CN101947409B - 一种基于光化学高级氧化作用的烟气脱汞系统 - Google Patents
一种基于光化学高级氧化作用的烟气脱汞系统 Download PDFInfo
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- CN101947409B CN101947409B CN2010102965928A CN201010296592A CN101947409B CN 101947409 B CN101947409 B CN 101947409B CN 2010102965928 A CN2010102965928 A CN 2010102965928A CN 201010296592 A CN201010296592 A CN 201010296592A CN 101947409 B CN101947409 B CN 101947409B
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- flue gas
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- liquid
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- 239000003546 flue gases Substances 0.000 title claims abstract description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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[O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reactions Methods 0.000 title claims abstract description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound 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[Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052753 mercury Inorganic materials 0.000 title abstract description 14
- 239000007921 sprays Substances 0.000 claims abstract description 84
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- 239000012288 hydrogen peroxide Substances 0.000 claims abstract description 57
- 239000007788 liquids Substances 0.000 claims abstract description 30
- 238000006243 chemical reactions Methods 0.000 claims abstract description 22
- 238000010521 absorption reactions Methods 0.000 claims abstract description 19
- 229910052956 cinnabar Inorganic materials 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 56
- 239000011734 sodium Substances 0.000 claims description 21
- -1 hydroxyl radical free radical Chemical class 0.000 claims description 19
- 239000007789 gases Substances 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 14
- 239000002245 particles Substances 0.000 claims description 14
- 230000005284 excitation Effects 0.000 claims description 10
- 238000000354 decomposition reactions Methods 0.000 claims description 6
- 230000001590 oxidative Effects 0.000 claims description 6
- 239000011800 void materials Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 229910000132 mercury(II) oxide Inorganic materials 0.000 abstract description 8
- 238000007599 discharging Methods 0.000 abstract description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl radical Chemical compound 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[OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 1
- 239000003344 environmental pollutants Substances 0.000 description 32
- 231100000719 pollutant Toxicity 0.000 description 32
- 238000005516 engineering processes Methods 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 9
- 239000000047 products Substances 0.000 description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound 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[Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000000034 methods Methods 0.000 description 7
- 239000007791 liquid phases Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000006552 photochemical reactions Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000011901 water Substances 0.000 description 3
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical compound 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Abstract
Description
一种基于光化学高级氧化作用的烟气脱汞系统
技术领域
[0001 ] 本发明涉及包括电厂锅炉、工业窑炉和垃圾焚烧炉等烟道气中的汞排放污染控制技术,尤其涉及一种基于光化学高级氧化作用的烟气脱汞系统。
背景技术
[0002] 汞是一种剧毒、高挥发性、在生物体内易于沉积且迟滞性长的重金属痕量元素,对人体健康和生态环境均具有极大的危害。研究表明,火力发电、垃圾焚烧和以化石燃料为动力的水泥、冶金等工业过程是人为汞污染的重要排放源源,其中又有70%左右来源于火力发电厂的煤燃烧过程。我国是世界第一大煤炭消费国,能源结构中煤炭的比例高达75%,并且这种格局在今后比较长的一段时间内还不会有大的改变。因此,如何有效控制燃煤烟气中汞排放已成为我国政府面临的一项重要任务之一。
[0003] 目前,国内外最常见的烟气脱汞技术主要包括活性炭吸附法,湿法脱硫(WFGD)联合洗涤法以及选择性催化还原(SCR)催化氧化法等。活性炭吸附法是目前最为成熟的脱汞技术,但具有活性炭消耗量大,再生能耗高等不足,目前还难以获得大规模应用。湿法脱硫 (WFGD)联合脱汞法能够脱除80-95%左右的二价汞(Hg2+),但对零价汞(Hg°)的脱除效率很低。选择性催化还原(SCR)催化氧化法能够将Hg°催化氧化为Hg2+,然后结合湿法洗涤进行脱除,但目前还处于实验研究阶段。因此,积极开发有效的烟气脱汞技术仍然是该领域科技人员的重要任务之一。
[0004] 湿法烟气脱汞具有工艺流程简单和投资成本低等优点,但是传统的湿法脱汞工艺研究一直进展缓慢,其主要原因就在于烟气中的汞主要以两种形式存在:Hg°和Hg2+的化合物。Hg°具有熔点低、平衡蒸气压高、不易溶于水等特点,根据煤质的不同,一般占烟气总共含量的40-80%左右。由双膜理论可知,Hgtl必须首先由气态经传质和扩散过程转入液相, 然后才能发生化学反应固定到吸收液中,Hg0难溶的特性使得其液相吸收的阻力大大增加, 仅通过调控PH和温度的方法难以显著提高Hg°在液相的溶解度,这一特性造成了传统的湿法脱汞技术普遍存在脱除效率低,能耗高等问题,阻碍了其工业化应用。因此,开发一种能够将Hg°快速转化为易溶形态的新技术是湿法烟气脱汞技术的关键问题之一。
发明内容
[0005] 本发明公开了一种基于光化学高级氧化作用的烟气脱汞系统,利用紫外光激发分解过氧化氢,并产生具有强氧化性的羟基自由基(·0Η)氧化脱除烟气中的零价汞(Hg°),Hg° 首先被氧化为可溶的二价汞(Hg2+)固定于溶液中,通过向分离塔投加Na2S溶液生成难溶的 HgS对Hg2+进行捕捉回收,最终达到烟气脱汞目的。
[0006] 为实现以上目的,本发明采用的实施方案是:一种基于光化学高级氧化作用的烟气脱汞系统,其特征在于:设有燃烧器、静电除尘器、换热器、喷淋塔、添液塔、烟囱以及分离塔构成的燃烧及排放系统,燃烧器产生的烟气通入静电除尘器脱除烟气颗粒物后通入换热器进行冷却降温后通入喷淋塔,喷淋塔内设有紫外灯管,来自添液塔内的过氧化氢溶液由循环泵抽取并通过雾化喷嘴喷入喷淋塔内经紫外光激发分解过氧化氢,产生强氧化性的羟基自由基(·0Η)与烟气在喷淋塔内接触后发生气液吸收反应,氧化脱除烟气中的Hg°,经吸收洗涤后的烟气从喷淋塔顶部通入烟®排放,喷淋塔内生成的Hg°被氧化为可溶的Hg2+固定于溶液中,由第二循环泵抽入分离塔并与添加Na2S的溶液生成难溶的HgS对Hg2+进行捕捉回收实现烟气脱汞。
[0007] 所述喷淋塔内生成的部分Hg2+溶液还经过第三循环泵重新抽入添液塔循环利用以提高喷淋塔内Hg2+溶液的浓度,抽取的循环溶液的体积占总溶液体积的比例在20-60%。
[0008] 所述紫外光波长范围为120nm-360nm,紫外光强度需要保持在5W/L-65W/L,此处单位W/L是指喷淋塔内未安装紫外灯前以及未通入烟气和溶液前,整个喷淋塔空塔的单位体积的紫外光辐射功率,紫外灯管与喷淋塔底面垂直设置。
[0009] 设置多根紫外灯管时,多根紫外灯管在喷淋塔底面上呈同心圆设置,相邻同心圆之间距离相同,取值为2cm-15cm,多根紫外灯管均布在不同直径的圆周上,沿同一直径线设置,各相邻两直径线之间的中心角相同,取值为15-50度,圆心处设有紫外灯管;雾化喷嘴设置在喷淋塔顶部且位于紫外灯管同心圆之间的同心圆上,设置在紫外灯管中心角内的直径线上。
[0010] 烟气脱汞的反应参数的取值范围如下:静电除尘器脱除粒径大于2. 5μπι的烟气颗粒物;烟气经换热器进行冷却降温后至5-60°C通入喷淋塔;喷入喷淋塔内的过氧化氢溶液的PH值0. 5-6. 5 ;过氧化氢溶液投加量为0. lmol/L-1. 5mol/L ;过氧化氢溶液的浓度为 0. lmol/L-1. 5mol/L ;雾化喷嘴对过氧化氢溶液的雾化后粒径0. 05mm-0. 8mm,喷淋塔内液气比5L/m3-35L/m3 ;添加Na2S的流量控制在进入分离塔内Hg2+溶液总流量的10-40%,添加的硫化钠摩尔浓度按下式计算:
m O VHgQ-Cm(Hga)-Qf-t
[0011] «(Να2Λ) = ---
MHg0
[0012] 式中,I1(Na2S)为添加硫化钠的摩尔浓度,mol/L ; nHg0为Hg°的脱除效率,% ; Cin(Hg0)为烟气中Hg°的入口初始浓度,ppm ;Qf为烟气总流量,m3/h ;MHg0为Hg°的摩尔质量, g/mol ;t-系统的运行时间,h。
[0013] 本发明的优点及显著效果:与单纯的过氧化氢、臭氧、高锰酸钾和次氯酸钠等传统的湿法氧化脱汞技术相比:
[0014] (1)由于· OH具有高达2. SOeV的氧化还原电势(仅次于氟的2. 87eV),具有极强的氧化能力,能够快速将Hg°氧化为易溶于吸收液的Hg2+,从而大大增加了 Hg°由气相到液相的传质推动力,提高了 Hg°的吸收速率,有效地克服了传统湿法脱汞工艺的瓶颈。
[0015] (2)由于· OH和过氧化氢均为洁净环保氧化剂,固定于液相中的Hg2+经过Na2S固定后可资源化利用,整个脱除过程无二次污染,而高锰酸钾和次氯酸钠等传统氧化法会产生复杂的副产物,给后处理带来很大困难;
[0016] (3)鉴于·0Η的强氧化性和无选择性,该技术具有同时脱除多种常见气相污染物, 比如硫氧化物,氮氧化物以及挥发性有机污染物的潜力,随着人们对环保要求的不断提高, 这一潜力和优势将逐渐得到凸显,而传统的湿法脱汞工艺则没有进一步综合处理多污染的潜力。附图说明
[0017] 图1是本发明系统流程图;
[0018] 图2.是本发明系统中紫外灯的安装布置横截面图;
[0019] 图3.是本发明系统中雾化喷嘴的安装布置横截面图。
具体实施方式
[0020] 参看图1,燃烧器1产生的烟气通入静电除尘器2脱除烟气颗粒物后通入换热器3 进行冷却降温后通入喷淋塔4,喷淋塔4内设有紫外灯管6,来自添液塔10内的过氧化氢溶液由循环泵7抽取并通过雾化喷嘴5喷入喷淋塔4内经紫外光激发分解过氧化氢,产生强氧化性的羟基自由基(·0Η)与烟气在喷淋塔4内接触后发生气液吸收反应,氧化脱除烟气中的零价汞Hg°,Hg0首先被氧化为可溶的二价汞Hg2+固定于溶液中,通过向分离塔11投加 Na2S溶液生成难溶的HgS对Hg2+进行捕捉回收,经沉淀分离后可实现汞的资源化利用,最终达到烟气脱汞目的。
[0021] 过氧化氢在紫外光照射下的反应机理:
[0022] (1)过氧化氢在紫外光照射下能够分解释放羟基自由基(· OH):
[0023] H202+hv — 2 · OH (1)
[0024] 0)Hg° 被氧化成 Hg2+:
[0025] Hg0+ · OH — HgO+ · H (2)
[0026] Hg°+2 · OH — Hg (OH) 2 (3)
[0027] Hg°+H202 — HgCHH2O (4)
[0028] 由于燃烧器1流出的烟道气含有大量的颗粒物,如果直接进入喷淋塔4后会引起紫外光的反射,导致喷淋塔4内紫外光的穿透率、辐照距离大幅度下降,进而降低了光能利用率。因此,喷淋塔4必须置于静电除尘器2之后,即只有经过静电除尘后的烟气方可进入喷淋塔4接受洗涤脱除,烟气中粒径大于2. 5 μ m的颗粒物必须脱除。
[0029] 在烟气经过静电除尘之后,由于烟气的温度通常在200-400°C之间,烟气温度太高将会导致喷淋塔4内的溶液温度增加。随着溶液温度的增加,气体在溶液中的溶解度将会大大下降,污染物的脱除效率也会随之降低。此外,随着温度的增加,过氧化氢将会自分解为水和氧气,而不是分解为羟基自由基,这将使得过氧化氢的有效利用率大幅度降低,最终增加了应用成本。因此,在烟气流出静电除尘器2进入喷淋塔4之前,烟气还需经过热交换器3的冷却降温,待烟气温度降为5-60°C时方可进入喷淋塔4内参与气液吸收反应。
[0030] 紫外灯6套有石英套管,采用浸没式安装,紫外灯6主要是通过向环绕在周围的过氧化氢溶液辐射紫外光,并产生羟基自由基。此外,由光辐射原理可知,光垂直辐射到表面时光强度最大,因而为了能够最大限度地利用紫外光能,提高光辐射强度,紫外灯6需要与喷淋塔4底部表面保持垂直,且紫外灯6之间必须保持平行,以达到光能的最大化利用;喷淋塔4内安装紫外灯6后,塔内烟气流动阻力将会增加,从而增加了引风机的运行负荷。因此,紫外灯6在喷淋塔4内的布置密度不能太小,但如果紫外灯6布置密度太大,则会导致喷淋塔4的体积急剧增加,整个系统的占地面积也会随之增大,导致应用成本增大;此外, 紫外灯6布置密度太小还会降低单位体积溶液的紫外光辐射强度,造成污染物脱除效果恶化。因此,紫外灯6之间的间距a和中心角b不宜太大也不宜太小,紫外灯间距和中心角的最佳范围分别是2cm-15cm和15-50度,在满足以上间距和中心角的条件下,紫外灯6之间的间距a和中心角b还必须保持相同(图2),若间距和中心角如果不相等则势必引起喷淋塔4内溶液的紫外光辐射的不均勻,进而导致喷淋塔4内的光化学反应速率差异较大,不利于污染物的脱除和光能的有效利用。紫外灯6辐照强度关系到光量子产率的大小,进而影响到羟基自由基的产率。紫外光辐照强度太小则难以产生足够的羟基自由基氧化脱除污染物,但紫外光辐照强度太大时,系统的能耗则显著增加,导致应用成本大幅度增加。因此,紫外光强度需要保持在5W/L-65W/L,其中单位W/L是指喷淋塔在未安装紫外灯以及未通入反应溶液和烟气之前,喷淋塔为空塔时单位体积所需要的紫外光辐射功率(或者辐射强度)。 紫外光波长的选择对于光化学反应过程具有重要的影响,紫外光波长关系到紫外光的有效传播距离和光子的活化程度,进而关系到单位功率紫外光的污染物处理能力和单位光子的激发能大小。紫外光波长较短时,尽管此时紫外光的光子激发能变大,但紫外光的传播距离却较短,表现为单位功率紫外光的污染物处理能力较低,难以实际应用,但当紫外光波长较长时,尽管紫外光的传播距离将会增加,但此时紫外光光子的激发能却大大减小,导致紫外光光子激发分解过氧化氢释放羟基自由基的能量严重不足,最终导致污染物的脱除效率难以满足要求。因此,紫外光的波长应保持在120nm-360nm范围内;
[0031] 过氧化氢溶液从喷淋塔4的顶部喷入时,为了能够实现最佳的气液传质条件,降低气液反应过程的传质阻力,过氧化氢溶液在喷入喷淋塔4之前实现充分的雾化,以尽量达到足够大的气液接触面积。因此,在过氧化氢喷入喷淋塔4前需要经过雾化喷嘴5的强力雾化,经过雾化后的小液滴喷洒入喷淋塔4,才能与烟气充分接触并发生气液吸收反应; 此外,雾化后的液滴粒径如果太大则难以保证足够的气液接触面积,太小则增加了循环泵 7的运行负荷和能耗。因此,过氧化氢溶液的雾化粒径不宜过大也不宜过小,需要保持在 0. 05mm-0. 8mm范围内,同时雾化喷嘴5在安装时必须要安装在紫外灯6之间的同心圆上。 (图3中的A,B,C点),同心圆上需要安装雾化喷嘴的数量则需要根据所选雾化喷嘴的型号和大小而定.。
[0032] 过氧化氢作为羟基自由基的释放剂,如果投加量太小,则生成的羟基自由基数量太少,不足以充分氧化脱除污染物,但当过氧化氢的投加量太大时,过氧化氢还会引发若干副反应自消耗大量的羟基自由基,导致脱除效率反而下降,而且过氧化氢投加量太大也会带来应用成本过高的问题。因此,过氧化氢的投加量应保持在0. lmol/L-1. 5mol/L,过氧化氢溶液的有效浓度为0. 05mol/L-2. 5mol/L过氧化氢溶液投加量为0. lmol/L-1. 5mol/L ;过氧化氢溶液的浓度为0. lmol/L-1. 5mol/L。
[0033] 液气比在气液吸收反应过程中是一个极为关键的参数,关系到系统的脱除效率和运行成本。当液气比太小时,污染物无法得到充分的气液接触反应,导致污染物的脱除效率下降,但当液气比太大时,整个系统的体积将显著增加,循环泵(7)的运行负荷和能耗也导致喷淋塔4的体积急剧增加,整个系统的占地面积也会随之增大,导致应用成本增大;此夕卜,紫外灯6布置密度太小还会降低单位体积溶液的紫外光辐射强度,造成污染物脱除效果恶化。因此,紫外灯6之间的间距a和中心角b不宜太大也不宜太小,紫外灯间距和中心角的最佳范围分别是2cm-20cm和10-45度,在满足以上间距和中心角的条件下,紫外灯6 之间的间距a和中心角b还必须保持相同(图2),若间距和中心角如果不相等则势必引起喷淋塔4内溶液的紫外光辐射的不均勻,进而导致喷淋塔4内的光化学反应速率差异较大,不利于污染物的脱除和光能的有效利用。紫外灯6辐照强度关系到光量子产率的大小,进而影响到羟基自由基的产率。紫外光辐照强度太小则难以产生足够的羟基自由基氧化脱除污染物,但紫外光辐照强度太大时,系统的能耗则显著增加,导致应用成本大幅度增加。因此,紫外光强度需要保持在5W/L-80W/L,其中单位W/L是指喷淋塔在未安装紫外灯以及未通入反应溶液和烟气之前,喷淋塔为空塔时单位体积所需要的紫外光辐射功率(或者辐射强度)。紫外光波长的选择对于光化学反应过程具有重要的影响,紫外光波长关系到紫外光的有效传播距离和光子的活化程度,进而关系到单位功率紫外光的污染物处理能力和单位光子的激发能大小。紫外光波长较短时,尽管此时紫外光的光子激发能变大,但紫外光的传播距离却较短,表现为单位功率紫外光的污染物处理能力较低,难以实际应用,但当紫外光波长较长时,尽管紫外光的传播距离将会增加,但此时紫外光光子的激发能却大大减小,导致紫外光光子激发分解过氧化氢释放羟基自由基的能量严重不足,最终导致污染物的脱除效率难以满足要求。因此,紫外光的波长应保持在120nm-360nm范围内;
[0034] 过氧化氢溶液从喷淋塔4的顶部喷入时,为了能够实现最佳的气液传质条件,降低气液反应过程的传质阻力,过氧化氢溶液在喷入喷淋塔4之前实现充分的雾化,以尽量达到足够大的气液接触面积。因此,在过氧化氢喷入喷淋塔4前需要经过雾化喷嘴5的强力雾化,经过雾化后的小液滴喷洒入喷淋塔4,才能与烟气充分接触并发生气液吸收反应; 此外,雾化后的液滴粒径如果太大则难以保证足够的气液接触面积,太小则增加了循环泵 7的运行负荷和能耗。因此,过氧化氢溶液的雾化粒径不宜过大也不宜过小,需要保持在 0. Olmm-O. 5mm范围内,同时雾化喷嘴5在安装时必须要安装在紫外灯6之间的同心圆上。 (图3中的A,B,C线上),同心圆上需要安装雾化喷嘴的数量则需要根据所选雾化喷嘴的型号和大小而定.。
[0035] 过氧化氢作为羟基自由基的释放剂,如果投加量太小,则生成的羟基自由基数量太少,不足以充分氧化脱除污染物,但当过氧化氢的投加量太大时,过氧化氢还会引发若干副反应自消耗大量的羟基自由基,导致脱除效率反而下降,而且过氧化氢投加量太大也会带来应用成本过高的问题。因此,过氧化氢的投加量应保持在0.05mOl/L-2.5mOl/L。过氧化氢溶液的有效浓度为0. 05mol/L-2. 5mol/L
[0036] 液气比在气液吸收反应过程中是一个极为关键的参数,关系到系统的脱除效率和运行成本。当液气比太小时,污染物无法得到充分的气液接触反应,导致污染物的脱除效率下降,但当液气比太大时,整个系统的体积将显著增加,循环泵(7)的运行负荷和能耗也将增加,最终导致系统运行成本大大增加。因此,喷淋塔内液气比保持在5L/m3-35L/m3范围内。
[0037] 过氧化氢溶液的pH值也是一个非常重要的参数,当溶液pH值太低时,整个吸收过程的吸收平衡将会向左移动,导致气液吸收反应不能充分进行,进而影响脱除效率。但当溶液PH值太高时,由于过氧化氢具有水解的特性,水解产物过氧化氢跟离子是一种极为有效的羟基自由基侵蚀剂,能都明显降低羟基自由基的浓度。此外,溶液PH值太高将强化过氧化氢的水解反应,导致过氧化氢的自分解速率增加,最终将大大增加过氧化氢的消耗量,增加了实际应用成本。因此,溶液PH应当保持在0.5-6. 5之间;
[0038] 脱除过程的产物为Hg2+溶液,考虑反应产物的回收利用问题是十分重要的。如果 Hg2+溶液浓度太小,则将会使得反应过程的耗水量增加。同时,Hg2+溶液浓度太小也会使得反应产物的后处理量增加,势必也会导致产物的后处理成本增加。因此,系统需要设计反应产物部分再循环装置,即Hg2+溶液部分被返回喷淋塔4内继续参与气液吸收反应,仅部分被抽入分离塔11接受后处理,这样既可以保证Hg2+溶液的浓度,又可以保证后处理成本不至于太高,但抽取的循环液占总溶液的比例不宜太高,否则会影响系统的脱除效率和安全性, 故应抽取的循环溶液的体积占总溶液体积的比例应该严格控制在保持在20-60%之间;
[0039] 反应产物Hg2+溶液经过后处理后,可通过添加Na2S的方法生成HgS,经沉淀分离后实现可资源化资源,这样既能保证整个反应过程无二次排放,还能将反应产物直接转化为经济效益,实现真正的高效低污染低减排目标,但添加的硫化钠需要有严格的浓度和流量要求,硫化钠添加流量过大势必会导致溶液处理量也增大,太小则会导致分离塔内的化学反应不均勻。因此,建议硫化钠的流量控制在进入分离塔内Hg2+溶液总流量的10-40%。 此外,如果硫化钠浓度太高,未来得及参与反应的硫化钠就会掺杂在反应产物中排放掉,并引发二次污染,太少则不能充分有效吸收固定溶液中的Hg2+。因此,添加的硫化钠摩尔浓度 (国际单位:mol/L)计算方法如下:
[0040]
[0041] 式中,I1(Na2S)为添加硫化钠的摩尔浓度,mol/L ; nHg0为Hg°的脱除效率,% ; Cin(Hg0)为烟气中Hg°的入口初始浓度,ppm ;Qf为烟气总流量,m3/h ;MHg0为Hg°的摩尔质量, g/mol ;t-系统的运行时间,h。
[0042] 实施例1.
[0043]
操作紫外光波长过氧化氢浓度反应温度 Hg巧农度溶液pH 液气比 UV强度参数 253.7nm 1.0mol/L 25°C 100ug/m3 3.0 20 L/m3 40W/L
脱除 Hgl兑除率指标 92.2%
[0044] 实施例2.
[0045]
[0046] 实施例3·
[0047]
[0048] 由实施1,2,3可以看出,表格上部份内容为操作参数,下部分为污染物脱除效率的变化情况。具体的操作方法是:单改变紫外光波长,其它参数均保持不变。由结果看出, 紫外光在253. 7nm处取得最佳的脱除效率。
[0049] 实施例4.
[0050]
[0051] 实施例5·
[0052]
[0053] 由实施1,4,5可以看出,表格上部份内容为操作参数,下部分为污染物脱除效率的变化情况。具体的操作方法是:单改变过氧化氢浓度,其它参数均保持不变。由结果可以看出,污染物脱除效率随着过氧化氢浓度的增加而增加,但为了保持较低的应用成本,过氧化氢的浓度也不宜设的太高,需要保持在0. 5-1. 5mol/L范围内。
[0054] 实施例6.
[0055]
[0056] 实施例7·
[0057]
[0058] 由实施1,6,7可以看出,表格上部份内容为操作参数,下部分为污染物脱除效率的变化情况。具体的操作方法是:单改变溶液温度,其它参数均保持不变。由结果可以看出, 污染物脱除效率随着溶液温度的增加而下降。因此,溶液温度应当保持一个相对较低值, 但溶液温度设定不过则会导致换热器冷却成本增加,因而溶液温度也需要保持一个最佳值 25 °C。
[0059] 实施例8.
[0060]
[0061] 实施例9·
[0062]
[0063] 由实施1,8,9可以看出,表格上部份内容为操作参数,下部分为污染物脱除效率的变化情况。具体的操作方法是:单改变Hg°的浓度,其它参数均保持不变。由结果可以看出,污染物脱除效率随着Hg°的浓度增加而下降。因此,Hg0的浓度值应当保持一个最佳范围内,Hg°的浓度太低则使得该技术使用范围变窄,Hg0的浓度太高则导致脱除效率达不到环保要求,宜设定在5ug/m3-200ug/m3范围内。
[0064] 实施例10.
[0065]
[0066] 实施例11.
[0067]
[0068] 由实施1,10,11可以看出,表格上部份内容为操作参数,下部分为污染物脱除效率的变化情况。具体的操作方法是:单改变溶液的PH值,其它参数均保持不变。由结果可以看出,污染物脱除效率随着溶液PH值的增加而增加,但溶液pH值过高则会导致过氧化氢的自分解率急剧上升,最终导致应用成本增加。因此,溶液PH值宜设定在0.5-6. 5之间;
[0069] 实施例12.
[0070]
[0071] 实施例13.
[0072]
[0073] 由实施1,14,15可以看出,表格上部份内容为操作参数,下部分为污染物脱除效率的变化情况。具体的操作方法是:单改变溶液的液气比,其它参数均保持不变。由结果可以看出,污染物脱除效率随着液气比的增加而增加,但液气比过高则会导致反应系统体积庞大,最终导致应用成本大大增加。因此,液气比的值宜设定在5-35之间。
[0074] 实施例14.
[0075]
[0076] 实施例15.
[0077]
[0078] 由实施1,14,15可以看出,表格上部份内容为操作参数,下部分为污染物脱除效率的变化情况。具体的操作方法是:UV强度,其它参数均保持不变。由结果可以看出,污染物脱除效率随着UV强度的增加而增加,但UV强度过高则会导致能耗过大,最终导致应用成本大大增加。因此,UV强度值宜设定在5-65W之间。
[0079] 最佳实施例参数:
[0080]
[0081] 结合现场的实际情况,并且在综合考虑污染物的脱除效率和应用成本的前提下, 本发明按照最佳实施例参数能够取得良好的脱汞效果,脱除效率可达96. 8 %,尤其在实现污染物高效脱除的基础上,反应产物还可资源化利用,无二次污染。
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CN102166471B (zh) * | 2011-02-25 | 2013-01-30 | 东南大学 | 一种基于非均相Photo-Fenton的一体化烟气净化系统 |
CN102160959A (zh) * | 2011-02-25 | 2011-08-24 | 东南大学 | 一种基于高级氧化结合湿法洗涤的烟气净化系统 |
CN103111182A (zh) * | 2011-11-17 | 2013-05-22 | 范庆峰 | 一种燃煤电厂烟气强氧化脱汞工艺 |
CN103657373B (zh) * | 2013-12-06 | 2015-11-25 | 无锡雪浪环境科技股份有限公司 | 一种应用于垃圾焚烧的氧化脱汞装置 |
CN103990365B (zh) * | 2014-05-20 | 2016-08-17 | 江苏大学 | 一种臭氧/过氧化氢诱导自由基的烟气净化方法及系统 |
CN103990366A (zh) * | 2014-05-20 | 2014-08-20 | 江苏大学 | 一种基于臭氧/过氧化氢产生自由基脱汞的方法及系统 |
CN105521704B (zh) * | 2015-11-12 | 2018-09-18 | 河南理工大学 | 一种基于可见光的烟气脱汞方法 |
CN105833685B (zh) * | 2016-04-18 | 2018-10-09 | 江苏大学 | 一种光辐射氯原子和羟基脱除烟气汞的方法及装置 |
CN106823723A (zh) * | 2017-03-10 | 2017-06-13 | 东南大学 | 一种光电诱导自由基联合蒸汽相变烟气净化装置和方法 |
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