CN104353336B - 一种低温焦炉烟道废气洁净化工艺及其设备 - Google Patents
一种低温焦炉烟道废气洁净化工艺及其设备 Download PDFInfo
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- CN104353336B CN104353336B CN201410699385.5A CN201410699385A CN104353336B CN 104353336 B CN104353336 B CN 104353336B CN 201410699385 A CN201410699385 A CN 201410699385A CN 104353336 B CN104353336 B CN 104353336B
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- Prior art keywords
- ammonia
- unit
- pipeline
- coke oven
- primary cycle
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- 239000007789 gases Substances 0.000 title claims abstract description 135
- 238000000034 methods Methods 0.000 title claims abstract description 118
- 281000066869 Coke (fuel) companies 0.000 title claims abstract description 116
- 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 277
- 230000003009 desulfurizing Effects 0.000 claims abstract description 134
- 238000006477 desulfuration reactions Methods 0.000 claims abstract description 73
- 239000003054 catalysts Substances 0.000 claims abstract description 51
- 239000007788 liquids Substances 0.000 claims description 151
- PDCNZSPWVGYKGD-UHFFFAOYSA-O [NH4+].[S+2] Chemical compound 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[NH4+].[S+2] PDCNZSPWVGYKGD-UHFFFAOYSA-O 0.000 claims description 106
- 239000007921 sprays Substances 0.000 claims description 92
- 239000003570 air Substances 0.000 claims description 75
- 239000003546 flue gases Substances 0.000 claims description 67
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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[O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 64
- 239000011901 water Substances 0.000 claims description 44
- 235000019504 cigarettes Nutrition 0.000 claims description 38
- 239000010410 layers Substances 0.000 claims description 38
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,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 [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 30
- 239000000908 ammonium hydroxide Substances 0.000 claims description 29
- 238000005507 spraying Methods 0.000 claims description 16
- 238000005276 aerator Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000006200 vaporizer Substances 0.000 claims description 5
- 239000002912 waste gases Substances 0.000 abstract description 53
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound 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N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000126 substances Substances 0.000 abstract description 16
- 238000005516 engineering processes Methods 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
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- 239000006227 byproducts Substances 0.000 abstract description 6
- 210000003660 Reticulum Anatomy 0.000 abstract description 4
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- 229910000477 molybdenum trioxide Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound 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[S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910000504 titanium dioxide Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N Potassium nitrate Chemical compound 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Abstract
Description
技术领域
[0001]本发明涉及一种焦炉烟道废气洁净化工艺,特别涉及一种温度介于170°C_250°C之间的低温焦炉烟道废气脱除氮氧化物、硫氧化物的工艺,属于煤焦化行业大气污染防治领域。
背景技术
[0002]焦炉烟道废气是干馏精煤生产焦炭用焦炉煤气燃烧后产生的废气,主要含有S02、NOx等污染物。仅2013年,我国国内焦化厂焦炉烟道废气中的302排放量约为75.86万吨,占当年302排放总量的4% ;NOx排放量约为606.88万吨,占当年国内NOx排放总量的27%。
[0003] 2012年6月,环境保护部及国家质量监督检验检疫局联合发布了《炼焦化学工业污染物排放标准GB16171-2012》,明确规定了焦化工业的大气污染物排放标准:2012年10月I日起新建企业和2015年I月I日起现有企业,焦炉烟囱502排放浓度由> 100mg/Nm3变为>50mg/Nm3,N0x排放浓度由> 800mg/Nm3变为> 500mg/Nm3;特别限值为焦炉烟囱502排放浓度> 30mg/Nm3,N0x排放浓度> 150mg/Nm3。因此如何对焦炉烟道废气进行脱硫脱硝使其达到国家的环保标准,成为焦化行业必须且亟需解决的问题。
[0004]焦炉烟道废气脱硫脱硝在焦化行业内的应用尚属空白,因行业特点,不能照搬原电厂、钢铁烧结烟气、锅炉、水泥等行业的脱硫脱硝工艺。主要的应用症结有以下几个方面:
[0005] SCR(选择性催化还原)技术是当前NOx减排的主流技术,但SCR技术核心的催化剂要求烟气温度在350°C以上才能完成催化还原反应,而目前焦炉烟道废气温度普遍在170-250°C之间,尤其是经过余热回收的焦炉烟道废气,温度低到170°C以下,属于低温烟气脱硝的范畴。而在低温条件下为达到理想的脱硝效果,几乎所有的脱硝技术都需要将处理烟气加热至350°C以上,而后续的脱硫系统又需要将烟气进口温度降低至100°C以下,这样就浪费了大量的热能,并不符合当下国家提倡的节能降耗的思想。因此,研发一种可在低温(170-250°C)条件下脱硝的SCR技术,成为SCR技术在低温烟气脱硝领域,尤其是焦炉烟道废气脱硝领域亟待解决的问题。
[0006]目前国内电力、钢铁等行业主流的脱硫工艺为石灰石-石膏法,但由于其投资成本及运行费用较高,且存在二次废渣污染等问题,随着脱硫技术的不断革新、进步,已经越来越显出其应用的不科学、不经济性。焦化企业剩余氨水较多,在焦炉烟道废气脱硫时,引进更能体现循环经济理念的“氨法脱硫”已是行业内的趋势。但由于焦炉烟道废气温度、S02、NOx及烟尘含量等参数均不同于氨法脱硫已有较广泛应用的其他行业,因此,设计何种合理的适用于焦化行业的氨法脱硫工艺,减少氨逃逸现象,成为制约该技术推广应用的重要因素之一。
发明内容
[0007] 针对现有的其他行业内烟气脱硫脱硝技术应用至焦化行业内时存在的上述缺陷、症结,本发明提供了一种低温焦炉烟道废气洁净化工艺,充分利用焦化企业富余的剩余氨水,采用低温SCR催化脱硝与氨法脱硫相结合的工艺,脱硝效率>88 %,脱硫效率>95 %,同时副产出硫酸铵作化肥、化工原料,有效地降低了焦化企业脱硫脱硝的运行成本。
[0008]为达到上述目的,本发明采用以下技术方案实现:
[0009] —种低温焦炉烟道废气洁净化工艺,该工艺将焦化厂剩余氨水资源化利用、低温SCR脱硝技术、氨法脱硫技术相结合,采用焦化厂蒸氨工段产生的剩余氨水蒸发出来的氨气作为脱硝还原剂;采用低温脱硝催化剂,利用选择性催化还原法进行脱硝,脱硝催化剂采用蜂窝煤状结构;采用氨法脱硫工艺去除焦炉废气中的S02,副产(NH4)2SO4t3由各单元组成的系统在实现高效脱硫脱硝同时,氨逃逸率低,副产(NH4)2SO4产品,在达到国家相关环保政策要求的同时,降低了焦化企业脱硫脱硝的运行成本。
[0010] 该工艺包括低温脱硝过程和氨法脱硫过程;
[0011]其具体步骤为:
[0012] (I)氨气与热空气混合,形成氨气空气混合气体;
[0013] (2)焦炉烟道废气与氨气空气混合气体混合均匀,催化剂催化脱硝;
[0014] (3)脱硝后的焦炉烟道废气依次与雾化的硫铵二级循环液和雾化的硫铵一级循环液进行脱硫反应后排出;
[0015]当采用雾化的硫铵一级循环液进行脱硫反应时,脱硝后的焦炉烟道废气依次采用硫钱一级循环液的上、中、下层进行喷淋;硫钱一级循环液的上层pH值为5-6,中层pH值为4-5,下层pH值为3-4。
[0016]为了实现上述工艺,本发明还提供了一种低温焦炉烟道废气洁净化设备,该设备主要包括通过主管路相连的烟风单元、低温SCR脱硝单元、氨法脱硫单元、氨制备单元;烟风单元和低温SCR脱硝单元之间的管路上连接有喷氨单元;
[0017]所述的烟风单元包括烟气进口 1、烟气出口 I和引风机,引风机安装在SCR反应器烟气出口 II的管路上;
[0018] 所述的低温SCR脱硝单元包括SCR反应器,SCR反应器上部为烟气进口 II,下部为烟气出口 II; SCR反应器内部从上至下依次设有整流器和三层催化剂层;SCR反应器上设有与催化剂层相适应的吹扫装置;;
[0019]所述的喷氨单元包括通过管路连接的风机、空气加热装置、氨气/空气混合器、喷氨格栅、烟气混合器;喷氨格栅和烟气混合器设于SCR反应器烟气进口 II的管路上;
[0020] 所述的氨法脱硫单元包括脱硫塔,脱硫塔下方设有烟气进口 III且烟气进口 III通过管路与烟风单元的引风机相连;脱硫塔内部从下至上依次设有二级循环液槽、与二级循环液槽连通的二级循环喷淋装置、分离板、一级循环喷淋装置和除雾器;脱硫塔外部设有与一级循环喷淋装置连通的一级循环液槽;脱硫塔顶部的烟气出口 III通过管路与烟风单元的烟气出口 I连通;
[0021] —级循环喷淋装置从上至下分为上、中、下三级喷淋管,且上级喷淋管与一级循环液槽下层管路连通,下级喷淋管与一级循环液槽上层管路连通;
[0022]所述的氨制备单元包括通过管路连接的卸氨栗、氨储罐、氨水输送栗、氨蒸发器、氨缓冲罐、脱硫单元氨水输送栗;
[0023] —级循环液槽通过管路与脱硫单元氨水输送栗连通;
[0024]氨缓冲罐通过管路与氨气/空气混合器连通;
[0025] 二级循环液槽和一级循环液槽底部分别设有曝气装置;
[0026] 分离板上设有溢流口,溢流口通过管路与一级循环液槽连通。
[0027]首先,来自焦化厂蒸氨工段的浓度为10%_19%的剩余氨水通过卸氨栗栗入氨储罐,氨储罐内储存的氨水可同时供喷氨单元和氨法脱硫单元两个单元使用。供喷氨单元使用的氨水经氨水输送栗输送至氨蒸发器,氨蒸发所需的热量由低压饱和蒸汽提供。氨蒸发器上装有压力控制阀,将氨气压力控制在一定范围,当出口压力超过0.3MPa时,则关闭氨水输送栗。在氨气出口管路上装有温度检测器,当温度过低时关闭氨水输送栗,使氨缓冲罐维持温度不超过80°C及压力不超过0.3MPa,避免因氨气温度及压力过高造成安全事故。氨蒸发器上也装有安全阀,可防止设备压力异常过高。从氨蒸发器蒸发的氨气流进氨缓冲罐,再通过氨气输送管路送到喷氨单元的氨气/空气混合器中。
[0028]与此同时,低压饱和蒸汽在空气加热装置处,将来自风机的空气加热至180-250°c,加热后的热空气在氨气/空气混合器处与进入来自氨缓冲罐的氨气混合形成氨气空气混合气体。为防止当氨气与焦炉废气混合气体中氨气体积比超过15%时,会发生的爆炸危险,因此控制氨气与热空气的体积比为3:97〜5:95。同时,控制氨气空气混合气体的温度为170-250°C,接近焦炉烟道废气温度,若混合气体温度过低,与焦炉废气混合后降低了混合烟气的温度,会影响后续低温SCR催化剂的催化活性进而降低烟气的脱硝率;若混合气体温度过高,虽然低温SCR催化剂适应温度范围为160°C-300°C,并且温度越高其脱硝率相对越高,但是过高的温度会浪费蒸汽源,并不经济。
[0029]本发明所述的低压饱和蒸汽为1.0MPa、184°C低压饱和蒸汽或其他焦化厂内现成的蒸汽源。
[0030]与此同时,低温焦炉烟道废气在烟风单元引风机的作用下,经过烟气进口 I进入与低温SCR脱硝单元的SCR反应器相连通的管路。氨气空气混合气体经喷氨格栅均匀喷射进入与低温SCR脱硝单元的SCR反应器相连通的管路,与低温焦炉烟道废气初步混合后再经烟气混合器进一步混合均匀,进入低温SCR脱硝单元的SCR反应器进行脱硝。其中,焦炉烟道废气与氨气空气混合气体的体积比为35:1〜45:1,若体积比过大,则混合气体无法彻底的还原焦炉废气中的N0X,若两者体积比过小,则会造成混合气体中多余的NH3与焦炉废气中的SO2发生反应,形成亚硫铵颗粒,颗粒物附着在低温SCR催化剂上,会使催化剂中毒失效;焦炉烟道废气温度为 170-250°C,S02 含量为 200-300mg/Nm3,N0x 含量为800-1000mg/Nm3。
[0031 ] 进入SCR反应器的氨气、空气、焦炉烟道废气混合气体经整流器布置均匀,进入SCR反应器三层催化剂层,保证烟气无偏流,使催化剂层的催化还原点位得到最大程度的利用。本发明所述的催化剂具体制备方法参考中国专利申请200810224495.0。每一层催化剂层均为V2O5-MoO3-T12组分的复合物,T12作为活性物质V2O5和MoO3的载体,而V2O5作为主要的活性物质,对NOx的还原具有催化作用,控制其质量百分比3%-10%,即可确保其在有效的催化还原NOx的前提下,不会导致S02的氧化和N2O的产生;M0O3则可降低催化还原反应的起始温度,提高催化剂的热稳定性和机械性能,控制其质量分数10%_15%,该催化剂可在低至160°C-170°C的温度下有效的催化还原焦炉烟道废气中的Ν0Χ。脱硝催化剂采用蜂窝式结构,相比板式脱硝催化剂,蜂窝式具有比表面积更大的特点,可为NH3与NOx提供更多的催化还原点位,更加有效的促进NH3还原NOxSN2的反应。反应方程式为:
[0032] 4ΝΗ3+4Ν0+02^4Ν2+6Η20 (I)
[0033] 4ΝΗ3+2Ν02+02^3Ν2+6Η20 (2)
[0034]其中95%的NOx为NO,方程(I)为主要反应。本发明通过通过控制氨气空气混合气体与焦炉废气的体积比,保证氨气全部用于还原焦炉废气中的NOx,在170°C左右,氨气与SO2的反应不会优先发生。
[0035]低温SCR脱硝单元运行一段时间后,为防止烟气中的飞灰及其他杂质在低温催化剂层上沉积,堵塞催化剂孔道,须依据运行时催化剂层压力损失情况,及时启动吹扫装置,吹去灰尘以及其他杂质,以维持催化剂层的催化活性。
[0036] 经过低温SCR脱硝单元处理后,低温焦炉烟道废气中NOx的含量可由SOO-1OOOmg/Nm3降至 150-190mg/Nm3,NOx去除率 > 80 %。
[0037]脱硝后的焦炉烟道废气在引风机的作用下,经过管路,在烟气进口 III处,进入氨法脱硫单元的脱硫塔内。焦炉烟道废气进入脱硫塔内后,自下至上流动,首先与经二级循环喷淋装置雾化的硫铵二级循环液换热,烟气温度降至60°C以下,此温度下烟气中的SO2同氨以及亚硫铵的反应效率是最高的,同时,硫铵二级循环液内富余的氨水可与烟气中的SO2发生初步反应,生成亚硫铵;降温后的烟气经过分离板,继续上升,与经一级循环液喷淋装置雾化的硫铵一级循环液接触,硫铵一级循环液内富余的氨水可与烟气中的SO2进一步发生反应,生成亚硫铵。生成亚硫铵反应方程式如下:
[0038] S02+H20+xNH3^(NH4)xH2-xS03
[0039]在分离板的作用下,烟气上升流速低,保证烟气中的SO2被高效吸收。一级循环喷淋装置从上至下分为上、中、下三级喷淋管,且上级喷淋管与一级循环液槽下层管路连通,下级喷淋管与一级循环液槽上层管路连通;当采用雾化的硫铵一级循环液进行脱硫反应时,脱硝后的焦炉烟道废气依次采用硫铵一级循环液的上、中、下层进行喷淋;硫铵一级循环液的上层pH值为5-6,中层pH值为4-5,下层pH值为3_4。通过控制硫钱一级循环液的pH值,可以保证整个脱硫塔中硫铵溶液中的氨含量相对于烟气中的二氧化硫和氮氧化物不会过量很多,大大减少了多余氨的逃逸。在脱硫塔内将硫铵溶液进行两级循环,以保证氨水能与焦炉烟道废气中的SO2充分的反应,提高氨水的利用率,降低烟气的氨逃逸量。而分别从一级循环液槽上层、中层、下层抽取硫铵一级循环液,并且上层抽取的硫铵一级循环液首先与烟气接触,是因为一级循环液槽内的硫铵一级循环液因为氨的传质效率问题,各层的PH并不相同,并且循环槽上部因为首先与加入的氨水接触而PH最高,氨含量最高,将其与烟气接触,可以更加利于烟气中SO2的吸收,同时提高氨水的利用率,降低其逃逸率。
[0040]所述的一级循环喷淋装置上方设有除雾器以及与之配套的反冲洗喷淋装置。含有少量S02(低于50mg/Nm3)和逃逸氨(低于5mg/Nm3)的焦炉烟道废气继续上升,经过除雾器捕捉烟气中的H2O,防止因为烟气含水量过高而产生的拖尾现象,同时除雾器上的水滴也可以进一步的捕捉烟气中的逃逸氨,使脱硫塔逃逸氨的量符合要求。在除雾器下方设置除雾器反冲洗喷淋装置,用以定期冲洗除雾器。
[0041]在脱硫塔底部的硫铵二级循环液经过二级循环喷淋装置不断与来自烟气进口 III的焦炉废气换热,一部分水分会随着烟气向上飘动,硫铵二级循环液会不断浓缩,为保证其在脱硫塔底部保持一定液位,同时为防止烟尘在分离板处沉积,分离板下方设置了一级循环反向喷淋装置,该装置与一级循环液喷淋装置中的上级喷淋管连通,当一级循环液槽内硫铵一级循环液比重超过1.lkg/L时,打开一级循环反向喷淋装置,抽取一级循环液槽中的硫铵一级循环液,向脱硫塔补液,同时反冲洗分离板。
[0042]分别通过位于二级循环液槽和一级循环液槽底部的曝气装置对硫铵一级、二级循环液进行曝气,发生如下反应:
[0043 ] (NH4) xH2-xS03+1 /202+ (2-x) NH3^ (NH4) 2 SO4
[0044]为保证氧化效果,氧化空气分布系统采用喷管式,氧化空气被分布管注入,分散为细小的气泡并均布于硫铵一级、二级循环液中,HSOr被氧化空气完全氧化。
[0045] 本发明所述的设备还包括工艺水单元和硫铵制备单元;
[0046] 所述的工艺水单元包括通过管路连接的工艺水箱和工艺水栗;工艺水栗通过管路与脱硫塔内的反冲洗喷淋装置连通;
[0047]所述的硫铵制备单元包括通过管路连接的旋流器、离心机、干燥机、包装机;旋流器与二级循环液槽连通。
[0048]脱硫塔底部二级循环液槽内的硫铵二级循环液比重一般为1.lkg/L-1.2kg/L,随着二级硫铵循环液的不断循环,水分逐渐流失,二级硫铵循环液的比重逐渐增大,当硫铵二级循环液比重超过1.2kg/L后,经过硫铵排出栗输送至硫铵制备单元,制取成品硫铵。
[0049] —级循环液槽上部设有溢流口,通过管路连通至脱硫塔内,以使一级循环液槽内的硫铵一级循环液维持在一定液位不至溢出;一级循环液槽上部设有氨水投加口,氨水由脱硫单元氨水输送栗输送,栗采用变频控制,当焦炉废气中的SO2含量发生变化时,一级循环液槽内各层硫铵一级循环液的PH会发生变化,控制一级循环液槽上部溶液pH为5-6之间,中部pH为4-5之间,底部pH为3-4之间,一旦各部分pH发生变化,则变频控制氨水投加量,pH若升高,则降低脱硫单元氨水输送栗的频率以降低氨水投加量;pH若降低,则增大脱硫单元氨水输送栗的频率以提升氨水投加量;确保氨法脱硫单元的脱硫效率不低于95%以及氨逃逸率不超过5mg/Nm3。
[0050]另外,硫铵二级循环液经二级循环喷淋装置雾化后,与温度为170°C-250°C的焦炉烟道废气接触后,焦炉烟道废气温度降为50-60°C,在两者接触换热时,硫铵二级循环液中的氨以及亚硫铵对烟气中的NOx仍旧有还原作用,可进一步降低烟气中NOx的含量,去除率约为40%左右。
[0051 ] 经过氨法脱硫单元处理后,焦炉烟道废气中SO2含量约为10-30mg/Nm3,N0x含量约为90-110mg/Nm3,各项指标均满足《炼焦化学工业污染物排放标准GB16171-2012》自2015年I月I日起实施的大气污染物排放标准,同时,水滴携带量> 75mg/Nm3,氨逃逸率> 5mg/Nm3,处理后的焦炉烟道废气经脱硫脱硝后烟气经过烟风单元的烟气出口 I达标排放。
[0052] 本发明工艺水单元包括通过管路连接的工艺水箱和工艺水栗;工艺水栗通过管路与脱硫塔内的反冲洗喷淋装置连通,工艺水通过工艺水栗输送至除雾器反冲洗喷淋装置,经装置雾化,反向冲洗除雾器。通过工艺水栗输送至其他用水处,可冲洗烟道以及脱硫塔的内壁,以防止烟气中的灰尘在各处沉积。
[0053]硫铵制备单元包括通过管路连接的旋流器、离心机、干燥机、包装机;旋流器与二级循环液槽连通。达到相应比重的硫铵溶液由硫铵排出栗送入旋流器,经过浓缩后的浆液自流进入离心机,进一步脱水后,由干燥机进行烘干,达到标准后的硫铵由包装机封袋包装,旋流器以及离心机分离出的硫铵母液回流至脱硫塔内。由包装机封装的硫铵成品外卖,降低焦化企业脱硫脱硝成本。
[0054]综上所述,与现有技术相比,本发明的有益效果是:
[0055] 1、脱硫脱硝一体化
[0056] 低温焦炉烟道气(170°C-250°C)在引风机的负压吸引下,首先进入SCR脱硝单元,在催化剂的催化作用下,与NH3发生氧还原反应生成N2和H2O,脱除80%左右的N0x,SCR反应器出口温度160°C-24(TC,进入脱硫塔内,利用氨法脱除95%以上的SO2后,进入焦炉烟囱,排入大气。
[0057]本工艺在对焦炉烟道废气脱硫脱硝保证废气达标排放的同时,副产有价值的硫铵产品,有效的降低了工艺运行成本。
[0058] 2、以废治废,变废为宝
[0059]焦化企业蒸氨工段产生的剩余氨水并无其他消纳办法,只能作为废水处理,而氨法脱硫脱硝可有效的利用焦化企业多余的氨水,将废气中的二氧化硫和焦化厂的废氨水转化为化肥,不产生任何废水、废液和废渣,没有二次污染,既解决了剩余氨水无处消纳的问题,又创造了经济效益,降低了焦化企业脱硫脱硝工艺的运行成本,是一项真正意义上的将污染物全部资源化,符合循环经济要求的脱硫技术。
[0060] 3、氨法脱硫设备体积小、占地少、能耗低且设备不易结垢
[0061]氨是一种良好的碱性吸收剂,氨法脱硫属于气-液反应,反应速度快,反应完全,吸收剂利用率高,减少了设备的体积和能耗。而由于氨具有很高的反应活性,且硫酸铵具有极易溶解的化学特性,因此氨法脱硫系统不易产生结垢现象。另外,一级循环液槽单独设置,内盛硫铵一级循环液,既降低了脱硫塔高度,相应的栗扬程降低,节约设备投资,同时硫铵一级循环液同脱硫塔底部的硫铵二级循环液分开,硫铵一级循环液比重一般为1.0kg/L-
1.lkg/L,硫钱二级循环液比重一般为1.lkg/L-1.2kg/L,将两种循环液分开,更加利于硫钱塔内结晶的控制,硫铵成品的制备成本更低、工艺更加合理。
[0062] 4、既脱硫又脱硝
[0063]在氨法脱硫单元,氨对NOx同样有吸收作用,另外脱硫过程中形成的亚硫铵对NOx还具有还原作用,所以氨法脱硫的同时也可实现一部分脱硝的目的,可去除40%左右的N0X,使得本发明最终的脱硝效率超过88%,可以满足更加严格的NOx排放要求,适应更高的环保要求。
[0064] 5、大大降低氨的逃逸量
[0065]传统工艺中,一般是采用经喷淋装置雾化的氨水与烟气逆向接触,将烟气温度降至60°C以下的同时,氨水与烟气中的SO2发生初步反应,去除一部分S02,但是喷洒氨水的弊端在于,雾化的氨水与温度为160 °C以上的焦炉烟道废气瞬时接触时,相当一部分的氨水会优先分解为氨气和水,且氨气相对于SO2是远远过量的,从而造成氨气的逃逸;而本申请中,通过设定硫铵一级循环液的PH值以及采用多级循环等手段,确保氨法脱硫单元的脱硫效率不降低以及氨逃逸率不超过5mg/Nm3。
附图说明
[0066]图1是本发明的工艺流程图。
[0067]图中:1.烟风单元,Ia.焦炉烟囱,Ib.烟气进口 I,lc.烟气出口 I,ld.引风机,Ie焦炉烟道。2.低温SCR脱硝单元,2a.膨胀节,2b.整流器,2c.催化剂层,2d.吹扫装置,2e.SCR反应器,2f.烟气进口 II,2g.烟气出口 11。3.喷氨单元,3a.低压蒸汽,3b.风机,3c.空气加热装置,3d.氨气/空气混合器,3e.喷氨格栅,3f.烟气混合器。4.氨制备单元,4a.卸氨栗,4b.氨储罐,4c.氨水输送栗,4d.氨蒸发器,4e.氨缓冲罐,4f.脱硫单元氨水输送栗。5.氨法脱硫单元,5a.烟气进口 III,5b.硫铵排出栗,5c.二级硫铵循环栗,5d.事故栗,5e.曝气装置,5f.二级循环喷淋装置,5g.一级循环反向喷淋装置,5h.溢流口,51.分离板,5 j.—级循环喷淋装置,5k.除雾器,51.曝气装置,5m.一级循环栗,5n.一级循环液槽溢流口,5ο.—级循环液槽,5ρ.脱硫塔,5q.氨水投加口,5r.烟气出口 III,5s.二级循环液槽。6.工艺水单元,6a.工艺水箱,6b.工艺水栗,6c.反冲洗喷淋装置,6d.其他用水处。7.硫铵制备单元,7a.旋流分离器,7b.离心机,7c.干燥机,7d.包装机,Te.硫铵成品,7f.硫铵母液回流。
具体实施方式
[0068]下面通过非限定性的实施例并结合附图对本发明进一步的说明:
[0069] 实施例1
[0070] 一种低温焦炉烟道废气洁净化工艺,该工艺包括低温脱硝过程和氨法脱硫过程;
[0071]其具体步骤为:
[0072] (I)氨气与热空气混合,形成氨气空气混合气体;
[0073] (2)焦炉烟道废气与氨气空气混合气体混合均匀,催化剂催化脱硝;
[0074] (3)脱硝后的焦炉烟道废气依次与雾化的硫铵二级循环液和雾化的硫铵一级循环液进行脱硫反应后排出;
[0075]当采用雾化的硫铵一级循环液进行脱硫反应时,脱硝后的焦炉烟道废气依次采用硫铵一级循环液的上、中、下层进行喷淋;硫铵一级循环液的上层PH值为6,中层pH值为5,下层pH值为4。
[0076]步骤(I)中氨气与热空气的体积比为3:97;热空气的温度为180°C,混合后氨气空气混合气体的温度为170°C ;
[0077]步骤(2)中焦炉烟道废气与氨气空气混合气体的体积比为35:1;焦炉烟道废气温度为170°C;
[0078]步骤(3)中与雾化的硫铵二级循环液反应后焦炉烟道废气的温度为60°C;
[0079] 步骤(3)中硫铵一级循环液比重为1.0kg/L〜1.lkg/L,硫铵二级循环液比重为1.lkg/L〜1.2kg/L;
[0080] 实现上述工艺所用的设备主要包括通过主管路相连的烟风单元、低温SCR脱硝单元、氨法脱硫单元、氨制备单元;烟风单元和低温脱硝单元之间的管路上连接有喷氨单元;
[0081]所述的烟风单元包括烟气进口 1、烟气出口 I和引风机,引风机安装在SCR反应器烟气出口 II的管路上;
[0082] 所述的低温SCR脱硝单元包括SCR反应器,SCR反应器上部为烟气进口 II,下部为烟气出口 II; SCR反应器内部从上至下依次设有整流器和三层催化剂层;SCR反应器上设有与催化剂层相适应的吹扫装置;
[0083]所述的喷氨单元包括通过管路连接的风机、空气加热装置、氨气/空气混合器、喷氨格栅、烟气混合器;喷氨格栅和烟气混合器设于SCR反应器烟气出口 II的管路上;
[0084] 所述的氨法脱硫单元包括脱硫塔,脱硫塔下方设有烟气进口 III且烟气进口 III通过管路与烟风单元的引风机相连;脱硫塔内部从下至上依次设有二级循环液槽、与二级循环液槽连通的二级循环喷淋装置、分离板、一级循环喷淋装置和除雾器;脱硫塔外部设有与一级循环喷淋装置连通的一级循环液槽;脱硫塔顶部的烟气出口 III通过管路与烟风单元的烟气出口 I连通;
[0085] 一级循环喷淋装置从上至下分为上、中、下三级喷淋管,且上级喷淋管与一级循环液槽下层管路连通,下级喷淋管与一级循环液槽上层管路连通;
[0086]所述的氨制备单元包括通过管路连接的卸氨栗、氨储罐、氨水输送栗、氨蒸发器、氨缓冲罐、脱硫单元氨水输送栗;
[0087] —级循环液槽通过管路与脱硫单元氨水输送栗连通;
[0088]氨缓冲罐通过管路与氨气/空气混合器连通;
[0089] 二级循环液槽和一级循环液槽底部分别设有曝气装置;
[0090] 分离板上设有溢流口,溢流口通过管路与一级循环液槽连通。
[0091] 实施例2
[0092] —种低温焦炉烟道废气洁净化工艺,该工艺包括低温脱硝过程和氨法脱硫过程;
[0093]其具体步骤为:
[0094] (I)氨气与热空气混合,形成氨气空气混合气体;
[0095] (2)焦炉烟道废气与氨气空气混合气体混合均匀,催化剂催化脱硝;
[0096] (3)脱硝后的焦炉烟道废气依次与雾化的硫铵二级循环液和雾化的硫铵一级循环液进行脱硫反应后排出;
[0097]当采用雾化的硫铵一级循环液进行脱硫反应时,脱硝后的焦炉烟道废气依次采用硫钱一级循环液的上、中、下层进行喷淋;硫钱一级循环液的上层pH值为5.5,中层pH值为4.5,下层pH值为3.5。
[0098]步骤(I)中氨气与热空气的体积比为5:95;热空气的温度为250°C,混合后氨气空气混合气体的温度为220°C ;
[0099]步骤(2)中焦炉烟道废气与氨气空气混合气体的体积比为45:1;焦炉烟道废气温度为220°C;
[0100]步骤(3)中与雾化的硫铵二级循环液反应后焦炉烟道废气的温度为50°C;
[0101] 步骤(3)中硫铵一级循环液比重为1.0kg/L〜1.lkg/L,硫铵二级循环液比重为1.lkg/L〜1.2kg/L;
[0102] 实现上述工艺所用的设备主要包括通过主管路相连的烟风单元、低温SCR脱硝单元、氨法脱硫单元、氨制备单元;烟风单元和低温脱硝单元之间的管路上连接有喷氨单元;
[0103]所述的烟风单元包括烟气进口 1、烟气出口 I和引风机,引风机安装在SCR反应器烟气出口 II的管路上;
[0104] 所述的低温SCR脱硝单元包括SCR反应器,SCR反应器上部为烟气进口 II,下部为烟气出口 II; SCR反应器内部从上至下依次设有整流器和三层催化剂层;SCR反应器上设有与催化剂层相适应的吹扫装置;
[0105]所述的喷氨单元包括通过管路连接的风机、空气加热装置、氨气/空气混合器、喷氨格栅、烟气混合器;喷氨格栅和烟气混合器设于SCR反应器烟气出口 II的管路上;
[0106] 所述的氨法脱硫单元包括脱硫塔,脱硫塔下方设有烟气进口 III且烟气进口 III通过管路与烟风单元的引风机相连;脱硫塔内部从下至上依次设有二级循环液槽、与二级循环液槽连通的二级循环喷淋装置、分离板、一级循环喷淋装置和除雾器;脱硫塔外部设有与一级循环喷淋装置连通的一级循环液槽;脱硫塔顶部的烟气出口 III通过管路与烟风单元的烟气出口 I连通;
[0107] —级循环喷淋装置从上至下分为上、中、下三级喷淋管,且上级喷淋管与一级循环液槽下层管路连通,下级喷淋管与一级循环液槽上层管路连通;
[0108]所述的氨制备单元包括通过管路连接的卸氨栗、氨储罐、氨水输送栗、氨蒸发器、氨缓冲罐、脱硫单元氨水输送栗;
[0109] —级循环液槽通过管路与脱硫单元氨水输送栗连通;
[0110]氨缓冲罐通过管路与氨气/空气混合器连通;
[0111] 二级循环液槽和一级循环液槽底部分别设有曝气装置;
[0112] 分离板上设有溢流口,溢流口通过管路与一级循环液槽连通。
[0113]所述的一级循环喷淋装置上方设有除雾器以及与之配套的反冲洗喷淋装置。
[0114] 实施例3
[0115] —种低温焦炉烟道废气洁净化工艺,该工艺包括低温脱硝过程和氨法脱硫过程;
[0116]其具体步骤为:
[0117] (I)氨气与热空气混合,形成氨气空气混合气体;
[0118] (2)焦炉烟道废气与氨气空气混合气体混合均匀,催化剂催化脱硝;
[0119] (3)脱硝后的焦炉烟道废气依次与雾化的硫铵二级循环液和雾化的硫铵一级循环液进行脱硫反应后排出;
[0120]当采用雾化的硫铵一级循环液进行脱硫反应时,脱硝后的焦炉烟道废气依次采用硫钱一级循环液的上、中、下层进行喷淋;硫钱一级循环液的上层pH值为5.7,中层pH值为4.7,下层pH值为3.7。
[0121 ]步骤(I)中氨气与热空气的体积比为4:96;热空气的温度为220°C,混合后氨气空气混合气体的温度为250°C ;
[0122]步骤(2)中焦炉烟道废气与氨气空气混合气体的体积比为40:1;焦炉烟道废气温度为250°C;
[0123]步骤(3)中与雾化的硫铵二级循环液反应后焦炉烟道废气的温度为55°C;
[0124] 步骤(3)中硫铵一级循环液比重为1.0kg/L〜1.lkg/L,硫铵二级循环液比重为1.lkg/L〜1.2kg/L;
[0125] 实现上述工艺所用的设备主要包括通过主管路相连的烟风单元、低温SCR脱硝单元、氨法脱硫单元、氨制备单元;烟风单元和低温脱硝单元之间的管路上连接有喷氨单元;
[0126]所述的烟风单元包括烟气进口 1、烟气出口 I和引风机,引风机安装在SCR反应器烟气出口 II的管路上;
[0127] 所述的低温SCR脱硝单元包括SCR反应器,SCR反应器上部为烟气进口 II,下部为烟气出口 II; SCR反应器内部从上至下依次设有整流器和三层催化剂层;SCR反应器上设有与催化剂层相适应的吹扫装置;
[0128]所述的喷氨单元包括通过管路连接的风机、空气加热装置、氨气/空气混合器、喷氨格栅、烟气混合器;喷氨格栅和烟气混合器设于SCR反应器烟气出口 II的管路上;
[0129] 所述的氨法脱硫单元包括脱硫塔,脱硫塔下方设有烟气进口 III且烟气进口 III通过管路与烟风单元的引风机相连;脱硫塔内部从下至上依次设有二级循环液槽、与二级循环液槽连通的二级循环喷淋装置、分离板、一级循环喷淋装置和除雾器;脱硫塔外部设有与一级循环喷淋装置连通的一级循环液槽;脱硫塔顶部的烟气出口 III通过管路与烟风单元的烟气出口 I连通;
[0130] —级循环喷淋装置从上至下分为上、中、下三级喷淋管,且上级喷淋管与一级循环液槽下层管路连通,下级喷淋管与一级循环液槽上层管路连通;
[0131]所述的氨制备单元包括通过管路连接的卸氨栗、氨储罐、氨水输送栗、氨蒸发器、氨缓冲罐、脱硫单元氨水输送栗;
[0132] 一级循环液槽通过管路与脱硫单元氨水输送栗连通;
[0133]氨缓冲罐通过管路与氨气/空气混合器连通;
[0134] 二级循环液槽和一级循环液槽底部分别设有曝气装置;
[0135] 分离板上设有溢流口,溢流口通过管路与一级循环液槽连通。
[0136]所述的一级循环喷淋装置上方设有除雾器以及与之配套的反冲洗喷淋装置。
[0137]分离板下方设有与一级循环喷淋装置中的上级喷淋管连通的一级循环反向喷淋
目.ο
[0138] 实施例4
[0139] —种低温焦炉烟道废气洁净化工艺,该工艺包括低温脱硝过程和氨法脱硫过程;
[0140]其具体步骤为:
[0141] (I)氨气与热空气混合,形成氨气空气混合气体;
[0142] (2)焦炉烟道废气与氨气空气混合气体混合均匀,催化剂催化脱硝;
[0143] (3)脱硝后的焦炉烟道废气依次与雾化的硫铵二级循环液和雾化的硫铵一级循环液进行脱硫反应后排出;
[0144]当采用雾化的硫铵一级循环液进行脱硫反应时,脱硝后的焦炉烟道废气依次采用硫钱一级循环液的上、中、下层进行喷淋;硫钱一级循环液的上层pH值为5.3,中层pH值为4.3,下层pH值为3.3。
[0145]步骤(I)中氨气与热空气的体积比为5:95;热空气的温度为200°C,混合后氨气空气混合气体的温度为170°C ;
[0146]步骤(2)中焦炉烟道废气与氨气空气混合气体的体积比为45:1;焦炉烟道废气温度为170°C;
[0147]步骤(3)中与雾化的硫铵二级循环液反应后焦炉烟道废气的温度为60°C;
[0148] 步骤(3)中硫铵一级循环液比重为1.0kg/L〜1.lkg/L,硫铵二级循环液比重为1.lkg/L〜1.2kg/L;
[0149] 实现上述工艺所用的设备主要包括通过主管路相连的烟风单元1、低温SCR脱硝单元2、氨法脱硫单元5、氨制备单元4;烟风单元I和低温SCR脱硝单元2之间的管路上连接有喷氨单元3;
[0150] 所述的烟风单元I包括烟气进口 Ilb、烟气出口 Ilc和引风机ld,引风机Id安装在SCR反应器2e烟气出口 II2g的管路上;
[0151] 所述的低温SCR脱硝单元2包括SCR反应器2e,SCR反应器2e上部为烟气进口 II2f,下部为烟气出口 II2g; SCR反应器2e内部从上至下依次设有整流器2b和三层催化剂层2c ;SCR反应器上设有与催化剂层相适应的吹扫装置2d;
[0152]所述的喷氨单元3包括通过管路连接的风机3b、空气加热装置3c、氨气/空气混合器3d、喷氨格栅3e、烟气混合器3f ;喷氨格栅3e和烟气混合器3f设于SCR反应器2e烟气出口II2g的管路上;
[0153] 所述的氨法脱硫单元5包括脱硫塔5p,脱硫塔5p下方设有烟气进口 III5a且烟气进口 III5a通过管路与烟风单元I的引风机Id相连;脱硫塔5p内部从下至上依次设有二级循环液槽5s、与二级循环液槽5s连通的二级循环喷淋装置5f、分离板51、一级循环喷淋装置5j和除雾器5k;脱硫塔5p外部设有与一级循环喷淋装置5 j连通的一级循环液槽5ο;脱硫塔5p顶部的烟气出口 III5a通过管路与烟风单元I的烟气出口 Ilc连通;
[0154] —级循环喷淋装置5j从上至下分为上、中、下三级喷淋管,且上级喷淋管与一级循环液槽下层管路连通,下级喷淋管与一级循环液槽上层管路连通;
[0155]所述的氨制备单元4包括通过管路连接的卸氨栗4a、氨储罐4b、氨水输送栗4c、氨蒸发器4d、氨缓冲罐4e、脱硫单元氨水输送栗4f;
[0156] 一级循环液槽5ο通过管路与脱硫单元氨水输送栗4f连通;
[0157]氨缓冲罐4e通过管路与氨气/空气混合器3d连通;
[0158] 二级循环液槽5s和一级循环液槽5ο底部分别设有曝气装置5e、51;
[0159] 分离板5i上设有溢流口 5h,溢流口 5h通过管路与一级循环液槽5ο连通。
[0160]所述的一级循环喷淋装置5j上方设有除雾器5k以及与之配套的除雾器反冲洗喷淋装置6c。
[0161]分离板5i下方设有与一级循环喷淋装置5 j中的上级喷淋管连通的一级循环反向喷淋装置5g。
[0162] 该设备还包括工艺水单元6和硫铵制备单元7;
[0163] 所述的工艺水单元6包括通过管路连接的工艺水箱6a和工艺水栗6b;工艺水栗6b通过管路与脱硫塔5p内的除雾器反冲洗喷淋装置6c连通;
[0164]所述的硫铵制备单元7包括通过管路连接的旋流器7a、离心机7b、干燥机7c、包装机7d;旋流器7a与二级循环液槽5s连通。
[0165] 烟风单元包括烟气进口 Ilb、烟气出口 Ilc和引风机ld,引风机Id安装在SCR反应器烟气出口 II的管路上,用于吸入来自焦炉烟道If的焦炉烟道废气,并将焦炉烟道废气输送至焦炉烟囱Ia,各项污染物达标排放进入大气。
[0166] 待处理的焦炉烟道废气SO2含量一般为200-300mg/Nm3,N0x含量一般为800-1000mg/Nm3,工艺系统运行时,烟气由焦炉烟道If被引风机Ie引入工艺系统内。
[0167]来自焦化厂蒸氨工段的浓度为10%_19%的剩余氨水通过卸氨栗4a栗入氨储罐4b,氨储罐4b内储存的氨水可同时供喷氨单元3和氨法脱硫单元5两个单元使用。供喷氨单元3使用的氨水经氨水输送栗4c输送至氨蒸发器4d,氨蒸发所需的热量由低压饱和蒸汽3a提供,氨蒸发器4d上装有压力控制阀将氨气压力控制在一定范围,当出口压力超过0.3MPa时,则关闭氨水输送栗4c。在氨气出口管线上装有温度检测器,当温度过低时关闭氨水输送栗4c,使氨缓冲罐4e维持适当温度及压力,氨蒸发器4d也装有安全阀,可防止设备压力异常过高。从氨蒸发器4d蒸发的氨气流进氨缓冲罐4e,再通过氨气输送管线送到喷氨单元3。
[0168]低压饱和蒸汽3a在空气加热装置3c处,将来自风机3b的空气加热,加热空气在氨气/空气混合器3d处与进入来自氨缓冲罐4e的氨气混合均匀后,经喷氨格栅3e均匀喷射进入焦炉废气管道,与来自烟道的低温焦炉烟道废气混合后,经烟气混合器3f使其进一步混合均匀,进入低温SCR脱硝单元2。
[0169]焦炉烟道废气由烟风单元I引入,经烟道输送,在喷氨格栅3e处与来自喷氨单元3的氨气/空气混合气体初步混合,经过烟气混合器3f进一步混合均匀后,进入低温SCR脱硝单元2的膨胀节2a,由膨胀节2a补偿因温度差与机械振动引起的附加应力后,经整流器2b将氨气、空气、焦炉烟道废气混合气体布置均匀,进入SCR反应器2e的SCR催化剂层2c,保证烟气无偏流,使SCR催化剂层2c的催化还原点位得到最大程度的利用。
[0170] SCR反应器2e内填充有三层低温SCR脱硝催化剂2c(第一层作为备用层),可在温度低至170°C仍旧有较高的催化活性,其主要成分为一定质量配比的V2O5-MoO3-T12组分的复合物,T12作为活性物质V2O5和MoO3的载体,而V2O5作为主要的活性物质,对NOx的还原具有催化作用,控制其质量百分比3%_10%,即可确保其在有效的催化还原NOx的前提下,不会导致SO2的氧化和N2O的产生;MoO3则可降低催化还原反应的起始温度,提高催化剂的热稳定性和机械性能,控制其质量分数为10%_15%,该催化剂可在低至160°C-170°C的温度下有效的催化还原焦炉烟道废气中的N0X。脱硝催化剂采用蜂窝式结构,相比板式脱硝催化剂,蜂窝式具有比表面积更大的特点,可为NH3与NOx提供更多的催化还原点位,更加有效的促进NH3还原NOx为N2的反应。反应方程式为:
[0171] 4ΝΗ3+4Ν0+02^4Ν2+6Η20 (I)
[0172] 4ΝΗ3+2Ν02+02^3Ν2+6Η20 (2)
[0173] 其中95%的NOx为NO,方程(I)为主要反应。
[0174] 低温SCR脱硝单元2运行一段时间后,为防止烟气中的飞灰及其他杂质在低温SCR催化剂2c上沉积,堵塞催化剂孔道,须依据运行时低温SCR催化剂2c压力损失情况,及时启动吹扫装置2d,吹去灰尘以及其他杂质,以维持低温SCR催化剂2c的催化活性。
[0175] 经过低温SCR脱硝单元2处理后,低温焦炉烟道废气中NOx的含量可由SOO-1OOOmg/Nm3 降至 150-190mg/Nm3,N0x 去除率 >80%。
[0176]低温SCR脱硝单元2处理脱硝后的焦炉烟道废气在引风机Ie的作用下,经过烟道,在烟气进口 III5a处,进入氨法脱硫单元5的脱硫塔5p内。烟气进入脱硫塔5p内后,自下至上流动,首先与经二级循环喷淋装置5f雾化的硫铵二级循环液换热,烟气温度降至50°C-60°C,同时,硫铵二级循环液内富余的氨水可与烟气中的SO2发生初步反应,生成亚硫铵;降温后的烟气经过分离板5i,继续上升,与经一级循环液喷淋装置5j雾化的硫铵一级循环液分别接触,硫铵一级循环液内富余的氨水可与烟气中的SO2进一步发生反应,生成亚硫铵。生成亚硫铵反应方程式如下:
[0177] SO2+H2O+XNH34 (NH4) xH2-xS03
[0178]硫铵一级循环液分别来自一级循环液槽5ο的上层、中层、底层,经一级循环栗A/B/C5m输送至一级循环液喷淋装置A/B/C5j。喷淋下的硫铵一级循环液经分离板5i收集后,通过分离板溢流口 5h溢流进入一级循环液槽5ο。
[0179]在脱硫塔5ρ内将硫铵溶液进行两级循环,以保证氨水能与焦炉烟道废气中的SO2充分的反应,提高氨的利用率,降低焦炉废气中的氨逃逸量。含有少量S02(低于50mg/Nm3)和逃逸氨(低于5mg/Nm3)的焦炉烟道废气继续上升,经过除雾器A/B5k捕捉烟气中的H2O,防止因为烟气含水量过高而产生的拖尾现象,同时除雾器A/B5k上的水滴也可以进一步的捕捉烟气中的逃逸氨,使脱硫塔逃逸氨的量符合要求。在除雾器A/B5k下方设置除雾器反冲洗喷淋装置6c,用以定期冲洗除雾器A/B5k。
[0180]在脱硫塔5p底部的硫铵二级循环液经过二级循环喷淋装置5f不断与来自烟气进口5a的焦炉废气换热,一部分水分会随着烟气向上飘动,硫铵二级循环液会不断浓缩,为保证其在脱硫塔5p底部保持一定液位,同时为防止烟尘在分离板5i处沉积,设置了一级循环反向喷淋装置5g,以定期反冲洗分离板5i并维持脱硫塔5p底部硫铵二级循环液液位。
[0181 ]分别通过位于一级循环液槽5o底部的曝气装置B51和位于脱硫塔5p底部的曝气装置A5e对硫铵一级、二级循环液进行曝气,强制氧化一、二级循环液槽内的硫铵溶液,发生如下反应:
[0182] (NH4) xH2-xS03+1 /202+ (2-x) NH3^ (NH4) 2 SO4
[0183]随着脱硫塔5p底部的硫铵二级循环液的不断循环,水分逐渐流失,硫铵二级循环液的比重逐渐增大,当增加比重大于1.2kg/L后,经过硫铵排出栗5b输送至硫铵制备单元7,制取成品硫铵。
[0184]脱硫塔5p底部设置有事故栗5d,硫铵二级循环液出现异常时,可由事故栗5d将循环液排至事故池。
[0185] 一级循环液槽5ο上部设有溢流口 5n,通过管道连通至脱硫塔5p内,以使循环槽5ο内的硫铵一级循环液维持在一定液位不至溢出;循环槽5ο上部设有氨水投加口 5q,剩余氨水由脱硫单元氨水输送栗4f输送,栗采用变频控制,当烟气中SO2的含量和脱硫塔内pH变化时,变频控制氨水投加量,确保氨法脱硫单元5的脱硫效率大于95%以及氨逃逸率不超过5mg/Nm3。
[0186]另外,硫铵二级循环液经二级循环喷淋装置5f雾化后,与温度为170°C_250°C的焦炉烟道废气接触时,此温度下,硫铵二级循环液中的氨水以及亚硫铵对烟气中的NOx仍旧有还原作用,可进一步降低烟气中NOx的含量,去除率约为40%左右。
[0187] 经过氨法脱硫单元5处理后,焦炉烟道废气中SO2含量约为10-30mg/Nm3,N0x含量约为90-110mg/Nm3,各项指标均满足《炼焦化学工业污染物排放标准GB16171-2012》自2015年I月I日起实施的大气污染物排放标准,同时,水滴携带量> 75mg/Nm3,氨逃逸率> 5mg/Nm3,处理后的焦炉烟道废气经脱硫脱硝后烟气经过烟气出口 Ilc,进入焦炉烟囱la,达标排放。
[0188] 工艺水单元6包括工艺水箱6a、工艺水栗6b,工艺水通过工艺水栗6b输送至除雾器反冲洗喷淋装置6c,经装置雾化,反向冲洗除雾器5k。通过工艺水栗6b输送至其他用水处6d,可冲洗烟道以及脱硫塔5p的内壁,以防止烟气中的灰尘在各处沉积。
[0189 ] 硫铵制备单元7包括旋流器7a、离心机7b、干燥机7c、包装机7d。达到设计浓度的硫铵溶液由硫铵排出栗5b送入旋流器7a,经过浓缩后的浆液自流进入离心机7b,进一步脱水后,由干燥机7c进行烘干,达到标准后的硫铵由包装机7d封袋包装,旋流器7a以及离心机7b分离出的硫钱母液7f回流至脱硫塔5p内。由包装机7d封装的硫钱成品7e外卖,降低焦化企业脱硫脱硝成本。
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