CN102365233B - 耐自燃性热活化的碳 - Google Patents
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Abstract
通过暴露于卤素和/或含卤素的化合物,热活化的纤维素-基碳被赋予更具热稳定性。这样处理的纤维素-基碳适用于降低烟道气、特别是温度在约100℃至约420℃的范围内的烟道气中危险物质的含量。
Description
技术领域
本发明涉及耐自燃性热活化的纤维素-基碳及其制备方法。此外,本发明涉及使用这种耐自燃性碳从烟道气中除去危险物质。
背景技术
期望和必须的是减少工业烟道气的危险物质含量。危险物质可对于公众健康和环境造成有害的影响。工业界和政府已经努力使用发展的良好的方法来减少这些物质的排放。特别关注于燃煤炉的烟道气,例如发电厂中发现的那些。但是有更多事情要来处理。危险物质包括颗粒,例如飞灰、酸性气体如Sox、NOx、二恶英、呋喃、重金属等。
用于减轻危险物质的排放的方法取决于危险物质的性质、寻求的最小排放水平、每单位时间待处理的排放气体的体积、以及降低方法的成本。一些危险物质通过机械方式使它们从气态流出物中除去,例如使用静电除尘器(ESP)、织物过滤器(FF)或湿式除尘器来捕获和除去。其他物质不使它们直接机械除去。
考虑到从气流中直接机械除去任何特定气态组分是有困难的,气态流出物中存在的危险气态物质展现出吸引人的挑战。然而,已知工业实践通过下列方式从气态流出物中除去危险气态组分:使微细颗粒吸附物均匀地分散在流出物中,以在飞行中接触和捕获靶气态组分。这在下列步骤之后:通过ESP、FF或湿式除尘器来从流出物蒸汽中使吸附剂和其被吸附物机械除去。高效吸附剂是碳,例如纤维素-基碳、粉末活性炭(PAC)等。PAC例如可在使用或不使用改性的条件下来使用。改性的PAC可通过增强吸附效果来增强靶危险物质的捕获。PAC改性示例于US 4,427,630;US 5,179,058;US 6,514,907;US 6,953,494;US 2001/0002387;US 2006/0051270和US2007/0234902。纤维素-基碳包括但不限于衍生自木材材料、椰子壳材料或其他蔬菜材料的碳。
在工业应用中使用纤维素-基碳的问题在于它们不可靠的热稳定性,即缺乏保证它们是耐自燃的。当纤维素-基碳用于处理暖或热的气态流出物时或当包装或收集为大量时,自燃是特别成问题的。例如,当下列情况时遇到大批PAC:(i)PAC被包装时,例如在超级麻袋中;或(ii)当在FF单元中形成为过滤器滤饼时或在和ESP、TOXECON单元与集尘室有关的料槽或贮煤槽中收集时。自燃源自碳的未减轻的氧化,并且可导致其阴燃或燃烧。自燃通过温暖或加热碳而加剧,当用于处理燃煤炉流出物时可能是这样的情况。如果氧气(空气)不否认是氧化位点或如果该位点未被冷却,来自初始氧化的热量将传播直到碳阴燃或点燃。这种点燃可以是灾难性的。公用厂关于自燃特别敏感,因为流出物线内的阴燃或燃烧可引起工厂关闭,并且对服务的客户造成普遍的后果。
对于PAC热稳定性的另外的信息可发现于US 6,843,831,“Process forthe Purification of Flue Gas”。一些碳比其他碳更加耐自燃。在US,煤-衍生的PAC的使用是实用烟道气处理的工业标准,部分是由于煤-衍生的PAC的良好的热稳定性。
如果纤维素-基碳(包括纤维素-基PAC)可以被改性以更加热稳定,使得从业者可以享受到纤维素-基碳的优异的吸附质量的益处,这将是有利的。
发明概述
本发明涉及一种热活化的纤维素-基碳,其已经暴露于卤素和/或含卤素的化合物并且具有下列中的至少一种:(i)初始能量释放的温度大于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的初始能量释放的温度;(ii)自维持点火温度大于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的自维持点火温度;以及(iii)早期阶段的能量释放值小于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的早期阶段的能量释放值。据信(i),(ii)和(iii)中引用的任何一种或多种质量都指示:和未暴露于卤素和/或含卤素的化合物的相同热活化的纤维素-基碳相比,卤素和/或含卤素的化合物暴露处理的热活化的纤维素-基碳的热稳定性增强。从商业观点考虑,对于煤衍生的碳/PAC获得相等或者近似相等的能量释放的数值,这高度预测了良好的、可接受的热稳定性。参照下文的表(I),示出本发明的卤素和/或含卤素的化合物处理的纤维素-基碳和报道的非纤维素衍生的碳/PAC相比是有利的。卤素例如可以是Br2。本发明还涉及一种提高热活化的纤维素-基碳的热稳定性的方法。该方法包括:在一定温度下使所述热活化的纤维素-基碳暴露于卤素和/或含卤素的化合物足够的时间,使得所述暴露的热活化的纤维素-基碳具有下列中的至少一种:(i)初始能量释放的温度大于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的初始能量释放的温度;(ii)自维持点火温度大于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的自维持点火温度;以及(iii)早期阶段的能量释放值小于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的早期阶段的能量释放值。本发明还涉及一种暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳,其含有约2至约20重量%的卤素,并且具有下列中的至少一种:(i)初始能量释放的温度大于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的初始能量释放的温度;(ii)自维持点火温度大于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的自维持点火温度;以及(iii)早期阶段的能量释放值小于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的早期阶段的能量释放值。本发明还涉及一种降低气态危险物质从含有这些物质的烟道气中大气释放的方法,该方法包括:使所述烟道气接触热活化的纤维素-基碳,所述热活化的纤维素-基碳已经暴露于卤素和/或含卤素的化合物并且具有下列中的至少一种:(i)初始能量释放的温度大于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的初始能量释放的温度;(ii)自维持点火温度大于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的自维持点火温度;以及(iii)早期阶段的能量释放值小于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的早期阶段的能量释放值。
附图简述
图1是未处理的热活化的木材-基碳和溴蒸汽处理的热活化的木材-基碳的热流对温度的比较图。
图2是未处理的热活化的椰子壳衍生的PAC和溴蒸汽处理的热活化的椰子衍生的PAC的热流对温度的比较图。
图3是未处理的热活化的烟煤衍生的PAC和溴蒸汽处理的热活化的烟煤衍生的PAC的热流对温度的比较图。
图4是未处理的热活化的无烟煤衍生的PAC和溴蒸汽处理的热活化的无烟煤衍生的PAC的热流对温度的比较图。
图5是未处理的热活化的褐煤衍生的PAC和2.5重量%NaBr处理的热活化的褐煤衍生的PAC的热流对温度的比较图。
发明详述
如上所述,本发明的热活化的纤维素-基碳可衍生自纤维素材料。
热活化的纤维素-基碳例如木材-基PAC的制备是熟知的,并且通常需要:(i)纤维素材料的脱挥发或碳化以制备木炭;(ii)木炭的活化;以及(iii)活化的木炭的冷却/淬火。更多细节参见Kirk-Othmer Encyclopedia ofChemical Technology,lst版,卷4,页741-761 2001。热活化的木材-基碳可从任何木材源来制备,例如锯末、木材屑或其他颗粒状木材产品。
热活化的纤维素-基碳是市售的。例如,热活化的木材-基碳可得自MeadWestvaco Corporation,Specialty Chemical Division。热活化的纤维素-基碳的特征可以为它们的粒径分布(D10、D50和D90);平均粒径;BET表面积;碘No.;总孔体积;孔体积分布(大/中和小孔);元素分析;含水量;以及灰分规格和含量。特别有用的热活化的纤维素-基碳具有一种或多种下列特性:
依照本发明用于处理纤维素衍生的碳的卤素和/或含卤素的化合物可包括溴、氯、氟、碘、溴化铵、其他含氮卤素盐、溴化钙、其他无机卤化物等。
纤维素-基碳的卤素和/或含卤素的化合物的处理可受到分批法或连续法的影响。合适的分批法将纤维素-基碳供料至烘干反应器/干燥器。在完成供料后,供入的纤维素-基碳可根据需要干燥,特别是如果其含水量超过5重量%(基于供入的纤维素-基碳的总重量)。获得约75℃至约82℃的初始温度。在一种应用中,气态Br2(在其沸点温度)加入反应器/干燥器。反应器/干燥器压力便捷地保持为大致周围压力。在供料过程和之后,干燥器以烘干方式运行。供料后的烘干周期为约30分钟至1小时。定量地,供料的Br2的量和处理的纤维素-基碳的期望溴含量对应相等或接近相等。例如,如果期望处理的纤维素-基碳的溴含量为约5重量%(基于处理的纤维素-基碳的总重量),则供料的Br2的量为5份Br2/95份纤维素-基碳。Br2的供料速率在整个Br2的供料期间是基本上均匀的。在供料后的烘干周期后,处理的纤维素-基碳从反应器/干燥器除去以储存或包装。
处理纤维素-基碳的合适的连续法的特征在于气态Br2和纤维素-基碳单独共同供料至混合T。颗粒纤维素-基碳通过空气运输至并通过混合T。纤维素-基碳的温度为约80℃至约105℃。气态Br2在其沸点下供入T的其他支路。可以使用周围压力。混合T提供约0.5至约2.0秒的停留时间。为了提高混合,下游排泄器可用于确保涡轮混合。定量地,和分批法中使用的比例相同的比例用于连续法。
在所述的分批法和连续法中,所有Br2引入进料引入到纤维素-基碳中。因此,便捷的是通过参考供料至反应器的Br2和纤维素-基碳的量来参考处理的纤维素-基碳中的Br2的量。5kg的Br2的供料和95kg的纤维素-基碳的供料将被认为产生含有5重量%溴的气态溴处理的纤维素-基碳。然而,如果参与者应该期望直接测量引入的溴,这种测量可通过下列方式来实施:进行Schoniger燃烧,然后进行硝酸盐滴定。
气态卤素接触的纤维素-基碳可含有约2至约20重量%的溴,所述重量%基于接触的纤维素-基碳的总重量。当处理来自燃煤炉的烟道气时,溴的重量%在约5至约15重量%的范围内是有用的。
为了测定(i)初始能量释放的温度;(ii)自维持点火温度;和(iii)早期阶段的能量释放值,有用的是当它们被可控加热时,具有处理的和未处理的热活化的纤维素-基碳样品的热流值对温度(℃)的差示扫描热量法(DSC)痕迹。DSC条件可如下所示:样品尺寸约10mg;载气是流速为100ml/分钟的空气;温度跃升速率为以10摄氏度/分钟从周围温度至850℃。DSC可在TA Instruments Thermal Analyst 5000 Controller上运行,其具有型号2960DSC/TGA模块。从DSC测试结果中产生的DSC痕迹可用TA InstrumentsUniversal Analysis Software,版本4.3.0.6来进行分析。样品可以在递送至DSC测试之前完全干燥。热干燥是可接受的,例如在110℃的温度下干燥0.5至5.0克的样品1小时。
从DSC测试获得的数值可在热流(瓦特/克)对温度(℃)的图上追踪到。图1-5是可以获得的DSC痕迹的例子。
初始能量释放的温度,又称为初始氧化点(PIO)为这样的温度,在该温度下由于氧化反应达到任意水平的显著性,表面性能开始改变。建议PIO定义为这样的温度,在该温度下作为温度曲线函数的热流值超过0.2W/g,热流值被调节以在125℃的温度下给出零值基线。
自维持点火温度通常定义为基线和作为温度曲线的函数的热流拐点的斜率的交叉。该拐点通过上述软件测定。通常,拐点在微分学上定义为曲线的点,在该曲线处出现曲率改变。从凹形向上(正曲率)至凸形向下(负曲率)的曲线改变,或反之亦然。例如,在图1中,未处理的TAWPAC(热活化的木材-基粉末活性炭)的自维持点火温度为约400℃,并且气态溴处理的TAWPAC的自维持点火温度为约434℃。
早期阶段的能量释放值通过在125℃至425℃和在125℃至375℃之间积分DSC痕迹来测定。来自这两个积分的值分别针对获得用于PAC的相同数值进行比较,所述PAC已知通常具有合适的热稳定性,即“基准碳”。这样的基准碳的例子是褐煤衍生的PAC,其浸渍Norit Americas,Inc.销售的类型NaBr,发现涂覆的PAC(参见图5)的早期阶段的能量释放值(125℃至425℃)为1,378焦耳/克,和125℃至375℃的早期阶段的能量释放值为370焦耳/克。在图1中,纤维素衍生的未处理的TAWPAC的值为5,873焦耳/克(125℃至425℃)和2,709焦耳/克(125℃至375℃)。气态溴处理的TAWPAC示于图1,其值为1,247(125℃至425℃)和345焦耳/克(125℃至375℃)。可以看出,气态溴处理的TAWPAC的早期阶段的能量释放值和Norit benchmark的碳产品的早期阶段的能量释放值相当。未处理的TAWPAC的早期阶段的能量释放值和Norit benchmark的碳产品的早期阶段的能量释放值相差较大。
基于DSC分析,下表(I)记录了各种PAC的初始能量释放的温度(PIO)、自维持点火温度(SIT)和早期阶段的能量释放值。
表(I)
Claims (10)
1.一种热活化的纤维素-基碳,其通过由将热活化的纤维素-基碳暴露于卤素和/或含卤素的化合物组成的方法形成,并且具有下列中的至少一种:
(i)初始能量释放的温度大于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的初始能量释放的温度;
(ii)自维持点火温度大于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的自维持点火温度;以及
(iii)早期阶段的能量释放值小于未暴露于所述卤素和/或含卤素的化合物的相同热活化的纤维素-基碳的早期阶段的能量释放值,
其中所述已经暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳含有2至20重量%的卤素,所述重量%基于所述已经暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳的总重量。
2.权利要求1所述的热活化的纤维素-基碳,其中所述卤素和/或含卤素的化合物包括溴、氯、氟、碘、一种或多种含氮卤素盐、或溴化钙。
3.权利要求2所述的热活化的纤维素-基碳,其中所述一种或多种含氮卤素盐包含溴化铵。
4.权利要求1所述的热活化的纤维素-基碳,其中所述已经暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳含有5至20重量%的卤素,所述重量%基于所述已经暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳的总重量。
5.权利要求1所述的热活化的纤维素-基碳,其中当处理来自燃煤炉的烟道气时,已经暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳是气态卤素接触的含有5至15重量%溴的纤维素-基碳,所述重量百分比基于已经暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳的总重量。
6.一种形成如权利要求1所述的热活化的纤维素-基碳的方法,该方法组成为:在一定温度下使所述热活化的纤维素-基碳暴露于卤素和/或含卤素的化合物足够的时间,使得所述已经暴露于卤素和/或含卤素的化合物的热活化的纤维素-基碳具有下列中的至少一种:
(i)初始能量释放的温度大于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的初始能量释放的温度;
(ii)自维持点火温度大于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的自维持点火温度;以及
(iii)早期阶段的能量释放值小于暴露于所述卤素和/或含卤素的化合物之前相同热活化的纤维素-基碳的早期阶段的能量释放值。
7.权利要求6所述的方法,其中所述卤素和/或含卤素的化合物包括溴、氯、氟、碘、一种或多种含氮卤素盐、或溴化钙。
8.权利要求7所述的方法,其中所述一种或多种含氮卤素盐包含溴化铵。
9.权利要求6所述的方法,其中所述热活化的纤维素-基碳在82至105℃的温度下暴露于所述卤素和/或含卤素的化合物0.1至3秒内的时间。
10.一种降低气态危险物质从含有这些物质的烟道气中大气释放的方法,该方法包括:使所述烟道气接触如权利要求1所述的热活化的纤维素-基碳,其中所述烟道气的温度在100℃至420℃的范围内。
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