CN100354028C - 通过与过氧化氢反应从废气中脱除二氧化硫的方法 - Google Patents

通过与过氧化氢反应从废气中脱除二氧化硫的方法 Download PDF

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CN100354028C
CN100354028C CNB2003801067013A CN200380106701A CN100354028C CN 100354028 C CN100354028 C CN 100354028C CN B2003801067013 A CNB2003801067013 A CN B2003801067013A CN 200380106701 A CN200380106701 A CN 200380106701A CN 100354028 C CN100354028 C CN 100354028C
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waste gas
reaction
gas
acid
gases
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CN1729039A (zh
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莫顿·特勒弗森·尼尔森
P·斯考布耶
K·A·克里斯滕森
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Topsoe AS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/507—Sulfur oxides by treating the gases with other liquids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/20—Sulfur; Compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2217/00—Intercepting solids
    • F23J2217/10—Intercepting solids by filters
    • F23J2217/102—Intercepting solids by filters electrostatic
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2219/00—Treatment devices
    • F23J2219/40—Sorption with wet devices, e.g. scrubbers

Abstract

在具有30-150℃的温度和含有0.001-1vol%SO2的废气中移除SO2的方法，其中SO2通过将H2O2的水溶液喷雾到废气中被氧化成H2SO4，该步骤在通过由气溶胶过滤器将产出的硫酸从废气中移除之前。

Description

通过与过氧化氢反应从废气中脱除二氧化硫的方法
本发明涉及通过与H2O2反应从废气中脱除SO2的方法。
30多年来，如在1989年8月出版的2164e来自Lurgi/SüdchemieAG的所述，已知SO2可以通过在吸收塔中将废气与回流的含H2O2的稀硫酸溶液接触而除去，由此SO2在溶液中被溶解和被氧化成硫酸。回流的溶液一般含有30-60％的硫酸和0.1-0.5％的H2O2。吸收一般在温度为50-80℃的回流溶液中进行。H2O2既可以浓缩的H2O2水溶液形式加入回流的酸，又可以通过电解回流的酸的侧流制备。所产生的酸从回流的酸中抽出。
已知的工艺通常要求在吸收塔的下游安装一个低速的气溶胶过滤器来除去硫酸气溶胶(酸雾)，以满足酸雾释放规定所要求的烟道气中低于约5mol ppm H2SO4。可能存在于废气中的微细的酸雾(气溶胶)在吸收塔中没有被有效地除去。微细的酸雾也通过从吸收塔本身的吸收液体中蒸发的SO2和H2O2间反应形成。
已知工艺的缺陷是既要求安装吸附塔，又要求安装低速雾过滤器。
在根据本发明的工艺中，废气中的SO2无需吸附塔通过将H2O2在水中或在稀硫酸中的溶液喷雾到废气中与H2O2反应而被除去，所述废气在低速气溶胶过滤器或湿静电沉淀器(WESP)的上游。
本发明的优选实施方案中示于图1。在管线1的0.1-30％H2O2溶液通过喷嘴3喷雾到管线2中的通常含有100-1000ppm SO2和通常温度范围为50-120℃的废气流中。喷嘴设置在管道4中，使得喷雾均匀地分散在位于雾过滤器5之前的气流中，在雾过滤器中气体平行通过多个低速过滤烛管6。在本工艺中液滴在气体中均匀分散是理想的，而液滴最均匀的分散通过使用空气雾化喷嘴产生非常小的微滴而达到。在工艺中形成的H2SO4累积在过滤器元件或烛管中并从中通过管线7排出。绝大部分或全部质量的液滴在气体进入过滤器烛管前挥发，由此绝大部分H2O2挥发并以气相进行反应，形成硫酸气溶胶。然而液滴在气体进入过滤单元前完全挥发是没有必要的。在雾过滤器元件中SO2和H2O2之间的反应将会完成并将建立热平衡，而不会降低SO2脱除的效率。
因此，H2O2水溶液的喷射用于两个目的：
首先，向废气中加入所述量的H2O2，其为达到由SO2到H2SO4的理想转化是所需的，其转化通过下面的反应式进行：
H2O2+SO2＝H2SO4
大部分的转化是通过SO2和挥发的H2O2之间进行气相反应形成酸雾或通过SO2和H2O2溶解在液滴中进行。反应在气溶胶过滤器中完成，气溶胶过滤器中残留的SO2被吸收并与包含在润湿纤维材料的稀硫酸中的残留H2O2反应。
其次，溶液中所含水通过液滴的挥发冷却管线2中的废气，从而使废气冷却到过滤器元件或烛管的理想温度，一般为50℃-70℃的温度。产出酸中H2SO4的浓度将和气相中在实际温度下和H2O分压下的H2SO4浓度达到平衡。
典型地，在H2O2利用率为约95％时，可以获得高达98％的SO2脱除率。
实施例
100℃时1000Nm3/h的废气流含有200ppm SO2+10％H2O，温度为100℃。96％SO2的脱除率是理想的。气溶胶过滤器被设计为最高在70℃下运行。选择在67-70℃下运行，以取得最高可能性的酸强度和在产出酸中低残余量的H2O2。
该工艺按如下步骤进行：将含有2.0重量％H2O2的15.7kg/h的水喷射到废气中，由此废气热平衡时冷却到65-70℃。雾过滤器为75mm厚和具有2.5m2的通流面积。纤维的直径为约8μm。在这些条件下进行实验，表现出约96％的SO2被移除，产出了含约500ppm H2O2的1.7kg/h的50％的H2SO4。经处理的气体含有低于2ppm的H2SO4且H2O2的含量低于检测限。

Claims (3)

1.一种在具有30-150℃的温度和含有0.001-1vol％SO2的废气中脱除SO2的方法，其中通过将H2O2的水溶液喷雾到废气中而使SO2氧化成H2SO4，该步骤在通过由气溶胶过滤器将产出的硫酸从废气中脱除之前。
2.权利要求1的方法，其中废气被位于过滤器之前喷射到废气中的溶液中所含的水挥发冷却。
3.权利要求1的方法，其中用湿静电分离器代替气溶胶过滤器。
CNB2003801067013A 2002-12-21 2003-12-04 通过与过氧化氢反应从废气中脱除二氧化硫的方法 Ceased CN100354028C (zh)

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CN100463847C (zh) * 2006-06-23 2009-02-25 李开春 以烟道气制备硫酸的方法
DE102007020141A1 (de) * 2007-04-26 2008-10-30 Bayer Materialscience Ag Recyclegaswäscher zur Entfernung von SOx und Schwefelsäureaerosolen aus chlorhaltigen Prozessgasen
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CA2511311C (en) 2011-09-20
EP1578517A2 (en) 2005-09-28
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RU2005123041A (ru) 2006-01-27
US20060057047A1 (en) 2006-03-16
AU2003288228B2 (en) 2009-08-06
KR20050084454A (ko) 2005-08-26
WO2004056449A2 (en) 2004-07-08
CA2511311A1 (en) 2004-07-08
RU2346731C2 (ru) 2009-02-20
AU2003288228A1 (en) 2004-07-14
EP1578517B1 (en) 2008-03-12
WO2004056449A3 (en) 2004-09-30
DE60319738D1 (de) 2008-04-24
US7776299B2 (en) 2010-08-17
CN1729039A (zh) 2006-02-01
DE60319738T2 (de) 2009-04-02
BR0317462A (pt) 2005-11-16
JP2006512190A (ja) 2006-04-13

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