh) |
RS (1) | RS54134B1 (zh) |
SG (1) | SG187939A1 (zh) |
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US9090314B2 (en) | 2013-06-14 | 2015-07-28 | Mehmet Nevres ULGEN | Modular underwater foil for a marine vessel |
CN116829497A (zh) * | 2022-01-28 | 2023-09-29 | 德拉戈·科西克 | 作为燃煤电厂用的添加剂的节能和环保燃料 |
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- 2010-09-08 US US13/821,252 patent/US20130167761A1/en not_active Abandoned
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- 2010-09-08 JP JP2013527687A patent/JP2013538904A/ja active Pending
- 2010-09-08 BR BR112013005477A patent/BR112013005477A2/pt not_active IP Right Cessation
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- 2010-09-08 MA MA35796A patent/MA34594B1/fr unknown
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ES2542601T3 (es) | 2015-08-07 |
ME02168B (me) | 2015-10-20 |
TN2013000072A1 (en) | 2014-06-25 |
EA201370050A1 (ru) | 2013-06-28 |
SG187939A1 (en) | 2013-03-28 |
MA34594B1 (fr) | 2013-10-02 |
MX2013002540A (es) | 2013-07-29 |
EP2614130B1 (en) | 2015-04-15 |
KR20130107294A (ko) | 2013-10-01 |
CA2808790A1 (en) | 2012-03-15 |
JP2013538904A (ja) | 2013-10-17 |
WO2012032363A1 (en) | 2012-03-15 |
RS54134B1 (en) | 2015-12-31 |
AP2013006792A0 (en) | 2013-04-30 |
EA023454B1 (ru) | 2016-06-30 |
AU2010360471A1 (en) | 2013-03-21 |
PL2614130T3 (pl) | 2015-10-30 |
BR112013005477A2 (pt) | 2019-09-24 |
UA107033C2 (uk) | 2014-11-10 |
US20130167761A1 (en) | 2013-07-04 |
ECSP13012479A (es) | 2013-04-30 |
EP2614130A1 (en) | 2013-07-17 |
CU20130032A7 (es) | 2013-05-31 |
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