CN103990376A - 从烟道气流中除去二氧化硫的方法 - Google Patents
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Abstract
本发明提供了一种从含有SO2的烟道气流中除去SO2的方法,包括提供天然碱源和将该天然碱喷射到烟道气流中。烟道气的温度为约600°F到约900°F。保持天然碱与烟道气接触足够的时间,以使部分天然碱与部分SO2反应,以降低烟道气流中SO2的浓度。
Description
本申请是申请日为2006年8月7日、申请号为200680029990.5、发明名称为“从烟道气流中除去二氧化硫的方法”(PCT/EP2006/065097,进入国家阶段日期2008年2月18日)之申请的分案申请。
技术领域
本发明涉及气体的净化,并且更具体地涉及一种净化含有有害气体例如SO2的烟道气的方法。
背景技术
已经采用多种吸收剂利用干式吸收剂喷射(dry sorbent injection,DSI)来从烟道气中除去SOx和其他气体。然而,DSI过去通常在远低于400°F的温度下进行,因为设备材料例如集尘室介质不能经受较高的温度。此外,许多吸收剂物质在接近或高于400°F的温度下烧结或熔化,这使其在除去气体时效力降低。许多吸收剂物质的反应产物在较高温度下还粘附到设备和管道上,这需要频繁地清洁工艺设备。为了在这些较低的温度下操作,通常必须在喷射吸收剂之前冷却燃烧气。这是不希望的额外的工序。
因此,需要一种在高温下除去SOx气体时有效的吸收剂喷射方法。
发明内容
一方面,提供一种从含有SO2的烟道气流中除去SO2的方法。该方法包括提供天然碱源和将该天然碱喷射到烟道气流中。所述烟道气的温度为约600°F到约900°F。保持天然碱与烟道气接触足够的时间,以使部分天然碱与部分SO2反应,以降低烟道气流中SO2的浓度。
另一方面,提供一种用于从含有SO2的烟道气流中除去SO2的系统。该系统包括天然碱源和烟道气流。该系统还包括用于将天然碱喷射到烟道气流中的喷射器。烟道气的温度为约600°F到约900°F。该系统还包括保持天然碱与烟道气接触足够时间的区域,以使部分天然碱与部分SO2反应,从而降低烟道气流中SO2的浓度。
附图说明
前述段落通过一般介绍提供并且并非旨在限制所附权利要求的范围。通过参考下面的详细描述连同附图将更好地理解目前优选的实施方案以及其他优点。
图1是烟道气脱硫系统的一个实施方案的示意图。
图2是显示作为天然碱和碳酸氢钠的归一化学计量比(normalizedstochiometric ratio,NSR)的函数的SO2除去%的图。
图3是显示作为烟道气脱硫系统的一个实施方案的烟道气温度(以°F计)的函数的SO2除去%的图。
图4显示在使用天然碱的烟道气脱硫系统的一个实施方案中操作后的静电沉积器的穿孔板。
图5显示在使用碳酸氢钠的烟道气脱硫系统的一个实施方案中操作后的静电沉积器的穿孔板。
具体实施方式
参照附图描述本发明,其中相同的组成部分通过相同的附图标记表示。通过下面的详细描述更好地理解本发明的不同组成部分的关系和功能。然而,如下所述的本发明的实施方案仅作为实施例,并且本发明不限于图中所示的实施方案。
干式吸收剂喷射(DSI)一直用作用于除去SO2的喷雾干燥或湿法洗涤系统的低成本的替代方法。在DSI方法中,储存吸收剂并将其干喷到烟道中,在烟道中所述吸收剂与酸性气体反应。本发明提供一种优选通过将吸收剂例如天然碱喷射到烟道气流中以与SO2反应而从含有SO2的烟道气流中除去SO2的方法。天然碱是含有约85~95%倍半碳酸钠(Na2CO3·NaHCO3·2H2O)的矿物。在怀俄明州的西南部靠近格林河处发现大量矿物天然碱的矿床。如在本文所用的,术语“天然碱”包括其他倍半碳酸钠源。然而优选倍半碳酸盐源为开采的天然碱的实施方案。术语“烟道气”包括来自任何类型燃烧过程(包括煤、油、天然气、玻璃原料等)的废气。烟道气通常包含SO2以及其他酸性气体例如HCl、SO3和NOx。
所述方法的示意图如图1所示。给炉或燃烧器10供以燃料源12(例如煤),然后供以空气14以燃烧所述燃料源12。将燃烧气体从燃烧器10引导至换热器或空气加热器40。换热器或空气加热器40的出口连接到颗粒收集装置50。在烟道气被引导至用于排气的气体烟囱60之前,颗粒收集装置50从烟道气中除去在燃烧过程中产生的颗粒例如飞灰。颗粒收集装置50可以是静电沉积器(ESP)。其他类型的颗粒收集装置例如集尘室也可以用于除去固体。集尘室包含用于将在燃烧过程中产生的颗粒与烟道气分离的过滤器。由于在本方法中所用的相对小的粒径,天然碱可作为集尘室过滤介质上的滤料层。
SO2除去系统包括天然碱源30。天然碱30优选具有约10微米到约40微米的平均粒径,最优选为约24微米到约28微米。天然碱优选为干燥颗粒形式。合适的天然碱源是天然碱,其是可得自SolvayChemicals,Green River,WY的机械精制的天然碱矿产品。天然碱含有约97.5%的倍半碳酸钠,平均粒径为约24~28微米。SO2除去系统还可以包括球磨粉碎机32或其他类型的磨,以就地降低和/或控制天然碱的粒径。
将天然碱从天然碱源30运送到喷射器20。可气动地或通过任何其他合适的方法运送天然碱。可容易地将天然碱鼓风以气动输送。用于喷射天然碱或倍半碳酸钠的设备示意性地如图1所示。天然碱喷射设备20将天然碱引入到烟道气管道段42中,所述烟道气管道段42设置在集尘室入口的上游和换热器40(如果换热器或预热器存在的话)的上游的位置。优选将天然碱喷射系统设计为使天然碱与烟道气流中的SOx的接触最大化。可以使用本领域已知的任何类型的喷射设备以将天然碱引入到气体管道中。例如,可以通过压缩的空气驱动喷射器直接实现喷射。
如果储存天然碱并将天然碱干喷到其与酸性气体反应的烟道42中,则该方法不需要浆料设备或反应容器。然而,该方法也可以与烟道气的加湿或天然碱的湿式喷射一起使用。此外,如果该方法用于酸雾的清洁洗涤,则可以通过存在的湿式洗涤容器湿式收集颗粒。
烟道气的温度随喷射系统中的位置变化,并且在操作过程中还可以随时间稍微变化。喷射天然碱处的烟道气的温度为约600°F到约900°F。保持天然碱与烟道气接触足够的时间,以使部分天然碱与部分SO2反应,从而降低烟道气流中SO2的浓度。烟道气的温度优选高于约630°F,并且最优选高于约700°F。烟道气的温度优选低于约800°F,并且最优选低于约750°F。烟道气的温度最优选为约700°F到约750°F。
也可以改变该方法,以控制烟道气的温度。例如,可以调节天然碱上游的烟道气温度,以得到所希望的喷射天然碱处的烟道气温度。此外,可以将环境空气引入到烟道气流中并在喷射天然碱处监测烟道气温度。其他可能的控制烟道气温度的方法包括使用换热器和/或空气冷却器。该方法也可以改变天然碱的喷射位置或包括多个用于天然碱喷射的位置。
为了实现脱硫,天然碱优选以相对于SO2流量的一定速率喷射,以提供约1.0~1.5的钠与硫的归一化学计量比(NSR)。NSR是所喷射的反应物的量相对于理论上所需的量的尺度。NSR表示与所有酸性气体反应所需的吸收剂的化学计量的量。例如,1.0的NSR是指喷射了足够的物质以在理论上百分之百除去入口烟道气中的SO2;0.5的NSR是指理论上除去百分之五十的SO2。每一摩尔存在的SO2需要两摩尔的钠来进行SO2中和。
与碳酸氢钠不同,天然碱在高温下不熔。相反,当在275°F或275°F以上加热时倍半碳酸钠经历所包含的碳酸氢钠的快速煅烧成为碳酸钠。认为“爆米花状的”分解通过将未反应的碳酸钠带到颗粒表面上进行SO2中和而产生大的活性表面。反应的副产物是硫酸钠并与飞灰一起收集。天然碱与SO2的化学反应如下所示:
2[Na2CO3·NaHCO3·2H2O]→3Na2CO3+5H2O+CO2
Na2CO3+SO2→Na2SO3+CO2
Na2SO3+1/2O2→Na2SO4
可以在静电沉积器或其他颗粒收集装置中收集天然碱与SO2的固体反应产物(主要是硫酸钠)和未反应的苏打灰。总的脱硫率优选为至少约70%,更优选为至少约80%,并且最优选为至少约90%。
在一个实施方案中,烟道气流还含有SO3。保持天然碱与烟道气接触足够的时间,以使部分天然碱与部分SO3反应,从而降低烟道气流中SO3的浓度。与SO2相比,SO3通常更易与吸收剂反应,因此天然碱将先除去SO3。天然碱与SO3的化学反应如下所示:
2[Na2CO3·NaHCO3·2H2O]→3Na2CO3+5H2O+CO2
Na2CO3+SO3→Na2SO4+CO2
天然碱喷射系统也可以与其他SOx除去系统例如碳酸氢钠、石灰、石灰石等结合,以便提高性能或除去另外的有害气体例如HCl、NOx等。
实施例
在Verona,CA的商业玻璃厂中采用热侧静电沉积器(ESP)而没有集尘室进行研究。将天然气用作燃料源,硫源来自玻璃原料。烟道气中SO2的浓度为800ppm。所用的天然碱为来自Solvay Chemicals的使用压缩空气鼓风机和气闸进料器在管道中喷射天然碱。通过用天然碱储仓中的天然碱的重量损失标定气闸的每分钟转数来测量天然碱流量。天然碱的进料量从50磅/小时变为211磅/小时。
实施例1
在750°F的温度下以1.0、1.2和1.4的NSR值将天然碱喷射到烟道气中。图2显示作为天然碱的归一化学计量比(NSR)的函数的SO2除去%。从这些实验可以看出NSR为1.2时天然碱得到约80%的SO2除去率。图4显示SO2除去系统在使用天然碱操作五个月后玻璃厂中的ESP的穿孔板。可以看出该板相对没有固体物累积。
实施例2
作为对比实施例,在NSR为1.2时在与实施例1相同的条件下喷射碳酸氢钠。结果如图2所示。72%的SO2除去%明显低于相同温度和NSR下的天然碱的SO2除去%。图5显示使用碳酸氢钠操作SO2除去系统后玻璃厂中的ESP的穿孔板。可以看出该板有明显的固体物累积。
实施例3
在750°F到805°F的温度下在NSR为1.5时将天然碱喷射到烟道气中。图3显示作为烟道气温度函数的SO2除去%。从这些实验可以看出天然碱得到至多91%的SO2除去率并且在宽广的高温范围内有效。
从上面的试验可以看出在高温下从烟道气流中除去SO2时天然碱比碳酸氢钠更有效。因此,为了实现相同的硫降低,所述系统可以使用比碳酸氢钠系统更少的吸收剂物质。此外,可以看出天然碱在宽广的高温范围内具有良好的性能。最后,与使用碳酸氢钠的系统相比,使用天然碱的SO2除去系统在ESP的穿孔板中具有少得多的固体物累积。
如上所述和在此所示的实施方案是示例性的和非限制性的。本发明的范围通过权利要求而不是通过前述描述和附图表示。本发明可以体现为其他特定形式而不背离本发明的精神。因此,这些和在权利要求范围内的任何其他改变均意在包含于本发明的范围内。
以下内容对应于母案申请中的原始权利要求书,现作为说明书的一部分并入此处:
1.一种从含有SO2的烟道气流中除去SO2的方法,其包括:
-提供天然碱源;
-将所述天然碱喷射到所述烟道气流中,其中所述烟道气的温度为约600°F到约900°F;以及
-保持所述天然碱与所述烟道气接触足够的时间,以使部分所述天然碱与部分所述SO2反应,以降低所述烟道气流中所述SO2的浓度。
2.如项1所述的方法,其中所述天然碱的平均粒径小于约40微米。
3.如项1所述的方法,其中所述天然碱的平均粒径为约10微米到约40微米。
4.如项1所述的方法,其中所述天然碱的平均粒径为约24微米到约28微米。
5.如项1所述的方法,其中所述烟道气的温度高于约630°F。
6.如项1所述的方法,其中所述烟道气的温度高于约700°F。
7.如项1所述的方法,其中所述烟道气的温度低于约800°F。
8.如项1所述的方法,其中所述烟道气的温度低于约750°F。
9.如项1所述的方法,其中所述烟道气的温度为约700°F到约750°F。
10.如项1所述的方法,其中所述天然碱以相对于所述SO2流量的一定速率喷射,以提供约1.0~1.5的钠与硫的归一化学计量比。
11.如项1所述的方法,其中将所述天然碱作为干物质喷射。
12.如项1所述的方法,其还包括在接近所述烟道气流的位置处将所述天然碱研磨到所希望的平均粒径。
13.如项1所述的方法,其还包括在静电沉积器中收集所述天然碱与所述SO2的反应产物。
14.如项1所述的方法,其中所述烟道气流还含有SO3,所述方法还包括保持所述天然碱与所述烟道气接触足够的时间,以使部分所述天然碱与部分所述SO3反应,以降低所述烟道气流中所述SO3的浓度。
15.一种从含有SO2的烟道气流中除去SO2的方法,其包括:
提供平均粒径为约10微米到约40微米的天然碱源;
将所述作为干颗粒物质的天然碱喷射到所述烟道气流中,其中所述烟道气的温度为约600°F到约900°F;以及
保持所述天然碱与所述烟道气接触足够的时间,以使部分所述天然碱与部分所述SO2反应,以降低所述烟道气流中所述SO2的浓度。
16.如项15所述的方法,其中所述天然碱的平均粒径为约24微米到约28微米。
17.如项15所述的方法,其中所述烟道气的温度为约700°F到约750°F。
18.如项15所述的方法,其中所述天然碱以相对于所述SO2流量的一定速率喷射,以提供约1.0~1.5的钠与硫的归一化学计量比。
19.如项15所述的方法,其还包括调节所述天然碱上游的所述烟道气的温度,以得到所希望的喷射所述天然碱处的烟道气温度。
20.如项19所述的方法,其中所述调节还包括将环境空气引入到所述烟道气流中以及监测喷射所述天然碱处的烟道气温度。
21.如项19所述的方法,其中所述调节还包括通过与所述烟道气连通的换热器控制物料流。
Claims (21)
1.一种从含有SO2的烟道气流中除去SO2的方法,其包括:
-提供天然碱源;
-将所述天然碱喷射到所述烟道气流中,其中所述烟道气的温度为约600°F到约900°F;以及
-保持所述天然碱与所述烟道气接触足够的时间,以使部分所述天然碱与部分所述SO2反应,以降低所述烟道气流中所述SO2的浓度。
2.如权利要求1所述的方法,其中所述天然碱的平均粒径小于约40微米。
3.如权利要求1所述的方法,其中所述天然碱的平均粒径为约10微米到约40微米。
4.如权利要求1所述的方法,其中所述天然碱的平均粒径为约24微米到约28微米。
5.如权利要求1所述的方法,其中所述烟道气的温度高于约630°F。
6.如权利要求1所述的方法,其中所述烟道气的温度高于约700°F。
7.如权利要求1所述的方法,其中所述烟道气的温度低于约800°F。
8.如权利要求1所述的方法,其中所述烟道气的温度低于约750°F。
9.如权利要求1所述的方法,其中所述烟道气的温度为约700°F到约750°F。
10.如权利要求1所述的方法,其中所述天然碱以相对于所述SO2流量的一定速率喷射,以提供约1.0~1.5的钠与硫的归一化学计量比。
11.如权利要求1所述的方法,其中将所述天然碱作为干物质喷射。
12.如权利要求1所述的方法,其还包括在接近所述烟道气流的位置处将所述天然碱研磨到所希望的平均粒径。
13.如权利要求1所述的方法,其还包括在静电沉积器中收集所述天然碱与所述SO2的反应产物。
14.如权利要求1所述的方法,其中所述烟道气流还含有SO3,所述方法还包括保持所述天然碱与所述烟道气接触足够的时间,以使部分所述天然碱与部分所述SO3反应,以降低所述烟道气流中所述SO3的浓度。
15.一种从含有SO2的烟道气流中除去SO2的方法,其包括:
提供平均粒径为约10微米到约40微米的天然碱源;
将所述作为干颗粒物质的天然碱喷射到所述烟道气流中,其中所述烟道气的温度为约600°F到约900°F;以及
保持所述天然碱与所述烟道气接触足够的时间,以使部分所述天然碱与部分所述SO2反应,以降低所述烟道气流中所述SO2的浓度。
16.如权利要求15所述的方法,其中所述天然碱的平均粒径为约24微米到约28微米。
17.如权利要求15所述的方法,其中所述烟道气的温度为约700°F到约750°F。
18.如权利要求15所述的方法,其中所述天然碱以相对于所述SO2流量的一定速率喷射,以提供约1.0~1.5的钠与硫的归一化学计量比。
19.如权利要求15所述的方法,其还包括调节所述天然碱上游的所述烟道气的温度,以得到所希望的喷射所述天然碱处的烟道气温度。
20.如权利要求19所述的方法,其中所述调节还包括将环境空气引入到所述烟道气流中以及监测喷射所述天然碱处的烟道气温度。
21.如权利要求19所述的方法,其中所述调节还包括通过与所述烟道气连通的换热器控制物料流。
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-
2005
- 2005-08-18 US US11/208,432 patent/US7531154B2/en not_active Expired - Fee Related
-
2006
- 2006-08-07 DK DK06792721.0T patent/DK1919596T3/en active
- 2006-08-07 CN CNA2006800299905A patent/CN101242886A/zh active Pending
- 2006-08-07 CA CA2618202A patent/CA2618202C/en not_active Expired - Fee Related
- 2006-08-07 WO PCT/EP2006/065097 patent/WO2007020205A1/en active Application Filing
- 2006-08-07 BR BRPI0614344-0A patent/BRPI0614344A2/pt not_active IP Right Cessation
- 2006-08-07 JP JP2008526480A patent/JP2009504391A/ja active Pending
- 2006-08-07 ES ES06792721.0T patent/ES2527423T3/es active Active
- 2006-08-07 CN CN201410126211.XA patent/CN103990376A/zh active Pending
- 2006-08-07 EA EA200800616A patent/EA014304B1/ru not_active IP Right Cessation
- 2006-08-07 EP EP06792721.0A patent/EP1919596B1/en not_active Not-in-force
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2009
- 2009-03-27 US US12/413,057 patent/US7854911B2/en active Active
-
2015
- 2015-01-07 CY CY20151100009T patent/CY1116061T1/el unknown
- 2015-02-17 HK HK15101746.8A patent/HK1201226A1/zh unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115253657A (zh) * | 2022-08-31 | 2022-11-01 | 上海梅山钢铁股份有限公司 | 一种全烧煤气锅炉烟气脱硫效率提升控制装置 |
CN115253657B (zh) * | 2022-08-31 | 2023-08-15 | 上海梅山钢铁股份有限公司 | 一种全烧煤气锅炉烟气脱硫效率提升控制装置 |
Also Published As
Publication number | Publication date |
---|---|
CY1116061T1 (el) | 2017-02-08 |
EA014304B1 (ru) | 2010-10-29 |
EP1919596B1 (en) | 2014-10-08 |
CA2618202A1 (en) | 2007-02-22 |
JP2009504391A (ja) | 2009-02-05 |
US20070041885A1 (en) | 2007-02-22 |
BRPI0614344A2 (pt) | 2012-11-27 |
WO2007020205A1 (en) | 2007-02-22 |
US7531154B2 (en) | 2009-05-12 |
US20090241774A1 (en) | 2009-10-01 |
CA2618202C (en) | 2013-01-22 |
DK1919596T3 (en) | 2015-01-12 |
EA200800616A1 (ru) | 2008-08-29 |
HK1201226A1 (zh) | 2015-08-28 |
EP1919596A1 (en) | 2008-05-14 |
CN101242886A (zh) | 2008-08-13 |
US7854911B2 (en) | 2010-12-21 |
ES2527423T3 (es) | 2015-01-23 |
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