CN101484554B - 伴随着碱金属化合物的回收和再循环的催化的蒸汽气化方法 - Google Patents
伴随着碱金属化合物的回收和再循环的催化的蒸汽气化方法 Download PDFInfo
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Abstract
描述了用于把碳质固体转化成甲烷的高效率气化工艺以及用于该操作的装置。该工艺包括:在碱金属催化剂存在下使蒸汽和包含灰分的碳质固体在气化反应器中反应制备可燃气体和包含灰分与碱金属催化剂组分的焦化颗粒,在碱金属催化剂再生系统中处理该焦化颗粒流以把上述催化剂组分再生为碱金属化合物,以及再循环该再生的化合物。在上述碱金属催化剂再生系统内部,该工艺包括:用水淬火焦化颗粒流以此冷却和破碎该颗粒,从破碎的固体中溶解可溶性碱金属催化剂组分以形成第一碱金属催化剂溶液和洗涤的固体,可选的使该洗涤的固体在碱性溶液中反应以形成第二碱金属催化剂溶液,提高所述第一和可选的第二碱溶液的品位以把该碱金属催化剂组分再生为所述的碱金属化合物。
Description
发明领域
本发明涉及在碱金属催化剂的存在下气化诸如煤的碳质固体以生产诸如甲烷或者合成气燃气的方法,一起伴随着简化的催化剂回收的方法。
背景技术
石油是用于液体与气态的燃料的主要来源。人们已经很久就关注到因为已知的石油储量正在耗费并且新储量的勘探正变得愈加困难,石油的可得性将会降低。由于这么多的技术依靠液体与气体燃料,人们普遍的意识到需要开发方法以从可替代来源制造这样的燃料。
为了解决这个关注已经发展了几种技术,许多集中在诸如煤、石油焦的碳质固体,以及甚至有机物废料。已经开发了方法来把这些原料转换成各种可燃气体,例如一氧化碳与氢的混合物“合成气”,或者又名合成天然气的甲烷。
煤的气化典型的通过使蒸汽与煤在高温下或者在存在碱金属催化剂的情况下在适中的温度下反应来完成。一个这样的方法,把煤催化地转换成甲烷,公开于发行于1978年6月13日的美国专利第4,094,650号中。上述′650专利公开了在碳-碱金属催化剂的存在下,碳质固体可以在相对热中性的方法中被气化以制造甲烷。
碱金属,包括锂、钠、钾、铷、与铯,可以在纯金属或者化合物或者复合物的组成下催化煤炭气化。通常,碱金属作为煤炭气化催化剂的相对活性随着原子量增加,那就是说,铯是最有效的以及锂是效力最低的。催化煤炭气化("CCG")方法的发展已经集中在钠与钾,因为它们展现出合理的活性同时与更重碱金属相比价格比较低廉并且更广泛易得。可以制备煤-催化剂混合物然后将其引入气化反应器,或者通过分别把碱金属催化剂与碳质颗粒引入反应器原地形成煤-催化剂混合物。
碱金属催化剂可以作为无机碱金属盐、有机碱金属盐、碱金属氢氧化物、碱金属氧化物、碱金属碳酸盐、碱金属重碳酸盐等等或者作为纯金属或者作为这样的化合物的混合物被引入CCG方法。碱金属催化剂可以包含多于一种碱金属,例如钾与钠,以及可以作为碱金属化合物的结合被引入,例如氢氧化钾、碳酸钾与氢氧化钠的混合物,该结合可能是易溶盐混合物。一种在文献中确认的用于CCG的优选的碱金属化合物是碳酸钾。
除了别的以外,煤典型的包含显著量的无机物,包括钙、铝、硅、铁、钒、与硫。这些化合物在气化反应器中形成无机氧化物或灰。众所周知at大约500或者600℃的温度以上,钾(或者其他的碱金属)可以与上述灰起反应形成不溶的碱性的铝硅酸盐。在这个组成下碱金属作为催化剂是没有活性的或者相对没有活性的。为了防止煤炭气化反应器中无机固体的增长,焦化(即上述灰、未转化的含碳物质以及碱性的粘结的固相组成)的固体清洗必须周期进行。这种焦化可以是20重量%或以上的例如钾金属,包括一些作为诸如K2CO3的可溶性的钾盐,与一些作为诸如KAlSiO4(合成的钾霞石或者高岭石)的不溶性的铝硅酸钾。
为了补偿在固体清除中催化剂的损失,传统的CCG方法需要相当大的催化剂补充流。通过从上述固体清除物回收碱金属可以最小化CCG方法的原料费与潜在的环境问题。
上述′650专利公开了固体清除物的水浸出以回收碱金属的可溶组分。来自气化器的固体被冷却到700°F,然后将其混合在该催化剂的浓水溶液中以溶解容易可溶的物质。利用上述富集水性催化剂溶液来制备气化器投料。将上述已经清洗过的固体转移到多阶段逆流液体固体提取系统中,在那使上述固体与越来越稀释的催化剂溶液在大约(230°F)110℃与30绝对压强下逐次的接触以回收较低可溶的碱性物质。上述′650专利公开了带有伴随的过滤器、泵与弥补流的混合容器的7-罐组。诸如KAlSiO4的不溶的金属碱性的化合物仍留在剩下的固体中,因此仅仅大约2/3的在固体清除中取出的碱金属可以被回收和再循环到上述气化方法。
众所周知通过在包含钙或者镁(它们在适当条件下从该铝硅酸盐中置换钾(或者其他的碱金属))的碱性溶液中"溶出"碱铝硅酸盐,可以从铝硅酸盐化合物回收不溶性碱性组分。
发行于1979年6月26日的美国专利第4,159,195号利用了这样的方法。按照上述′195专利,上述从初级产物气分离开的固体清除物和固体通过流化槽以在外面分离并将较轻颗粒再循环到气化器。剩余的较重颗粒流被冷却并送往水浸出单元,在那可溶的碱性组分溶解并形成稀释的碱溶液,其包含诸如碳酸盐与硫酸盐的各种碱金属化合物。上述′195专利陈述了水浸出单元代表性的包含多阶段逆流提取系统,建议了类似于′650公开的那样的复杂的方法。
上述′195专利预报了可溶的碱性组分能与上述溶出方法的碱性组分反应并形成不期望的副产品。为了避免这样的问题,上述′195专利把稀释的碱溶液直接送到气化器投料制备区域而没有进一步的处理。上述浸出的固体被从到石灰溶出单元,在那清洗的固体被与钙或者氢氧化镁的水泥浆在250-500°F(~120-260℃)之间有力的混合。按照上述′195专利,上述溶出池产物液一般包含碱金属氢氧化物与碱金属铝酸盐。为了避免可以增加灰负荷的铝酸盐再循环到上述气化器,上述′195专利公开了溶出池溶液可以与包含使氢氧化铝在剩余溶液再循环前沉淀的气体的二氧化碳接触。
带有溶出的多阶段水-洗方法是传统的。上述′195专利报告了通过石灰溶出以回收上述不溶性组分,更大量的钾回收(比仅仅用水-洗方法)是可能的。然而,在催化剂回收上的中型规模的工作(由美国能源部定约ET-78-C-01-2777保证并报道于利用了伴随有多阶段用水浸出的溶出的FE2777-31),显示石灰溶出的添加可能不是经济有利的。
石灰溶出也被提议用于别的煤技术中。例如,已经提议磁流体动力学(MHD)发电作为提高传统的火力发电厂的效率的技术。在磁流体电厂中,通过向燃烧气体添加容易电离的物质形成的等离子体在很高的温度和高速度下通过磁场并感生电流。按照Sheth等的美国专利第5,057,294号,其描述了用于在磁流体动力装置中回收和再循环消耗的种子的方法,碳酸钾是优选的种子材料。
按照上述′294专利,大多数钾种子在燃烧气体中与二氧化硫反应时转换成固体硫酸钾,通过在甲酸盐反应器中与石灰和一氧化碳反应上述种子可以随后恢复为甲酸钾。大约15%的钾种子与煤的铝和硅无机组分起反应并形成以MHD"矿渣"著称的不溶性的铝硅酸钾。通过压碎渣粒并在4∶1摩尔OH/K比和445°F到480°F(大约230-250℃)的温度下在水相中用石灰溶出它们,在该矿渣中的钾可以基本上回收。将上述所得非常碱性的氢氧化钾溶出池产物液与甲酸盐反应器产物结合以沉淀硫酸钙。带有甲酸钾与少量的氢氧化钾的剩余溶液可以被干燥并作为MHD"种子"再循环。
上述′294专利公开了通过在矿渣被溶出前把它把研磨到大约75筛目,最高大约80%的钾可以回收。可以以实质上分离流的形式收集矿渣与消耗的种子。上述′294专利没有涉及可溶性和不可溶性碱金属从单一固体流的回收。也没有建议上述颗粒可以被破碎而不是研磨到适当的大小用于溶出。
因此,煤方法中用于碱金属回收的已知方法是累赘的与昂贵的。非常期望发展能在更简化系统中回收碱性催化剂的CCG方法,并且如果这样的方法是灵活的和可靠的,将会更期望。
发明概要
本发明的方法被设计来克服现有技术的缺点。特别地,该提出的方法把来自气化的热的固体清除物冷却到催化剂回收温度,把取出的固体破碎成小颗粒以促进碱金属盐的完全的可浸出,以及全部在一个容器中从固体分离出可溶性碱金属部分。热的固体清除物的全部负荷都可以处理,因此分离与把较小颗粒返回到气化器的设备可能不是必需的。本发明利用了热的固体清除物的热能来在与水接触时破碎取出的颗粒而不需要过分的研磨设备。人们相信所得固体的较高的表面面积能使可溶性碱金属部分更容易的溶解,降低或消除了对多级水-洗单元的需要。固体沉积了并且以浓缩浆形式从包含溶解的碱金属组分的溶液内能容易的取出,因此避免了需要利用固液分离过滤器。
将会知道本发明提供了一种使碱金属催化剂回收并再循环到煤炭气化反应器的灵活的和简化的方法。本发明的催化剂回收方法有利的使用了取自气化器的在热焦化颗粒中的能量以把固体破碎成小颗粒。而且,本申请的体系需要较少的设备,因此它的建造价格比较低廉,维护与操作价格比较低廉,以及比传统的CCG体系更加可靠。
在本申请的一个实施方式中,本发明的煤气化方法具有气化反应器;产品分离带;以及碱金属催化剂回收系统。在气化反应器中,煤炭颗粒与蒸汽在碱金属盐的存在下被转化以制造气体与包含未反应的碳、煤炭的无机成分和碱金属化合物的焦化颗粒。焦化颗粒的固体清洗以足够的数量退出气化反应器以在气化反应器内部维持固体无机化合物的稳态负荷。在催化剂回收体系中,固体清除物的催化剂组分被回收用来再循环到该气化反应器。
上述催化剂回收体系具有用来接收热的焦化颗粒的固体清除流的破碎罐,以破碎焦化颗粒,并冷却固体清除流。焦化的可溶性碱金属组分溶解并分离成溶液。选择性地,石灰溶出单元可以用来分离取自上述破碎罐的固体并回收另外的不溶性催化剂组分。来自溶出单元的产物浆(其可以包括碱金属氢氧化物化合物、氢氧化钙、与铝硅酸钙)可以与来自破碎罐的可以包含包括氢氧化物、碳酸盐、重碳酸盐、硫化物与硫酸盐的各种碱金属化合物的溶液结合到一起。
在其他的实施方式中,钙(其可以是以例如氧化钙或者氢氧化钙的形式)被投料到气化反应器并且它被认为粘结或者缚牢煤炭的矾土与硅石组分,这样的以致于固体清除物包含几乎没有碱金属铝硅酸盐或者硅酸盐。在此情况下石灰溶出单元可以较小或者彻底省略。
来自破碎罐的溶液,与来自溶出单元的产物浆一起,如果存在的话,可以被过滤并浓缩,然后与二氧化碳富集气起反应以把碱金属化合物转换成碱金属碳酸盐。在一些实施方式中上述混合物在过滤前或者在过滤的同时被碳酸化。在此情况下,来自溶出单元的氢氧化钙可以变为固体碳酸钙并通过过滤除去。
在一些实施方式中所得碱金属碳酸盐溶液可以作为液体被存储和/或再循环。二者择一地,碱金属碳酸盐溶液可以被干燥并且干燥的碱金属碳酸盐可以作为固体被存储和/或再循环。
发明目的
因此,本发明的一个目的是改进碱金属催化剂从催化的煤炭气化反应器的固体清除物的回收以及改进综合技术经济指标。
另一个目的是从CCG反应器的固体清除物中有效地分离碱金属催化剂以改善CCG方法的总效率与经济性。
本发明的另一个目的是提供碱金属催化剂回收方法,其中碱金属组分可以在单级方法中从CCG反应器的固体清除物中分离出来。
另一个目的是利用固体清除物的热来把焦化颗粒破碎成较小颗粒并由此促进来自CCG反应器固体清除物的碱金属催化剂的有效增溶作用。
另一个目的是以方便的形式在CCG方法中回收碱金属催化剂。
根据下面的发明说明书,本发明的这些以及其他目的将会变得显而易见的。
附图的简要说明
图1是图解了本发明优选实施方式的特征的示意图。
各个实施方式的详细说明
这里所用的"碱金属催化剂"指的是被引入方法以促进气化反应并且可以被回收和再循环的碱金属化合物。该术语并不意味着建议或者限于激活碳表面或者事实上催化气化反应的具体的一部分或者部分们。
在下述的方法流程图中,本申请提供了用来把煤炭转换成诸如合成气或者甲烷的燃气的综合方法。该方法回收和再循环碱金属催化剂并且与热气化相比保持了它的全面的吸引力。更适宜的,该方法包括用于投料制备、气化与产物纯化的区域,以及碱金属催化剂回收系统。
投料制备区域可以包含用来混合煤炭颗粒(更适宜通过为显示的设备研磨到大约125目)与碱金属化合物的水溶液以形成投料浆的混合罐。该投料制备区域也可以包括干燥塔,在那里通过过热蒸汽除掉水以形成附加的蒸汽和由掺杂了碱金属催化剂的煤炭组成的干燥固体流。该投料制备区域可以进一步包括螺旋搅拌器,在那里煤炭颗粒被水性碱金属盐溶液浸透。二者择一地煤炭颗粒可以是与碱金属化合物干混的。该投料制备区域可以包括用来加热浸渍的或干燥的掺合煤炭颗粒的设备以增加碳和碱金属催化剂接触的表面面积和/或改进煤炭颗粒的气孔内部的碱金属催化剂的集成。混合煤炭颗粒与碱金属催化剂的其他的方法是已知的,例如,碱金属化合物与煤炭颗粒可以作为单独的物流直接投料到气化器,没有首先在投料制备区域混合它们。本发明包括所有已知的煤炭气化进料制备技术。无论混合的还是作为单独的物流,制备的煤炭颗粒与碱金属催化剂被投料给气化反应器。
在气化区域中,在反应器("气化器")中煤炭与蒸汽在碱金属催化剂的存在下起反应,形成可能包含合成气、甲烷或者其他的碳质物流以及未反应的蒸汽的初级产物流。在优选实施方式中,气化器在大约500℃与700℃之间运行。碱金属催化剂到煤炭的最适负荷取决于煤炭的种类、煤炭性质、以及特定的气化条件,但是代表性地大约5到20wt%。在确定的实施方式中,氢与一氧化碳流也供应给上述气化器。在一些实施方式中,氧化钙或者其他的钙化合物流可以供应给上述气化器。
煤炭典型的包含预计不会气化的无机矿物组分(有时被称为灰分)。这样的无机矿物组分可能包括,例如,矾土与硅石。钙化合物,如果以充分的量存在于反应器中,可以与CO2粘结并形成CaCO3颗粒和/或与煤炭的无机矿物组分粘结并形成例如铝硅酸钙和/或硅酸钙。
在运行期间,由未反应的碳、煤炭的灰组分以及碱金属盐组成的焦化颗粒在反应器中形成。包含焦化(与钙固体,如果存在)的固体清除物被周期地从气化器取出以防止这样的固体在气化器中积累。如下所述固体清除物涉及从固体清除中回收碱金属组分的催化剂回收体系。
当其退出反应器时初级产品气流可以携带细的夹带的焦化颗粒。上述焦化被从初级产品气流中分离并送回到上述气化反应器中。初级产品流被进一步处理以离析诸如合成气或者甲烷的产物。从初级产品流中用于除去未反应的蒸汽和/或诸如硫化氢与二氧化碳的酸性气体(如果存在的话)以及用于分离任何氢与一氧化碳(如果存在的话)的设备与方法可以是传统的。
催化剂回收体系包括接收周期地或者连续地从气化器取出的热的焦化的破碎罐。在一个优选实施方式中,该破碎罐直接地低于气化反应器这样简单地通过打开固体排出流阀焦化就可以从气化器底部落入破碎罐中。选择性地,上述气化器与破碎罐是单一容器的两个隔室。
破碎罐可以包含热的固体清除物焦化被落入其中的水池。破碎罐可以可选的设置有直接对着焦化颗粒的水喷射器。在与相对较冷的水池或者水喷射器接触时,上述颗粒可以从气化器温度被迅速地冷却并且人们相信由于高的温差的高的热应力导致大块焦化破碎成小颗粒。破碎的颗粒有较高的表面和容积之比,这在碱金属催化剂回收方法中可以赋予包含固体清除物的碱金属更好的增溶作用。在破碎罐中适当的条件可以使得可溶性碱金属组分在没有过分需要研磨上述焦化的情况下能够基本上完全的溶解。来自破碎罐的蒸汽可以用于如下所述的石灰溶出单元内部或者气化器中。根据需要水补充流可以供应给破碎罐。破碎罐可以设计的最小化固体与水的接触时间,例如通过在集水池中集中分别地来自固体的来自水喷射器的水,或者通过使得任何水立即从积累在上述罐底部的固体流尽。
通过控制固体与水比率以及通过控制固体与破碎罐中水的接触时间,焦化颗粒可以从气化温度冷却到低到大约50℃或者到高达大约300℃。通过使热的焦化与池水接触并将其冷却到大约50℃到95℃的温度,可以获得最大的固体表面面积,这是可以预期的。二者择一地,通过用水喷射器冷却焦化,这样固体仅仅冷却到大约120℃到300℃,可以获得伴随着溶出单元(如果存在的话)的更好的热联合。在较高的温度下,在随后的石灰溶出单元中将会需要少量的加热。本方法提供了灵活性因此破碎罐操作可以为了煤炭性质和CCG反应器中的条件被优化。
本发明的破碎罐可以把水洗与冷却集成。它可以这样配置以致于固体清除物中焦化的相当大的数量的可溶性碱金属组分在破碎罐中溶解进溶液。可溶性碱金属组分可以在那形成能分别从沉淀到或者集中到破碎罐底部的清洗的固体中取出的水溶液。按照本申请,来自破碎罐的水溶液可以包括固体清除物的大部分可溶性碱金属组分,以及清洗的固体可以包括大部分不溶性碱金属组分。
破碎罐也可以这样的设计以致于在不过分的需要分离过滤步骤的情况下清洗的固体和溶液可以分别地取出。破碎罐可以包含热的固体掉到其中的水池,在这种情况下固体将会沉淀到破碎罐的底部并能从那提取出来。破碎罐的底部可以有倾斜底以把固体推到一起并从沉积的清洗的固体中挤出额外的液体。在其他的实施方式中,热的固体可以下落经过一系列水喷射器,并且破碎罐可以这样的设计以致于清洗的固体作为基本上热的煤渣集中在上述罐的底部以及来自喷射器的水(在经过并冷却落下的焦化颗粒之后)可以分别地集中或者立即从集中的、清洗的固体中排出。
本申请的催化剂回收体系可以进一步包括石灰溶出单元来提供额外的催化剂回收。来自破碎罐的清洗的固体被送到石灰溶出容器中。诸如水性浆形式的钙或者镁化合物(如同,例如,氢氧化钙)的碱土溶出剂按照需要被添加以获得最适宜的5到25的碱性OH与碱金属比率。在一些实施方式中,在焦化中可能有充分的钙这样几乎不需要额外的石灰。通过蒸汽的直接注入可以把热供应给溶出池。在大约50℃到大约300℃的温度下和大约10到大约500psig的压力下将溶出池容纳物强力地混合2到4小时。在溶出方法期间,溶出剂与固体起反应,形成水性碱金属盐溶液(例如氢氧化钾)与不溶性铝硅酸盐化合物(例如铝硅酸钙)。通过适当地同时发生装载、混合与卸载操作,溶出可以在一个步骤中进行。
破碎罐溶液,其包含以氢氧化物、碳酸盐、重碳酸盐、硫化物、硫酸盐等等形式的大部分可溶性碱金属组分,可以绕过上述溶出器单元并直接送到如下面更完全地描述的升级方法中。该方法因此有助于避免或者最小化由于将可溶性组分引入到溶出单元而引起的潜在问题或者复杂情况。
破碎罐溶液与溶出器产物浆(如果存在的话)可以被结合起来作为回收催化剂溶液并且通过滤出固体,然后在多效蒸发器或者相似设备中浓缩该溶液来提高品位。如有必要利用助滤剂,过滤器适宜的能除去下至几微米的固体。为了把碱金属盐转化成碳酸盐形式,使溶液接触富含CO2的气体。碳酸化步骤也会将诸如氢氧化钙的任何可溶性碱土化合物转化成不溶性碳酸盐形式。如果蒸发器内部的盐沉积是关切的问题,那么上述碳酸化优于或者发生在过滤器过滤步骤(如在加压的过滤装置中)。在另一个替换方式中,上述碳酸化可以发生在溶液被过滤和浓缩之后。
如所指示的,通过破碎热的焦化颗粒,上述碱性催化剂可以更容易地和完全地溶解。如此,基本上所有可溶性碱性催化剂可以溶于上述破碎罐溶液中,这是一级水洗。同样地,几乎所有碱铝硅酸盐或者碱金属硅酸盐组分(上述不能解决的碱金属组分)的碱金属有价值部分可以溶于上述溶出器产物浆。根据本申请的一个方面,在没有采用多级洗涤或者沥滤法的情况下,相当大的量的可溶性的与不溶性的碱金属组分可以被回收、提高品位并且再循环。
对再循环液流的净化有助于避免不期望的诸如氯化物、磷酸盐、硅酸盐等等的积累。碱金属催化剂补充流可以用来置换伴随着过滤的固体或者在再循环清除中的取出的催化剂损失。
如果对气化方法的碳质投料用碱金属化合物浸渍,那么很少有必要进一步的结晶以把碱金属回收为固体催化剂。浓缩的碱金属催化剂溶液可以被储备和如需要再循环到气化器投料。在该替换方式中,可以将碱金属催化剂溶液直接送到结晶器/干燥器以把碱金属催化剂回收为干燥化合物,可以将其储备起来和如需要再循环到气化器投料。
关于图1,大略展示了本申请的催化煤气化法中用于投料制备、气化与产物分离的分区。碱金属催化剂回收系统包括破碎罐30、溶出器单元40、过滤器50与多效蒸发器55、用来使溶液与富含二氧化碳的气体接触的碳酸化容器60、结晶器/干燥剂干燥器70和回收的碱金属催化剂储存容器80。
在气化器20中,处理大约每天100吨的包含大约10%灰分和所用的20wt%的催化剂负载的煤,固体清除物总量可以为大约每天35吨。用于从上述气化器20到破碎罐30传输固体清除物的导管25可以只须包含分离阀,其(打开时)容许热的固体焦化颗粒从气化器20的底部掉落入破碎罐中,该破碎罐本身直接位于气化器上述气化器下面并且可以包含水箱或者对着落下来的固体的水喷射器。用于在容器之间传输固体的其他的方法对于本领域技术人员来说是周知的。本申请不局限于所述的分离阀并且意图是包括这样的别的固体转换装置。
来自破碎罐的蒸汽可以通过线路31被引出并且有用地使用来把热传递给溶出单元40。水可以通过线路32添加。
在一个优选实施方式中溶出单元40包括三个溶出器容器,它们以平行,但是交错次序的操作,这样以致于,例如,一个容器41在积极地溶出一批固体,而另一个容器42正在卸载,以及第三容器43正在从破碎罐30的底部连续地接收洗涤的固体取出物。溶出方法次序这样的安排时间以致于当第一容器接收洗涤的固体充满时,第二容器是空的并且当第一容器开始溶出反应时可以开始接收洗涤的固体。上述次序这样的延续以致于当第二容器充满洗涤的固体时,第三容器是空的并且可以开始接收洗涤的固体,以及当该第三容器充满时,第一容器是空的并且可以开始被填料,等等。
回到图1的流程图,沉淀到或者聚集在破碎罐30的底部的洗涤的固体通过线路35被取出送到处于溶出次序的充料部分的容器43。如需要石灰通过线路45添加到充料容器43。最佳地,在溶出期间氢氧化物与碱金属的摩尔比率在大约5到25。根据需要蒸汽通过线路31和线路46添加到混合容器41。最佳地,溶出反应在大约50到300℃的温度下进行。
溶出反应方法的产物是包含水性碱金属盐溶液(例如氢氧化钾)、不溶性硅酸盐或者铝硅酸盐化合物(例如铝硅酸钙)、与未反应的石灰的浆液。这个浆液通过线路48离开卸载的容器42并与通过线路36从破碎罐30取出的破碎罐溶液结合。在线路49中的回收的碱金属催化剂溶液的结合液流被送到过滤装置50。
过滤装置包含用来利用或者不利用助滤剂除去大多数固体的过滤床。固体通过线路51取出并可以送去进一步处理,或者处理掉。过滤的碱金属催化剂溶液通过线路53送到浓缩上述催化剂溶液的多效蒸发器55或者类似设备。最佳地,蒸发器55降低上述溶液的含水量到大约40-50%强度。
然后浓缩的溶液通过线路58被送到根据需要配备有多个塔板或者挡板或者密封材料的碳酸化器60以确保良好的气体-液体接触。上述溶液通过线路58被投料到碳酸化器60的顶部,当富含CO2的气体(通过线路61投料到碳酸化器60的底部)鼓泡通过或者相反广泛地接触上述落下来的液体时,上述溶液从一个塔板流到另一个塔板。CO2贫化的气体通过线路63被从碳酸化器取出。上述碳酸化的溶液通过线路65流到结晶器/干燥器70,在那上述溶液被干燥。如小片的固体或者沉淀颗粒通过线路75被传输到存储容器80。清除物可以从线路72取出。
回收的固体经由线路85传输到投料制备区。如需要,补充的碱金属化合物通过线路87添加。
如从上所述可以知道的,这里公开的发明提供了用于从净化自煤炭气化反应器的固体回收碱金属催化剂,以及用于把该碱金属催化剂再循环到上述煤炭气化反应器的有效率的方法。
有利地,通过利用取自上述气化器的热的焦化的热量把上述固体破碎成小颗粒,在没有复杂的多级水洗或者溶出器单元与没有过分的研磨上述焦化,或者根本没有研磨的情况下,本发明能使上述焦化颗粒的可溶性和不溶性碱金属催化剂组分回收。
与传统的CCG体系相比,本申请的催化的煤炭气化体系包括较少数步骤和较少设备,以及可以更经济的建造和操作以及更可靠。
虽然这里已经结合具体的流程图和操作条件图解了本发明的具体的实施方式,然而在没有脱离本发明精神和范围的情况下,可以对本发明进行各种修改与替换或者将其结合和具体化作为本发明的部分,这是显而易见的。除了下面的权利要求书指出的那些,不应该设置任何限制。
Claims (15)
1.用于碳质固体气化的方法,所述方法包括:
在碱金属催化剂存在下使碳质固体颗粒与蒸汽在反应器中接触,在那形成了粗产物气体并且制备了焦化颗粒,所述焦化颗粒包含碳、无机组分,以及碱金属催化剂组分;
从所述反应器取出所述粗产物气体流;
从所述粗产物气体流回收产物气体流;
在破碎单元中用水接触来自所述反应器的焦化颗粒流,以使焦化颗粒冷却至50℃到300℃的温度,借此所述焦化颗粒破碎以及一部分所述碱金属催化剂组分溶解进所述水形成破碎单元溶液和洗涤的固体;和
从所述破碎单元取出所述洗涤的固体流以及所述破碎单元溶液流。
2.权利要求1的方法,进一步包括:
使所述洗涤的固体流与碱土金属化合物溶液在50℃到300℃的温度下反应以形成用过的固体的浆液,将所述用过的固体的浆液与所述破碎单元溶液流结合起来以形成催化剂回收流;
过滤和碳酸化所述催化剂回收流以回收碱金属碳酸盐化合物流;以及
再循环所述碱金属碳酸盐化合物用于与所述碳质固体颗粒接触。
3.权利要求2的方法,其中在再循环从所述用过的固体的浆液回收的所述碱金属碳酸盐化合物之前所述用过的固体的浆液没有经受多级水洗。
4.权利要求1的方法,进一步包括:
过滤和碳酸化所述破碎单元溶液流以回收碱金属碳酸盐化合物流;以及
再循环所述碱金属碳酸盐化合物用于与所述碳质固体颗粒接触。
5.权利要求2或4的方法,其中所述碱金属碳酸盐化合物包含碳酸钾或碳酸钠。
6.权利要求2的方法,其中所述碱土金属化合物溶液包含氢氧化钙,以及
在所述洗涤的固体中氢氧化钙与碱金属的摩尔比为5到25。
7.权利要求2或4的方法,其中所述碳酸化跟随着所述过滤。
8.权利要求2或4的方法,其中所述碳酸化通过使所述催化剂回收流暴露至包含二氧化碳的物流来实施。
9.权利要求1的方法,其中所述产物流包含甲烷或合成气。
10.权利要求1的方法,其中所述在破碎单元中来自所述反应器的焦化颗粒流与水的接触包括:
(a)水喷射器碰撞所述焦化颗粒流,或
(b)所述焦化颗粒流落入水池中。
11.权利要求2或4的方法,其中所述碱金属碳酸盐以水溶液形式再循环。
12.权利要求2或4的方法,进一步包括干燥所述碱金属碳酸盐化合物流以及以固体形式再循环所述碱金属碳酸盐化合物。
13.权利要求1的方法,其中所述水洗涤的固体流在以下温度下被取出:
(a)50℃到95℃,或者
(b)125℃到300℃。
14.权利要求1的方法,其中所述碳质固体是煤。
15.权利要求14的方法,其中所述煤包含矾土和硅石。
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US11/421,511 US7922782B2 (en) | 2006-06-01 | 2006-06-01 | Catalytic steam gasification process with recovery and recycle of alkali metal compounds |
PCT/US2007/069265 WO2007143376A1 (en) | 2006-06-01 | 2007-05-18 | Catalytic steam gasification process with recovery and recycle of alkali metal compounds |
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Families Citing this family (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8114176B2 (en) | 2005-10-12 | 2012-02-14 | Great Point Energy, Inc. | Catalytic steam gasification of petroleum coke to methane |
US7922782B2 (en) | 2006-06-01 | 2011-04-12 | Greatpoint Energy, Inc. | Catalytic steam gasification process with recovery and recycle of alkali metal compounds |
US8163048B2 (en) | 2007-08-02 | 2012-04-24 | Greatpoint Energy, Inc. | Catalyst-loaded coal compositions, methods of making and use |
WO2009048724A2 (en) * | 2007-10-09 | 2009-04-16 | Greatpoint Energy, Inc. | Compositions for catalytic gasification of a petroleum coke and process for their conversion to methane |
CN101910371B (zh) | 2007-12-28 | 2014-04-02 | 格雷特波因特能源公司 | 用于制备合成气衍生产物的方法 |
AU2008345189B2 (en) * | 2007-12-28 | 2011-09-22 | Greatpoint Energy, Inc. | Petroleum coke compositions for catalytic gasification |
WO2009086408A1 (en) * | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Continuous process for converting carbonaceous feedstock into gaseous products |
US20090165380A1 (en) * | 2007-12-28 | 2009-07-02 | Greatpoint Energy, Inc. | Petroleum Coke Compositions for Catalytic Gasification |
US20090165376A1 (en) | 2007-12-28 | 2009-07-02 | Greatpoint Energy, Inc. | Steam Generating Slurry Gasifier for the Catalytic Gasification of a Carbonaceous Feedstock |
WO2009086383A2 (en) * | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Catalytic gasification process with recovery of alkali metal from char |
WO2009086374A2 (en) * | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Catalytic gasification process with recovery of alkali metal from char |
WO2009086361A2 (en) * | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Catalytic gasification process with recovery of alkali metal from char |
CN101910373B (zh) * | 2007-12-28 | 2013-07-24 | 格雷特波因特能源公司 | 从焦炭中回收碱金属的催化气化方法 |
US8709113B2 (en) | 2008-02-29 | 2014-04-29 | Greatpoint Energy, Inc. | Steam generation processes utilizing biomass feedstocks |
WO2009111342A2 (en) | 2008-02-29 | 2009-09-11 | Greatpoint Energy, Inc | Carbonaceous fines recycle |
US8297542B2 (en) | 2008-02-29 | 2012-10-30 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification |
US8652222B2 (en) | 2008-02-29 | 2014-02-18 | Greatpoint Energy, Inc. | Biomass compositions for catalytic gasification |
US8366795B2 (en) | 2008-02-29 | 2013-02-05 | Greatpoint Energy, Inc. | Catalytic gasification particulate compositions |
WO2009111335A2 (en) * | 2008-02-29 | 2009-09-11 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification |
US8114177B2 (en) | 2008-02-29 | 2012-02-14 | Greatpoint Energy, Inc. | Co-feed of biomass as source of makeup catalysts for catalytic coal gasification |
US8286901B2 (en) | 2008-02-29 | 2012-10-16 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification |
US20090260287A1 (en) * | 2008-02-29 | 2009-10-22 | Greatpoint Energy, Inc. | Process and Apparatus for the Separation of Methane from a Gas Stream |
US7926750B2 (en) | 2008-02-29 | 2011-04-19 | Greatpoint Energy, Inc. | Compactor feeder |
US8361428B2 (en) | 2008-02-29 | 2013-01-29 | Greatpoint Energy, Inc. | Reduced carbon footprint steam generation processes |
CN101981163B (zh) | 2008-04-01 | 2014-04-16 | 格雷特波因特能源公司 | 从气体物流中分离甲烷的方法 |
WO2009124019A2 (en) | 2008-04-01 | 2009-10-08 | Greatpoint Energy, Inc. | Sour shift process for the removal of carbon monoxide from a gas stream |
CN102076829B (zh) * | 2008-06-27 | 2013-08-28 | 格雷特波因特能源公司 | 用于合成气制备的四列催化气化系统 |
WO2009158579A2 (en) * | 2008-06-27 | 2009-12-30 | Greatpoint Energy, Inc. | Three-train catalytic gasification systems |
US20090324460A1 (en) * | 2008-06-27 | 2009-12-31 | Greatpoint Energy, Inc. | Four-Train Catalytic Gasification Systems |
WO2009158583A2 (en) * | 2008-06-27 | 2009-12-30 | Greatpoint Energy, Inc. | Four-train catalytic gasification systems |
US20100120926A1 (en) * | 2008-09-19 | 2010-05-13 | Greatpoint Energy, Inc. | Processes for Gasification of a Carbonaceous Feedstock |
JP5384649B2 (ja) * | 2008-09-19 | 2014-01-08 | グレイトポイント・エナジー・インコーポレイテッド | 炭素質フィードストックのガス化のための方法 |
KR101330894B1 (ko) | 2008-09-19 | 2013-11-18 | 그레이트포인트 에너지, 인크. | 차르 메탄화 촉매를 사용한 기체화 방법 |
WO2010033850A2 (en) | 2008-09-19 | 2010-03-25 | Greatpoint Energy, Inc. | Processes for gasification of a carbonaceous feedstock |
KR101275429B1 (ko) | 2008-10-23 | 2013-06-18 | 그레이트포인트 에너지, 인크. | 탄소질 공급원료의 기체화 방법 |
EP2370549A1 (en) | 2008-12-30 | 2011-10-05 | Greatpoint Energy, Inc. | Processes for preparing a catalyzed coal particulate |
KR101290453B1 (ko) | 2008-12-30 | 2013-07-29 | 그레이트포인트 에너지, 인크. | 촉매된 탄소질 미립자의 제조 방법 |
AU2010213320B2 (en) | 2009-02-11 | 2015-07-09 | Tiger Ecoremediation And Energy Inc. | Process for the conversion of organic material to methane rich fuel gas |
AU2010249091B2 (en) | 2009-05-13 | 2013-05-23 | Greatpoint Energy, Inc. | Processes for hydromethanation of a carbonaceous feedstock |
US8268899B2 (en) | 2009-05-13 | 2012-09-18 | Greatpoint Energy, Inc. | Processes for hydromethanation of a carbonaceous feedstock |
WO2010132551A2 (en) | 2009-05-13 | 2010-11-18 | Greatpoint Energy, Inc. | Processes for hydromethanation of a carbonaceous feedstock |
US20110031439A1 (en) | 2009-08-06 | 2011-02-10 | Greatpoint Energy, Inc. | Processes for hydromethanation of a carbonaceous feedstock |
CN102021036B (zh) * | 2009-09-14 | 2013-08-21 | 新奥科技发展有限公司 | 煤的气化过程中催化剂的循环方法 |
WO2011034891A1 (en) | 2009-09-16 | 2011-03-24 | Greatpoint Energy, Inc. | Two-mode process for hydrogen production |
CA2771578A1 (en) | 2009-09-16 | 2011-03-24 | Greatpoint Energy, Inc. | Processes for hydromethanation of a carbonaceous feedstock |
CN102549121B (zh) * | 2009-09-16 | 2015-03-25 | 格雷特波因特能源公司 | 整体加氢甲烷化联合循环方法 |
US20110062722A1 (en) * | 2009-09-16 | 2011-03-17 | Greatpoint Energy, Inc. | Integrated hydromethanation combined cycle process |
WO2011049858A2 (en) | 2009-10-19 | 2011-04-28 | Greatpoint Energy, Inc. | Integrated enhanced oil recovery process |
WO2011049861A2 (en) | 2009-10-19 | 2011-04-28 | Greatpoint Energy, Inc. | Integrated enhanced oil recovery process |
FR2951383B1 (fr) | 2009-10-20 | 2012-09-21 | Solvay | Procede pour la valorisation conjointe de sels solubles contenus dans un residu d'un procede industriel |
WO2011084581A1 (en) | 2009-12-17 | 2011-07-14 | Greatpoint Energy, Inc. | Integrated enhanced oil recovery process injecting nitrogen |
US8733459B2 (en) | 2009-12-17 | 2014-05-27 | Greatpoint Energy, Inc. | Integrated enhanced oil recovery process |
US20110197510A1 (en) * | 2010-02-16 | 2011-08-18 | Boris Nickolaevich Eiteneer | Method and apparatus to reactivate carbon solids |
WO2011106285A1 (en) | 2010-02-23 | 2011-09-01 | Greatpoint Energy, Inc. | Integrated hydromethanation fuel cell power generation |
US8652696B2 (en) | 2010-03-08 | 2014-02-18 | Greatpoint Energy, Inc. | Integrated hydromethanation fuel cell power generation |
KR101440710B1 (ko) | 2010-04-26 | 2014-09-17 | 그레이트포인트 에너지, 인크. | 바나듐 회수를 동반한 탄소질 공급원료의 히드로메탄화 |
JP5559428B2 (ja) | 2010-05-28 | 2014-07-23 | グレイトポイント・エナジー・インコーポレイテッド | 液体重質炭化水素フィードストックのガス状生成物への変換 |
DE102010026172B4 (de) * | 2010-07-06 | 2018-04-26 | Siemens Aktiengesellschaft | Verfahren zur Verhinderung von Ablagerungen aus karbonatreichen Wässern bei der Flugstromvergasung |
CA2806673A1 (en) | 2010-08-18 | 2012-02-23 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock |
JP2013537248A (ja) | 2010-09-10 | 2013-09-30 | グレイトポイント・エナジー・インコーポレイテッド | 炭素質フィードストックの水添メタン化 |
AU2011323648A1 (en) * | 2010-11-01 | 2013-05-02 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock |
CA2815243A1 (en) | 2010-11-01 | 2012-05-10 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock |
CN102476008B (zh) * | 2010-11-30 | 2015-05-20 | 新奥科技发展有限公司 | 回收并循环使用碱金属催化剂的方法 |
CN103391989B (zh) | 2011-02-23 | 2015-03-25 | 格雷特波因特能源公司 | 伴有镍回收的碳质原料加氢甲烷化 |
CN103492537A (zh) | 2011-04-22 | 2014-01-01 | 格雷特波因特能源公司 | 伴随焦炭选矿的碳质原料加氢甲烷化 |
WO2012166879A1 (en) | 2011-06-03 | 2012-12-06 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock |
US20130046124A1 (en) | 2011-08-17 | 2013-02-21 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock |
US20130042824A1 (en) | 2011-08-17 | 2013-02-21 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock |
CN103974897A (zh) | 2011-10-06 | 2014-08-06 | 格雷特波因特能源公司 | 碳质原料的加氢甲烷化 |
JP5974730B2 (ja) * | 2012-08-20 | 2016-08-23 | 株式会社Ihi | ガス化ガス生成システム、および、ガス化ガス生成方法 |
WO2014055349A1 (en) | 2012-10-01 | 2014-04-10 | Greatpoint Energy, Inc. | Agglomerated particulate low-rank coal feedstock and uses thereof |
US9328920B2 (en) | 2012-10-01 | 2016-05-03 | Greatpoint Energy, Inc. | Use of contaminated low-rank coal for combustion |
US9034058B2 (en) | 2012-10-01 | 2015-05-19 | Greatpoint Energy, Inc. | Agglomerated particulate low-rank coal feedstock and uses thereof |
WO2014055351A1 (en) | 2012-10-01 | 2014-04-10 | Greatpoint Energy, Inc. | Agglomerated particulate low-rank coal feedstock and uses thereof |
KR101890951B1 (ko) * | 2012-12-20 | 2018-08-22 | 에스케이이노베이션 주식회사 | 합성 가스 및 고품위 석탄의 동시 생산을 위한 건조 및 가스화 통합 공정 |
CN103351014B (zh) * | 2013-06-28 | 2015-05-27 | 新奥科技发展有限公司 | 一种从煤灰中提取和制备氧化铝的方法 |
CN104043485B (zh) * | 2014-06-09 | 2016-03-23 | 新奥科技发展有限公司 | 一种催化剂回收及负载方法 |
US11268038B2 (en) | 2014-09-05 | 2022-03-08 | Raven Sr, Inc. | Process for duplex rotary reformer |
KR20170116059A (ko) | 2015-02-10 | 2017-10-18 | 시리스 에너지 인코포레이티드 | 해 중합 방법 |
CA3015050C (en) | 2016-02-18 | 2024-01-02 | 8 Rivers Capital, Llc | System and method for power production including methanation |
CN108728174B (zh) * | 2017-04-21 | 2020-09-11 | 中国石油化工股份有限公司 | 一种用于煤催化气化反应的催化剂回收方法 |
CN107586562A (zh) * | 2017-10-16 | 2018-01-16 | 新奥科技发展有限公司 | 一种煤催化气化合成气循环返炉的方法 |
CN108410722B (zh) * | 2018-03-06 | 2021-04-06 | 张英华 | 沼气发生装置与煤炭秸秆气化装置及控制方法 |
CN108479742B (zh) * | 2018-03-19 | 2021-02-23 | 新奥科技发展有限公司 | 一种煤催化气化灰渣中催化剂的回收方法以及采用该回收方法回收获得的催化剂及其应用 |
US10464872B1 (en) | 2018-07-31 | 2019-11-05 | Greatpoint Energy, Inc. | Catalytic gasification to produce methanol |
CN109107595A (zh) * | 2018-09-12 | 2019-01-01 | 中国科学院山西煤炭化学研究所 | 一种二氧化碳-水-醇体系回收碱金属催化剂的方法 |
CN109111958A (zh) * | 2018-09-12 | 2019-01-01 | 中国科学院山西煤炭化学研究所 | 一种催化气化耦合气化灰提取氧化铝的方法 |
US10344231B1 (en) | 2018-10-26 | 2019-07-09 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock with improved carbon utilization |
US10435637B1 (en) | 2018-12-18 | 2019-10-08 | Greatpoint Energy, Inc. | Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation |
US10618818B1 (en) | 2019-03-22 | 2020-04-14 | Sure Champion Investment Limited | Catalytic gasification to produce ammonia and urea |
CN114437833B (zh) * | 2020-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | 一种生物质制氢方法和系统 |
Family Cites Families (243)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB593910A (en) | 1945-01-15 | 1947-10-29 | Standard Oil Dev Co | Improved process for the catalytic synthesis of hydrocarbons from carbon monoxide and hydrogen |
FR797089A (fr) | 1935-10-30 | 1936-04-20 | Procédé de fabrication de combustibles solides spéciaux pour gazogènes produisant les gaz pour les moteurs de véhicules | |
GB676615A (en) | 1946-08-10 | 1952-07-30 | Standard Oil Dev Co | Improvements in or relating to processes involving the contacting of finely divided solids and gases |
GB640907A (en) | 1946-09-10 | 1950-08-02 | Standard Oil Dev Co | An improved method of producing normally gaseous fuels from carbon-containing materials |
GB701131A (en) | 1951-03-22 | 1953-12-16 | Standard Oil Dev Co | Improvements in or relating to gas adsorbent by activation of acid sludge coke |
GB798741A (en) | 1953-03-09 | 1958-07-23 | Gas Council | Process for the production of combustible gas enriched with methane |
BE529007A (zh) | 1953-05-21 | |||
US2813126A (en) | 1953-12-21 | 1957-11-12 | Pure Oil Co | Process for selective removal of h2s by absorption in methanol |
US2886405A (en) * | 1956-02-24 | 1959-05-12 | Benson Homer Edwin | Method for separating co2 and h2s from gas mixtures |
US3114930A (en) | 1961-03-17 | 1963-12-24 | American Cyanamid Co | Apparatus for densifying and granulating powdered materials |
GB996327A (en) | 1962-04-18 | 1965-06-23 | Metallgesellschaft Ag | A method of raising the calorific value of gasification gases |
GB1033764A (en) | 1963-09-23 | 1966-06-22 | Gas Council | Improvements in or relating to the production of methane gases |
DE1494806C3 (de) | 1966-10-14 | 1975-07-10 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Schwefelwasserstoff- und Kohlendioxyd-Wäsche von Brenn- und Synthesegasen und Regenerierung des beladenen Waschmittels |
US3435590A (en) * | 1967-09-01 | 1969-04-01 | Chevron Res | Co2 and h2s removal |
US3615300A (en) | 1969-06-04 | 1971-10-26 | Chevron Res | Hydrogen production by reaction of carbon with steam and oxygen |
US3594985A (en) * | 1969-06-11 | 1971-07-27 | Allied Chem | Acid gas removal from gas mixtures |
US3759036A (en) | 1970-03-01 | 1973-09-18 | Chevron Res | Power generation |
US3689240A (en) | 1971-03-18 | 1972-09-05 | Exxon Research Engineering Co | Production of methane rich gases |
US3740193A (en) * | 1971-03-18 | 1973-06-19 | Exxon Research Engineering Co | Hydrogen production by catalytic steam gasification of carbonaceous materials |
US3915670A (en) | 1971-09-09 | 1975-10-28 | British Gas Corp | Production of gases |
US3746522A (en) | 1971-09-22 | 1973-07-17 | Interior | Gasification of carbonaceous solids |
US3969089A (en) * | 1971-11-12 | 1976-07-13 | Exxon Research And Engineering Company | Manufacture of combustible gases |
US3779725A (en) | 1971-12-06 | 1973-12-18 | Air Prod & Chem | Coal gassification |
US3985519A (en) | 1972-03-28 | 1976-10-12 | Exxon Research And Engineering Company | Hydrogasification process |
US3929431A (en) | 1972-09-08 | 1975-12-30 | Exxon Research Engineering Co | Catalytic reforming process |
US4094650A (en) * | 1972-09-08 | 1978-06-13 | Exxon Research & Engineering Co. | Integrated catalytic gasification process |
CA1003217A (en) | 1972-09-08 | 1977-01-11 | Robert E. Pennington | Catalytic gasification process |
US3920229A (en) | 1972-10-10 | 1975-11-18 | Pcl Ind Limited | Apparatus for feeding polymeric material in flake form to an extruder |
US3870481A (en) | 1972-10-12 | 1975-03-11 | William P Hegarty | Method for production of synthetic natural gas from crude oil |
GB1448562A (en) | 1972-12-18 | 1976-09-08 | British Gas Corp | Process for the production of methane containing gases |
US3828474A (en) | 1973-02-01 | 1974-08-13 | Pullman Inc | Process for producing high strength reducing gas |
US4021370A (en) * | 1973-07-24 | 1977-05-03 | Davy Powergas Limited | Fuel gas production |
US3847567A (en) | 1973-08-27 | 1974-11-12 | Exxon Research Engineering Co | Catalytic coal hydrogasification process |
US3904386A (en) | 1973-10-26 | 1975-09-09 | Us Interior | Combined shift and methanation reaction process for the gasification of carbonaceous materials |
US4053554A (en) | 1974-05-08 | 1977-10-11 | Catalox Corporation | Removal of contaminants from gaseous streams |
US3958957A (en) * | 1974-07-01 | 1976-05-25 | Exxon Research And Engineering Company | Methane production |
US3904389A (en) | 1974-08-13 | 1975-09-09 | David L Banquy | Process for the production of high BTU methane-containing gas |
US4104201A (en) | 1974-09-06 | 1978-08-01 | British Gas Corporation | Catalytic steam reforming and catalysts therefor |
US4046523A (en) | 1974-10-07 | 1977-09-06 | Exxon Research And Engineering Company | Synthesis gas production |
GB1508712A (en) * | 1975-03-31 | 1978-04-26 | Battelle Memorial Institute | Treating solid fuel |
US3975168A (en) | 1975-04-02 | 1976-08-17 | Exxon Research And Engineering Company | Process for gasifying carbonaceous solids and removing toxic constituents from aqueous effluents |
US3998607A (en) | 1975-05-12 | 1976-12-21 | Exxon Research And Engineering Company | Alkali metal catalyst recovery process |
US4091073A (en) * | 1975-08-29 | 1978-05-23 | Shell Oil Company | Process for the removal of H2 S and CO2 from gaseous streams |
US4005996A (en) * | 1975-09-04 | 1977-02-01 | El Paso Natural Gas Company | Methanation process for the production of an alternate fuel for natural gas |
US4077778A (en) * | 1975-09-29 | 1978-03-07 | Exxon Research & Engineering Co. | Process for the catalytic gasification of coal |
US4057512A (en) | 1975-09-29 | 1977-11-08 | Exxon Research & Engineering Co. | Alkali metal catalyst recovery system |
DE2551717C3 (de) * | 1975-11-18 | 1980-11-13 | Basf Ag, 6700 Ludwigshafen | und ggf. COS aus Gasen |
US4069304A (en) * | 1975-12-31 | 1978-01-17 | Trw | Hydrogen production by catalytic coal gasification |
US3999607A (en) * | 1976-01-22 | 1976-12-28 | Exxon Research And Engineering Company | Recovery of hydrocarbons from coal |
US4330305A (en) * | 1976-03-19 | 1982-05-18 | Basf Aktiengesellschaft | Removal of CO2 and/or H2 S from gases |
JPS5311893A (en) * | 1976-07-20 | 1978-02-02 | Fujimi Kenmazai Kougiyou Kk | Catalysts |
ZA78154B (en) * | 1977-01-24 | 1978-12-27 | Exxon Research Engineering Co | System for the recovery of alkali metal compounds for re-use in a catalytic coal conversion process |
US4159195A (en) * | 1977-01-24 | 1979-06-26 | Exxon Research & Engineering Co. | Hydrothermal alkali metal recovery process |
BR7800381A (pt) * | 1977-01-24 | 1978-08-22 | Exxon Research Engineering Co | Processo aperfeicoado para a conversao de um material de alimentacao carbonaceo solido na presenca de um catalisador contendo metal alcalino em liquidos e/ou gases |
US4211538A (en) * | 1977-02-25 | 1980-07-08 | Exxon Research & Engineering Co. | Process for the production of an intermediate Btu gas |
US4118204A (en) | 1977-02-25 | 1978-10-03 | Exxon Research & Engineering Co. | Process for the production of an intermediate Btu gas |
US4100256A (en) * | 1977-03-18 | 1978-07-11 | The Dow Chemical Company | Hydrolysis of carbon oxysulfide |
GB1599932A (en) | 1977-07-01 | 1981-10-07 | Exxon Research Engineering Co | Distributing coal-liquefaction or-gasifaction catalysts in coal |
US4152119A (en) * | 1977-08-01 | 1979-05-01 | Dynecology Incorporated | Briquette comprising caking coal and municipal solid waste |
US4204843A (en) * | 1977-12-19 | 1980-05-27 | Exxon Research & Engineering Co. | Gasification process |
US4617027A (en) | 1977-12-19 | 1986-10-14 | Exxon Research And Engineering Co. | Gasification process |
US4200439A (en) * | 1977-12-19 | 1980-04-29 | Exxon Research & Engineering Co. | Gasification process using ion-exchanged coal |
US4157246A (en) * | 1978-01-27 | 1979-06-05 | Exxon Research & Engineering Co. | Hydrothermal alkali metal catalyst recovery process |
US4265868A (en) | 1978-02-08 | 1981-05-05 | Koppers Company, Inc. | Production of carbon monoxide by the gasification of carbonaceous materials |
US4193771A (en) * | 1978-05-08 | 1980-03-18 | Exxon Research & Engineering Co. | Alkali metal recovery from carbonaceous material conversion process |
US4219338A (en) * | 1978-05-17 | 1980-08-26 | Exxon Research & Engineering Co. | Hydrothermal alkali metal recovery process |
US4193772A (en) * | 1978-06-05 | 1980-03-18 | Exxon Research & Engineering Co. | Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue |
DE2829629C2 (de) * | 1978-07-06 | 1982-07-29 | Ruhrchemie Ag, 4200 Oberhausen | Verfahren und Vorrichtung zum Ausschleusen von Rückständen aus dem Drucksystem einer Druckvergasungsanlage |
US4318712A (en) * | 1978-07-17 | 1982-03-09 | Exxon Research & Engineering Co. | Catalytic coal gasification process |
GB2027444B (en) | 1978-07-28 | 1983-03-02 | Exxon Research Engineering Co | Gasification of ash-containing solid fuels |
US4211669A (en) * | 1978-11-09 | 1980-07-08 | Exxon Research & Engineering Co. | Process for the production of a chemical synthesis gas from coal |
DE2852710A1 (de) | 1978-12-06 | 1980-06-12 | Didier Eng | Verfahren zur katalytischen vergasung von kunststoff in form von kohle oder koks |
US4235044A (en) | 1978-12-21 | 1980-11-25 | Union Carbide Corporation | Split stream methanation process |
US4243639A (en) * | 1979-05-10 | 1981-01-06 | Tosco Corporation | Method for recovering vanadium from petroleum coke |
US4260421A (en) * | 1979-05-18 | 1981-04-07 | Exxon Research & Engineering Co. | Cement production from coal conversion residues |
US4334893A (en) * | 1979-06-25 | 1982-06-15 | Exxon Research & Engineering Co. | Recovery of alkali metal catalyst constituents with sulfurous acid |
US4315758A (en) * | 1979-10-15 | 1982-02-16 | Institute Of Gas Technology | Process for the production of fuel gas from coal |
US4462814A (en) * | 1979-11-14 | 1984-07-31 | Koch Process Systems, Inc. | Distillative separations of gas mixtures containing methane, carbon dioxide and other components |
US4284416A (en) | 1979-12-14 | 1981-08-18 | Exxon Research & Engineering Co. | Integrated coal drying and steam gasification process |
US4292048A (en) | 1979-12-21 | 1981-09-29 | Exxon Research & Engineering Co. | Integrated catalytic coal devolatilization and steam gasification process |
US4331451A (en) * | 1980-02-04 | 1982-05-25 | Mitsui Toatsu Chemicals, Inc. | Catalytic gasification |
US4336034A (en) * | 1980-03-10 | 1982-06-22 | Exxon Research & Engineering Co. | Process for the catalytic gasification of coal |
GB2072216A (en) | 1980-03-18 | 1981-09-30 | British Gas Corp | Treatment of hydrocarbon feedstocks |
DK148915C (da) | 1980-03-21 | 1986-06-02 | Haldor Topsoe As | Fremgangsmaade til fremstilling af hydrogen eller ammoniaksyntesegas |
GB2078251B (en) | 1980-06-19 | 1984-02-15 | Gen Electric | System for gasifying coal and reforming gaseous products thereof |
US4353713A (en) | 1980-07-28 | 1982-10-12 | Cheng Shang I | Integrated gasification process |
US4540681A (en) | 1980-08-18 | 1985-09-10 | United Catalysts, Inc. | Catalyst for the methanation of carbon monoxide in sour gas |
US4347063A (en) | 1981-03-27 | 1982-08-31 | Exxon Research & Engineering Co. | Process for catalytically gasifying carbon |
NL8101447A (nl) * | 1981-03-24 | 1982-10-18 | Shell Int Research | Werkwijze voor de bereiding van koolwaterstoffen uit koolstofhoudend materiaal. |
EP0061326B1 (en) * | 1981-03-24 | 1985-06-19 | Exxon Research And Engineering Company | Apparatus for converting a fuel into combustible gas |
DE3113993A1 (de) * | 1981-04-07 | 1982-11-11 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur gleichzeitigen erzeugung von brenngas und prozesswaerme aus kohlenstoffhaltigen materialien |
EP0067580B1 (en) | 1981-06-05 | 1986-01-15 | Exxon Research And Engineering Company | An integrated catalytic coal devolatilisation and steam gasification process |
JPS6053730B2 (ja) | 1981-06-26 | 1985-11-27 | 康勝 玉井 | ニツケル精錬法 |
US4365975A (en) | 1981-07-06 | 1982-12-28 | Exxon Research & Engineering Co. | Use of electromagnetic radiation to recover alkali metal constituents from coal conversion residues |
US4500323A (en) * | 1981-08-26 | 1985-02-19 | Kraftwerk Union Aktiengesellschaft | Process for the gasification of raw carboniferous materials |
US4348486A (en) | 1981-08-27 | 1982-09-07 | Exxon Research And Engineering Co. | Production of methanol via catalytic coal gasification |
US4432773A (en) * | 1981-09-14 | 1984-02-21 | Euker Jr Charles A | Fluidized bed catalytic coal gasification process |
US4439210A (en) * | 1981-09-25 | 1984-03-27 | Conoco Inc. | Method of catalytic gasification with increased ash fusion temperature |
US4348487A (en) | 1981-11-02 | 1982-09-07 | Exxon Research And Engineering Co. | Production of methanol via catalytic coal gasification |
US4397656A (en) | 1982-02-01 | 1983-08-09 | Mobil Oil Corporation | Process for the combined coking and gasification of coal |
EP0093501B1 (en) * | 1982-03-29 | 1988-07-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for thermal cracking of carbonaceous substances which increases gasoline fraction and light oil conversions |
US4468231A (en) | 1982-05-03 | 1984-08-28 | Exxon Research And Engineering Co. | Cation ion exchange of coal |
DE3217366A1 (de) * | 1982-05-08 | 1983-11-10 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur herstellung eines weitgehend inertfreien gases zur synthese |
US4407206A (en) | 1982-05-10 | 1983-10-04 | Exxon Research And Engineering Co. | Partial combustion process for coal |
US5630854A (en) * | 1982-05-20 | 1997-05-20 | Battelle Memorial Institute | Method for catalytic destruction of organic materials |
DE3222653C1 (de) | 1982-06-16 | 1983-04-21 | Kraftwerk Union AG, 4330 Mülheim | Verfahren zum Umsetzen von kohlenstoffhaltigem Brennstoff zu einem brennbaren Produktgas |
US4436531A (en) * | 1982-08-27 | 1984-03-13 | Texaco Development Corporation | Synthesis gas from slurries of solid carbonaceous fuels |
US4597776A (en) * | 1982-10-01 | 1986-07-01 | Rockwell International Corporation | Hydropyrolysis process |
US4459138A (en) * | 1982-12-06 | 1984-07-10 | The United States Of America As Represented By The United States Department Of Energy | Recovery of alkali metal constituents from catalytic coal conversion residues |
JPS6035092A (ja) * | 1983-04-11 | 1985-02-22 | エクソン・リサーチ・アンド・エンジニアリング・カンパニー | 石炭転化残分からのアルカリ金属触媒成分の回収 |
US4551155A (en) | 1983-07-07 | 1985-11-05 | Sri International | In situ formation of coal gasification catalysts from low cost alkali metal salts |
EP0134344A1 (en) | 1983-08-24 | 1985-03-20 | Exxon Research And Engineering Company | The fluidized bed gasification of extracted coal |
GB2147913A (en) | 1983-10-14 | 1985-05-22 | British Gas Corp | Thermal hydrogenation of hydrocarbon liquids |
US4515764A (en) * | 1983-12-20 | 1985-05-07 | Shell Oil Company | Removal of H2 S from gaseous streams |
FR2559497B1 (fr) | 1984-02-10 | 1988-05-20 | Inst Francais Du Petrole | Procede de conversion de residus petroliers lourds en hydrogene et hydrocarbures gazeux et distillables |
GB2154600A (en) | 1984-02-23 | 1985-09-11 | British Gas Corp | Producing and purifying methane |
US4619864A (en) | 1984-03-21 | 1986-10-28 | Springs Industries, Inc. | Fabric with reduced permeability to down and fiber fill and method of producing same |
US4597775A (en) * | 1984-04-20 | 1986-07-01 | Exxon Research And Engineering Co. | Coking and gasification process |
US4558027A (en) | 1984-05-25 | 1985-12-10 | The United States Of America As Represented By The United States Department Of Energy | Catalysts for carbon and coal gasification |
US4704136A (en) | 1984-06-04 | 1987-11-03 | Freeport-Mcmoran Resource Partners, Limited Partnership | Sulfate reduction process useful in coal gasification |
DE3422202A1 (de) | 1984-06-15 | 1985-12-19 | Hüttinger, Klaus J., Prof. Dr.-Ing., 7500 Karlsruhe | Verfahren zur katalytischen vergasung |
DE3439487A1 (de) * | 1984-10-27 | 1986-06-26 | M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 4200 Oberhausen | Energieguenstiges verfahren zur erzeugung von synthesegas mit einem hohen methangehalt |
US4682986A (en) * | 1984-11-29 | 1987-07-28 | Exxon Research And Engineering | Process for separating catalytic coal gasification chars |
US4854944A (en) | 1985-05-06 | 1989-08-08 | Strong William H | Method for gasifying toxic and hazardous waste oil |
US4690814A (en) | 1985-06-17 | 1987-09-01 | The Standard Oil Company | Process for the production of hydrogen |
US4668428A (en) * | 1985-06-27 | 1987-05-26 | Texaco Inc. | Partial oxidation process |
US4668429A (en) * | 1985-06-27 | 1987-05-26 | Texaco Inc. | Partial oxidation process |
US4720289A (en) * | 1985-07-05 | 1988-01-19 | Exxon Research And Engineering Company | Process for gasifying solid carbonaceous materials |
IN168599B (zh) | 1985-11-29 | 1991-05-04 | Dow Chemical Co | |
US4675035A (en) * | 1986-02-24 | 1987-06-23 | Apffel Fred P | Carbon dioxide absorption methanol process |
US4747938A (en) * | 1986-04-17 | 1988-05-31 | The United States Of America As Represented By The United States Department Of Energy | Low temperature pyrolysis of coal or oil shale in the presence of calcium compounds |
US5223173A (en) * | 1986-05-01 | 1993-06-29 | The Dow Chemical Company | Method and composition for the removal of hydrogen sulfide from gaseous streams |
CA1300885C (en) * | 1986-08-26 | 1992-05-19 | Donald S. Scott | Hydrogasification of biomass to produce high yields of methane |
IT1197477B (it) | 1986-09-10 | 1988-11-30 | Eniricerche Spa | Processo per ottenere una miscela gassosa ad alto contenuto di metano dal carbone |
JPS6395292A (ja) * | 1986-10-09 | 1988-04-26 | Univ Tohoku | 塩化物を利用した石炭の接触ガス化法 |
US4876080A (en) | 1986-12-12 | 1989-10-24 | The United States Of Americal As Represented By The United States Department Of Energy | Hydrogen production with coal using a pulverization device |
US4803061A (en) * | 1986-12-29 | 1989-02-07 | Texaco Inc. | Partial oxidation process with magnetic separation of the ground slag |
US5132007A (en) * | 1987-06-08 | 1992-07-21 | Carbon Fuels Corporation | Co-generation system for co-producing clean, coal-based fuels and electricity |
US5055181A (en) | 1987-09-30 | 1991-10-08 | Exxon Research And Engineering Company | Hydropyrolysis-gasification of carbonaceous material |
IT1222811B (it) * | 1987-10-02 | 1990-09-12 | Eniricerche Spa | Procedimento per la liquefazione del carbone in un unico stadio |
US4781731A (en) | 1987-12-31 | 1988-11-01 | Texaco Inc. | Integrated method of charge fuel pretreatment and tail gas sulfur removal in a partial oxidation process |
US4861346A (en) * | 1988-01-07 | 1989-08-29 | Texaco Inc. | Stable aqueous suspension of partial oxidation ash, slag and char containing polyethoxylated quaternary ammonium salt surfactant |
US5093094A (en) * | 1989-05-05 | 1992-03-03 | Shell Oil Company | Solution removal of H2 S from gas streams |
US4960450A (en) | 1989-09-19 | 1990-10-02 | Syracuse University | Selection and preparation of activated carbon for fuel gas storage |
JPH075895B2 (ja) * | 1989-09-29 | 1995-01-25 | 宇部興産株式会社 | ガス化炉壁へのアッシュ分の付着防止法 |
US5057294A (en) | 1989-10-13 | 1991-10-15 | The University Of Tennessee Research Corporation | Recovery and regeneration of spent MHD seed material by the formate process |
US5059406A (en) * | 1990-04-17 | 1991-10-22 | University Of Tennessee Research Corporation | Desulfurization process |
US5094737A (en) * | 1990-10-01 | 1992-03-10 | Exxon Research & Engineering Company | Integrated coking-gasification process with mitigation of bogging and slagging |
US5277884A (en) * | 1992-03-02 | 1994-01-11 | Reuel Shinnar | Solvents for the selective removal of H2 S from gases containing both H2 S and CO2 |
US5250083A (en) | 1992-04-30 | 1993-10-05 | Texaco Inc. | Process for production desulfurized of synthesis gas |
CA2137261C (en) * | 1992-06-05 | 2003-08-19 | Douglas C. Elliott | Method for the catalytic conversion of organic materials into a product gas |
US5865898A (en) * | 1992-08-06 | 1999-02-02 | The Texas A&M University System | Methods of biomass pretreatment |
US5733515A (en) * | 1993-01-21 | 1998-03-31 | Calgon Carbon Corporation | Purification of air in enclosed spaces |
US5720785A (en) * | 1993-04-30 | 1998-02-24 | Shell Oil Company | Method of reducing hydrogen cyanide and ammonia in synthesis gas |
US5435940A (en) * | 1993-11-12 | 1995-07-25 | Shell Oil Company | Gasification process |
US5536893A (en) | 1994-01-07 | 1996-07-16 | Gudmundsson; Jon S. | Method for production of gas hydrates for transportation and storage |
US5964985A (en) * | 1994-02-02 | 1999-10-12 | Wootten; William A. | Method and apparatus for converting coal to liquid hydrocarbons |
US6506349B1 (en) * | 1994-11-03 | 2003-01-14 | Tofik K. Khanmamedov | Process for removal of contaminants from a gas stream |
US5641327A (en) | 1994-12-02 | 1997-06-24 | Leas; Arnold M. | Catalytic gasification process and system for producing medium grade BTU gas |
US5855631A (en) * | 1994-12-02 | 1999-01-05 | Leas; Arnold M. | Catalytic gasification process and system |
US5496859A (en) | 1995-01-28 | 1996-03-05 | Texaco Inc. | Gasification process combined with steam methane reforming to produce syngas suitable for methanol production |
US6028234A (en) * | 1996-12-17 | 2000-02-22 | Mobil Oil Corporation | Process for making gas hydrates |
US6090356A (en) | 1997-09-12 | 2000-07-18 | Texaco Inc. | Removal of acidic gases in a gasification power system with production of hydrogen |
US6180843B1 (en) * | 1997-10-14 | 2001-01-30 | Mobil Oil Corporation | Method for producing gas hydrates utilizing a fluidized bed |
US6187465B1 (en) * | 1997-11-07 | 2001-02-13 | Terry R. Galloway | Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions |
US6168768B1 (en) * | 1998-01-23 | 2001-01-02 | Exxon Research And Engineering Company | Production of low sulfer syngas from natural gas with C4+/C5+ hydrocarbon recovery |
US6015104A (en) * | 1998-03-20 | 2000-01-18 | Rich, Jr.; John W. | Process and apparatus for preparing feedstock for a coal gasification plant |
JP2979149B1 (ja) | 1998-11-11 | 1999-11-15 | 財団法人石炭利用総合センター | 熱化学的分解による水素の製造方法 |
US6389820B1 (en) * | 1999-02-12 | 2002-05-21 | Mississippi State University | Surfactant process for promoting gas hydrate formation and application of the same |
CA2300521C (en) | 1999-03-15 | 2004-11-30 | Takahiro Kimura | Production method for hydrate and device for proceeding the same |
JP4006560B2 (ja) | 1999-04-09 | 2007-11-14 | 大阪瓦斯株式会社 | 燃料ガスの製造方法 |
JP4054934B2 (ja) | 1999-04-09 | 2008-03-05 | 大阪瓦斯株式会社 | 燃料ガスの製造方法 |
US6641625B1 (en) | 1999-05-03 | 2003-11-04 | Nuvera Fuel Cells, Inc. | Integrated hydrocarbon reforming system and controls |
AUPQ118899A0 (en) * | 1999-06-24 | 1999-07-22 | Woodside Energy Limited | Natural gas hydrate and method for producing same |
US6790430B1 (en) | 1999-12-09 | 2004-09-14 | The Regents Of The University Of California | Hydrogen production from carbonaceous material |
US6506361B1 (en) * | 2000-05-18 | 2003-01-14 | Air Products And Chemicals, Inc. | Gas-liquid reaction process including ejector and monolith catalyst |
KR100347092B1 (ko) | 2000-06-08 | 2002-07-31 | 한국과학기술원 | 하이드레이트 촉진제를 이용한 혼합가스의 분리방법 |
JP2002105467A (ja) | 2000-09-29 | 2002-04-10 | Osaka Gas Co Ltd | 水素−メタン系燃料ガスの製造方法 |
US7074373B1 (en) | 2000-11-13 | 2006-07-11 | Harvest Energy Technology, Inc. | Thermally-integrated low temperature water-gas shift reactor apparatus and process |
AU3276302A (en) | 2000-12-21 | 2002-07-01 | Future Energy Resources Corp | Biomass gasification system and method |
US6894183B2 (en) * | 2001-03-26 | 2005-05-17 | Council Of Scientific And Industrial Research | Method for gas—solid contacting in a bubbling fluidized bed reactor |
WO2002079355A1 (fr) * | 2001-03-29 | 2002-10-10 | Mitsubishi Heavy Industries, Ltd. | Dispositif de production d'hydrate de gaz et dispositif de deshydratation d'hydrate de gaz |
JP4259777B2 (ja) | 2001-07-31 | 2009-04-30 | 井上 斉 | バイオマスのガス化方法 |
JP5019683B2 (ja) * | 2001-08-31 | 2012-09-05 | 三菱重工業株式会社 | ガスハイドレートスラリーの脱水装置及び脱水方法 |
US6797253B2 (en) | 2001-11-26 | 2004-09-28 | General Electric Co. | Conversion of static sour natural gas to fuels and chemicals |
CN1190475C (zh) * | 2001-12-27 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | 流化床煤与富甲烷燃料气共气化制合成气的方法 |
US6955695B2 (en) | 2002-03-05 | 2005-10-18 | Petro 2020, Llc | Conversion of petroleum residua to methane |
US7220502B2 (en) * | 2002-06-27 | 2007-05-22 | Intellergy Corporation | Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions |
US7132183B2 (en) | 2002-06-27 | 2006-11-07 | Intellergy Corporation | Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions |
JP2004292200A (ja) | 2003-03-26 | 2004-10-21 | Ube Ind Ltd | セメントクリンカーの焼成工程における可燃性燃料の燃焼性改良方法 |
JP2004298818A (ja) | 2003-04-01 | 2004-10-28 | Tokyo Gas Co Ltd | 有機物の超臨界水処理における前処理方法及び装置 |
CN1477090A (zh) | 2003-05-16 | 2004-02-25 | 中国科学院广州能源研究所 | 生物质间接液化一步法合成二甲醚的方法 |
US7205448B2 (en) * | 2003-12-19 | 2007-04-17 | Uop Llc | Process for the removal of nitrogen compounds from a fluid stream |
CN100473447C (zh) | 2004-03-22 | 2009-04-01 | 巴布考克及威尔考克斯公司 | 用于从烟气中除汞的吸附剂的动态卤化 |
US7309383B2 (en) | 2004-09-23 | 2007-12-18 | Exxonmobil Chemical Patents Inc. | Process for removing solid particles from a gas-solids flow |
US7575613B2 (en) | 2005-05-26 | 2009-08-18 | Arizona Public Service Company | Method and apparatus for producing methane from carbonaceous material |
US20070000177A1 (en) * | 2005-07-01 | 2007-01-04 | Hippo Edwin J | Mild catalytic steam gasification process |
AT502064A2 (de) | 2005-07-04 | 2007-01-15 | Sf Soepenberg Compag Gmbh | Verfahren zur gewinnung von kaliumkarbonat aus asche |
DE202005021662U1 (de) * | 2005-09-07 | 2009-03-05 | Siemens Aktiengesellschaft | Vorrichtung zur Erzeugung von Synthesegasen durch Partialoxidation von aus aschehaltigen Brennstoffen erzeugten Slurries mit Teilquenchung und Abhitzegewinnung |
US8114176B2 (en) * | 2005-10-12 | 2012-02-14 | Great Point Energy, Inc. | Catalytic steam gasification of petroleum coke to methane |
US7758663B2 (en) | 2006-02-14 | 2010-07-20 | Gas Technology Institute | Plasma assisted conversion of carbonaceous materials into synthesis gas |
US7922782B2 (en) | 2006-06-01 | 2011-04-12 | Greatpoint Energy, Inc. | Catalytic steam gasification process with recovery and recycle of alkali metal compounds |
US8163048B2 (en) * | 2007-08-02 | 2012-04-24 | Greatpoint Energy, Inc. | Catalyst-loaded coal compositions, methods of making and use |
WO2009048723A2 (en) * | 2007-10-09 | 2009-04-16 | Greatpoint Energy, Inc. | Compositions for catalytic gasification of a petroleum coke and process for conversion thereof to methane |
WO2009048724A2 (en) * | 2007-10-09 | 2009-04-16 | Greatpoint Energy, Inc. | Compositions for catalytic gasification of a petroleum coke and process for their conversion to methane |
CN101910373B (zh) | 2007-12-28 | 2013-07-24 | 格雷特波因特能源公司 | 从焦炭中回收碱金属的催化气化方法 |
WO2009086383A2 (en) | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Catalytic gasification process with recovery of alkali metal from char |
CN101910371B (zh) | 2007-12-28 | 2014-04-02 | 格雷特波因特能源公司 | 用于制备合成气衍生产物的方法 |
US20090165361A1 (en) | 2007-12-28 | 2009-07-02 | Greatpoint Energy, Inc. | Carbonaceous Fuels and Processes for Making and Using Them |
WO2009086363A1 (en) | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification and process for its preparation |
AU2008345189B2 (en) | 2007-12-28 | 2011-09-22 | Greatpoint Energy, Inc. | Petroleum coke compositions for catalytic gasification |
US20090170968A1 (en) | 2007-12-28 | 2009-07-02 | Greatpoint Energy, Inc. | Processes for Making Synthesis Gas and Syngas-Derived Products |
WO2009086361A2 (en) | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Catalytic gasification process with recovery of alkali metal from char |
WO2009086408A1 (en) | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Continuous process for converting carbonaceous feedstock into gaseous products |
US20090165380A1 (en) | 2007-12-28 | 2009-07-02 | Greatpoint Energy, Inc. | Petroleum Coke Compositions for Catalytic Gasification |
US20090165376A1 (en) | 2007-12-28 | 2009-07-02 | Greatpoint Energy, Inc. | Steam Generating Slurry Gasifier for the Catalytic Gasification of a Carbonaceous Feedstock |
WO2009086374A2 (en) | 2007-12-28 | 2009-07-09 | Greatpoint Energy, Inc. | Catalytic gasification process with recovery of alkali metal from char |
US8366795B2 (en) | 2008-02-29 | 2013-02-05 | Greatpoint Energy, Inc. | Catalytic gasification particulate compositions |
US8361428B2 (en) | 2008-02-29 | 2013-01-29 | Greatpoint Energy, Inc. | Reduced carbon footprint steam generation processes |
US20090260287A1 (en) | 2008-02-29 | 2009-10-22 | Greatpoint Energy, Inc. | Process and Apparatus for the Separation of Methane from a Gas Stream |
US8709113B2 (en) | 2008-02-29 | 2014-04-29 | Greatpoint Energy, Inc. | Steam generation processes utilizing biomass feedstocks |
WO2009111342A2 (en) | 2008-02-29 | 2009-09-11 | Greatpoint Energy, Inc | Carbonaceous fines recycle |
US7926750B2 (en) | 2008-02-29 | 2011-04-19 | Greatpoint Energy, Inc. | Compactor feeder |
US20090220406A1 (en) | 2008-02-29 | 2009-09-03 | Greatpoint Energy, Inc. | Selective Removal and Recovery of Acid Gases from Gasification Products |
WO2009111330A1 (en) | 2008-02-29 | 2009-09-11 | Greatpoint Energy, Inc. | Processes for making adsorbents and processes for removing contaminants from fluids using them |
US8297542B2 (en) | 2008-02-29 | 2012-10-30 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification |
US8114177B2 (en) | 2008-02-29 | 2012-02-14 | Greatpoint Energy, Inc. | Co-feed of biomass as source of makeup catalysts for catalytic coal gasification |
US8652222B2 (en) | 2008-02-29 | 2014-02-18 | Greatpoint Energy, Inc. | Biomass compositions for catalytic gasification |
US8286901B2 (en) | 2008-02-29 | 2012-10-16 | Greatpoint Energy, Inc. | Coal compositions for catalytic gasification |
CN101981163B (zh) | 2008-04-01 | 2014-04-16 | 格雷特波因特能源公司 | 从气体物流中分离甲烷的方法 |
WO2009124019A2 (en) | 2008-04-01 | 2009-10-08 | Greatpoint Energy, Inc. | Sour shift process for the removal of carbon monoxide from a gas stream |
US20090324461A1 (en) | 2008-06-27 | 2009-12-31 | Greatpoint Energy, Inc. | Four-Train Catalytic Gasification Systems |
US20090324460A1 (en) | 2008-06-27 | 2009-12-31 | Greatpoint Energy, Inc. | Four-Train Catalytic Gasification Systems |
WO2009158583A2 (en) | 2008-06-27 | 2009-12-30 | Greatpoint Energy, Inc. | Four-train catalytic gasification systems |
CN102076829B (zh) | 2008-06-27 | 2013-08-28 | 格雷特波因特能源公司 | 用于合成气制备的四列催化气化系统 |
WO2009158579A2 (en) | 2008-06-27 | 2009-12-30 | Greatpoint Energy, Inc. | Three-train catalytic gasification systems |
US20100120926A1 (en) * | 2008-09-19 | 2010-05-13 | Greatpoint Energy, Inc. | Processes for Gasification of a Carbonaceous Feedstock |
WO2010033850A2 (en) * | 2008-09-19 | 2010-03-25 | Greatpoint Energy, Inc. | Processes for gasification of a carbonaceous feedstock |
KR101330894B1 (ko) * | 2008-09-19 | 2013-11-18 | 그레이트포인트 에너지, 인크. | 차르 메탄화 촉매를 사용한 기체화 방법 |
JP5384649B2 (ja) * | 2008-09-19 | 2014-01-08 | グレイトポイント・エナジー・インコーポレイテッド | 炭素質フィードストックのガス化のための方法 |
KR101275429B1 (ko) | 2008-10-23 | 2013-06-18 | 그레이트포인트 에너지, 인크. | 탄소질 공급원료의 기체화 방법 |
KR101290453B1 (ko) | 2008-12-30 | 2013-07-29 | 그레이트포인트 에너지, 인크. | 촉매된 탄소질 미립자의 제조 방법 |
EP2370549A1 (en) | 2008-12-30 | 2011-10-05 | Greatpoint Energy, Inc. | Processes for preparing a catalyzed coal particulate |
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2006
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AU2007256969A1 (en) | 2007-12-13 |
CA2653348A1 (en) | 2007-12-13 |
CA2653348C (en) | 2012-02-28 |
AU2007256969B2 (en) | 2010-05-20 |
JP2009538977A (ja) | 2009-11-12 |
US20070277437A1 (en) | 2007-12-06 |
EA200870600A1 (ru) | 2009-06-30 |
US7922782B2 (en) | 2011-04-12 |
WO2007143376A1 (en) | 2007-12-13 |
EP2038377A1 (en) | 2009-03-25 |
CN101484554A (zh) | 2009-07-15 |
ZA200809986B (en) | 2009-11-25 |
JP5193194B2 (ja) | 2013-05-08 |
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