CN102716648A - 基于pH值和ORP值自动控制的烟气脱硫脱硝方法及其装置 - Google Patents
基于pH值和ORP值自动控制的烟气脱硫脱硝方法及其装置 Download PDFInfo
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- CN102716648A CN102716648A CN2012101530805A CN201210153080A CN102716648A CN 102716648 A CN102716648 A CN 102716648A CN 2012101530805 A CN2012101530805 A CN 2012101530805A CN 201210153080 A CN201210153080 A CN 201210153080A CN 102716648 A CN102716648 A CN 102716648A
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- flue gas
- value
- absorption liquid
- oxidation
- denitration
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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[O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003546 flue gases Substances 0.000 title claims abstract description 99
- 239000007788 liquids Substances 0.000 claims abstract description 126
- 238000010521 absorption reactions Methods 0.000 claims abstract description 108
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound 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[S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 methods Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001590 oxidative Effects 0.000 claims abstract description 12
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Ammonium sulfite Chemical compound 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[NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007254 oxidation reactions Methods 0.000 claims description 66
- 230000003647 oxidation Effects 0.000 claims description 65
- 238000005201 scrubbing Methods 0.000 claims description 30
- 238000003860 storage Methods 0.000 claims description 28
- 239000005864 Sulphur Substances 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- 239000007921 sprays Substances 0.000 claims description 21
- 238000006477 desulfuration reactions Methods 0.000 claims description 20
- 230000003009 desulfurizing Effects 0.000 claims description 17
- 239000007789 gases Substances 0.000 claims description 11
- 239000000126 substances Substances 0.000 claims description 7
- 238000006243 chemical reactions Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injections Substances 0.000 claims description 4
- 206010058490 Hyperoxia Diseases 0.000 claims description 3
- 210000002381 Plasma Anatomy 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- 230000000222 hyperoxic Effects 0.000 claims description 3
- 239000000203 mixtures Substances 0.000 claims description 3
- 238000006479 redox reactions Methods 0.000 claims description 3
- 230000001105 regulatory Effects 0.000 claims description 3
- -1 thiosulfate anion Chemical class 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound 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[O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 3
- 238000005842 biochemical reactions Methods 0.000 claims description 2
- 239000000969 carriers Substances 0.000 claims description 2
- 230000001186 cumulative Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000002245 particles Substances 0.000 claims description 2
- 239000011901 water Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound 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N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 6
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 6
- 239000006227 byproducts Substances 0.000 abstract description 5
- 239000003595 mist Substances 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 229910002089 NOx Inorganic materials 0.000 abstract 1
- 238000005516 engineering processes Methods 0.000 description 15
- 239000000779 smoke Substances 0.000 description 12
- 230000001360 synchronised Effects 0.000 description 9
- 239000000428 dust Substances 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound 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[NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L Sodium thiosulphate Chemical compound 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[Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N Thiosulfuric acid Chemical class 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OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 239000003897 fog Substances 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound 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[O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound 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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Description
基于pH值和ORP值自动控制的烟气脱硫脱硝方法及其装置
技术领域
[0001 ] 本发明属于环境保护技术领域,是一种基于pH值和ORP值自动控制技术对湿式氨法吸收液进行调控,从而实现同步高效稳定脱硫脱硝的烟气处理方法。
背景技术
[0002] 燃煤、工业炉窑和垃圾焚烧等过程产生的烟气中含有大量污染大气环境的污染物,包括烟尘,S0jPN0x(X=l,2)等。其中SO2与NOx (x=l,2)会引起酸雨、光化学烟雾等环境问题,严重威胁着人类的日常生活和身心健康,烟气脱硫脱硝对于保障大气环境质量起着非常重要的作用。
[0003] 烟气脱硫方法分为湿法、干法和半干法。其中,湿法脱硫技术最为成熟,常用的湿法脱硫技术包括石灰石(石灰)_石膏法、氨水吸收法等。其中,石灰石(石灰)_石膏法是 目前利用最广泛的烟气脱硫方法,但此法也存在投资大,设备腐蚀、磨损、堵塞严重,运行维护费用高等问题。湿式氨法脱硫具有吸收液碱性强、吸收反应速度快且吸收液利用率高、系统简单、副产物硫酸铵和硝酸铵可资源再利用等特点,是一种高效的脱硫方法,但也存在氨污染等问题。干法和半干法脱硫技术虽具有工艺紧凑,占地面积小,投资运行费用低等优点,但脱硫效率通常较低。
[0004] 烟气脱硝技术主要包括选择性催化还原法、选择性非催化还原法、碱液吸收法等。选择性催化还原技术是目前应用最为广泛且净化效果最佳的脱硝技术,但其工艺与设备复杂,催化剂制备及作用环境要求较高,建设运行费用也较高。选择性非催化还原法脱硝系统最主要的优点是建设为一次性投资,运行成本低,设备占地面积小,但脱硝效率较低,难以达到日益严格的排放要求。碱液吸收法具有工艺设备简单,操作温度低,耗能少等优点,但因燃煤烟气中N0x(x=l,2)主要以低溶解度的NO形式存在,限制了该法在烟气脱硝领域的发展。
[0005] 传统烟气脱硫脱硝技术采用的是一对一污染物处理方案,即采用脱硫和脱硝装置分别处理SO2和NOx(x=l,2),这必然导致处理流程长,设备复杂,占地面积大,建设、运行和维护的费用比较高等问题,因此,实现烟气同步脱硫脱硝成为现今烟气治理领域的新目标。目前,湿式洗涤法被认为是实现同步脱硫脱硝最有效的方法之一,在公告号为CN101053747A和CN1923341A的专利说明书《同步脱硫脱硝的湿式氨法烟气结晶工艺及其系统》和《燃煤锅炉烟气臭氧氧化同时脱硫脱硝及其方法》中,均提出了采用O3或H2O2注入的烟气氧化技术结合碱液或氨液吸收实现烟气的同步脱硫脱硝,通过预氧化将NO氧化成NO2,而后与H2O反应生成N02_和NO3-实现NOx (x=l,2)的吸收,化学反应式如下所示。
[0006] 2N02+H20 — 2H++N02>N(V
[0007] 然而,经过实验证明,单纯依靠氨液或碱液吸收NO2的效率很低,整体脱硝效率并不理想。
发明内容[0008] 本发明的目的在于提供一种利用pH值和ORP值(0RP是英文Oxidation-Reduction Potential的缩写,它表示溶液的氧化还原电位)自控技术调控吸收过程的湿式氨法同步脱硫脱硝方法。该方法利用氨法脱硫产物四价硫与NO2发生快速氧化还原反应的原理,具体步骤如下:
[0009] 烟气进入预洗涤和洗涤前先进行除尘和预氧化,所述的预氧化是使烟气中NO氧化为NO2,所述的预洗涤和洗涤采用吸收液对烟气中SO2和NO2洗涤吸收,洗涤后,气相SO2被吸收后转化生成的四价硫组分,NO2发生氧化还原反应还原为N2,洗涤吸收过程中,调节控制吸收液的PH值和ORP值,维持吸收液pH值为5. 5^6. 5,ORP值为_150mV、mV。
[0010] 本发明还提供一种用于实现上述方法的实现装置,所述的实现装置通过烟道与锅炉出口连接,主要包括顺序通过连接在锅炉出口和烟囱之间的除尘设备、烟气氧化设备、预洗涤塔、洗涤塔,以及与预洗涤塔连接的氧化浓缩系统,与洗涤塔连接的氨水储液池、氧化抑制剂储液池。
[0011] 本发明的优点在于:本发明可有效提高吸收液脱硫脱硝效率,具有工艺流程简单,投资及运行费用较低,副产物可资源化利用等特点。
附图说明
[0012] 图I是本发明基于pH值和ORP值自动控制的氨吸收烟气脱硫脱硝装置示意图。
[0013] 图中:
[0014] I.锅炉;2.烟道;3.除尘设备;4.烟气氧化设备;5.预洗涤塔;6.洗涤塔;7.储液槽;8.电除雾装置;9.电磁阀;10.氨水储液池;11.氧化抑制剂储液池;12.氧化浓缩系统;13.烟囱。
具体实施方式
[0015] 下面结合附图和实施例对本发明进行详细说明。
[0016] 对于吸收液吸收脱硫脱硝的过程,提高吸收液中四价硫浓度可显著提升氨液或碱液吸收脱除NO2的效率,其主要原因在于:四价硫可显著提高吸收液的还原能力,降低吸收液ORP值,在四价硫浓度足够的情况下,依靠四价硫的还原性可将NO2还原为N2,化学反应式如下:
[0017] 2N02+4S0 广—N2+4S042_
[0018] 2N02+4HS(V — 4H++N2+4S042_
[0019] 上述过程中,烟气中气相氮化物NO2进入吸收液后,并不是生成硝酸盐或亚硝酸盐,而是还原为N2,四价硫是作为NO2还原剂,存在于吸收液之中。因此,对于氨法脱硫脱硝来说,pH值和ORP值控制都至关重要。
[0020] 本发明所设计的基于pH值和ORP值自动控制的氨吸收同步脱硫脱硝烟气净化方法,处理对象为含有硫化物SO2和氮化物NOx (主要是NO,x=l,2)的工业烟气,如燃煤烟气等,采用以下步骤进行烟气处理:
[0021] 第一步,烟气首先经过除尘设备去除烟尘。
[0022] 依照现有除尘技术,可选用电除尘器、布袋除尘器或者湿式除尘器等,除尘效率达到99%以上。所述的烟气是指含有硫化物和氮化物的工业烟气,烟气中主要污染成份为SO2和NOx (x=l,2),氮化物主要为NO。
[0023] 第二步,除尘后烟气经过烟气氧化,使烟气中NO被氧化成N02。
[0024] 经过除尘后的烟气中主要包含SO2和NO,还含有少量的NO2,烟气氧化可采用低温等离子体氧化法,将等离子体放电设备安装于烟道内部,直接在烟气中形成具有高氧化性的活性自由基或O3氧化粒子作用于NO使其氧化;亦或者采用O3注入法,通过于烟道外增设的O3发生设备,将产生的O3通过空气载气流引入烟道中与烟气混合,使NO氧化,称为N02。在该步骤中,759T90%N0都可以氧化为NO2。
[0025] 第三步,烟气经预氧化后,进入预洗涤塔,采用喷淋方式实现预洗涤。
[0026] 预氧化后的烟气中主要包含SO2和NO2,还有少量的未氧化的NO和烟气氧化过程中携带的氧化性气体(如臭氧03)。所述的预洗涤采用吸收液喷淋洗涤的方式,所述的吸收 液源自洗涤塔储液槽,吸收液用量约为洗涤塔内吸收液总体积的1/15,喷淋后的吸收液经过初步收集,进入氧化浓缩系统12。
[0027] 此过程中,因吸收液温度低,为25〜35°C,而烟气温度高,可达120°C,故吸收液可通过水汽蒸发吸收烟气热量,将烟气温度降至60°C以下,并实现吸收液的初步浓缩,浓缩后的吸收液回收至氧化浓缩系统;另一方面,预洗涤可吸收烟气中部分SO2和N0x(x=l,2),减轻后续洗涤环节的脱硫脱硝压力;同时,预洗涤还可以通过烟气中携带的氧化性气体与吸收液中四价硫反应,实现去除烟气中残余氧化性气体和初步氧化吸收液中四价硫为六价硫(即硫酸根),尽量避免残余氧化性气体进入下一步的洗涤过程,这样既保证了后续洗涤过程吸收液中四价硫稳定性,又减轻了氧化浓缩系统的处理负担。
[0028] 所述的吸收液与后续洗涤塔中采用的吸收液是相同的,吸收液主要成分为亚硫酸铵和氧化抑制剂,其中四价硫浓度约0. 8mol/L,氧化抑制剂可选用硫代硫酸盐,如硫代硫酸钠等,主要起稳定吸收液四价硫的作用,初始吸收液中四价硫浓度与硫代硫酸根浓度为3〜3. 5。
[0029] 第四步,预洗涤后烟气进入洗涤塔进行洗涤脱硫脱硝。
[0030] 预洗涤后的烟气中含有的污染物主要为SO2和NO2,其余的部分残余氧化性气体和NO由于含量很少,可以忽略。洗涤塔内吸收液主要成分为亚硫酸铵和氧化抑制剂,其中四价硫浓度约0. 8mol/L,氧化抑制剂可选用硫代硫酸盐,主要起稳定吸收液四价硫的作用,初始吸收液中四价硫浓度与硫代硫酸根浓度比为3〜3. 5,吸收液的PH为5. 5飞.5,ORP值为-150mV〜OmV。
[0031] 洗涤过程通过多层喷淋方式由洗涤塔上端将吸收液喷入洗涤塔内与预洗涤后的烟气充分混合,使烟气中的SO2和NO2通过气液传质进入吸收液中并发生化学反应,SO2被亚硫酸铵吸收后生成为NH4HSO3, NO2被吸收后还原为N2。化学反应式如下:
[0032] SO2+ (NH4) 2S03+H20 — 2NH4HS03
[0033] 2N02+4 (NH4) 2S03 — N2+4 (NH4) 2S04
[0034] 吸收液位于洗涤塔内下部的储液槽内,多层喷淋采用的吸收液是通泵装置将储液槽内吸收液抽入喷淋管中,喷淋后的吸收液通过重力回收又回收至储液槽内,通过多次循环,由于吸收液内不断的发生上述的化学反应,吸收液内的四价硫浓度降低,因此需要对吸收液内的PH值和ORP值进行检测监测,保证洗涤的充分进行,为了提高四价硫浓度,洗涤喷淋同时,在储液槽中对吸收液进行PH值和ORP值调控,通过由pH值、ORP值检测探头及其控制仪表、电磁阀、氨水储液池和氧化抑制剂储液池构成的控制系统实现。控制储液槽内吸收液PH值为5. 5飞.5,当pH值低于5. 5时,电磁阀打开,使氨水储液池中的氨水流入吸收液之中,直到PH值升至6. 5,电磁阀关闭。控制储液槽内吸收液的ORP值为-150mV、mV,当ORP值高于OmV时,电磁阀打开,使氧化抑制剂储液池中的氧化抑制剂(如硫代硫酸盐饱和溶液)流入吸收液之中,直到ORP值降至-150mV,电磁阀关闭。
[0035] 优选的,所述的氨水储液池和氧化抑制剂储液池的设置液面高度高于储液槽内吸收液高度,使得氨水和氧化抑制剂可以电磁阀打开后直接通过重力作用进入储液槽,而不需要额外的动力系统。
[0036] 在洗涤过程中,由于采用吸收液中含有氨水,因此会在烟气中有液态氨雾,随烟气上升的液态氨雾通过吸收塔上端电除雾装置8,依靠放电电场将雾粒荷电并使其定向运动实现捕集回收,防止二次污染的发生。经过电除雾装置8后的烟气可以直接通过烟囱13排入大气中。
[0037] 因洗涤后的烟气中SO2浓度大于NO2,故循环吸收液中(NH4) 2S03/NH4HS03的摩尔浓度比将随吸收液循环次数的增多而不断降低。当比值达到0. 9时,即可自洗涤塔储液槽中导出一部分吸收液进入氧化浓缩系统12(硫酸铵副产品处理系统),利用空气中O2将吸收液中四价硫离子完全氧化为S042—,并通过浓缩结晶最终得到副产品硫酸铵,实现资源化利用,其化学反应式如下:
[0038] 2 (NH4) 2S03+02 — 2 (NH4) 2S04
[0039] 2NH4HS03+02+2NH3 — 2 (NH4) 2S04
[0040] 综上所述,本发明具有投资小、工艺简单、能耗低、高效同步脱硫脱硝、吸收液利用率高以及可回收硫酸铵副产品等特点,其脱硫效率可达95%以上,脱硝效率可达85%以上,氨逃逸量低于5mg/m3,净化后烟气符合国家烟气SO2和N0x(x=l,2)的排放标准。
[0041] 本发明还提供一种基于pH值和ORP值自动控制的氨吸收同步脱硫脱硝烟气净化装置,如图I所示,所述的装置包括通过烟道2与锅炉I出口连接,主要包括顺序通过连接在烟道2和烟囱13之间的除尘设备3、烟气氧化设备4、预洗涤塔5、洗涤塔6,以及与预洗涤塔5连接的氧化浓缩系统12,与洗涤塔6连接的氨水储液池10、氧化抑制剂储液池11。以燃煤烟气为例,应用该装置的脱硫脱硝流程如下:
[0042] 首先,燃煤锅炉I炉膛排出的烟气通过烟道2进入除尘设备3,采用布袋除尘等现有公知方法进行除尘,除尘效率99%以上;经除尘后的烟气进入烟气氧化设备4进行预氧化,采用向氧气氧化设备4内注入氧化剂如臭氧或高氧化性的活性自由基的方式,使得烟气中的NO氧化为NO2,氧化效率约80% ;而后烟气进入预洗涤塔5,预洗涤塔5内吸收液由洗涤塔6储液槽7提供,通过喷淋方式与烟气充分混合,使烟气温度降低至60°C以下。
[0043] 经过除尘、预氧化和预洗涤后烟气进入洗涤塔6内,采用喷淋方式,使洗涤塔6内吸收液与烟气充分混合,洗涤后烟气经过位于洗涤塔6上部的电除雾装置8进行捕雾处理,降低烟气中NH3浓度至5mg/m3,而后通过烟道进入烟囱13并最终排入大气。
[0044] 预洗涤塔5和洗涤塔6内喷淋方式的吸收液均由位于洗涤塔6下方的储液槽7提供。所述的储液槽7设置在洗涤塔6内的底部,通过泵抽装置与喷淋系统连接,同时为预洗涤塔5和洗涤塔6内的喷淋提供吸收液。
[0045] 所述的储液槽7与氨水储液池10和氧化抑制剂储液池11连通,在连通的管路上设置电磁阀9,并且所述的氨水储液池10和氧化抑制剂储液池11内液面高度均高于储液槽7内液面高度,保证打开电磁阀9后,氨水储液池10和氧化抑制剂储液池11内的溶液在重力作用下进入储液槽7,而不需要额外的动力。
[0046] 储液槽7内置pH电极与ORP电极,用于监测吸收液的pH值与ORP值。pH值和ORP值调节液分别存于氨水储液池10和氧化抑制剂储液池11中,吸收液pH值保持5. 5飞.5范围,ORP值-150mV〜0mV之间。通过进一步优选,确定最佳pH范围为6. 0〜6. 5,ORP值范围为-150mV〜-75mV。
[0047] 洗涤塔6内多次循环喷淋后吸收液[(NH4)2S03/NH4HS03摩尔浓度比达到0. 9时]进入氧化浓缩系统12,将吸收液中四价硫离子完全氧化为硫酸根,并经过浓缩结晶后,得到硫酸铵副产品实现资源回收。
[0048] 实施例I
[0049] 烟气净化装置布置如图I所示,处理烟气为燃煤锅炉烟气,烟气中烟尘、302和 N0x(x=l或2)浓度分别为5000mg/m3、2000mg/m3和450mg/m3,锅炉出口烟气温度为120°C,处理气量10000m3/h。经文丘里除尘后,烟尘浓度降为50mg/m3。烟气氧化过程采用直流叠加脉冲(直流基压50kV,脉冲电压50kV,频率6kHz,脉冲电压变化率大于200V/ u s)电晕放电产生的O3氧化NO,氧化率为78%〜86%左右间,出口臭氧剩余浓度75〜90mg/m3。采用四价硫浓度0. 8mol/L,控制pH值为6. 0〜6. 5,ORP值为_150mV〜_75mV的亚硫酸铵吸收液对上述预氧化后烟气进行洗涤,平均脱硫效率约98%,脱硝效率约85%,氨逃逸浓度低于4. lmg/m3。
[0050] 实施例2
[0051] 烟气净化装置布置如图I所示。处理烟气与实施例I烟气情况相同,处理气量10000m3/h。经电除尘后,烟尘浓度降为80mg/m3。烟气氧化过程采用O3发生注入方式,注入O3浓度600mg/m3,烟气NO氧化率72%〜76. 5%,出口臭氧剩余浓度35〜45mg/m3,采用采用四价硫浓度0. 8mol/L, pH值为6. 0飞.5,ORP值为-75mV〜-0mV的亚硫酸铵吸收液对烟气进行洗涤,平均烟气吸收脱硫效率约95%,脱硝效率约72%,氨逃逸浓度低于3. 5mg/m3。
[0052] 实施例3
[0053] 烟气净化装置布置如图I所不,处理烟气情况与实施例I相同,处理气量IOOmVh。经文丘里除尘后,烟尘浓度降为50mg/m3。氧化过程采用O3注入方式,注入O3浓度IOOOmg/m3,烟气NO氧化率85%〜89%之间,出口臭氧剩余浓度100〜150mg/m3。循环吸收液采用四价硫浓度0. 8mol/L,pH控制5. 5〜6. 0范围内,ORP值为_150mV〜_75mV,NOx (x=l或2)吸收平均脱除效率为83%,SO2吸收脱除效率始终保持在939^95%范围内,氨逃逸浓度低于2. 5mg/m3。
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