CN101225342A - 安全燃烧添加剂及其配制方法 - Google Patents
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Abstract
本发明涉及用于电站炉和工业炉的安全的、含金属的燃烧添加剂及其配制方法。添加剂包括含金属的催化剂、用于与催化剂配合的配体和用于承载催化剂/配体配合物的溶剂。添加剂在100℉的蒸气压低于约200×10-5托。
Description
技术领域
本发明涉及用于电站炉(utility furnace)和工业炉的含金属的燃烧添加剂。特别地,从健康评定角度讲所述添加剂及其配制方法是相对安全的,因此实现了更加用户友好的工作条件。
背景技术
由于颗粒物、NOx和SOx污染物的排放,烧油和烧煤的电站锅炉和炉子遭受着环境问题的困扰。因为通过添加剂处理发电厂使用的燃料来控制环境排放变得越来越重要,所以厂内添加剂的安全储存和使用问题也越来越引人关注。因此,电厂操作人员不再只关心添加剂的功效能否如预期实现,还要注意现场这些化学品的存储和使用安全。所以,配制这些添加剂时需要着重考虑这一点。
这些添加剂不得不在现场存储合理的量,以完成预期任务而不中断燃料的处理。这是因为其最好效果通常依赖于燃料的连续处理,以在辐射区(炉)和对流区(炉的下游)的表面上维持添加剂燃烧副产物的新鲜活性层。尽管这些添加剂在燃烧燃料蒸气和颗粒时大多以气相工作,但在看到预期效果的标志前常常可以观察到诱导期;这表明,表面负载的多相化学也起到了主要作用。因为表面活性层将很快被来自未处理的燃料的沉积物覆盖,所以添加剂处理中断将导致表面负载的活性停止。为了避免出现此问题,添加剂供应者需要现场储存大量的添加剂,并且这些量可以是油罐拖车的容积(2500加仑和更多)。厂区添加剂储存位置通常是位于地面以上的、由添加剂供应者构建的半永久性和永久性结构,根据选定的燃料处理位置附近的空间来确定确切的位置。
化学品的HMIS危害标记将危害等级定为0到4之间,按照安全性下降的顺序。HMIS标记为1或更低的化学品通常认为是安全的,因为通过呼吸暴露是没有危险的。任何HMIS标记高于1的物质通过皮肤接触、摄入和吸入可被认为有潜在危害,并有存储和使用安全风险,需要这些直接环境中的人员专门预防。
发明内容
因此,本发明的目的是提供用于电站炉和工业炉的安全的燃烧添加剂及安全燃烧添加剂的配制方法,以解决上述关注和需求问题。本发明不但符合HMIS标准要求,而且由于认识到在可能操作比如燃料添加剂的化学品的现实环境中通过呼吸吸入可能是重大的健康危害,所以也有了进一步深入。
在一个例子中,电站炉和工业炉使用的燃烧添加剂包含含金属的催化剂。添加剂进一步包含与该催化剂配合的配体,以及用于承载催化剂/配体配合物的溶剂。添加剂在100的蒸气压低于约200×10-5托。催化剂可以包含多种金属。催化剂可以含锰。催化剂可以包含选自锰、钙、镁、钾、锌和铝的多种金属。配体可以选自化石燃料衍生的羧酸盐/酯(carboxylate)、天然产物衍生的羧酸盐/酯、基因工程天然产物衍生的羧酸盐/酯、合成羧酸盐/酯及其混和物。添加剂的HMIS健康等级可以为1或0。添加剂在100的蒸气压可以低于约70×10-5托。
在另一替换性例子中,本发明包括用于电站和工业炉的燃烧添加剂的配制方法。该方法包括选择用于电站和工业炉的含金属催化剂,使该含金属催化剂与配体配合,然后添加溶剂以承载催化剂/配体的配合物。添加剂在100的蒸气压低于约200×10-5托。催化剂可以包含多种金属。催化剂可以包含锰。催化剂可以包含选自锰、钙、镁、钾、锌和铝的多种金属。配体可以选自化石燃料衍生的羧酸盐/酯、天然产物衍生的羧酸盐/酯、基因工程天然产物衍生的羧酸盐/酯、合成羧酸盐/酯及其混和物。添加剂的HMIS健康等级可以为1或0。添加剂在100的蒸气压可以低于约70×10-5托。
具体实施方式
如下方式可导致健康危害:吸入、眼睛接触、皮肤接触、以及摄入燃料和/或燃料添加剂。眼睛接触、皮肤接触和吸入引起的健康危害可以通过在容器上加警告标记以带手套和避免化学物质接近眼睛或者嘴来防止。然而,“吸入”危害更成问题,这是因为在人读标签时他们可能已经暴露到该危害中了。
要吸入物质,该物质必须处于蒸气状态或雾状。因此,添加剂转变到该物理状态的能力必须最小化。对于添加剂操作人员的被动吸入而言,在环境存储和操作条件下组分蒸气压为零的添加剂制剂可以合理假设是无危害的。因此,设计添加剂使这种健康危害最小化规定:第一,添加剂包内制剂中所有组分的蒸气压必须降到最小。第二,添加剂浓缩物必须处于使每种组分的HMIS健康危害等级降低到“1”或更低的稀释水平。
本发明力争使得通过蒸气媒介(vapor vector)在添加剂制剂中的健康暴露最小化。燃料添加剂中的大部分活性组分或是高分子量化合物,或是无机物,或是有机金属化合物,所有这些物质都呈现出低的蒸气压以至于通过吸入的暴露最小化。然而,流化性液体基质(fluidizing liquid matrix)可能含蒸气压相对较高的有机物。这些低蒸气压有机物有助于添加剂活性成分的挥发。本发明通过提供方法确保添加剂流化性基质自身具有低蒸气压,从而解决上述问题。
因为通过呼吸摄入的潜在危险,所以挥发性是影响金属添加剂HMIS危害等级的关键特征。本发明认识到这些有机金属化合物的挥发性很大程度上依赖于稳定金属的配体。因此,使这些有机金属化合物挥发性最小化的最重要的第一步是选择自身不挥发的并且HMIS健康危害等级为1或更低的配体。所述配体包括羧酸,如环烷酸、水杨酸、酚酸、松浆油衍生脂肪酸如CENTURY 1164(Arizona Chemical Co.)、其它的植物和动物衍生的脂肪酸及其混和物。为了改善低温性能,带烷基支链和不饱和键的羧酸的混和物是优选的,因为随着温度降低,潜在的晶格有序排列被打乱。因为在层流火焰加速中的作用,配体骨架中的不饱和键是高度优选的。其它的配体可以从适当的有机磺酸酯/盐(organosulfonate)和有机膦酸酯/盐(organophosphonate)中选择。
本发明也认识到,如果完成添加剂制剂需要溶剂,那么这些溶剂也可具有1或更低的HMIS健康危害等级标记。本文使用的术语“溶剂”通常包括载体和流化剂以及用于承载本文描述的催化剂/配体的其它化合物。这些溶剂可以在在100℃为4cSt的低芳香度的I类和II类基料中找到。合适的溶剂的实例是:1)出自Motiva的在100℃为大约4.0cSt的GP II 100SN,98 VI,和b)出自ExxonMobil的100℃为4.5cSt的GP I 150SN,88 VI。其它具有相似性能且HMIS危害标记为1和更低的溶剂也可以使用。
根据本配方可以衍生出来以在电厂中用作燃烧催化剂的单种金属是Ca、Cr、Mn、Fe、Co、Cu(只用于煤)、Sr、Y、Ru、Rh、Pd、La、Re、Os、Ir、Pt和Ce。各种羧酸盐可以由适当的金属原材料(氧化物、氢氧化物等)与羧酸以及上述溶剂制备。
为了拓宽功能范围,可能需要多金属物质(multimetallics)。在这种情况下,可能需要第一助催化剂。例如,如果需要另外的渣改性(slag modification),可以根据上述配方制备羧酸镁助催化剂,并与上述的单金属燃烧催化剂混合。催化剂/助催化剂的比值范围可以为1/0.5到1/6。如果添加剂制剂将用于含钒的燃料油中,那么Mg助催化剂的量应该是和燃料中钒的浓度大约成化学计量的。当燃烧催化剂是Mn基的,那么最终制剂应该是经设计以提供约10到50ppm的Mn金属或约20到30ppm的Mn金属的浓缩物。因为Mn、Pd、Pt和Cu基燃烧催化剂被认为是最有效的碳燃烧催化剂之一,所以使用诸如由Ca、Cr、Fe、Co、Sr、Y、Ru、Rh、La、Re、Os、Ir和Ce制得的金属羧酸盐燃烧催化剂的处理率(treat rate)会可能需要更高,可以具有约10-100ppm,或可替换地,约20-80ppm的金属。
在其中含碳燃烧副产物趋于生成大颗粒尺寸的难加工的粘性固体的情况下,那么就需要衍生自碱金属族(Li、Na、K等)的第二助催化剂。由于它们的电离能低,所以已知碱金属在火焰中将极快地离子化,并且在烟灰形成时迅速占据到新生成的烟灰上。由于带电,它们抑制烟灰颗粒的聚结,从而保持最大可能的烟灰表面进行氧化。因为这种第二助催化剂的效率与离子化的原子数成比例,所以为了达到理想效果可能需要更高的浓度。因此,在制剂浓缩物中的碱金属羧酸盐应该经设计以向燃料提供约10-500ppm,或替换地约20-100ppm的金属。
表1提供了按照本发明概念实现的添加剂制剂的实施例。在本系列实施例中,在许多环境下会推动各个添加剂制剂的HMIS健康危害等级的金属催化剂是锰。在同等浓度时,源自MMT的锰和源自羧酸锰的锰相比,吸入的风险要高的多,原因是前者在20℃的蒸气压是0.05毫米汞柱,而后者在相同温度下的蒸气压是0.00毫米汞柱。仅基于此方面,采用羧酸锰作为添加剂制剂中的燃烧催化剂应得到按吸入计低于“2”的HMIS健康危害等级,前提是如本文其它地方所述使用的羧酸配体和溶剂的等级低于“2”。
金属比 | Wt%,Mn | ||||||
实施例 | Mn | Ca | Mg | K | Zn | Al | |
1 | 1(MMT) | 1.26 | |||||
2 | 1(MMT) | 9(配体) | 1.26 | ||||
3 | 1(MMT) | 7(配体) | 2(配体) | 1.26 | |||
4 | 1(MMT) | 6(配体) | 1.26 | ||||
5 | 1(MMT) | 3(配体) | 1(配体) | 1(配体) | 1.26 | ||
6 | 1(MMT) | 4(配体) | 1(配体) | 1.26 | |||
7 | 1(MMT) | 1(配体) | 4(配体) | 1.26 | |||
8 | 1(MMT)/1(配体) | 3(配体) | 1(配体) | 2.57 | |||
9 | 1(MMT)/1(配体) | 2.57 | |||||
10 | 1(MMT)/1(配体) | 1(配体) | 2.57 | ||||
11 | 1(MMT)/1(配体) | 2(配体) | 3.78 | ||||
12 | 1(MMT)/2(配体) | 1(配体) | 1(配体) | 3(配体) | 3.78 | ||
13 | 1(MMT)/2(配体) | 2(配体) | 1(配体) | 3(配体) | 3.78 | ||
14 | 1(配体) | 0.2(配体) | 0.2(配体) | 0.5(配体) | 12 |
表1:经设计使得通过吸入的暴露最小化的固定燃烧器添加剂制剂
表1中,金属比的单位是重量百分比(wt%)。主燃烧催化剂是以甲基环戊二烯基锰三羰基(methylcyclopentadienyl manganese tricarbonyl,MMT)或羧酸锰形式存在的锰。“Lig”是指配体,其可以是羧酸衍生的、乙酰丙酮化物、螯合烯烃、芳香化合物如环戊二烯、和取代的环戊二烯、以及其它的HMIS健康危害等级为“2”和更低的稳定配体,其可以提高锰化合物的油溶性。助催化剂是钙(Ca)和钾(K)衍生的有机金属化合物。镁(Mg)、锌(Zn)和铝(Al)是渣和沉积物改性剂。通常,镁和锌对酸性渣和沉积物(燃料油燃烧沉积物)是优选的,而锌和铝对碱性渣(煤燃烧沉积物)的改性是理想的。因为锰是表1中HMIS等级最高的金属,所以本发明的设计主要集中在控制通过该金属吸入引起的可能的健康危害。纯工业级MMT(24.7%Mn)的HMIS健康危害等级为“3”。单独根据稀释因子,稀释到5%MMT(1.26%Mn)时,HMIS等级降低到为“1”的安全水平。这就是添加剂制剂中标题“Wt%Mn”的列中“1.26”的由来。因此,只要MMT是添加剂包的组分,Mn的浓度就不能超过此值。
为了提高制剂中Mn的浓度,具有更低HMIS健康危害等级的第二Mn源被用作终端处理(top treat)。典型的实例是在20℃蒸气压为0.00毫米汞柱的羧酸锰,此处的逻辑就是,如果其在工厂存储点不是处于蒸气相,其就不会被吸入。
实施例1到7是用于燃料油中改善燃烧、暗度、渣/沉积物,并且对热和冷腐蚀都能最小化的适合的添加剂制剂。
实施例8到14是针对燃煤电站和其它固定式燃烧器装置的,具有如上列出的相同的优点。
对市场上可购买到的添加剂流化剂组分的蒸气压进行了研究,从该研究中确定了在68的蒸气压不高于1.5×10-4托、在100的蒸气压低于70×10-5托的“超级”流体(见表2)。这些是在运输、存储和在最终使用场所的处理期间可能经历的温度条件。同样,确定了在68蒸气压低于5.0×10-4托、在100蒸气压低于200×10-5托的“良好”流体(见表3)。列出的只是适合流体的示例。更重要的是可以用作选择适合的流化组分的指导的各个蒸气压范围。
超级流体 | 测试蒸气压的温度()(单位×10-5托) | |||
供应商 | 油名称 | 类别 | 68 | 100 |
Petro Canada | P5300 | II | 0.14 | 1.00 |
Petro Canada | VHV18 | III | 0.21 | 1.10 |
Motiva | Star12 | II | 0.07 | 3.70 |
Petro Canada | VHV14 | III | 0.95 | 5.40 |
Petro Canada | VHV16 | III | 1.70 | 9.00 |
Petro Canada | P1003 | (II+) | 6.60 | 32.00 |
Petro Canada | P2305 | II | 7.00 | 35.00 |
Petro Canada | P1020 | II | 9.00 | 43.00 |
Petro Canada | P1017 | II | 15.00 | 70.00 |
表2
良好流体 | 测试蒸气压的温度()(单位×10-5托) | |||
供应商 | 油名称 | 类别 | 68 | 100 |
SK | Yubase4 | III | 18.00 | 75.00 |
Petro Canada | P1810 | II | 23.00 | 90.00 |
Motiva | Star5 | II | 40.00 | 170.00 |
Petro Canada | EVHV124 | III | 47.00 | 200.00 |
Petro Canada | PL65 | II | 47.00 | 200.00 |
表3
采用由此限定的关键组分,这些添加剂可以根据已知的技术采用适当的溶剂和所需的辅助组分(冷流改进剂、清洁剂、抗静电剂等)进行配制。给出的比例可以变更,以和改变的燃料组成和燃烧器/炉子/锅炉操作参数相符合。本发明认识到了这些区别,并将其涵盖在内。
其它的可以用作燃烧催化剂且可以替换Mn的金属是Ca、Sr、Cr、Fe、Cu、Ru、Rh、Pd、La、Ir、Pt和Ce。为了测定安全浓度,对于蒸汽压和稀释会采用相同的逻辑。
根据以上描述的配方制得的更安全的添加剂制剂会被添加到燃油和燃煤的炉子和锅炉系统中的燃料、燃烧空气、二次空气、过热空气、燃烧料,或废气中,以控制诸如颗粒和NOx的排放;使分阶段的低-NOx燃烧器附近的富含水墙燃料区中的腐蚀最小化,以及通过阻止SO2氧化成腐蚀性的SO3使废气中的低温腐蚀最小化。
本发明还涉及包含本文所述的添加剂的包装制品。简单来说,添加剂可以在使用之前存储到包装里——所述包装包括但不限于鼓形圆桶、包、桶、罐等等。这些包装会在其上面,或者在其附近或者紧邻处,包括标志或标记,指明HMIS健康等级为1或0。包装上的这种标记或标志的史无前例的优点是很显著的。在电站工作场所或附近的任何人员都明白包装的内容物是相对安全的,不挥发的。
本发明在其实施中允许相当的变化。因此,前文的说明并不是旨在限制,也不应该认为是限制本发明于本文前面给出的特定实例。确实,意图涵盖的是后面权利要求书中所给出的及其作为法律实体许可的等效。
专利权人没有意图向公众提供任何公开的实施方案,并且在一定程度上任何公开的修改或者变更可能在字面上不在权利要求的范围之内,但是根据等同原则其被视为本发明的一部分。
Claims (21)
1.用于在电站炉和/或工业炉中使用的燃烧添加剂,该添加剂包括:
含金属的催化剂;
与所述催化剂配合的配体;和
承载所述催化剂/配体配合物的溶剂,
其中,所述添加剂在100的蒸气压低于约200×10-5托。
2.权利要求1所述的燃烧添加剂,其中所述催化剂包含多种金属。
3.权利要求1所述的燃烧添加剂,其中所述催化剂包含锰。
4.权利要求2所述的燃烧添加剂,其中所述催化剂包含多种选自锰、钙、镁、钾、锌、铜和铝的金属。
5.权利要求1所述的燃烧添加剂,其中所述催化剂包含选自锰、钙、镁、钾、锌、铜和铝的金属。
6.权利要求1所述的燃烧添加剂,其中所述配体选自化石燃料衍生的羧酸盐/酯、天然产物衍生的羧酸盐/酯、合成羧酸盐/酯及其混和物。
7.权利要求1所述的燃烧添加剂,其中所述添加剂的HMIS健康等级为1或0。
8.权利要求6所述的燃烧添加剂,其中所述添加剂的HMIS健康等级为1或0。
9.权利要求1所述的燃烧添加剂,其中所述添加剂在100的蒸气压低于约70×10-5托。
10.在电站炉和/或工业炉中使用的燃烧添加剂的配制方法,该方法包括:
选择在电站炉和/或工业炉中使用的含金属催化剂,
将所述含金属催化剂与配体配合,和
添加溶剂以承载所述催化剂/配体配合物,
其中,所述添加剂在100的蒸气压低于约200×10-5托。
11.权利要求10所述的方法,其中所述催化剂包含多种金属。
12.权利要求10所述的方法,其中所述催化剂包含锰。
13.权利要求11所述的方法,其中所述催化剂包含多种选自锰、钙、镁、钾、锌、铜和铝的金属。
14.权利要求10所述的方法,其中所述催化剂包含选自锰、钙、镁、钾、锌、铜和铝的金属。
15.权利要求10所述的方法,其中所述配体选自化石燃料衍生的羧酸盐/酯、天然产物衍生的羧酸盐/酯、合成羧酸盐/酯及其混和物。
16.权利要求10所述的方法,其中所述添加剂的HMIS健康等级为1或0。
17.权利要求10所述的方法,其中所述添加剂的HMIS健康等级为1或0。
18.权利要求10所述的方法,其中所述添加剂在100的压力低于70×10-5托。
19.使对用于电站炉和/或工业炉中的燃烧添加剂的健康暴露最小化的方法,该方法包括:
选择在电站炉和/或工业炉中使用的含金属催化剂,
将所述含金属催化剂与配体配合,和
添加溶剂以承载催化剂/配体配合物,
其中,所述添加剂在100的蒸气压低于约200×10-5托。
20.权利要求19所述的方法,其中所述添加剂在100的压力低于70×10-5托。
21.一种包装产品,包括:
(a)权利要求1中的燃烧添加剂,
(b)在所述添加剂上面、周围或者与之相连的包装,和
(c)在所述包装上的标志或标记,所述标志或标记表明HMIS健康等级为1或0。
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US2943925A (en) * | 1956-08-27 | 1960-07-05 | Gulf Research Development Co | Residual fuel oils |
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US3692503A (en) * | 1969-02-26 | 1972-09-19 | Apollo Chem | Activated manganese containing additive for fuels |
CA966148A (en) * | 1971-05-07 | 1975-04-15 | Mack W. Hunt | Preparation of oil-soluble metal sulfonates |
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US8257450B2 (en) * | 2002-12-18 | 2012-09-04 | Afton Chemical Intangibles Llc | Manganese compounds to inhibit both low-and high-temperature corrosion in utility and industrial furnace systems |
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