CN111266079A - 一种高炉煤气脱氯除湿剂及其制备和使用方法 - Google Patents
一种高炉煤气脱氯除湿剂及其制备和使用方法 Download PDFInfo
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- CN111266079A CN111266079A CN202010065538.6A CN202010065538A CN111266079A CN 111266079 A CN111266079 A CN 111266079A CN 202010065538 A CN202010065538 A CN 202010065538A CN 111266079 A CN111266079 A CN 111266079A
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- dechlorination
- blast furnace
- furnace gas
- dehumidification
- gas
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及一种高炉煤气脱氯除湿剂及其制备和使用方法，高炉煤气脱氯除湿剂活性组分为Ca(OH)2、CaO、SiO2、MgO、Al2O3、MnO等碱及碱金属或碱土金属氧化物，活性组分含量60～85wt％。制备原料来自钢厂冶炼过程废弃钢渣，孔隙结构发达、机械强度高，粒径为1～20mm，经破碎研磨、水化、固液分离、烘干粉化、造粒、焙烧等过程获得粒径0.5～2mm成品脱氯除湿剂，其径向抗压碎强度50～80N/cm。脱氯除湿剂作为固定床填料进行煤气脱氯除湿，穿透失效后返回渣场，进行后续资源化利用。本发明原料本身为固废，就地取材，成本低，制作工艺简单，脱氯除湿效果好，净化后煤气HCl浓度小于1ppm，含水量小于环境温度下煤气饱和含水量，脱氯除湿后煤气品质提高，钢渣中f‑CaO转化为稳定相，带来额外经济附加值。
Description
技术领域
本发明涉及钢铁行业煤气净化与固废利用领域，具体涉及一种以钢渣为主要原料制备煤气脱氯除湿剂及其使用的方法。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
高炉煤气是炼铁过程中副产的可燃气体，大中型高炉在冶炼炼钢生铁时副产高炉煤气主要成分含量(体积分数)为二氧化碳16％～22％、一氧化碳21％～26％、氢气1％～4％、氮气53％～57％及少量烃类，低位发热量2760～3720kJ/m3，是一种热值较低的煤气。
事实上，高炉直接排出的荒煤气还含有10～50g/m3颗粒物需先经过除尘后才能进入TRT进行余压发电，高炉煤气除尘工艺分湿法和干法，干法除尘因具有水耗及电耗低、干法TRT发电负荷较湿法高30％以上、煤气显热可以充分利用等优点。目前，国内外钢铁企业及中国钢铁工业协会普遍推广应用高炉煤气干法工艺进行除尘。
高炉冶炼原料尤其是烧结矿和球团矿，所用含铁物料在海运及海水选矿过程中进入海水，以及烧结及球团制作过程加入CaCl2助剂是高炉冶炼副产煤气中氯的主要来源。同时，燃料焦炭或煤粉中所含氯在高温冶炼过程中也会以气态HCl形式混入煤气。加之干法除尘工艺使得过程中产生的HCl只能进入煤气，HCl含量高达100mg/m3。
高炉煤气经过除尘、TRT余压利用及管道运输等一系列过程后去往用户，随着温度降至HCl露点温度以下，因其极易遇水冷凝，故会在沿途设备、管道及用户处冷凝产生盐酸，对设备及管道造成严重腐蚀。不能冷凝的HCl去往煤气用户燃烧，最终排入大气，形成酸雨，严重危害人类生存环境及身体健康。
CN 1037942C公开了一种氯化氢吸附剂，由γ-氧化铝和碱金属碳酸盐或碱土金属碳酸盐助剂组成，该吸附剂脱除氯化氢能力强，可将气体或液体烃中氯化氢杂质含量降低至0.5ppm以下，氯化氢吸附量可达25％(重量)。
CN 100344363C公开了一种吸附气体或液体中氯化氢杂质的吸附剂，其成分组成为氧化铝、白土或膨润土填充剂及氧化锌、氧化镁或氧化钠等金属氧化物。
CN 104689781A公开了一种干燥炉氯化氢吸附剂，其原料组成为碱金属和/或碱土金属化合物以及钛、铜、锌、锰、铁、铬的金属氧化物。
以上脱氯剂虽能对氯化氢起到一定的吸附脱除效果，但制备原料均需外购，成本较高、配制过程较为复杂。
钢渣是钢铁冶炼过程中产生的大量固态废弃物，据统计，每生产一吨粗钢，钢渣产量约占12～15％，我国钢渣产量呈逐年增加态势，到2018年我国粗钢累计产量达到8.56亿吨，钢渣排放比例为12-15％，钢渣排放量在1.03亿吨以上，但其利用率仅20％左右，主要用于水泥及道路建设，但由于其中的不稳定相f-CaO在后期的体积膨胀对其在建材方面应用也带来一定风险。剩余80％左右钢渣只能露天堆存，大量占用土地资源并存在钢渣中重金属向环境中迁移的风险。
发明内容
为了克服上述问题，本发明提供了一种成本低廉、机械及化学性能优良、充分利用废弃钢渣制备煤气脱氯除湿剂及其使用的方法，解决现有脱氯剂制备原料成本高、原料无法就地取材、钢渣固废无法实现资源化利用的问题。
为实现上述技术目的，本发明采用的技术方案如下：
一种高炉煤气脱氯除湿剂的制备方法，包括：
将钢渣破碎研磨成粉末，然后水化处理，固液分离后，将固相干燥，并研磨粉化；
将粉化后的固相与粘结剂混合均匀，造粒，即得。
本发明所用钢渣富含的CaO、MgO、SiO2、Al2O3等本身是优良的碱性吸附干燥剂，对氯化氢和水有很好的吸附效果，同时吸附氯化氢后的化学反应产物CaCl2等金属氯化物亦是一种优良的吸湿剂。
研究发现：本发明所用钢渣具有发达的孔隙结构，在微观视角下显示为蜂窝状多孔结构，具有良好的吸附效果。利用其表面积很大的多孔物质，在表面吸附氯化氢和毛细管凝结作用下吸收煤气水分。
在一些实施例中，所述粉末的粒径在150μm以下。本发明所用脱氯剂制备原料钢渣来自钢铁厂高炉渣、转炉渣、平炉渣或电炉渣，其主要成分及含量为全铁(15％～25％)、CaO(40％～50％)、SiO2(10％～16％)、MgO(5％～10％)、Al2O3(1％～5％)、MnO(1％～4％)、TiO2(0～1％)、Na2O(0～0.3％)、K2O(0～0.1％)，另外还含有少量Zn、Pb、Cr、Ni、Cu、S、P等。
在一些实施例中，所述水化处理的条件为在常温下处理1～2h。本发明所用钢渣制备脱氯除湿剂过程中需经过水化处理，水化过程中部分CaO溶于水生成Ca(OH)2溶液，对脱氯剂表面产生浸渍作用，同时亦可向悬浊液中投加NaOH或KOH等碱类，增强其对氯化氢吸附性能。
在一些实施例中，所述干燥的温度为105～120℃，将干燥后的固相制成粉末便于后续造粒。
本申请对粘结剂的具体来源并不作特殊的限定，在一些实施例中，所述粘结剂为膨润土或硅藻土，粘结剂的加入量为4～8wt％，以提高造粒效率和颗粒的强度。
本发明还提供了任一上述的方法制备的高炉煤气脱氯除湿剂。本发明所用钢渣经过研磨、水化、焙烧、脱氯后其中的不稳定相f-CaO转化为Ca(OH)2，吸附煤气中HCl和CO2后转化为CaCO3和CaCl2稳定相，降低其后期体积膨胀风险，吸湿膨胀容小于5％，同时具有良好的机械强度，径向抗压碎强度可达50～80N/cm，使用后可作为建材行业原材料实现资源化利用。
本发明还提供了一种高炉煤气脱氯除湿剂，包括：活性组分，所述活性组分为碱及碱金属或碱土金属氧化物，所述活性组分含量占60～85wt％。本发明所用钢渣制备的脱氯除湿剂主要成分为钙基碱性脱氯除湿剂，对煤气中CO2也有一定的吸附效果，可减少煤气中不可燃气体组分含量，提升净煤气热值。
在一些实施例中，所述碱及碱金属或碱土金属氧化物包括：Ca(OH)2、CaO、SiO2、MgO、Al2O3、MnO。
本发明还提供了一种高炉煤气脱氯除湿系统，包括：高炉、重力除尘装置、布袋除尘器、TRT余压发电装置、发电机、水洗塔、脱氯除湿固定床、高炉煤气柜，所述高炉、重力除尘装置、布袋除尘器、水洗塔、脱氯除湿固定床、高炉煤气柜依次相连，所述布袋除尘器、水洗塔还设置有TRT余压发电装置，所述TRT余压发电装置与发电机相连。
本发明使用的关键在于：
(1)所用原料主要为钢渣及一定的粘结剂；
(2)钢渣磨粉后需经过水化处理方可进行造粒，避免后续床料出现吸湿膨胀，确保填料吸湿膨胀容小于5％；
(3)本发明脱氯除湿剂用于高炉干法除尘TRT余压利用之后，使用压力20～40kPa，使用温度50～100℃；
(4)介质煤气需具有一定的含湿量，保证HCl和吸附剂活性组分之间的酸碱中和吸附反应；
(5)煤气通过固定床填料空速在1000～2000h-1；
(6)床层失效条件为固定床后尾气HCl浓度大于1ppm。
本发明的有益效果在于：
(1)就地取材及固废利用，原料成本更低，且因煤气质量提高及钢渣资源化利用带来额外经济附加值。
(2)制备工艺简单。
(3)脱氯除湿效率高，净化后煤气HCl浓度小于1ppm，含水量小于环境温度下煤气饱和含水量。
(4)本申请的操作方法简单、成本低、具有普适性，易于规模化生产。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。
图1为脱氯除湿剂使用工艺流程示意图。图中1为高炉、2为重力除尘装置、3为布袋除尘器、4为减压阀组、5为TRT余压发电装置、6为发电机、7为水洗塔旁路阀、8为水洗塔进口阀、9为水洗塔、10为脱氯除湿固定床、11为高炉煤气柜。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本申请使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
正如背景技术所介绍的，针对高炉煤气脱氯剂成本高、配制过程复杂，以及钢渣废弃物利用困难，环境危害大的问题。因此，本发明提出一种高炉煤气脱氯除湿剂，其活性组分为Ca(OH)2、CaO、SiO2、MgO、Al2O3、MnO等碱及碱金属或碱土金属氧化物，上述活性组分含量占60～85wt％。
优选的，制备原料来自钢厂冶炼过程废弃钢渣，其来源为钢铁厂高炉渣、转炉渣、平炉渣或电炉渣。其特征是孔隙结构发达、机械强度高，选用原料粒径为1～20mm。
优选的，制备过程先将钢渣破碎研磨成150μm以下粒径粉末后加入常温去离子水进行水化处理，处理时间1～2h，破碎研磨工具为球磨机或其他制粉设备。固液分离后对固相在105～120℃下烘干至恒重，并研磨粉化。混入烘干后固相5wt％的粘结剂混合均匀，粘结剂为膨润土或硅藻土。
优选的，将所述混合均匀的粉末通过圆盘造粒机喷水雾化造粒，制得粒径0.5～2mm的颗粒在300～500℃下焙烧1～2h获得成品脱氯除湿剂。
优选的，所述成品脱氯剂径向抗压碎强度为50～80N/cm。
优选的，用于高炉干法除尘TRT余压利用之后，作为固定床填料使用。
优选的，所净化煤气为含湿量为所处温度下饱和或接近饱和状态时的含湿量，或经喷水洗涤后含有一定机械水的过饱和煤气。
优选的，在固定床中被HCl穿透失效后f-CaO转化为稳定相，返回渣场进行后续资源化利用。
下面结合具体的实施例，对本发明做进一步的详细说明，应该指出，所述具体实施例是对本发明的解释而不是限定。
实施例1：
结合图1给出本发明的最佳实施方式。
从钢铁厂堆渣场取粒径1～20mm的钢渣原料，用球磨机磨粉过100目筛，将筛下的钢渣粉末放置于专用容器中，不断加入常温去离子水直至浸没，静待2h。选用30～50μm滤纸用真空抽滤机对固液混合物进行抽滤，抽滤后的固相物质放入110℃烘箱中烘至恒重，从烘箱取出后将结块的固态粉末研磨成粉，并加入其重量5％的膨润土混合均匀。混合均匀的固体粉末放入圆盘造粒机，通过不断喷入雾化水进行造粒，筛选粒径0.5～2mm的颗粒放入加热炉焙烧1h，加热炉温度设定450℃，焙烧完冷却至室温得到脱氯除湿剂成品作为脱氯除湿固定床填料。
高炉冶炼产生的煤气自炉顶排出后经过重力除尘和布袋除尘两级干法除进入TRT余压发电装置。干法除尘煤气含水量约30～60g/Nm3。进入TRT煤气温度约120～160℃，压力约200～240kPa，经TRT余压利用后温度降至50～100℃，压力降至20～30kPa，此时尚未达到煤气露点温度或即将达到露点温度，HCl尚未冷凝析出，此时，通过开启阀门7，关闭阀门8，含有HCl、含湿量接近饱和的高炉煤气进入装有脱氯除湿剂的固定床，煤气温度继续降低，在固定床层中煤气温度降至露点温度以下，HCl具有极易溶于水的特性，冷凝形成的液态盐酸酸雾与脱氯除湿剂表面的活性组分反应被吸附脱除。洁净干燥的净煤气进入下游管道、设备及用户。此法为直接吸附净化法，原煤气中HCl仅靠脱氯除湿剂吸收，通过HCl、水分在线检测分析仪对固定床前后煤气HCl浓度和含水量进行实时监测。由于原煤气HCl浓度较高，在空速1500h-1时，脱氯除湿剂穿透时间相对较短约5～7小时，填料更换周期较短。
当环境温度较高时，TRT出口煤气温度远高于煤气露点温度，进入固定床的煤气远未达到饱和，HCl不会冷凝形成盐酸，影响填料表面酸碱离子中和反应，脱氯除湿效果将大大减弱，此时关闭阀门7，打开阀门8，使高炉煤气先经过9水洗塔洗涤降温，形成含有一定机械水饱和气体进入固定床进行脱氯除湿，得到干燥洁净的煤气。此法需先经过水洗降温过程，过程中约60～80％的HCl气体被水洗进入浆液，剩余约20～40％的HCl进入固定床被吸附脱除，通过HCl、水分在线检测分析仪对固定床前后煤气HCl浓度和含水量进行实时监测。在空速1500h-1时，脱氯除湿剂穿透时间可达16～18小时，填料更换周期较长。
穿透失效的脱氯除湿剂返回渣场，作为建材行业原材料进行后续资源化利用。
实施例2
该钢渣脱氯除湿剂制备及使用方法如下：
(1)将钢渣用钢球磨或其他制粉设备研磨过100目筛；
(2)取筛下物做水化处理，不断向筛下物中加入常温去离子水，直至将钢渣浸没，静待1.5h；
(3)应用真空抽滤机对钢渣粉悬浊液进行抽滤实现固液分离；
(4)取固相在110℃下烘干至恒重，并研磨避免结块；
(5)在烘干后的钢渣粉末中加入5wt％的膨润土并混合均匀，利用圆盘造粒机并通过雾化喷水将钢渣粉末和膨润土混合物滚球成型，筛选粒径在0.5～2mm的颗粒；
(6)将筛选出的颗粒在400℃下焙烧1.5h得到脱氯除湿剂成品。
(7)将制得的脱氯除湿剂作为填料装入特定的固定床反应器，床层高径比为3:1，空速1500h-1，将未脱除氯化氢气体的高炉煤气通过该固定床反应器，通过HCl、水分在线检测分析仪对固定床前后煤气HCl浓度和含水量进行实时监测。判断床层被穿透失效的依据为固定床后尾气HCl浓度大于1ppm，床层穿透时床料吸附的HCl量即为穿透氯容量。
实施例3
该钢渣脱氯除湿剂制备及使用方法如下：
(1)将钢渣用钢球磨或其他制粉设备研磨过100目筛；
(2)取筛下物做水化处理，不断向筛下物中加入常温去离子水，直至将钢渣浸没，静待1h；
(3)应用真空抽滤机对钢渣粉悬浊液进行抽滤实现固液分离；
(4)取固相在105℃下烘干至恒重，并研磨避免结块；
(5)在烘干后的钢渣粉末中加入5wt％的膨润土并混合均匀，利用圆盘造粒机并通过雾化喷水将钢渣粉末和膨润土混合物滚球成型，筛选粒径在0.5～2mm的颗粒；
(6)将筛选出的颗粒在300℃下焙烧2h得到脱氯除湿剂成品。
(7)将制得的脱氯除湿剂作为填料装入特定的固定床反应器，床层高径比为3:1，空速1500h-1，将未脱除氯化氢气体的高炉煤气通过该固定床反应器，通过HCl、水分在线检测分析仪对固定床前后煤气HCl浓度和含水量进行实时监测。判断床层被穿透失效的依据为尾气HCl浓度大于1ppm，床层穿透时床料吸附的HCl量即为穿透氯容量。
实施例4
该钢渣脱氯除湿剂制备及使用方法如下：
(1)将钢渣用钢球磨或其他制粉设备研磨过100目筛；
(2)取筛下物做水化处理，不断向筛下物中加入常温去离子水，直至将钢渣浸没，静待2h；
(3)应用真空抽滤机对钢渣粉悬浊液进行抽滤实现固液分离；
(4)取固相在120℃下烘干至恒重，并研磨避免结块；
(5)在烘干后的钢渣粉末中加入5wt％的膨润土并混合均匀，利用圆盘造粒机并通过雾化喷水将钢渣粉末和膨润土混合物滚球成型，筛选粒径在0.5～2mm的颗粒；
(6)将筛选出的颗粒在500℃下焙烧1h得到脱氯除湿剂成品。
(7)将制得的脱氯除湿剂作为填料装入特定的固定床反应器，床层高径比为3:1，空速1500h-1，将未脱除氯化氢气体的高炉煤气通过该固定床反应器，通过HCl、水分在线检测分析仪对固定床前后煤气HCl浓度和含水量进行实时监测。判断床层被穿透失效的依据为尾气HCl浓度大于1ppm，床层穿透时床料吸附的HCl量即为穿透氯容量。
最后应该说明的是，以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。上述虽然结合附图对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
Claims (10)
1.一种高炉煤气脱氯除湿剂的制备方法，其特征在于，包括：
将钢渣破碎研磨成粉末，然后水化处理，固液分离后，将固相干燥，并研磨粉化；
将粉化后的固相与粘结剂混合均匀，造粒，即得。
2.如权利要求1所述的高炉煤气脱氯除湿剂的制备方法，其特征在于，所述粉末的粒径在150μm以下。
3.如权利要求1所述的高炉煤气脱氯除湿剂的制备方法，其特征在于，所述水化处理的条件为在常温下处理1～2h。
4.如权利要求1所述的高炉煤气脱氯除湿剂的制备方法，其特征在于，所述干燥的温度为105～120℃。
5.如权利要求1所述的高炉煤气脱氯除湿剂的制备方法，其特征在于，所述粘结剂的加入量为4～8wt％；
或所述粘结剂为膨润土或硅藻土。
6.权利要求1-5任一项所述的方法制备的高炉煤气脱氯除湿剂。
7.一种高炉煤气脱氯除湿剂，其特征在于，包括：活性组分，所述活性组分为碱及碱金属或碱土金属氧化物，所述活性组分含量占60～85wt％。
8.如权利要求7所述的高炉煤气脱氯除湿剂，其特征在于，所述碱及碱金属或碱土金属氧化物包括：Ca(OH)2、CaO、SiO2、MgO、Al2O3、MnO。
9.如权利要求7所述的高炉煤气脱氯除湿剂，其特征在于，煤气净化后HCl浓度小于1ppm，含水量小于环境温度下煤气饱和含水量。
10.一种高炉煤气脱氯除湿系统，其特征在于，包括：高炉、重力除尘装置、布袋除尘器、TRT余压发电装置、发电机、水洗塔、脱氯除湿固定床、高炉煤气柜，所述高炉、重力除尘装置、布袋除尘器、水洗塔、脱氯除湿固定床、高炉煤气柜依次相连，所述布袋除尘器、水洗塔还设置有TRT余压发电装置，所述TRT余压发电装置与发电机相连。
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| CN114392643B (zh) * | 2021-12-30 | 2022-09-23 | 北京北科环境工程有限公司 | 一种高炉煤气用脱氯剂的制备方法 |
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