CN102272268B - 制备催化的煤微粒的方法 - Google Patents
制备催化的煤微粒的方法 Download PDFInfo
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- CN102272268B CN102272268B CN200980153189.5A CN200980153189A CN102272268B CN 102272268 B CN102272268 B CN 102272268B CN 200980153189 A CN200980153189 A CN 200980153189A CN 102272268 B CN102272268 B CN 102272268B
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- coal
- particulate
- catalyst
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- basic metal
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Abstract
本发明提供制备基本自由流动的载有碱金属气化催化剂的煤微粒的方法,所述煤微粒适合作为原料用于经由该载有催化剂的煤微粒在蒸汽存在下的催化气化生产气态产物,特别是甲烷。
Description
发明领域
本发明涉及制备基本自由流动的载有碱金属气化催化剂的煤微粒的方法,所述煤微粒适合作为原料用于经由该载有催化剂的煤微粒在蒸汽存在下的催化气化生产气态产物,特别是甲烷。
发明背景
考虑到许多因素,如更高的能源价格和环境关系,由较低燃料值的碳质原料,如石油焦和煤生产增值气态产物受到持续的关注。例如在US3828474、US3998607、US4057512、US4092125、US4094650、US4204843、US4468231、US4500323、US4541841、US4551155、US4558027、US4606105、US4617027、US4609456、US5017282、US5055181、US6187465、US6790430、US6894183、US6955695、US2003/0167961A1、US2006/0265953A1、US2007/000177A1、US2007/083072A1、US2007/0277437A1、US2009/0048476A1、US2009/0090056A1、US2009/0090055A1、US2009/0165383A1、US2009/0166588A1、US2009/0165379A1、US2009/0170968A1、US2009/0165380A1、US2009/0165381A1、US2009/0165361A1、US2009/0165382A1、US2009/0169449A1、US2009/0169448A1、US2009/0165376A1、US2009/0165384A1、US2009/0217584A1、US2009/0217585A1、US2009/0217590A1、US2009/0217586A1、US2009/0217588A1、US2009/0217589A1、US2009/0217575A1、US2009/0217587A1、US2009/0220406A1、US2009/0229182A1、US2009/0246120A1、US2009/0259080A1、US2009/0260287A1和GB1599932 中公开了此类材料的催化气化以制造甲烷和其它增值气体。
通常,碳质材料,如煤或石油焦可通过该材料在碱金属催化剂源和蒸汽存在下在升高的温度和压力下的气化转化成多种气体,包括增值气体,如甲烷。从气化器产生的粗制气体中除去细的未反应碳质材料,在多个工艺中冷却和洗涤该气体以除去不合意的污染物和其它副产物,包括一氧化碳、氢气、二氧化碳和硫化氢。
尽管已建议通过将煤与所选催化剂混合来改进煤的气化,但迄今提出的方法尚未完全成功。例如,用催化剂浸渍煤的已知方法包括(a)用催化剂溶液喷洒煤和(b)将煤浸泡在催化剂溶液中。这些催化剂浸渍方法的缺点在于产生催化剂载荷没有高度分散的煤和因此具有降低的气化效率的煤。
对之前并入的US2009/0048476A1中公开的将碱金属催化剂加载到煤上的传统方法的一种改进涉及扩散催化剂加载离子交换法(diffuse catalyst loading ion exchange
process)。这优化催化剂物类在整个煤基质中的分散和分布,从而产生具有更高气化活性的催化煤颗粒。为了获得最大益处,所公开的方法要求在催化剂水溶液中长期浸泡煤并仔细控制该溶液中的催化剂浓度。浸泡产生的湿滤饼具有高的水含量并通常必须在最终干燥前沥干,造成工艺低效性。
因此,在本领域中需要提供将催化剂加载到煤原料上的更有效方法,其在尽可能的程度上利用扩散催化剂离子交换加载的益处,同时改进总工艺效率。
发明概述
一方面,本发明提供由煤原料制备基本自由流动的载有碱金属气化催化剂的煤微粒的方法,该方法包括下列步骤:
(A)提供具有初始含湿量和初始酸性官能团浓度的煤原料;
(B)研磨该煤原料;
(C)将来自步骤(B)的煤原料分级至指定的粒度分布以产生具有基质并包含第二浓度的酸性官能团的煤微粒;
(D)使该煤微粒与一定量的包含一定浓度的碱金属气化催化剂的水溶液接触,以形成具有指定的碱金属原子/碳原子比和第二含湿量的载有碱金属气化催化剂的煤微粒湿滤饼;和
(E)按需要热处理该载有碱金属气化催化剂的煤微粒湿滤饼以降低第二含湿量,从而制造基本自由流动的微粒形式的载有碱金属气化催化剂的煤微粒,
其中:
(a)酸性官能团的第二浓度为初始浓度的至少大约50%;
(b)指定的粒度分布具有至少大约20微米的d5粒度、大约1000微米或更小的d95粒度和大约75至大约350微米的d50粒度;
(c)步骤(D)的指定的碱金属原子/碳原子比足以提供大约0.01至大约0.10的该基本自由流动的载有碱金属气化催化剂的煤微粒中的碱金属原子/碳原子比;
(d)来自步骤(D)的载有碱金属气化催化剂的煤微粒湿滤饼是基本不滴液的(non-draining);
(e)步骤(D)中水溶液的量和碱金属气化催化剂的浓度足以提供该载有碱金属气化催化剂的煤微粒湿滤饼中的指定的碱金属原子/碳原子比;
(f)步骤(D)中的接触在基本大气压下和在基本等于或低于该水溶液沸点的高温下,在搅拌下进行指定时间量,它们各自的量足以一起使该碱金属气化催化剂基本均匀分布在该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼中;
(g)该不滴液的载有碱金属气化催化剂的碳质微粒湿滤饼在第一温度下离开步骤(D)并在基本相同温度下送入热处理步骤(E);和
(h)该基本自由流动的载有碱金属气化催化剂的煤微粒包含一定含量的碱金属原子,其中大于大约50%的含量的碱金属原子通过酸性官能团上的离子交换与煤微粒基质缔合。
任选地,在步骤(B)中,干磨该煤原料。在这种情况下,任选降低该煤原料的初始含湿量以便在将步骤(D)中使用的水溶液的量计入考虑时,来自步骤(D)的湿滤饼是基本不滴液的(步骤(E)不要求脱水)。
或者,在步骤(B)中,湿磨该煤原料。在这种情况下,降低所得湿磨煤原料的含湿量以便在将步骤(D)中使用的水溶液的量计入考虑时,来自步骤(D)的湿滤饼是基本不滴液的(步骤(E)不要求脱水)。
本发明还涉及将微粒组合物转化成多种气态产物的方法,包括下列步骤:
(a)向气化反应器供应根据本发明制成的微粒组合物;
(b)使该微粒组合物在气化反应器中在蒸汽存在下和在合适的温度和压力下反应形成多种气体,包括甲烷以及氢气、一氧化碳、二氧化碳、硫化氢、氨和其它高级烃中的至少一种或多种;和
(c)至少部分分离所述多种气态产物以产生包含主要量的气态产物之一的蒸汽。
附图简述
图1是基本自由流动的载有碱金属气化催化剂的煤微粒的制备方法的一个实施方案的图。
详述
本公开涉及制备基本自由流动的载有碱金属气化催化剂的煤微粒的方法。该方法的优点在于,例如,通过将必要的碱金属催化剂溶液体积减至最小、消除用该催化剂溶液处理煤微粒后的工艺步骤,如脱水/沥干步骤来减少工艺废料,并通过(在干燥步骤中)利用湿滤饼中由于接触步骤(其在高温下进行)而已有的显热而具有提高的能量效率。
根据本发明的方法形成的微粒可用于例如催化气化法,如由一种或多种煤原料生成多种气态产物,包括至少甲烷的那些。
可以联系共有的US2007/0000177A1、US2007/0083072A1、US2007/0277437A1、US2009/0048476A1、US2009/0090056A1、US2009/0090055A1、US2009/0165383A1、US2009/0166588A1、US2009/0165379A1、US2009/0170968A1、US2009/0165380A1、US2009/0165381A1、US2009/0165361A1、US2009/0165382A1、US2009/0169449A1、US2009/0169448A1、US2009/0165376A1、US2009/0165384A1、US2009/0217582A1、US2009/0220406A1、US2009/0217590A1、US2009/0217586A1、US2009/0217588A1、US2009/0218424A1、US2009/0217589A1、US2009/0217575A1、US2009/0217587A1、US2009/0218424A1、US2009/0220406A1、US2009/0229182A1、US2009/0246120A1、US2009/0259080A1和US2009/0260287A1中公开的主题实施本发明。
此外,可以联系下列共有的美国专利申请序号中公开的主题实施本发明:各自在2009年6月26日提交的12/492,467、12/492,477、12/492,484、12/492,489和12/492,497;各自在2009年9月18日提交的12/562,919、12/562,921、12/562,922和12/562,925;和2009年10月23日提交的12/604,695。
如果没有另行指明,本文中提到的所有出版物、专利申请、专利和其它参考资料就像充分阐述一样明确地出于各种目的全文经此引用并入本文。
除非另行规定,本文所用的所有技术和科学术语具有与本公开所属领域的普通技术人员的通常理解相同的含义。在冲突的情况下,以本说明书,包括定义为准。
除非明文指明,商标以大写体显示。
尽管在本公开的实践或测试中可以使用与本文所述的那些类似或等效的方法和材料,但本文中描述了合适的方法和材料。
除非另行指明,所有百分比、份数、比率等按重量计。
在量、浓度或其它值或参数作为范围或一系列上限和下限值给出时,这被理解为明确公开由任何一对任何范围上限和下限形成的所有范围,无论是否独立公开这些范围。在本文中列举一数值范围时,除非另行指明,该范围旨在包括其端点和在该范围内的所有整数和分数。无意将本公开的范围限制于在规定一范围时列举的具体数值。
当使用术语“大约”描述数值或一范围的端点时,本公开应被理解为包括所提到的具体数值或端点。
本文所用的术语“包含”、“包括”、“具有”或它们的任何其它变体旨在涵盖非排他性的包含。例如,包含一系列要素的工艺、方法、制品或装置不一定仅限于这些要素,而是可包括未明确列举的或此类工艺、方法、制品或装置所固有的其它要素。此外,除非明确作出相反的指示,“或”是指可兼性的“或”而非排他性的“或”。例如,下列任一项都满足条件A或B:A真(或存在)B假(或不存在),A假(或不存在)B真(或存在),A和B都真(或存在)。
本文中使用“一”(“a” or“ an”)描述各种要素和组分仅是为方便起见和给出本公开的一般含义。这种描述应被解释为包括一或至少一,单数也包括复数,除非明显看出无意如此。
除非本文中另行规定,本文所用的术语“大部分(substantial portion)”是指大于大约90%的所述材料,优选大于95%的所述材料,更优选大于97%的所述材料。在提到分子(如甲烷、二氧化碳、一氧化碳和硫化氢)时,该百分比基于摩尔,否则基于重量(如对夹带的煤细粒(fines)而言)。
术语“单元”是指单元操作。当描述存在多于一个“单元”时,这些单元以并列方式运行。但是,单个“单元”可包含串联的多于一个单元。例如,酸气脱除单元可包含硫化氢脱除单元和其后串联着的二氧化碳脱除单元。作为另一实例,痕量污染物脱除单元可包含用于第一痕量污染物的第一脱除单元和其后串联着的用于第二痕量污染物的第二脱除单元。作为再一实例,甲烷压缩机单元可包含第一甲烷压缩机以将甲烷产物流压缩至第一压力,其后串联着第二甲烷压缩机以将甲烷产物流进一步压缩至第二(更高)压力。
本文中的材料、方法和实例仅是示例性的,除非明确地指明,无意构成限制。
煤原料
如下所述制成的本发明的基本自由流动的载有碱金属气化催化剂的煤微粒可以由包含一种或多种煤的煤原料制成。例如,该煤原料可包含煤,例如无烟煤、烟煤、次烟煤和/或褐煤的混合物。
本文所用的术语“煤”是指泥炭、褐煤、次烟煤、烟煤、无烟煤或其混合物。在某些实施方案中,该煤具有基于总煤重量(折干计算)的按重量计小于大约85%,或小于大约80%,或小于大约75%,或小于大约70%,或小于大约65%,或小于大约60%,或小于大约55%,或小于大约50%的碳含量。在另一些实施方案中,该煤具有基于总煤重量(折干计算)的按重量计最多大约85%,或最多大约80%,或最多大约75%的碳含量。可用的煤的实例包括,但不限于,Illinois #6、Pittsburgh #8、Beulah (ND)、Utah Blind Canyon和Powder River Basin
(PRB)煤。无烟煤、烟煤、次烟煤和褐煤可分别含有折干计算为煤总重量的大约10重量%,大约5至大约7重量%,大约4至大约8重量%和大约9至大约20重量%的灰分。但是,如本领域技术人员熟悉的那样,任何特定煤源的灰分含量取决于该煤的等级和来源。参见例如,“Coal Data: A
Reference”, Energy Information Administration, Office of Coal, Nuclear,
Electric and Alternate Fuels, U.S. Department of Energy, DOE/EIA-0064(93), 1995年2月。
如本领域技术人员熟悉的那样,煤产生的灰分通常包含飞灰和底灰(bottom
ash)。来自烟煤的飞灰可包含占该飞灰总重量的大约20至大约60重量%二氧化硅和大约5至大约35重量%氧化铝。来自次烟煤的飞灰可包含占该飞灰总重量的大约40至大约60重量%二氧化硅和大约20至大约30重量%氧化铝。来自褐煤的飞灰可包含占该飞灰总重量的大约15至大约45重量%二氧化硅和大约20至大约25重量%氧化铝。参见例如Meyers等人,“Fly Ash. A Highway
Construction Material.” Federal Highway Administration, Report No.
FHWA-IP-76-16, Washington, DC, 1976。
来自烟煤的底灰可包含占该底灰总重量的大约40至大约60重量%二氧化硅和大约20至大约30重量%氧化铝。来自次烟煤的底灰可包含占该底灰总重量的大约40至大约50重量%二氧化硅和大约15至大约25重量%氧化铝。来自褐煤的底灰可包含占该底灰总重量的大约30至大约80重量%二氧化硅和大约10至大约20重量%氧化铝。参见例如Moulton, Lyle K.
“Bottom Ash and Boiler Slag,” Proceedings of the Third International Ash
Utilization Symposium. U.S. Bureau of Mines, Information Circular No. 8640,
Washington, DC, 1973。
在使用煤的混合物时,可以根据各种煤来源的技术考虑、加工经济性、易得性和邻近性选择比率和类型。该煤来源的易得性和邻近性影响进料的价格并因此影响总催化气化法生产成本。例如,褐煤和次烟煤可以根据加工条件以在湿或干基础上按重量计大约5:95,大约10:90,大约15:85,大约20:80,大约25:75,大约30:70,大约35:65,大约40:60,大约45:55,大约50:50,大约55:45,大约60:40,大约65:35,大约70:20,大约75:25,大约80:20,大约85:15,大约90:10,或大约95:5掺合。
明显地,煤源以及煤原料的各组分的比率可用于控制该原料的其它材料特性。煤通常包括显著量的无机物,包括钙、氧化铝和二氧化硅,它们在催化气化器中形成无机氧化物(即灰分)。在高于大约500℃至大约600℃的温度下,钾和其它碱金属可以与灰分中的氧化铝和二氧化硅反应形成不可溶的碱金属硅铝酸盐。在这种形式下,该碱金属基本不溶于水并没有作为催化剂的活性。为防止残留物积聚在催化气化器中,可以定期提取包含灰分、未反应的煤和各种碱金属化合物(可水溶和不可水溶两者)的炭固体废料(solid purge)。
根据例如各种煤的比率和/或各种煤中的原始灰分,各种煤的灰分含量可以选择为例如,大约20重量%或更少,或大约15重量%或更少,或大约10重量%或更少,或大约7重量%或更少。在另一些实施方案中,该煤原料可包含占煤原料重量(折干计算)的从大约7重量%,或从大约10重量%,至大约20重量%,或至大约15重量%的灰分含量。在另一些实施方案中,该煤原料的灰分含量可包含占灰分重量的小于大约20重量%,或小于大约15重量%,或小于大约10重量%,或小于大约8重量%,或小于大约6重量%的氧化铝。在某些实施方案中,该煤原料可包含小于微粒重量的大约20重量%的灰分含量,其中该煤原料的灰分含量包含占灰分重量的小于大约20重量%的氧化铝,或小于大约15重量%的氧化铝。
煤原料中的这种较低的氧化铝值最终能够降低用于该催化气化法中的碱金属催化剂的损失。如上所述,氧化铝可以与碱金属源反应以产生包含例如碱金属铝酸盐或硅铝酸盐的不可溶炭。这种不可溶炭会造成降低的催化剂回收(即提高的催化剂损失)并因此在整个气化法中需要附加的补充催化剂的成本。
另外,该煤原料可具有明显更高的%碳和因此btu/lb值和每单位重量的甲烷产物。在某些实施方案中,该煤原料可具有占煤总重量(折干计算)的大约75重量%,或大约80重量%,或大约85重量%的碳含量。
也可以使用一种或多种煤与较小量(minor amounts)的如许多之前并入的参考资料中描述的一种或多种其它类型的碳质原料的混合物。此类其它碳质原料包括,例如,生物质和非生物质材料以及由它们的部分燃烧或气化生成的炭。例如,参见之前并入的US2009/0217589A1和US2009/0217575A1。所述其它类型的碳质原料的量可通常为基于煤与其它碳质原料总重量的大约25重量%或更小,或大约20重量%或更小,大约15重量%或更小,或大约10重量%或更小,或大约5重量%或更小。
本文所用的术语“生物质”是指由近代(例如在过去100年内)活生物体衍生成的碳质材料,包括植物基生物质和动物基生物质。为清楚起见,生物质不包括化石基碳质材料,如煤。例如,参见之前并入的US2009/0217575A1、US2009/0217587A1和US2009/0229182A1。
本文所用的术语“非生物质”是指如本文定义的术语“生物质”或“煤”不包含的那些碳质材料。例如,非生物质包括,但不限于,石油焦、沥青质、液体石油残渣或其混合物。
也可以使用一种或多种煤与如上文和许多之前并入的参考资料中所述的一种或多种其它碳质原料的混合物以控制该原料的材料特性。通常,在本发明中,原料包含至少大约75重量%,或至少大约80重量%,或至少大约85重量%,或至少大约90重量%,或至少大约95重量%,或基本全部的煤。
碱金属气化催化剂
合适的碱金属气化催化剂包括包含锂、钠、钾、铷、铯及其混合物的碱金属源。在某些实施方案中,该碱金属源包含钾、钠或两者。特别有用的是钾源。
合适的碱金属气化催化剂特别包括碱金属碳酸盐、碳酸氢盐、甲酸盐、草酸盐、氨化物、氢氧化物、乙酸盐或类似化合物。在某些其它实施方案中,该碱金属气化催化剂是选自碳酸盐、氢氧化物、乙酸盐、卤化物和硝酸盐的碱金属盐。例如,该催化剂可包含碳酸钠、碳酸钾、碳酸铷、碳酸锂、碳酸铯、氢氧化钠、氢氧化钾、氢氧化铷或氢氧化铯中的一种或多种,特别是碳酸钾和/或氢氧化钾。
可以使用任选的助催化剂或其它催化剂添加剂,如之前并入的参考资料中公开的那些。
催化的煤微粒的制备
本公开提供如图1中所示由煤原料制备基本自由流动的载有碱金属气化催化剂的煤微粒的方法。如上所述,煤原料(10)可包含各自具有初始含湿量的一种或多种煤。例如,来样形式的煤可具有大约20重量%至大约40重量%的初始含湿量。在某些实施方案中,煤原料(10)包含无烟煤、烟煤、次烟煤和/或褐煤。
可以根据本领域技术人员熟悉的方法,例如经由热解重量分析(TGA)Karl Fischer滴定或微波吸收测定煤原料(10)的初始含湿量(参见Vermueuen和Hancke, “Moisture
determination in coal using microwave techniques”, Proceedings of the 1991
Industrial Conference on Electronics, Control and Instrumentation (IECON ’91)
1991, 3, 2565-8)。
煤原料(10)还含有初始酸性官能团浓度。煤通常在表面上和在其内部基质中含有酸性官能团,如羧基和酚式羟基。可以根据本领域技术人员熟悉的方法测定煤样品中存在的酸性官能团的浓度。例如,可以通过滴定测定酸性官能团的浓度(参见例如,Walker等人, “Titration of Acidic
Functional Groups in Coal”, Mahler和Schafer, “Determination of Acidic
Functional Groups in low-rank coals: comparison of ion-exchange and non-aqueous
titration methods”, Fuel 1976, 55(2), 138-140;和Dutta和Holland, “Acidic
groups in coal and coal-derived materials”, Fuel
1983, 62(6), 732-737)。
通过根据本领域技术人员已知的方法研磨(101),将煤原料转化成第一煤微粒(14)。
例如,该煤原料可以在球磨机、辊磨机、锤磨机、滚磨机、胶体磨、碗磨机和/或棒磨机中湿或干磨。
通常,煤原料(10)在研磨和/或分级后的含湿量应使得,在步骤(103)中与水溶液(20)接触(在图1中)后,所得湿滤饼是“基本不滴液的(non-draining)”。
本文所用的术语“不滴液”是指所用水溶液的量不超过该载有碱金属气化催化剂的煤微粒湿滤饼的滴液点(drain point),即该湿滤饼不含例如放在网(具有适合微粒含量的尺寸)上时容易滴落的过量液体。特定湿滤饼的滴液点取决于例如粒度、微粒材料、表面活性剂的存在、温度和相关领域普通技术人员公认的许多其它因素。
“基本不滴液”在本文中是指该湿滤饼应具有最低过量的湿度,但不需要完全不滴液,从而避免额外的除湿步骤,且湿滤饼含湿量对干燥步骤而言不过多(以使能量需求最小化)。该术语旨在涵盖在根据本发明的类型的方法的商业运行中通常预期的轻微差异。
但是,如果测得该碳质原料(10)的初始含湿量太高以致无法形成基本不滴液的湿滤饼(将所用催化剂水溶液的量计入考虑),可以例如通过沥水、空气干燥、强制通风干燥或类似方法降低初始含湿量。
干燥(如果需要)也可以与干磨同时进行。当需要降低湿度时,可以在研磨之前、之中和/或之后使干和/或加热气体(如空气或氮气)通过该干磨装置。
作为一般实例,具有给定粒度范围的特定原料的湿滤饼可以被测得具有在50重量%含湿量(基于湿滤饼的总重量)下的滴液点。如果该原料的初始含湿量为40重量%(基于该原料的总重量)且所用量的催化剂水溶液具有相当于另外30重量%(基于该原料的总重量)的水含量,则由该原料和催化剂水溶液合并而得的湿滤饼具有大于大约50重量%(基于湿滤饼的总重量)的总含湿量,因此在湿滤饼的滴液点以上。为了抵消这种额外湿度,可以降低该原料的初始含湿量,可以使用更小体积的更浓催化剂溶液,或可以采取这两种措施。在一个具体实施方案中,在干磨阶段(101)中降低(按需要)初始含湿量。极高湿度的煤要求在例如用压机或辊磨机研磨之前干燥(例如US44360280)。
在湿磨的情况下,可以在湿磨之后和/或在分级步骤之中和/或之后实现湿度降低,例如通过沥水和干燥(如上所述)的任一项或组合。
但是,将煤干燥至太低含湿量会破坏离子交换所必需的酸性官能度,因此是不合意的。含湿量降低的煤原料应包含第二浓度的酸性官能团,其通常为初始浓度的至少大约50%,或至少大约66%,或至少大约75%,或至少大约90%。
当煤原料(10)包含多种煤时,可以将初始含湿量太高的煤原料部分(11)干燥(100)以将含湿量降至合适水平;初始含湿量合适的煤原料部分(12)可直接供应至干磨工序(101)。例如,可以将褐煤干燥至合适的水平,并在研磨步骤中或在研磨步骤前与第二合适干燥的煤(例如无烟煤)合并。
此外,当煤原料(10)包含多种煤时,可以将初始含湿量太高的煤原料部分(11)与干组分掺合以将总含湿量降至合适水平(即干燥原料13)。例如,较高湿度的煤可以在研磨步骤中与如之前并入的US2009/0166588A1中公开的较低含湿量的煤或石油焦掺合或在研磨步骤之前或之后与其合并。
或者,当煤原料(10)包含多种煤且整个煤原料(10)具有太高含湿量时,可以将整个煤原料(10)供应至干燥操作(100)以将其含湿量降至合适水平(13),或在干磨操作中部分干燥,或在研磨操作(湿或干磨)后干燥。
在研磨后,将第一煤微粒(14)分级(102)至指定的粒度分布以产生具有包含第二浓度的酸性官能团的基质的煤微粒(15)。本文所用的术语“基质”是指煤的多孔结构并包括煤和其上的酸性官能团的总内部和外部表面积。参见例如,Tarasevich, “Porous structure and adsorption
properties of natural porous coal”, Colloids
and Surfaces A: Physicochemical and Engineering Aspects 2001, 176(2-3), 267-272。
可以根据本领域技术人员熟悉的方法实现第一煤微粒(14)的分级(102)。分级设备可包括矿石分选机、气体旋风分离器、水力旋流器、耙式分级机、旋转滚筒筛或流化分级机。该指定的粒度分布具有至少大约20微米的d5粒度,大约1000微米或更小的d95粒度和大约75至大约350微米的d50粒度。例如,该指定的粒度分布可具有大约20微米和100微米之间的d5粒度;大约500和1000微米之间的d95粒度;和大约45和500微米之间的d50粒度。形式“d#粒度”的术语,如d5、d50和d95是指微粒的分级粒径,其中所述样品总分布中#%的粒子具有所述粒径或更小。例如,20微米的d5粒度是指样品中5%的粒子具有20微米或更小的直径。在另一实例中,1000微米的d95粒度是指样品中95%的粒子具有1000微米或更小的直径。
不满足适合随后用碱金属气化催化剂处理的前述指定的粒度分布的第一煤微粒的细粒部分(22)可例如用作蒸汽发生和/或发电用的燃料。例如,参见之前并入的US2009/0165361A1、US2009/0165376A1、US2009/0217584A1和US2009/0217585A1。或者,细粒部分(22)可以如上所述被压制成块以在制备煤微粒(15)的工艺中再循环以将煤废料减至最少。
不满足适合随后用碱金属气化催化剂处理的前述指定的粒度分布的第一煤微粒的粗粒部分(coarse portion)(21)也可再循环以在制备煤微粒(15)的方法内继续干磨(101)以将煤废料减至最少。
使煤微粒(15)与一定量的包含一定浓度的碱金属气化催化剂的水溶液(20)在适合形成具有指定的碱金属原子/碳原子比和第二含湿量的基本不滴液的载有碱金属气化催化剂的煤微粒湿滤饼(16)的条件下接触(103)。在一个实施方案中,该湿滤饼是不滴液的。在另一实施方案中,该湿滤饼的含湿量比该湿滤饼在滴液点下的含湿量小至少大约2重量%,或至少大约5重量%,或至少大约10重量%。
选择用于接触煤微粒(15)的水溶液(20)的量和碱金属气化催化剂的浓度,以足以提供该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼(16)中的指定的碱金属原子/碳原子比,和足以提供大约0.01至大约0.10的该基本自由流动的微粒(30,见下文)中的碱金属原子/碳原子比。通常,一种或多种碱金属源以足以提供从大约0.01,或从大约0.02,或从大约0.03,或从大约0.04,至大约0.10,或至大约0.08,或至大约0.07,或至大约0.06的该基本自由流动的微粒(30)中的碱金属原子/碳原子比的量存在。
通过控制该水溶液中的催化剂浓度来控制加载的催化剂总量。此外,控制该水溶液中的催化剂浓度以使离子交换的催化剂量最大化。通过给定的煤样品的吸附等温线控制通过离子交换加载到煤上的催化剂的量。该吸附等温线将煤吸附的催化剂量与平衡下的该水溶液中的催化剂浓度相关联。如之前并入的US2009/0048476A1中所公开,通过随给定温度下该水溶液中的催化剂浓度测量经离子交换加载的催化剂的平衡量,实验测定吸附等温线。该吸附等温线因此可用于测定在接触条件下实现所需催化剂载量所需的水溶液的所需浓度。在具有所需浓度的水溶液的使用产生滴液的湿滤饼的情况下,可以使用更浓的水溶液,可以干燥煤原料,或可以采用这两种措施的一定组合(如上论述)。
煤微粒(15)与一定量的包含一定浓度碱金属气化催化剂的水溶液(20)的接触在基本等于或低于水的沸点的高温下,在基本大气压下、在搅拌下进行指定时间量,它们各自的量足以一起使该碱金属气化催化剂基本均匀分布在该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼(16)中。
“基本等于或低于水沸点的高温”意在包括高于环境温度的温度,但没有高到使接触过程在加压条件下进行,与术语“在基本大气压”下联合。该术语旨在涵盖在根据本发明的类型的方法的商业运行中通常预期的轻微差异。换言之,该接触不要求在开始时加压或在结束时减压。例如,该接触可以在大气压下在从大约80℃,或从大约90℃,或从大约95℃,至大约100℃(或略高)的温度下进行。
该接触可以在空气或氮气流(不需要排除气态氧)下进行,但可能理想地在接触阶段过程中不显著改变含湿量,因此在升高的温度下,气流是不合意的。此外该接触可以进行例如,从大约5分钟至大约60分钟,或至大约45分钟,或至大约30分钟。
搅拌可包括已知用于混合湿滤饼组合物以提供基本均匀分布的任何方法,包括但不限于,捏合和剪切混合(例如掺合)。本文所用的术语“基本均匀分布”是指该碱金属气化催化剂一致地分布在整个湿滤饼中。
在某些实施方案中,该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼(16)根据本领域技术人员熟悉的方法和在上述条件下捏合以使该碱金属气化催化剂基本均匀分布在该不滴液的湿滤饼(16)中。例如,该不滴液的湿滤饼可以在加热的单或双螺杆混合器、搅拌机或相关领域普通技术人员公知类型的螺条混合器中捏合。混合可以是分批或连续的。
最后,该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼在上述搅拌完成后进行热处理(104)以降低第二含湿量,从而产生基本自由流动的微粒(30)形式的载有碱金属气化催化剂的煤微粒。本文所用的术语“基本自由流动”是指微粒不会由于含湿量而附聚。
该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼(16)在第一温度下离开接触步骤(103),所述第一温度通常是与接触步骤过程中存在的温度大致相同的温度。为了利用湿滤饼中已有的显热(用于改进效率),该湿滤饼在没有显著冷却的情况下从接触步骤(103)直接送往干燥步骤(104)。换言之,湿滤饼在其离开接触步骤的基本相同温度下送入热处理步骤。
该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼(16)的第二含湿量可以通过用流化床淤浆干燥器处理(即用过热蒸汽处理以使该液体气化)或通过热蒸发来降低,或可以在真空下或在惰性(干燥)气流下除去,或通过热交换除去,以提供基本自由流动的微粒。在一个实施方案中,应在干燥步骤中基本排除气态氧。
所得基本自由流动的微粒(30)可具有例如大约10重量%或更小,或大约8重量%或更小,或大约6重量%或更小,或大约5重量%或更小,或大约4重量%或更小的残留含湿量。
所得基本自由流动的微粒(30)还应具有一定含量的碱金属原子(例如,如上所述),其中碱金属原子含量的多于大约50%,或多于大约70%,或多于大约85%,或多于大约90%通过酸性官能团上的离子交换与煤微粒基质缔合。
可以通过之前并入的US2009/0048476A1中所述的程序测定无法通过与其盐抗衡离子(即在抗衡离子化学计算过量的情况下)缔合来计入的加载催化剂的百分比,由此测定例如通过离子交换与煤基质缔合的总加载催化剂的百分比。可以通过电感耦合的等离子体-原子发射光谱法(“ICP-AES”)测定载有催化剂的煤组合物内的催化剂总量。ICP-AES使用等离子体产生发出在特定元素特有的波长下的电磁辐射的激发原子。该发射的强度随该样品内的元素的浓度而变。在盐抗衡离子是碳酸根的实施方案中,可以通过粉末X-射线衍射(“XRD”)和/或傅里叶变换红外(FT-IR)光谱学测定煤样品内的碳酸根总量。XRD基于对着样品的X-射线弹性散射,并可用于识别结晶物质(通过衍射峰)和用于测定结晶物质的丰度。例如,无水碳酸钾表现出在2θ = 31.635°和2θ = 32.090°下的特征强反射。FT-IR光谱法可用于量化样品中的碳酸根。碳酸根在FT-IR光谱中表现出以大约1356 cm-1、879 cm-1和704 cm-1为中心的特征峰。峰的强度随样品中的碳酸根浓度而变。给出催化剂总量(例如通过ICP-AES测得)和碳酸根总量(例如通过XRD和/或FT-IR测得),可以测定碳酸根化学计算过量的催化剂的量。由此测得的碳酸根过量的催化剂的百分比是与煤基质缔合的催化剂(例如作为煤的酸性官能团上的离子交换催化剂)的最小百分比。据信,由于碳酸根与煤样品内的其它元素(即钙)缔合,实际百分比更高。其它抗衡离子可能遵循类似程序。其它细节可参见之前并入的US2009/0048476A1。
根据前述方法制成的基本自由流动的微粒(30)可以通过本领域技术人员已知的任何方法与第二煤微粒合并。第二煤微粒可包含一种或多种煤并可根据本领域技术人员熟悉的任何方法制备。将基本自由流动的微粒(30)与一种或多种第二煤微粒合并的方法包括,但不限于,捏合、和垂直或水平混合器,例如单或双螺杆、螺条混合器或鼓式混合器。所得掺合的微粒可以储存以备将来使用或转移至一个或多个进料操作以引入催化气化器。
综合气化法
由该基本自由流动的微粒制造富甲烷气体的本发明的集成工艺可以与本领域中已知的任何类型的碱金属催化的气化系统一起使用。此类系统的实例包括例如,之前并入的US2009/0165381A1、US2009/0170968A1、US2009/0217584A1、US2009/0217585A1、US2009/0217588A1、US2009/00217589A1、US2009/0220406A1、US2009/0246120A1、US2009/0259080A1和US2009/0260287A1;和美国专利申请序号Nos. 12/492,467、12/,492,477、12/492,484、12/492,489、12/492,497、12/562,919、12/562,921、12/562,922、12/562,925和12/604,695中公开的那些。
用于此类方法的催化气化器通常在适度高的压力和温度下运行,要求在保持所需的温度、压力和原料流速的同时将基本自由流动的微粒(30)引入该催化气化器的反应室。本领域技术人员熟悉用于向具有高压和/或高温环境的反应室供应催化的煤原料的进料入口,包括星形加料器、螺旋进料器、旋转活塞和闭锁料斗。应该理解的是,该进料入口可包括交替使用的两个或更多个压力平衡元件,如闭锁料斗。在一些情况下,可以在比该催化气化器的运行压力高的压力条件下制备催化的煤原料。因此,该微粒组合物无需进一步加压就可直接送入催化气化器。
可以使用若干类型的催化气化器的任一种。合适的催化气化器包括具有对流固定床、并流固定床、流化床、或气流床(entrained flow bed)或移动床反应室形式的反应室的那些。此类系统的实例包括例如,之前并入的美国专利申请序号Nos. 12/562,921、12/562,922、12/562,925和12/604,695中公开的那些。
催化气化器中的气化通常在至少大约450℃,或至少大约600℃,或至少大约650℃,至大约900℃,或至大约800ºC,或至大约750℃的适中温度;和在至少大约50 psig,或至少大约200 psig,或至少大约400 psig,至大约1000 psig,或至大约700 psig,或至大约600 psig的压力下进行。
催化气化器中用于微粒组合物的加压和反应的气体可包含例如蒸汽、氧气、氮气、空气、合成气体(一氧化碳和氢气的混合物)或惰性气体,如氩气,它们可根据本领域技术人员已知的方法供应到反应器中。
本领域技术人员已知的任何蒸汽锅炉可以向该催化气化器供应蒸汽。此类锅炉可以例如使用任何碳质材料,如粉煤、生物质等供能,包括但不限于,来自该原料制备操作的废弃碳质材料(例如上述细粒)。也可以由连接到燃气轮机的附加气化器供应蒸汽,其中来自该反应器的废气与水源热交换并产生蒸汽。或者,可以如之前并入的US2009/0165376A1、US2009/0217584A1和US2009/0217585A1;和美国专利申请序号No. 12/562,925中所述生成用于该催化气化器的蒸汽。
由其它工艺操作再循环或生成的蒸汽也可用作唯一蒸汽源,或与来自蒸汽发生器的蒸汽一起向该催化气化器供应蒸汽。例如,当如上所述用流化床淤浆干燥器干燥已制浆的碳质材料时,可以将通过气化生成的蒸汽送入该催化气化器。当热交换器单元用于蒸汽发生时,该蒸汽也可直接送入催化气化器。
在催化气化器中发生的碳源催化转化成甲烷通常涉及三个独立的反应:
蒸汽碳:C
+ H2O → CO + H2
水煤气变换:CO + H2O → H2 + CO2
加氢气化:2H2 + C → CH4
CO甲烷化:CO+3H2 → CH4 + H2O
这四个反应一起基本热平衡;但是,由于工艺热损失和其它能量需求(如随原料进入催化气化器的水分的蒸发所需),必须向催化气化器加入一些热以维持热平衡。添加在高于催化气化器运行温度的温度下的过热蒸汽是用于供应这种额外热的一种机制。本领域普通技术人员可以测定为基本保持热平衡而需要添加到该催化气化器中的热量。
离开催化气化器的反应室的热气体流出物流可以通过该催化气化器的细粒脱除单元部分(未绘图),其充当分离区,在此太重以致无法被离开催化气化器的气体夹带的粒子(即细粒)被送回反应室(例如,流化床)。该细粒脱除单元可包括一个或多个内部和/或外部旋风分离器或类似装置以从热第一气体中除去细粒和微粒。根据用于气化的煤的性质,离开催化气化器的热第一气体流出物通常包含CH4、CO2、H2、CO、H2S、NH3、未反应的蒸汽、夹带的细粒和其它污染物,如COS、HCN和/或元素汞蒸汽。
可以通过任何合适的装置(如外部旋风分离器,任选随后文丘里洗涤器)基本除去残留的夹带细粒。可以加工该回收的细粒以回收碱金属催化剂,或如之前并入的US2009/0217589A1中所述直接再循环回原料制备。
除去“大部分”细粒是指从该热第一气流中除去一定量的细粒以使下游加工不受负面影响;因此,应除去至少大部分细粒。一定较小量的超细材料可在不会显著不利地影响下游加工的程度上留在该热第一气流中。通常,除去至少大约90重量%,或至少大约95重量%,或至少大约98重量%的粒度大于大约20微米,或大于大约10微米,或大于大约5微米的细粒。
第一气流在离开反应器后通常包含占第一气流中的甲烷、二氧化碳、一氧化碳和氢气摩尔数的至少大约20摩尔%的甲烷。此外,第一气流通常包含占第一气流中的甲烷、二氧化碳、一氧化碳和氢气摩尔数的至少大约50摩尔%的甲烷加上二氧化碳。
第一气流可以在引入本文所述的用于甲烷化法的酸气脱除(AGR)工艺之前供应至热交换器以降低第一气流的温度(例如以产生温度小于第一气流的冷却气流)。
根据气化条件,可以生成在大约450℃至大约900℃(更通常大约650℃至大约800℃)的温度下、具有大约50 psig至大约1000 psig(更通常大约400 psig至大约600 psig)的压力和大约0.5 ft/sec至大约2.0 ft/sec(更通常大约1.0 ft/sec至大约1.5 ft/sec)的速度的第一气流。当存在时,由任何一个或多个热交换器单元提取的热能可以例如用于生成蒸汽。所得冷却气流通常在大约250℃至大约600℃(更通常大约300℃至大约500℃)的温度、大约50 psig至大约1000 psig(更通常大约400 psig至大约600 psig)的压力和大约0.5 ft/sec至大约2.5 ft/sec(更通常大约1.0 ft/sec至大约1.5 ft/sec)的速度下离开热交换器。
可以使用后继酸气脱除单元从第二气流中除去大部分的H2S和CO2并生成第三气流,其可以是甲烷产物流或可经过进一步提纯/处理以产生甲烷产物流。酸气脱除法通常包括使第二气流与溶剂,如单乙醇胺、二乙醇胺、甲基二乙醇胺、二异丙基胺、二乙二醇胺、氨基酸钠盐的溶液、甲醇、热碳酸钾等接触以生成负载(laden)CO2和/或H2S的吸收剂。一种方法涉及使用Selexol®(UOP LLC, Des Plaines,
IL USA)或Rectisol®(Lurgi AG, Frankfurt am
Main, Germany)溶剂,其具有两个序列(train);各序列由H2S吸收剂和CO2吸收剂构成。
所得第三气流可包含CH4、H2和当耐硫变换单元(见上)不是该方法的一部分时,任选CO,和通常少量的CO2和H2O。在之前并入的US2009/0220406A1中描述了从第二气流中除去酸气的一种方法。
应通过酸气脱除单元除去至少大部分(例如基本全部)CO2和/或H2S(和其它剩余痕量污染物)。在酸气脱除的情况下,“基本”除去是指除去足够高百分比的该组分以产生所需最终产物。实际脱除量因此可随组分而变。对“管道级天然气”而言,只可存在痕量(至多)H2S,尽管可能容许更高量的CO2。
通常,酸气脱除应从第二气流中除去至少大约85%,或至少大约90%,或至少大约92%的CO2,和至少大约95%,或至少大约98%,或至少大约99.5%的H2S。
应使所需产物(甲烷)在酸气脱除步骤中的损失最小化以使该酸气脱除流包含至少大部分(和基本全部)来自第二气流的甲烷。通常,这种损失应为来自冷却的第一气流的甲烷的大约2摩尔%或更少,或大约1.5摩尔%或更少,或大约1摩尔%或更少。
附加的集成气化实施方案
如上文更详细描述,在某些实施方案中,煤原料可包含多种煤。例如,在本发明的一个实施方案中,煤原料可包含无烟煤、烟煤、次烟煤和/或褐煤中的一种或多种。
在本发明的某些实施方案中,将该基本自由流动的微粒和过热蒸汽引入多个催化气化器。来自分开的催化气化器的第一气流可随后单独地进一步处理,或可以在下游工艺中的任何点重组。
本领域技术人员会认识到,本文所述的方法可以例如作为连续法或分批法进行。
在某些实施方案中,该方法是单程法。在“单程(once-through)”法中,碳基气体不从催化气化器下游的任何气流再循环至气化器。但是,在本发明的另一些实施方案中,该方法可包括再循环的碳基气流。例如,为了在启动条件中提供催化气化器中氢气和/或一氧化碳的平衡,含甲烷的料流(取自例如,富集甲烷的第一气流、富集甲烷的第二料流或甲烷产物流)可以在重整器中重整以形成一氧化碳和氢气,使它们与煤原料、富氧气流和气化催化剂一起进入催化气化器。但是,在连续运行中,以“单程”法形式运行该方法是合意的。
本发明提供在某些实施方案中能由煤原料的催化气化生成“管道级天然气”的方法。“管道级天然气”通常是指(1)在纯甲烷(其热值在标准大气条件下为1010 btu/ft3)的热值的±5%内,(2)基本不含水(通常露点为大约-40℃或更小)和(3)基本不含有毒或腐蚀性污染物的天然气。在本发明的一些实施方案中,上述方法中所述的甲烷产物流满足这样的要求。
管道级天然气可含有甲烷以外的气体,只要所得气体混合物具有在1010 btu/ft3的±5%内的热值并且既无毒又非腐蚀性。因此,甲烷产物流可包含热值小于甲烷并仍有资格作为管道级天然气的气体,只要其它气体的存在不会将该气流的热值降至低于950 btu/scf(折干计算)。甲烷产物流可例如包含最多大约4摩尔%氢气并仍充当管道级天然气。一氧化碳的热值高于氢气;因此,管道级天然气可以在不降低该气流的热值的情况下含有甚至更高的CO百分比。适合用作管道级天然气的甲烷产物流优选具有少于大约1000 ppm CO。
任选的补充气化法
(a)催化剂回收
基本自由流动的微粒(30)在所述条件下的反应通常提供第一气流和来自催化气化器的固体炭产物。固体炭产物通常包含一定量的未反应煤和夹带的催化剂。可经由炭出口从反应室中移除固体炭产物以用作甲烷化催化剂、取样、清除和/或催化剂回收。
含有夹带的催化剂的固体炭产物可送往催化剂回收单元,在此回收催化剂并再循环用于步骤(D)中使用的水溶液。
本文所用的术语“夹带的催化剂”是指包含碱金属组分的化学化合物。例如,“夹带的催化剂”可包括,但不限于,可溶碱金属化合物(如碱金属碳酸盐、碱金属氢氧化物和碱金属氧化物)和/或不可溶的碱金属化合物(如碱金属硅铝酸盐)。下面论述和在之前并入的US2007/0277437A1、US2009/0165383A1、US2009/0165382A1、US2009/0169449A1和US2009/0169448A1中详细论述与从催化气化器中提取的炭结合的催化剂组分的性质及其回收方法。
可以经炭出口(其是闭锁料斗系统)定期从各催化气化器中提取固体炭产物,尽管其它方法是本领域技术人员已知的。除去固体炭产物的方法是本领域技术人员公知的。可以使用例如EP-A-0102828教导的一种这样的方法。
可以将来自催化气化器的炭送入如下所述的催化回收单元。或者,这种炭可以送入如下所述的催化剂回收单元操作。这种炭还可以分成多个料流,其中之一可送入催化剂回收单元,另一个可用作甲烷化催化剂(如上所述)并且不用于催化剂回收处理。
在某些实施方案中,可以回收从催化气化器的反应室中提取的固体炭产物中的夹带的催化剂中的碱金属,并可以用催化剂补充流补偿任何未回收的催化剂。原料中的氧化铝和二氧化硅越多,获得更高碱金属回收率的成本越高。
在一个实施方案中,来自催化气化器的固体炭产物可以用再循环气体和水骤冷以提取一部分夹带的催化剂。可以将该回收的催化剂送入催化剂加载工艺以再利用碱金属催化剂。可以将废炭例如送往任何一个或多个原料制备操作以再用于制备催化原料,燃烧以向一个或多个蒸汽发生器供能(如之前并入的US2009/0165376A1和US2009/0217585A1中所公开),或就这样用于各种用途,例如,作为吸收剂(如之前并入的US2009/0217582A1中所公开)。
在US4459138以及之前并入的US2007/0277437A1、US2009/0165383A1、US2009/0165382A1、US2009/0169449A1和US2009/0169448A1中描述了其它特别有用的回收和再循环法。关于进一步工艺细节,必须参考这些文献。
催化剂可以再循环到一个催化剂加载过程或多个催化剂加载过程的组合。例如,所有再循环的催化剂可供应至一个催化剂加载过程,而另一过程仅使用补充催化剂。也可以基于各个催化剂加载过程控制再循环的催化剂 vs 补充催化剂的水平。
(b)气体提纯
产物提纯可包括例如,任选的痕量污染物脱除、氨脱除和回收,和耐硫变换工艺(sour shift processes)。可以在直接来自热交换器的冷却的第一气流上或在已经过如下所述的(i)一个或多个痕量污染物脱除单元;(ii)一个或多个耐硫变换单元;(iii)一个或多个氨回收单元和(iv)耐硫催化甲烷化反应器(见上)中的一个或多个的冷却的第一气流上进行酸气脱除。
(1)痕量污染物脱除
如本领域技术人员熟悉的那样,气流(例如,冷却的第一气流)的污染程度取决于用于制备该催化的煤原料的煤的性质。例如,某些煤,如Illinois #6,具有高硫含量,造成更高的COS污染;另一些煤,如Powder River Basin煤,含有显著的汞含量,其会在气化反应器中挥发。
可以从气流(例如,冷却的第一气流)中除去COS,例如,通过COS水解(参见US3966875、US4011066、US4100256、US4482529和US4524050),使该冷却的第一气流经过粒状石灰石(参见,US4173465)、酸性缓冲的CuSO4溶液(参见,US4298584)、含有环丁砜(tetramethylene sulfone)(环丁砜,参见,US3989811)的烷醇胺吸收剂,如甲基二乙醇胺、三乙醇胺、二丙醇胺或二异丙醇胺;或用冷藏液态CO2对流洗涤该冷却的第一气流(参见,US4270937和US4609388)。
可以如下从气流(例如,冷却的第一气流)中除去HCN:通过与硫化铵或多硫化铵反应生成CO2、H2S和NH3(参见,US4497784、US4505881和US4508693),或用甲醛、接着多硫化铵或多硫化钠两阶段洗涤(参见,US4572826),用水吸收(参见,US4189307)和/或通过经过氧化铝负载的水解催化剂,如MoO3、TiO2和/或ZrO2来分解(参见,US4810475、US5660807和US 5968465)。
可以如下从气流(例如,冷却的第一气流)中除去元素汞:通过被硫酸活化的碳吸收(参见,US3876393),通过被硫浸渍的碳吸收(参见,US4491609),通过被含H2S的胺溶剂吸收(参见,US4044098),通过被银或金浸渍的沸石吸收(参见,US4892567),用过氧化氢和甲醇氧化成HgO(参见,US5670122),在SO2存在下用含溴或碘的化合物氧化(参见,US6878358),用含H、Cl和O的等离子体氧化(参见,US6969494),和/或用含氯的氧化气体氧化(例如,ClO,参见,US7118720)。
当使用水溶液除去任何或全部COS、HCN和/或Hg时,可以将痕量污染物脱除单元中产生的废水送往废水处理单元。
当存在时,特定痕量污染物的痕量污染物脱除单元应从如此处理过的气流(例如,冷却的第一气流)中除去至少大部分(或基本全部)的该痕量污染物,通常至等于或低于所需产物流的规格界限的水平。通常,痕量污染物脱除单元应从冷却的第一气流中除去至少90%,或至少95%,或至少98%的COS、HCN和/或汞。
(2)耐硫变换
气流(例如,冷却的第一气流)也可以在水性介质(如蒸汽)存在下经受水煤气变换反应以将一部分CO转化成CO2并提高H2的比例。在某些实例中,提高的氢气含量的生成可用于形成可如下所述与甲烷分离的氢气产物气体。在另一些实例中,耐硫变换法可用于调节供应至后继甲烷化反应器的气流(例如冷却的第一气流)中的一氧化碳:氢气比。可以在直接来自热交换器的冷却的第一气流上或在已经过痕量污染物脱除单元的冷却的第一气流上进行该水煤气变换处理。
例如在US7074373中详细描述了耐硫变换法。该方法包括加入水或利用该气体中所含的水,并使所得水-气体混合物在蒸汽重整催化剂上绝热反应。典型的蒸汽重整催化剂包括在耐热载体上的一种或多种第VIII族金属。
在含CO的气流上进行高硫天然气变换反应(sour gas shift reaction)的方法和反应器是本领域技术人员公知的。合适的反应条件和合适的反应器可以随必须从该气流中脱除的CO的量而变。在一些实施方案中,该高硫天然气变换可以在单阶段中在从大约100℃,或从大约150℃,或从大约200℃,到大约250℃,或到大约300℃,或到大约350℃的温度范围内进行。在这些实施方案中,可以用本领域技术人员已知的任何合适的催化剂催化该变换反应。此类催化剂包括,但不限于,Fe2O3-基催化剂,如Fe2O3-Cr2O3催化剂,和其它过渡金属基催化剂和过渡金属氧化物基催化剂。在另一些实施方案中,可以在多个阶段中进行该高硫天然气变换。在一个具体实施方案中,在两个阶段中进行该高硫天然气变换。这种两阶段法使用高温序列,随后低温序列。该高温变换反应的气体温度为大约350℃至大约1050℃。典型的高温催化剂包括,但不限于,任选与较少量的氧化铬结合的氧化铁。低温变换的气体温度为大约150℃至大约300℃,或大约200℃至大约250℃。低温变换催化剂包括,但不限于,可负载在氧化锌或氧化铝上的氧化铜。在之前并入的US2009/0246120A1中描述了适用于该耐硫变换过程的方法。
通常用热交换器和蒸汽发生器进行蒸汽变换以便有效利用热能。利用这些构件的变换反应器是本领域技术人员公知的。在之前并入的US7074373中阐述了合适的变换反应器的一个实例,尽管本领域技术人员已知的其它设计也有效。在高硫天然气变换程序后,一种或多种冷却的第二气流各自通常含有CH4、CO2、H2、H2S、NH3和蒸汽。
在一些实施方案中,合意的是,从冷却气流中除去大部分的CO并由此转化大部分的CO。 “基本”转化在这种情况下是指转化足够高百分比的该组分以产生所需最终产物。通常,离开变换反应器(在此已转化大部分的CO)的料流具有大约250 ppm或更少CO,更通常大约100 ppm或更少CO的一氧化碳含量。
在另一些实施方案中,合意的是,仅转化一部分CO以提高用于后继甲烷化(例如整理甲烷化(trim methanation))的H2比例,其通常要求大约3或更大,或大于大约3,或大约3.2或更大的H2/CO摩尔比。
(3)氨回收
如本领域技术人员熟悉的那样,生物质的气化和/或利用空气作为催化气化器的氧源会在产物气流中产生显著量的氨。任选地,该冷却的第一气流可以在一个或多个氨回收单元中用水洗涤以回收氨。可以例如在直接来自热交换器的冷却的第二气流上或在已经过(i)一个或多个痕量污染物脱除单元;和(ii)一个或多个耐硫变换单元之一或两者的气流(例如,冷却的气流)上进行氨回收处理。
在洗涤后,该气流(例如,冷却的第一气流)可包含至少H2S、CO2、CO、H2和CH4。当该冷却的气流之前已经过耐硫变换单元时,在洗涤后,该气流可包含至少H2S、CO2、H2和CH4。
可以根据本领域技术人员已知的方法从洗涤器水中回收氨,其通常以水溶液(例如,20重量%)形式回收。可以将废洗涤器水送入废水处理单元。
当存在时,除氨法应从洗涤过的料流(例如,冷却的第一气流)中除去至少大部分(基本所有)的氨。“基本”除去在除氨情况下是指除去足够高百分比的该组分以产生所需最终产物。通常,除氨法除去洗涤过的第一气流的氨含量的至少大约95%,或至少大约97%。
(4)甲烷化
如刚刚描述,本发明的集成气化法可以利用至少一个甲烷化步骤由一个或多个第一气流(例如热第一气流和/或冷却的第一气流)和/或第三气流中存在的一氧化碳和氢气生成甲烷。例如,在本发明的一个实施方案中,冷却的第一气流中存在的至少一部分一氧化碳和至少一部分氢气在催化甲烷化反应器中、在耐硫的炭甲烷化催化剂存在下反应,以产生富集甲烷的第一气流,其随后可经受如上所述的酸气脱除。在本发明的另一些实施方案中,如果第二气流和/或第三气流包含氢气和多于100 ppm的一氧化碳,则该气流中存在的一氧化碳和氢气可以在催化甲烷化反应器,例如整理甲烷化反应器中在甲烷化催化剂,例如炭甲烷化催化剂存在下反应以产生富集甲烷的气流。在本发明的某些实施方案中,这两个甲烷化步骤都进行。
第一气流可能含有显著量的硫化氢,其会钝化甲烷化催化剂,如包含铁、镍和钴化合物的催化剂,因此,该甲烷化反应器可含有耐硫甲烷化催化剂,如上述炭甲烷化催化剂,或本发明的炭甲烷化催化剂和另外的耐硫甲烷化催化剂,例如硫化钼和/或硫化钨的混合物。例如参见之前并入的美国专利申请序号No. 12/562,919。耐硫甲烷化催化剂的其它实例包括,但不限于,US4243554、US4243553、US4006177、US3958957、US3928000、US2490488、Mills和Steffgen, in Catalyst
Rev. 8, 159(1973)和Schultz等人, U.S. Bureau of
Mines, Rep. Invest. No. 6974(1967)中公开的催化剂。
(c)甲烷脱除
可以通过本领域技术人员已知的任何合适的气体分离方法,包括但不限于,低温蒸馏和使用分子筛或气体分离(例如陶瓷)膜处理由煤原料气化生成的气流,例如第三气流以分离和回收CH4。例如,在存在耐硫变换单元时,气流可含有甲烷和氢气,它们可根据本领域技术人员熟悉的方法分离。
其它气体提纯法包括通过如之前并入的US2009/0246120A1、US2009/0259080A1和US2009/0260287A1中公开的甲烷水合物生成。
(d)发电
可以向一个或多个发电机,如汽轮机提供由蒸汽源生成的一部分蒸汽,以产生可用在该工厂内或可出售给电力网的电力。该气化法内产生的高温高压蒸汽也可供应给发电用的汽轮机。例如,在与热第一气流接触的热交换器中捕获的热能可用于生成向汽轮机供应的蒸汽。
(e)废水处理
由痕量物脱除、耐硫变换、除氨和/或催化剂回收工艺中的任一项或多项产生的废水中的残留污染物,可以在废水处理单元中除去以使回收的水能在该工厂内再循环和/或能根据本领域技术人员已知的任何方法处置来自该工厂工艺的水。此类残留污染物可包含例如酚、CO、CO2、H2S、COS、HCN、氨和汞。例如,可通过废水酸化至大约3的pH值、在汽提塔中用惰性气体处理酸性废水、将pH提高至大约10并用惰性气体二次处理废水以除去氨,来除去H2S和HCN(参见US5236557)。可通过在残留焦炭粒子存在下用氧化剂处理废水以将H2S转化成不可溶硫酸盐(其可通过浮选或过滤来除去)来除去H2S(参见US4478425)。可通过使废水与含有一价和二价碱性无机化合物的碳质炭(例如固体炭产物或在催化剂回收后的废炭,见上文)接触并调节pH来除去酚(参见US4113615)。也可以通过用有机溶剂萃取接着在汽提塔中处理废水来除去酚(参见US3972693、US4025423和US4162902)。
(f)多序列法
在本发明的方法中,各方法可以在一个或多个加工单元中进行。例如,可以从一个或多个催化剂加载和/或原料制备单元操作向一个或多个催化气化器供应煤原料。类似地,一个或多个催化气化器产生的第一气流可以如例如之前并入的美国专利申请序号Nos. 12/492,467、12/492,477、12/492,484、12/492,489和12/492,497中所公开的那样根据特定系统构造单独地或经它们的组合在热交换器、耐硫催化甲烷化反应器、酸气脱除单元、整理甲烷化反应器和/或甲烷脱除单元中加工或提纯。
在某些实施方案中,该方法采用两个或更多个催化气化器(例如,2 – 4个催化气化器)。在这些实施方案中,该方法可含有在催化气化器之前的用于最终向多个催化气化器提供催化的煤原料的发散性加工单元(divergent processing units)(即,小于催化气化器总数)和/或在催化气化器后的用于加工由多个催化气化器产生的多个第二气流的会聚性加工单元(convergent processing units)(即,小于催化气化器总数)。
例如,该方法可利用(i)发散性催化剂加载单元以向催化气化器提供催化的煤原料;(ii)发散性煤加工单元以向催化剂加载单元提供煤微粒;(iii)会聚性热交换器以从催化气化器接收多个第一气流;(iv)会聚性耐硫甲烷化反应器以从热交换器接收多个冷却的第一气流;(v)会聚性酸气脱除单元以接收来自热交换器的多个冷却的第一气流或来自耐硫甲烷化反应器的富集甲烷的第一气流(在存在时);或(vi)会聚性催化甲烷化反应器或整理甲烷化反应器以从酸气脱除单元接收多个第二气流。
当该系统含有会聚性加工单元时,各会聚性加工单元可被选择为具有接收大于供入会聚性加工单元的总气流的1/n部分的容积,其中n是会聚性加工单元数。例如,在利用4个催化气化器和2个热交换器从催化气化器中接收4个第二气流的方法中,可以选择热交换以具有接收大于这4个第二气流的总气体体积的1/2(例如1/2至3/4)的容积,并与两个或更多个催化气化器连通,以致无需关闭整个加工系统就能常规维护一个或多个热交换器。
类似地,当该系统含有发散性加工单元时,各发散性加工单元可被选为具有接收大于供入会聚性加工单元的总进料流的1/m部分的容积,其中m是发散性加工单元数。例如,在利用2个催化剂加载单元和单个煤加工单元向催化剂加载单元提供煤微粒的方法中,可以选择各自与煤加工单元连通的催化剂加载单元以具有从单个煤加工单元中接收煤微粒总体积的1/2至全部的容积,以致无需关闭整个加工系统就能常规维护催化剂加载单元之一。
Claims (10)
1.由煤原料制备基本自由流动的载有碱金属气化催化剂的煤微粒的方法,该方法包括下列步骤:
(A)提供具有初始含湿量和初始酸性官能团浓度的煤原料;
(B)研磨该煤原料;
(C)将来自步骤(B)的煤原料分级至指定的粒度分布以产生具有基质并包含第二浓度的酸性官能团的煤微粒;
(D)使该煤微粒与一定量的包含一定浓度的碱金属气化催化剂的水溶液接触,以形成具有指定的碱金属原子/碳原子比和第二含湿量的载有碱金属气化催化剂的煤微粒湿滤饼;和
(E)按需要热处理该载有碱金属气化催化剂的煤微粒湿滤饼以降低第二含湿量,从而制造基本自由流动的微粒形式的载有碱金属气化催化剂的煤微粒,
其特征在于:
(a)酸性官能团的第二浓度为初始浓度的至少50%;
(b)指定的粒度分布具有至少20微米的d5粒度、1000微米或更小的d95粒度和75至350微米的d50粒度;
(c)步骤(D)的指定的碱金属原子/碳原子比足以提供0.01至0.10的该基本自由流动的载有碱金属气化催化剂的煤微粒中的碱金属原子/碳原子比;
(d)来自步骤(D)的载有碱金属气化催化剂的煤微粒湿滤饼是基本不滴液的;
(e)步骤(D)中水溶液的量和碱金属气化催化剂的浓度足以提供该载有碱金属气化催化剂的煤微粒湿滤饼中的指定的碱金属原子/碳原子比;
(f)步骤(D)中的接触在基本大气压下和在基本等于或低于该水溶液的沸点的高温下,在搅拌下进行指定时间量,它们各自的量足以一起使该碱金属气化催化剂基本均匀分布在该不滴液的载有碱金属气化催化剂的煤微粒湿滤饼中;
(g)该不滴液的载有碱金属气化催化剂的碳质微粒湿滤饼在第一温度下离开步骤(D)并在基本相同温度下送入热处理步骤(E);和
(h)该基本自由流动的载有碱金属气化催化剂的煤微粒包含一定含量的碱金属原子,其中大于50%的含量的碱金属原子通过酸性官能团上的离子交换与煤微粒基质缔合。
2.根据权利要求1的方法,其特征在于该研磨步骤(B)是干磨步骤。
3.根据权利要求2的方法,其特征在于降低该碳质原料的初始含湿量以便在将步骤(D)中使用的水溶液的量计入考虑时,来自步骤(D)的湿滤饼是基本不滴液的。
4.根据权利要求2或权利要求3的方法,其特征在于在干磨的同时干燥该碳质原料。
5.根据权利要求1的方法,其特征在于该研磨步骤(B)是产生湿磨煤原料的湿磨步骤。
6.权利要求5的方法,其特征在于降低该湿磨煤原料的含湿量以便在将步骤(D)中使用的水溶液的量计入考虑时,来自步骤(D)的湿滤饼是基本不滴液的。
7.根据权利要求1的方法,其特征在于该煤包含无烟煤、烟煤、次烟煤或褐煤中的一种或多种;且该碱金属包含钾、钠或两者。
8.根据权利要求1的方法,其特征在于该湿滤饼是不滴液的。
9.根据权利要求1的方法,其特征在于步骤(D)的接触在80℃至100℃的温度下进行;且步骤(D)的接触进行5分钟至60分钟的一段时间。
10.将微粒组合物转化成多种气态产物的方法,包括下列步骤:
(a)向气化反应器供应碳质微粒组合物;
(b)使该微粒组合物在气化反应器中在蒸汽存在下和在合适的温度和压力下反应以形成多种气体,包括甲烷以及氢气、一氧化碳、二氧化碳、硫化氢、氨和其它高级烃中的至少一种或多种;和
(c)至少部分分离所述多种气态产物以产生包含主要量的气态产物之一的蒸汽,
其特征在于根据权利要求1-9任一项的方法制备该碳质微粒。
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AU2009335163A1 (en) | 2011-07-07 |
US8734548B2 (en) | 2014-05-27 |
EP2370549A1 (en) | 2011-10-05 |
KR101290423B1 (ko) | 2013-07-29 |
AU2009335163B2 (en) | 2013-02-21 |
US20100168494A1 (en) | 2010-07-01 |
CN102272268A (zh) | 2011-12-07 |
KR20110102927A (ko) | 2011-09-19 |
WO2010078298A1 (en) | 2010-07-08 |
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