CN101175948A - 降低煤燃烧中的汞排放量 - Google Patents
降低煤燃烧中的汞排放量 Download PDFInfo
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Abstract
本发明提供了用于降低燃料例如煤燃烧时的汞排放量的方法和组合物。本发明提供了多种含有减少煤燃烧时向大气中排放的汞和/或硫水平的组分的吸附剂组合物。在多种实施方案中,所述的吸附剂组合物在燃烧前直接加入燃料中;部分在燃烧前加入燃料中并且部分加入烟道气后燃区中;或完全加入烟道气后燃区中。在优选的实施方案中,该吸附剂组合物包括一种卤素源且优选包括一种钙源。在卤素中,优选碘和溴。在多种实施方案中,无机溴化物构成了吸附剂组合物的一部分。
Description
技术领域
本发明提供用于降低含汞燃料例如煤燃烧时向大气中排放汞的水平的组合物及方法。具体地说,本发明提供在燃烧过程中向燃煤系统加入各种卤素和其它吸附剂组合物。
背景技术
存在于全世界的大量煤资源能够满足下两个世纪世界能源的大部分需求。高硫煤含量丰富,但需要补救步骤以防止过量的硫燃烧时释放到大气中。在美国,低硫煤以低BTU值煤的形式存在于怀俄明和蒙大拿的Powder River盆地中,存在于北达科他和南达科他的中北部地区的褐煤矿床中,以及德克萨斯的褐煤矿床中。但即使煤中含硫量低,它们仍然含有不可忽视的游离的和氧化的汞。
不幸的是,在煤燃烧时汞至少被部分挥发。因此,汞不易残留在灰烬中,而是变成烟道气的一种成分。如果不采取补救措施,汞易于从燃煤设备中逃逸而引起环境问题。目前一些汞通过设备来捕获,例如用湿涤气器和SCR控制系统。但是,大部分汞未被捕获并因此通过排气烟囱释放。
在美国,1990年的清洁空气法修正案(Clean Air Act Amendment)关注了汞的管理和控制。由环保总署(Environmental Protection Agency)(EPA)于1997年向国会递交的一份关于汞的研究报告中进一步明确了对美国电厂排放汞的限制。2000年12月,EPA决定控制汞排放,并于2004年1月和3月出版了提议的清洁空气汞条例。至今,美国环保总署已公布了一套对美国燃煤工厂要求的汞排放量降低的条例。
除了倾向于从煤燃烧的烟道气中部分除去汞的湿涤气器和SCR控制系统外,其他的控制方法包括使用活性炭体系。这种体系的应用易造成高处理成本和高投资成本。此外,活性炭体系的应用导致废气处理中收集的飞灰的碳污染,所述的废气处理例如袋式除尘器(bag house)和静电除尘器。
在美国,进入大气中的汞排放量约为50吨/年。释放物的一大部分来自燃煤设施例如电厂的排放。汞是一种已知的环境有害物,并会导致人类和非人类的动物物种的健康问题。为了维护公众的健康并保护环境,动力工业正持续开发、测试并实施可降低其工厂的汞排放量的系统。人们希望在含碳物质的燃烧中,有一个方法能在燃烧阶段后捕获并保留汞和其它不需要的化合物,以使它们不被释放到大气中。
发明内容
本发明提供了用于降低燃料例如煤燃烧时汞排放量的方法和组合物。本发明提供了多种吸附剂组合物,其含有减少煤燃烧时向大气中排放汞和/或硫的水平的组分。在多种实施方案中,所述的吸附剂组合物在燃烧前直接加入燃料中;部分在燃烧前加入燃料中并且部分加入烟道气后燃区中;或完全加入烟道气后燃区中。在优选的实施方案中,该吸附剂组合物包括一个卤素源且优选地包括一个钙源。在卤素中,优选碘和溴。在多种实施方案中,无机溴化物构成了吸收剂组合物的一部分。
在多种实施方案中,含有溴或碘的汞吸附剂组合物在燃烧前以粉末或液体的形式被加入燃料中。或者,含有卤素如溴或碘的吸附剂组合物在燃烧室后的一点被注入烟道气中,该点的温度高于约1500(约800℃)。
在优选的实施方案中,所述的吸附剂组合物还含有其他组分,尤其是含有一个钙源。因此,在一个实施方案中,本发明提供将多元素氧化剂、助剂和吸附剂在燃烧前和/或燃烧后一次及多次施用于炉内的煤中。在多种实施方案中,燃烧时吸附剂组合物的组分产生陶瓷特性且随后该组分与含碳材料一起钙化。在多种实施方案中,吸附剂组合物的使用通过以下方式降低了汞排放量,即通过使用多元素补救处理材料,例如氧化钙、溴化钙、其他卤化钙以及硅、铝、铁、镁、钠和钾的氧化物捕获和稳定氧化的和游离的汞。
在优选的实施方案中,燃煤设施的汞排放量降低到这样一个程度,即煤中90%或更多的汞在释放入大气之前被捕获。所述的汞的补救处理方法可与吸附剂组合物和其它从燃烧气体中除去硫的方法一起使用。因此,在优选的实施方案中,伴随90%以上的汞排放量的降低,硫也大量减少。
从下文中的详细说明人们将清楚本发明其它应用领域。应当理解的是,尽管详细说明和具体的实施例表示了本发明的优选实施方案,但只打算用于示例说明而并不打算限制本发明的范围。
具体实施方式
以下对于一个或多个优选实施方案的说明在本质上是仅仅是示例性的,而不是想要限制本发明、其应用或用途。
在多种实施方案中,本发明提供了用于降低来自含汞燃料例如煤燃烧的汞排放量的组合物及方法。本发明中将描述燃烧含汞燃料的系统和设备,尤其关注燃煤设备诸如电力设施中使用的燃煤设备的实例。此类设备通常具有某种进料机械装置以向炉中加入煤,在炉中煤被点燃或燃烧。所述的进料机械装置可以是任何适于使用的装置或设备。非限制性的实例包括输送机系统、螺杆挤出系统等。操作时,将含汞燃料例如煤以适于从炉中获得所需产量的速率输入炉内。一般地,炉内的输出物用于使水沸腾生成蒸汽以提供直接热量,或将蒸汽用于驱动汽轮机,最终导致电的产生。
将煤送入炉内,并在氧的存在下点燃。燃烧温度中典型的火焰温度是2700至约3000。在用于燃烧输入的燃料的炉或锅炉之后,设备内提供燃烧气体的对流通道,为方便起见有时也将燃烧气体称为烟道气。热的燃烧气体和空气以对流的方式通过对流通道向下游方向(即相对于火球的下游)离开火焰。所述设备的对流通道包括多个区域,每个区域以其中的气体温度和燃烧产物为特征。一般地,燃烧气体的温度随着其从火球向下游的移动而降低。燃烧气体中含有二氧化碳以及多种不想要的含硫和汞的气体。对流通道中还存在着多种被高温气体夹带的灰尘。为在排放入大气之前除去灰尘,使用了微粒清除系统。在对流通道中可安置多种此类清除系统,如静电除尘器和袋式除尘器。另外,还可在对流通道中放置化学涤气器。此外,可提供多种仪表用于监测气体的成分,如硫和汞。
煤在炉内在约2700-3000的温度燃烧,飞灰和燃烧气体自炉内在对流通道中向下游移动到温度不断下降的区域。最接近火球的下游是一个温度低于2700的区域。再往下可到达温度已冷却至约1500的点。在这两点之间是温度介于约1500至约2700的区域。再往下游可到达温度低于1500的区域,等等。再沿对流通道往下,气体和飞灰通过更低温度的区域直至到达袋式除尘器或静电除尘器,其在气体被排放到烟囱之前,一般具有的温度为约300。
在多种实施方案中,本发明的方法需要将一种汞吸附剂以如下方式应用:
燃烧前直接加入燃料例如煤中(“燃烧前”添加);
燃烧后在温度为2700至1500的区域中直接加入气流中(“燃烧后”添加);或者
以燃烧前添加和燃烧后添加结合的方式。
在多种实施方案中,燃烧中产生的氧化汞进入袋式除尘器或静电除尘器,并成为燃煤设备总灰尘量的一部分。灰尘中的重金属不会降低到规定水平以下。
在多种实施方案中,监测燃煤设备的汞排放量。依据从设备排放前的烟道气中汞的水平,在燃烧前和/或燃烧后向燃料中加入的吸附剂组合物的量增加、减少、或维持不变。一般地,人们希望清除尽可能高的汞含量。在典型的实施方案中,以煤中汞的总量为基准,除汞率可达90%或更大。该值是指从烟道气中清除的汞,以使其不会通过烟囱释放入大气。为使燃煤过程中加入的吸附剂的量最小以减少炉中产生灰尘的总量,就需要在多种环境中进行汞排放量的检测,以将吸附剂组合物的添加比率降低至可获得所需的汞减少量而不会向系统中加入过量物质的数值。
因此,在一个实施方案中提供了一种用于燃烧煤时减少释放入大气的汞量的方法。该方法包括首先将含有一种卤素化合物的一种吸附剂组合物应用于煤中。然后将该煤输送至燃煤设备的炉内。然后,含有吸附剂组合物的煤在炉中燃烧形成灰尘和燃烧气体。该燃烧气体含有汞、硫和其它组分。为达到燃烧气体中汞的所需减少量以限制向大气中的排放,燃烧气体中汞的水平优选通过分析测量其水平而进行监测。在优选的实施方案中,燃烧前用于煤中的吸附剂组合物的量依据燃烧气体中测得的汞水平的数值进行调整。
在另一个实施方案中,在燃烧后在具有约1500至2700(约815℃至1482℃)的温度的区域中向燃煤系统中加入一种汞吸附剂。提供了一种用于减少含汞的煤燃烧时向大气中释放汞的水平的方法。该燃烧过程在一个包括一个炉和一条用于燃烧气体的对流通道的燃煤系统中进行。该方法包括在炉中燃烧煤,并向对流通道内燃烧气体温度为1500至2700的点处注入一种含有一种卤素的吸附剂。如需要,应监测并测量离开设备的气体中汞的水平。根据从设备中逃逸的汞的量——其由监测时测定的值反映,汞吸附剂的添加比率可以增加、减少或维持不变。在另一个实施方案中,一种含有一种卤素的汞吸附剂既可用于燃烧前的煤中,也可注入对流通道内燃烧气体温度为1500至2700的点处。
含一种卤素化合物的吸附剂组合物包括一种或多种含有一种卤素的有机或无机化合物。卤素包括氯、溴和碘。优选的卤素为溴和碘。上述的卤素化合物是卤素源,尤其是溴和碘源。对于溴,卤素源包括各种溴的无机盐,包括溴化物、溴酸盐和次溴酸盐。在多种实施方案中,有机溴化合物由于其成本或可得性的原因是次优选的。但是,含有适当高水平溴的有机溴源被认为在本发明的范围内。有机溴化合物的非限制性的实例包括二溴甲烷、溴乙烷、溴仿和四溴化碳。非限制性的碘源包括次碘酸盐、碘酸盐和碘化物,优选碘化物。
当卤素化合物是一种无机取代物时,其优选为一种碱金属或一种碱土金属元素的一种含溴或碘的盐。优选的碱金属包括锂、钠和钾,而优选的碱土金属元素包括铍、镁和钙。对于卤素化合物,尤其优选的是碱土金属例如钙的溴化物和碘化物。
含有卤素的吸附剂组合物以液体或固体组合物的形式提供。当其为一种液体组合物时,该吸附剂组合物优选包括一种如上描述的溴或碘的化合物的水溶液。本发明的降低煤燃烧时向大气中释放汞的水平的方法涉及将吸附剂组合物以液体或固体组合物的形式应用于燃煤工艺中。在一个实施方案中,该吸附剂组合物在燃烧前被加入煤中,而在另外一个实施方案中,该吸附剂组合物被注入燃煤设备的对流通道内一个温度为1500至2700的区域中。在多种实施方案中,吸附剂的加入可以既在燃烧前也在燃烧后进行。在一个优选的实施方案中,一种含有一种卤素的水性吸附剂在燃烧前喷洒在煤上,并且煤在仍被水润湿时送入炉内。
在多种实施方案中,液体汞吸附剂包括一种含有5至60重量%的一种可溶性溴盐或碘盐的溶液。优选的溴盐和碘盐的非限制性实例包括溴化钙和碘化钙。在多种实施方案中,液体吸附剂含有5-60重量%的溴化钙和/或碘化钙。考虑到燃烧前向煤中加料的效能,在多种实施方案中优选加入含有尽可能高水平的溴或碘化合物的汞吸附剂。在一个非限制性实施方案中,该液体吸附剂含有50重量%或更多的卤素化合物,例如溴化钙或碘化钙。
在多种实施方案中,含有一种卤素化合物的吸附剂组合物还含有一种硝酸盐化合物、一种亚硝酸盐化合物或一种硝酸盐化合物和亚硝酸盐化合物的混合物。优选的硝酸盐和亚硝酸盐化合物包括镁和钙的硝酸盐和亚硝酸盐,优选钙的硝酸盐和亚硝酸盐。因此,在一个优选的实施方案中,该汞吸附剂组合物含有溴化钙。溴化钙可与其它组分一起配制以形成一种粉末状吸附剂组合物或一种液体吸附剂组合物,所述的其它组分例如上述的硝酸盐和亚硝酸盐。该含有卤素的粉末状或液体吸附剂组合物可以下列方式加入,即燃烧前加入煤中、注入燃煤设备的对流通道中温度为约1500至约2700的区域,或上述两种方式的结合。
含有一种卤素化合物的汞吸附剂组合物优选地还包括一种钙源。钙源的非限制性实例包括氧化钙、氢氧化钙、碳酸钙、碳酸氢钙、硫酸钙、硫酸氢钙、硝酸钙、亚硝酸钙、醋酸钙、柠檬酸钙、磷酸钙、磷酸氢钙,以及含钙矿石,如磷灰石等。优选的钙源包括钙的卤化物,如溴化钙、氯化钙和碘化钙。也可使用有机钙化合物。非限制性的实例包括羧酸的钙盐、烷氧基化钙和有机钙化合物。和以上的卤素化合物一样,在多种实施方案中,该有机钙化合物倾向于为次优选的,原因在于其成本和可得性。
除了燃烧前或燃烧后向系统中加入汞吸附剂组合物以外,还可将一种硫吸附剂组合物随汞吸附剂一起加入。因此,在优选的实施方案中还提供了用于降低含硫和汞的煤燃烧时产生的烟道气中硫和汞的排放量的方法。在一个优选的实施方案中,一种方法涉及将一种第一吸附剂组合物和一种第二吸附剂组合物加入系统中。该第一和第二吸附剂组合物中的一种在燃烧前加入煤中,另外一种在燃烧室下游的对流通道中的一个区域被注入燃煤系统,所述区域优选温度在1500至2700之间。第一吸附剂组合物优选含有一种卤素组分,并以有效降低燃烧气体中的汞的量被加入。第二吸附剂组合物含有至少一种钙组分,且以有效降低燃烧气体中的硫的量被加入。
在上一段落的实施方案中,含有卤素组分的第一吸附剂组合物包含一种卤素化合物,如上述优选的溴和碘的化合物。第二吸附剂组合物含有以适于降低燃煤系统中硫排放量的形式存在的钙。含有一种钙组分的第二吸附剂组合物优选含有基于存在于煤中的硫的摩尔量计比值为1∶1的最小摩尔量的钙。优选地,随第二吸附剂组合物加入系统中的钙的水平相对于煤中硫的摩尔数计,比例不超过约3∶1。用更高水平的钙进行处理会浪费原料,并有可能阻塞炉子,从而阻碍燃烧过程并增加微粒控制系统的负担。
基本而言,期望加入的含钙的硫吸附剂的水平能够有效地从煤燃煤产生的烟道气中除去硫,但不过量以避免产生过多的灰尘。含有一种钙成分的第二吸附剂组合物可含有任何上述无机或有机钙化合物。此外,多种工业产品中含有适当水平的钙,例如水泥窑粉尘、石灰窑粉尘、硅酸盐水泥等。在多种实施方案中,含钙的硫吸附剂中含有一种如上所列出的钙粉,以及硅铝酸盐粘土,例如蒙脱石或高岭土。含钙的硫吸附剂组合物优选地含有足量的SiO2和Al2O3,以与燃烧所产生的硫酸钙一起形成类似耐熔质的混合物,以便通过炉中的微粒控制系统对硫酸钙进行处理。在优选的实施方案中,含钙的硫吸附剂含有最少量的2%的二氧化硅和2%的氧化铝。
在一个优选的实施方案中,一种含钙和溴的汞吸附剂组合物被用于煤中。在多种实施方案中,吸附剂组合物中含有溴化钙。或者,吸附剂组合物包括一种除溴化钙以外的溴化合物和一种除溴化钙以外的钙化合物。钙源的非限制性实例包括溴化钙、亚硝酸钙、硅酸盐水泥、氧化钙、氢氧化钙和碳酸钙。然后将含有钙和溴吸附剂组合物的煤燃烧形成灰尘和燃烧气体。期望地,对燃烧气体中汞的水平进行测量和监测。然后,根据测得的燃烧气体中汞的水平增加或减少以吸附剂组合物的形式加入煤中的溴的水平,或保持其不变。在多种实施方案中,该方法还对燃烧气体中硫的水平进行测量,并根据测得的硫的水平调整加入到煤中的钙的水平。在优选的实施方案中,从燃煤设备释放入环境中的汞排放量被减少了90%或更多。如本申请中所使用的,90%或更多的汞减少量意味着所燃烧的煤中至少有90%的汞被捕获以阻止其释放进入大气。优选地,在煤燃烧前向其中加入足量的溴以将汞向环境中的排放量降低90%或更多。
一方面,本发明涉及降低从燃烧含汞燃料的设备排放到大气的汞的水平。一种商业上有价值的实施方案为使用本发明以降低燃煤设备的汞排放量,以保护环境并符合政府法规和条约义务。以下大部分讨论将以煤为燃料。应理解的是,对于燃烧煤的描述只是出于例证性的目的,而本发明并不一定限于此。
在多种实施方案中,本发明的方法涉及以处理水平向燃烧燃料或燃煤的系统中加入一种汞吸附剂,所述处理水平足以使在燃料燃烧时从设备逃逸到大气中的汞的水平产生所需的降低。适当的汞吸附剂如上所述。在一个优选的实施方案中,汞吸附剂含有一个溴和/或碘源,优选为上述无机溴化物或碘化物盐的形式。
在一个实施方案中,汞吸附剂组合物在煤燃烧前被加入其中。该煤是颗粒煤,且任选通过常规过程粉碎或研成粉末。吸附剂组合物以液体或固体的形式加入到煤中。通常固体吸附剂组合物为粉末状形式。如果吸附剂是以液体形式(通常是一种或多种溴或碘盐的水溶液)加入,在一种实施方案中,当煤被送进燃烧器时仍保持润湿。吸附剂组合物可以下述方式连续加入燃煤设备的煤中,即通过喷雾或混合的方式加入位于输送带,螺杆挤出机或其它进料装置上的煤中。除此之外或作为替换的,吸附剂组合物可在燃煤设备或产煤装置中与煤单独混合。在一个优选的实施方案中,吸附剂组合物在煤被送至燃烧器时以液体或粉末的形式加入其中。例如,在一个优选的商业化的实施方案中,吸附剂被加入使注入前的煤粉碎的研磨机中。如果需要,可以改变加入吸附剂组合物的比率以达到所需的汞排放水平。在一个实施方案中,对烟道气中汞的水平进行监测,并且依据保持所需的汞水平的需要提高或降低吸附剂的加入量。
汞的水平可通过常规的分析仪器、使用工业上标准的检测和测定方法进行监测。在一个实施方案中,监测的实施是以手动或自动的方式间歇进行的。在一个非限制性的实例中,每小时监测一次汞排放的水平以确保符合政府法规。作为示例,使用Ontario Hydro法。该已知的方法中,在预定时间内、例如1小时内收集气体。从被收集的气体中沉淀汞,然后用适当的方法例如原子吸收法定量汞的水平。根据技术上和商业上的可行性,监测的频率也可比每小时一次高些或低些。可安装商用的连续汞监测仪以测量汞并以适当频率产生数值,如每3-7分钟产生一次。在多种实施方案中,使用汞监测仪的输出值控制汞吸附剂的添加比率。根据监测的结果,可通过增加添加水平、降低添加水平或保持其不变的方式来调整汞吸附剂的添加比率。作为示例,如果监测结果表明汞的水平高于期望值,则提高吸附剂的添加比率,直到汞的水平回到期望的水平。如果汞的水平正是期望的水平,吸附剂的添加比率则可保持不变。或者,可降低吸附剂的添加比率,直到监测结果表明其应被提高以避免高汞水平。通过这种方式,可以达到汞排放量的降低并避免过量使用吸附剂(伴随灰尘的增加)。
在对流通道的适当位置监测汞。在多种实施方案中,在微粒控制系统的清洁侧对释放到大气的汞进行监测和测量。还可以在对流通道内微粒控制系统上游的某点对汞进行监测。实验显示,当没有添加汞吸附剂时,煤中只有20%至30%的汞被捕获在灰尘中而未释放入大气。加入本发明的汞吸附剂后,被捕获的汞的量升高(并因此降低了汞的排放量)到90%或更多。
作为替换地或除此之外,将一种汞吸附剂组合物放入或注入燃煤设备的对流通道中以降低汞的水平。优选地,吸附剂组合物被加入火球(由煤的燃烧产生)下游的对流通道中的一个区域中,该区域的温度高于约1500并低于2700-3000的火球温度。在多种实施方案中,吸附剂的温度高于约1700。该区域优选温度低于约2700。在多种实施方案中,该注入区域的温度低于2600、低于约2500或低于约2400。在非限制性的实例中,注入的温度为1700至2300、1700至2200或约1500至约2200。如果是燃烧前添加,吸附剂的形式可为液体或固体(粉末),并含有有效水平的一种溴或碘化合物。在多种实施方案中,向对流通道中加入的吸附剂相对于燃烧前加入的吸附剂的比率根据上述汞监测的结果变化。
在优选的实施方案中,吸附剂组合物以差不多连续的方式被加入燃烧前的煤中和/或上述温度为1500-2700的对流通道区域中。在多种实施方案中,在汞监测装置和吸附剂进料装置之间提供有自动反馈回路。这使得可以对排放的汞进行连续监测以及对吸附剂加入比率进行调整以控制工艺过程。
与汞吸附剂一起,还优选加入一种硫吸附剂以控制向环境中释放的硫。在多种实施方案中,硫吸附剂在与加入汞吸附剂相同的位置被加入燃煤系统。硫吸附剂也可根据技术上的可行性在其它位置加入。在多种实施方案中,汞吸附剂和硫吸附剂组分被合并成单一的吸附剂被加入煤中,或被注入对流通道中。吸附剂无论分开或被合并,均可以液体或固体的形式被加入。固体组合物通常是粉末的形式。
硫吸附剂优选含有至少与被燃烧的煤中存在的硫水平等摩尔水平的钙。单凭经验的方法,钙的水平不应超过硫的摩尔数水平的三倍。为有效除去硫,优选1∶1的Ca∶S水平,优选的最高比例为3∶1以避免燃烧过程中产生过量的灰尘。在优选范围之外的处理水平也是本发明的一部分。例如,在2004年6月28日提交的共有临时申请60/583,420中描述了适当的硫吸附剂,其内容通过引证的方式纳入本说明书。
优选的硫吸附剂包括含有钙盐的碱性粉末,所述钙盐例如氧化钙、氢氧化钙和碳酸钙。其它含钙的碱性粉末包括硅酸盐水泥、水泥窑粉尘和石灰窑粉尘。在多种实施方案中,该硫吸附剂还含有一种硅铝酸盐粘土、蒙脱石和/或高岭石。优选地,硫吸附剂含有适当水平的二氧化硅和氧化铝(在一个优选的实施方案中,每种至少约2重量%),以与含硫煤燃烧形成的硫酸钙一起形成耐火材料。二氧化硅和氧化铝可被分开加入或作为其它材料例如硅酸盐水泥的组分加入。在多种实施方案中,硫吸附剂中还含有适当水平的镁,如MgO,其来自例如白云石或为硅酸盐水泥的组分。在一个非限制性实例中,硫吸附剂含有60-71%的CaO、12-15%的SiO2、4-18%的Al2O3、1-4%的Fe2O3、0.5-1.5%的MgO,以及0.1-0.5%的NaO。
汞吸附剂和硫吸附剂可被一起加入或分开加入。为方便起见,可在加入煤之前或注入对流通道之前将汞吸附剂组分和硫吸附剂组分合并。在一个优选的实施方案中,汞吸附剂除了含有一种卤素源以外,还含有钙。在多种实施方案中,汞吸附剂组合物还包括也可减少硫的组分。本发明提供向燃煤系统中加入多种吸附剂组合物以降低汞的排放量并优选也降低硫的排放量。
在多种实施方案中,硫和汞吸附剂是分开加入的。例如,一种汞吸附剂在燃烧前加入煤中,并且一种硫吸附剂在燃烧后加入。或者,一种汞吸附剂在燃烧后加入,而一种硫吸附剂在燃烧前加入煤中。无论采用何种加入方式,在一个优选的实施方案中,不同吸附剂加入的比率是根据通过监测所测定的排放的硫和汞的值按需要调整的。
汞和硫吸附剂以获得希望的降低的排放量所需要的水平加入。基于燃烧的煤中汞的总量计,优选的汞的降低量是70%或更多,优选80%或更多,更优选90%或更多。基于重量计,汞吸附剂通常以煤重量的约0.01-10%的水平加入。优选的范围包括0.05-5重量%和0.1-1重量%。处理水平根据吸附剂中卤素的含量和希望达到的汞排放量水平而变。0.3%的水平适合多种实施方案。在多种实施方案中,基于上述监测过程,初始处理水平可按照达到希望的排放水平的需要被调高或调低。吸附剂可分批或连续加入。在吸附剂连续加入的实施方案中,处理水平是基于被燃烧的煤的进料速率计。而当吸附剂是分批加入例如煤生产装置内或一个单独的混合设备内时,处理水平是基于被处理的煤的重量计。在一个优选的实施方案中,加入的比率或处理水平是根据对汞排放水平的测定值而进行调整。
类似地,硫吸附剂加入的水平或比率应使硫的排放水平降低至一个可接受的或预期的水平。在多种实施方案中,加入约1至9重量%的硫吸附剂。该水平或比率如有需要可以基于由监测结果确定的硫的排放水平而进行调整。
在优选的实施方案中,使用工业标准方法——例如美国材料试验协会(American Society for Testing and Materials)(ASTM)出版的工业标准方法——或国际标准化组织(International Standards Organization)(ISO)出版的国际标准监测汞和硫。一个含有一个分析仪器的装置优选置于对流通道中硫和汞吸附剂加入点的下游。在一个优选的实施方案中,一个汞监测仪被置于微粒控制系统的清洁侧。在多种实施方案中,测量的汞或硫的水平被用于向泵、螺线管、喷雾器及其它被操纵或控制的设备提供反馈信号,以调整向燃煤系统中加入吸附剂组合物的比率。作为替换地或除此之外,吸附剂加入的比率可由操作员基于观察到的汞和/或硫的水平而进行调整。
为进一步说明,本发明的一个实施方案涉及在燃烧前直接向原煤或碎煤中加入含溴化钙和水的液体汞吸附剂。含溴化钙的液体汞吸附剂的加入量范围是基于湿重的0.1-5%、优选0.025-2.5%,计算的前提是假设溴化钙约占吸附剂重量的50%。在一个典型的实施方案中,在燃烧前向煤中加入约1%的含有50%溴化钙的液体吸附剂。
在另一个实施方案中,本发明涉及向燃料中直接加入溴化钙溶液和在炉中的温度范围为2200至1500的区域中加入溴化钙溶液。在该实施方案中,液体汞吸附剂在燃烧前和燃烧后都被加入。优选的溴化钙处理水平可以任何比例在燃烧前和燃烧后加入量之间分配。
在另一个实施方案中,本发明提供了将例如上述的溴化钙溶液仅仅添加到炉中的温度范围为2200至1500的区域的气流中。
以上已就多种优选的实施方案对本发明进行了描述。以下的实施例中提供了本发明进一步的非限制性公开。它们示例说明了只将一种液体吸附剂以及将一种液体/固体吸附剂体系用于燃料中汞的补救处理时本发明的有效性。
实施例
在实施例中,将具有不同BTU值、硫含量和汞含量的煤于北达科他大学的能源环境研究中心(Energy Environmental Research Center)(EERC)的CTF炉中燃烧。所报道的汞和硫的百分含量的降低是基于燃烧前煤中元素的总量计。
实施例1
本实施例示例说明将一种溴化钙/水溶液应用于Powder River盆地的次烟煤中时其对汞的吸附能力。入炉煤中含水量为2.408%,灰分含量为4.83%,硫含量为0.29%,热值为8,999 BTU,且汞含量为0.122μg/g。无吸附剂时的燃烧在排出气体中具有13.9μg/m3的汞浓度。燃料被磨碎至有70%通过200目筛,并与基于煤重量计6%的一种吸附剂粉末和0.5%的一种吸附剂液体混合。所述粉末含有40-45重量%的硅酸盐水泥、40-45%氧化钙,剩余为钙蒙脱石或钠蒙脱石。所述液体是50重量%的溴化钙水溶液。
吸附剂与燃料直接混合三分钟,然后储存用于燃烧。已处理的煤被送进炉中。燃烧导致袋式除尘器出口处有90%的汞(总量)被除去,并测得袋式除尘器出口处有80%的硫被除去。
实施例2
本实施例示例说明将粉末吸附剂和液体吸附剂应用于三种不同汞含量的烟煤中的用途。所有的煤如实施例#1中的方法制备,吸附剂的加入水平也相同。
参数 | 煤 | 汞移除% | 硫移除% | |
水分%硫%汞BTU值 | 8.482.2816.2μg/m313,324 | Pittsburgh,Seam,BaileyCoal | 97.97 | 40.0 |
水分%硫%汞BTU值 | 10.464.248.53μg/m311,824 | FreemanCrown III | 97.9 | 36.0 |
水分%硫%汞BTU值 | 1.01.255.26μg/m312,937 | KentuckyBlend | 90.1 | 52.0 |
实施例3
本实施例示例说明燃烧后一种汞吸附剂的添加。将Pittsburgh Seam-Bailey Coal研磨至70%通过200目筛。燃烧前燃料中不加入吸附剂。含50%溶于水的溴化钙的液体吸附剂通过管道被注入炉内2200-1500区域的气流中。液体吸附剂被注入的比率约为煤重量的1.5%。
煤的类型 | 吸附剂成分 | S降低% | Hg降低% |
Pittsburgh,Seam-BaileyCoal | 50%CaBr250%H2O | 28.13 | 96.0 |
实施例4
本实施例示例说明燃烧后一种液体吸附剂和一种粉末吸附剂的添加。不向燃料直接加入任何吸附剂。两种燃料都是烟煤,分别称为FreemanCrown III和Pittsburgh Seam-Bailey Coal。两种情况下,都将煤在燃烧前研磨至70%在200目以下。粉末吸附剂和液体吸附剂与实施例1中所用相同。液体和粉末添加的比率(基于被燃烧的煤的重量计的百分数)以及汞和硫降低的水平如下表所示。
煤的类型 | 液体吸附剂注入比率 | 粉末吸附剂注入比率 | S降低 | Hg降低 |
FreemanCrown IIIPittsburghSeam-BaileyCoal | 1.01.5 | 4.06.10 | 36.2733.90 | 97.8996.00 |
实施例5
Pittsburgh Seam Bailey Coal的制备如实施例1。燃烧前向煤中加入9.5重量%的实施例1的粉末吸附剂。燃烧后向1500-2200的区域中注入实施例1的液体吸附剂(50%的溴化钙水溶液),其比率是基于煤燃烧率计的0.77%。硫降低了56.89%,汞降低了93.67%。
实施例6
Kentucky Blend Coal的制备如实施例1。燃烧前向煤中加入6重量%的实施例1的粉末吸附剂。燃烧后向1500-2200的区域中注入实施例1的液体吸附剂(50%的溴化钙水溶液),其比率是基于煤燃烧率计的2.63%。硫降低了54.91%,汞降低了93.0%。
尽管以上通过能够实现的方式对本发明进行了阐述,但应理解的是,本发明并不限于所公开的实施方案。本领域技术人员在阅读本说明书时想到的变型和改进也涵盖于由所附权利要求所限定的本发明的范围之内。
Claims (65)
1.一种用于在燃烧煤时降低释放入大气的汞量的方法,该方法包括
将含有一种卤素化合物的一种吸附剂组合物用于煤;
将煤输送至一个燃煤炉内;
使含有吸附剂的煤在燃煤炉内燃烧以形成灰尘和燃烧气体;
测量该燃烧气体中汞的水平;以及
根据该汞的水平的值调整用于煤中的吸附剂组合物的量。
2.一种根据权利要求1的方法,其中该吸附剂组合物包括一种溴化合物或一种碘化合物。
3.一种根据权利要求1的方法,其中该吸附剂组合物包括一种溴化物。
4.一种根据权利要求1的方法,其中该吸附剂组合物包括溴化钙。
5.一种根据权利要求1的方法,包括将一种含有一种溴化合物的溶液应用于煤。
6.一种根据权利要求1的方法,包括将一种含有一种碘化合物的溶液应用于煤。
7.一种根据权利要求1的方法,包括将一种固体组合物应用于煤。
8.一种根据权利要求4的方法,其中该吸附剂组合物包括溴化钙和硝酸钙。
9.一种根据权利要求4的方法,其中该吸附剂组合物包括溴化钙和亚硝酸钙。
10.一种根据权利要求2的方法,其中该吸附剂组合物还包括一种硝酸盐化合物。
11.一种根据权利要求2的方法,其中该吸附剂组合物还包括一种亚硝酸盐化合物。
12.一种根据权利要求1的方法,其中该吸附剂组合物包括水,并且煤在进入炉内时是被水润湿的。
13.一种根据权利要求1的方法,包括向煤上喷洒一种含有溴化钙的水溶液。
14.一种根据权利要求13的方法,其中该溶液包括5重量%至60重量%的溴化钙。
15.一种根据权利要求13的方法,其中该溶液包括20重量%至60重量%的溴化钙。
16.一种根据权利要求13的方法,其中该溶液包括大于50重量%的溴化钙。
17.一种根据权利要求13的方法,其中该溶液还包括一种化合物,该化合物选自一种硝酸盐化合物、一种亚硝酸盐化合物和一种硝酸盐化合物与亚硝酸盐化合物的混合物。
18.一种根据权利要求17的方法,其中该溶液包括硝酸钙、亚硝酸钙,或硝酸钙和亚硝酸钙两者。
19.一种根据权利要求1的方法,还包括加入一种硫吸附剂以减少燃烧气体中硫的量。
20.一种根据权利要求1的方法,包括持续监测汞的水平。
21.一种根据权利要求1的方法,包括对汞的水平定期抽样。
22.一种用于燃烧煤的系统,其具有降低的释放到系统外的汞水平,所述系统包括
一种含溴和/或碘的吸附剂组合物;
一个燃煤炉,包括一个燃烧室、一个用于将燃烧气体从燃烧室引到对流通道外部的一个出口的对流通道、及一个置于对流通道内的微粒收集设备;
一种用于将煤输送至炉子以进行燃烧的装置;
一种置于对流通道内用于测量对流通道内汞的水平的装置;
一种吸附剂输送装置,用于在将煤输送至炉子之前将吸附剂组合物输送至煤中;以及
一种控制器,用于接收汞测定仪器的输出信号,并且与吸附剂输送装置有效连接,以根据该输出信号的值调整吸附剂的输送。
23.一种根据权利要求22的系统,其中该吸附剂组合物包括一种溴化物。
24.一种根据权利要求22的系统,其中该吸附剂组合物包括溴化钙。
25.一种根据权利要求22的系统,其中该吸附剂组合物包括水和一种可溶的溴化合物。
26.一种根据权利要求22的系统,其中该吸附剂组合物还包括一种硝酸盐化合物。
27.一种根据权利要求26的系统,其中该硝酸盐化合物包括硝酸钙。
28.一种根据权利要求22的系统,其中该吸附剂组合物还包括一种亚硝酸盐化合物。
29.一种根据权利要求28的系统,其中该亚硝酸盐化合物包括亚硝酸钙。
30.一种用于降低煤在燃煤系统内燃烧时硫和汞的排放量的方法,该燃煤系统包括一个炉子和燃烧气体对流通道,该方法包括将第一吸附剂组合物和第二吸附剂组合物应用于该系统中,
其中燃烧前向煤中加入第一吸附剂组合物和第二吸附剂组合物中的一种,并将另一种注入燃煤系统中燃烧室下游对流通道内的一个区域中,以及
其中第一吸附剂组合物含有溴,并以有效水平加入以降低燃烧气体中的汞,且第二吸附剂组合物含有钙,并以有效水平加入以降低燃烧气体中的硫。
31.一种根据权利要求30的方法,包括监测燃烧气体中的汞的水平,并根据该汞水平的值调整第一吸附剂组合物加入的量。
32.一种根据权利要求30的方法,还包括监测燃烧气体中的硫的水平,并根据该硫的水平调整加入煤中的第二吸附剂组合物的量。
33.一种根据权利要求30的方法,其中进入环境中的汞排放量与未向煤中加入溴时产生的排放量相比降低了90%或更多。
34.一种根据权利要求30的方法,包括向煤中加入足量的溴以使进入环境中的汞排放量与未加入溴时燃烧煤所产生的排放量相比降低90%或更多。
35.一种根据权利要求30的方法,其中该第一吸附剂组合物包括溴化钙。
36.一种根据权利要求30的方法,其中该第一吸附剂组合物包括一种除溴化钙以外的溴化合物和一种除溴化钙以外的钙化合物。
37.一种根据权利要求30的方法,其中该第二吸附剂组合物包括至少一种选自溴化钙、硝酸钙、亚硝酸钙、硅酸盐水泥、氧化钙、氢氧化钙和碳酸钙的含钙组分。
38.一种用于燃烧煤的方法,可降低逃逸到环境中的不想要的元素的水平,该方法包括
向煤中加入一种含有钙和溴的吸附剂组合物;
燃烧煤以形成灰尘和燃烧气体;
测量燃烧气体中汞的水平;以及
根据该汞的水平调整加入煤中的溴的水平。
39.一种根据权利要求38的方法,还包括测量燃烧气体中硫的水平,并根据该硫的水平调整加入煤中的钙的水平。
40.一种根据权利要求38的方法,其中汞向环境中的排放量与未向煤中加入溴时产生的排放量相比降低了90%或更多。
41.一种根据权利要求38的方法,包括向煤中加入足量的溴以使进入环境中的汞排放量与未加入溴时燃烧煤所产生的排放量相比降低90%或更多。
42.一种根据权利要求38的方法,其中该吸附剂组合物包括溴化钙。
43.一种根据权利要求38的方法,其中该吸附剂组合物包括一种除溴化钙以外的溴化合物和一种除溴化钙以外的钙化合物。
44.一种根据权利要求38的方法,其中该吸附剂组合物包括至少一种选自溴化钙、硝酸钙、亚硝酸钙、硅酸盐水泥、氧化钙、氢氧化钙和碳酸钙的含钙组分。
45.一种根据权利要求38的方法,其中该吸附剂组合物包括硅酸盐水泥;氧化钙、氢氧化钙和碳酸钙中的至少一种;硅铝酸盐粘土;以及至少一种溴化合物。
46.一种根据权利要求45的方法,其中所述的至少一种溴化合物包括一种溴化物。
47.一种根据权利要求45的方法,其中所述的至少一种溴化合物包括溴化钙。
48.一种根据权利要求45的方法,其中该吸附剂组合物还包括一种亚硝酸盐化合物、一种硝酸盐化合物,或硝酸盐化合物与亚硝酸盐化合物的一种混合物。
49.一种根据权利要求48的方法,其中该吸附剂组合物包括硝酸钙、亚硝酸钙,或硝酸钙与亚硝酸钙的一种混合物。
50.一种根据权利要求38的方法,包括将含有一种溴化合物的一种液体组合物用于煤。
51.一种根据权利要求50的方法,其中该液体组合物还包括一种亚硝酸盐化合物、一种硝酸盐化合物,或硝酸盐化合物与亚硝酸盐化合物的一种混合物。
52.一种根据权利要求50的方法,其中该液体组合物包括亚硝酸钙、硝酸钙,或硝酸钙与亚硝酸钙的一种混合物。
53.一种根据权利要求50的方法,其中该液体组合物包括溴化钙。
54.一种根据权利要求50的方法,还包括将一种含钙的粉末吸附剂应用于煤。
55.一种根据权利要求54的方法,其中该粉末吸附剂包括硅酸盐水泥,氧化钙、氢氧化钙和碳酸钙中的至少一种,以及一种硅铝酸盐粘土。
56.一种用于降低含汞的煤在燃煤系统中燃烧时释放入大气中的汞的水平的方法,该燃煤系统包括一个炉子和一个燃烧气体对流通道,该方法包括
在炉中燃烧煤;以及
将含有一种卤素的一种吸附剂注入对流通道中燃烧气体温度为1500至2200的一点。
57.一种根据权利要求56的方法,其中该吸附剂包括一种溴化合物。
58.一种根据权利要求56的方法,其中该吸附剂还包括钙。
59.一种根据权利要求56的方法,其中该吸附剂包括溴化钙。
60.一种根据权利要求59的方法,包括以0.01至10重量%的水平加入溴化钙,该百分比基于煤的重量计。
61.一种根据权利要求60的方法,其中该水平是0.05-5重量%。
62.一种根据权利要求60的方法,其中该水平是0.1-1重量%。
63.一种根据权利要求56的方法,其中该吸附剂包括溴化钙的一种水溶液。
64.一种根据权利要求63的方法,其中该吸附剂包括5-50重量%的溴化钙。
65.一种根据权利要求56的方法,还包括在燃烧前或燃烧后加入一种硫吸附剂,其中该硫吸附剂包括一种含有钙的碱性粉末。
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