利用钢厂赤泥和碱厂白泥研制燃气（H_2S）脱硫剂
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摘要
本课题研究了利用钢厂赤泥和碱厂白泥复合制备脱硫剂脱除燃气中的H2S。该脱硫剂净化效率高,制备工艺简单,能耗少,而且再生方法简单易行,具有一定的研究发展潜力。
H2S是一种有害物质,不仅对输运管路、设备等造成腐蚀,影响后续加工(如导致催化剂中毒),而且会严重威胁人身安全,属必须控制的污染源之一。
将赤泥和白泥烘干粉碎筛分,添加少量助剂,制成具有一定机械强度的成型脱硫剂,在固定床反应装置上进行燃气脱硫活性评价。通过考察赤泥与白泥配比,助剂用量和制备方式等因素对脱硫剂脱硫性能的影响,进一步改进脱硫剂制备工艺,提高硫容；通过XRD表征对脱硫剂成分进行验证,从而深入研究脱硫机理。
对原料成分含量分析结果：所用青岛钢厂赤泥含铁氧化物总量66.57%,并含部分CaCO3、MgO等碱性物质；青岛碱厂白泥含CaCO353.21％。
以赤泥白泥为原料,筛选添加剂,并优化各制备工艺参数,制得性能最佳的脱硫剂,制备的最佳配方为：主原料含量占90%,助剂含量共占10%。主原料的最佳配比为赤泥：白泥=2：1(wt%),即赤泥60%,白泥30%。主原料粉碎越细越好。助剂分别为粘结剂——Na；造孔剂——Za；润滑剂——R。按照上述优选的脱硫剂成分和含量添加适量水混匀,采用挤条机挤条成型,直径Φ3mm,长度为2～5cm。烘箱110℃6h烘干；马弗炉中焙烧温度600℃,焙烧时间在6h时脱硫效果最好。
考察了最佳脱硫剂的脱硫反应条件,结果表明：脱硫剂在中低温度下反应效果好,50～70℃温度范围内,脱硫效果很好；反应温度过高或过低都会对反应造成影响；空速对脱硫效果影响也很大,400～1200h-1空速范围内,脱硫剂在越小空速下反应脱硫效果越好；模拟燃气中含水量对脱硫效果的影响也较大,含水量过多过少均对脱硫效果不利,最佳含水量为7.28%；燃气中含O2量对脱硫效果也有较大影响,在工业燃气O2含量限度内越多,O2量越多,脱硫效果越好,当O2含量为2%时达到最大值。最佳工艺条件：反应温度：50℃,H2O含量：7.28%,O2含量：2%,400h-1时,穿透硫容可以达到25.3%。
XRD表征表明,制备脱硫剂时,600℃高温焙烧使得原料中FeO、Fe3O4向活性Fe2O3转变；在30～110℃温度范围内,反应温度越低,越有利于的脱硫反应进行。
本文利用钢厂赤泥和碱厂白泥联合烟气脱硫脱除燃气中H2S,实验证实脱硫效果很好。本课题“以废治废”,使经济与环保共赢,在我国具有非常现实的意义。
In this study, the desulfurizer prepared by red mud from Steel Plant and white mud from Soda Plant were conductded to purify the fuel gas contained hydrogen sulfide.The desulferization process was featured with high purification efficiency,simple preparation mehthod and low energy consumption,easy to regenerate.Also,the available adsorbents were suited to control H2S pollution.
H2S is a harmful impurity in the fuel gas.It can not only cause the pipeline and equipment to be corroded so as to influence the follow up processing(as leading to catalyst poisoning) but also seriously threaten the personal safety,belonging to one of the environmental pollution sources which must be controlled.
The preparation for a flue gas desulfurizer with red mud from Steel Plant and white mud from Soda Plant. Drying, crushing and sieving the red mud and white mud, joining a few body aids, to prepare molding desulfurizer which is strong, then Flue Gas Desulfurizion activity tests are carried out in fixed bed reactor. In order to improve the preparation technics of desulfurizer and H2S capacity, the ratio of red mud and white mud, body aids content and preparation methods et al are reviewed. XRD is studied to review desulfurizer components and thereby the desulfurizion mechanism is studied thoroughly.
The components and content of raw materials are analyzed:The red mud from Qingdao Steel Plant contains iron-oxide 66.57% in all, some CaCO3 and MgO as well;The white mud from Qingdao Soda Plant contains CaCO3 53.21%.
The main component of the adsorbents were red mud and white mud. the feasible content that main materials are 90% and the body aids are 10% is ascertained. The best ratio of main materials is red mud:white mud=2:1(wt%), that is to say, red mud 60%,white mud 30%.The main materials are the finer the better. The best components of body aids are binders, pore-making agents, lube. According to the above chosen desulfurizer components and content, desulfurizer is made intoφ3mm and 2-5cm in length after mixing well-proportioned in water and crushing it strip-shaped in extrusion press. The desulfurizer which dried at 110℃for 6h,then calcined at 600℃in muffle 6h, has best desulfurizion effect.
The optimal reaction conditions of desulfurizer were reviewed.Those show:the desulfurizer must react in a low temperature, the desulfurizion effect is very good in 50～70℃.The space velocity has a great effect on desulfurizion, the less the greater in 400～1200 h-1. The H2O content in fule gas also has a great influence on desulfurizion, the best content is7.28%, more or less is not well. The O2 content in fule gas has a great effect on desulfurizion too, according to the O2 Content in the fuel gas,the more the better, until 2% in best. The optimal conditions of H2S removal were desulfurization temperature:50℃, H2O content:7.28%, O2 content:2%, when space velocity is 400h-1, the sulfur capacity of the best desulfurizer reaction could get to 25.3%.
The aim of this paper is to purify the fuel gas contained hydrogen sulfide with red mud from Steel Plant, and white mud from Soda Plant, and the good effect is conformed. This task "treat waste by waste", makes the economy and environmental protection win-win. It has a very practical significance in China.
H2S是一种有害物质,不仅对输运管路、设备等造成腐蚀,影响后续加工(如导致催化剂中毒),而且会严重威胁人身安全,属必须控制的污染源之一。
将赤泥和白泥烘干粉碎筛分,添加少量助剂,制成具有一定机械强度的成型脱硫剂,在固定床反应装置上进行燃气脱硫活性评价。通过考察赤泥与白泥配比,助剂用量和制备方式等因素对脱硫剂脱硫性能的影响,进一步改进脱硫剂制备工艺,提高硫容；通过XRD表征对脱硫剂成分进行验证,从而深入研究脱硫机理。
对原料成分含量分析结果：所用青岛钢厂赤泥含铁氧化物总量66.57%,并含部分CaCO3、MgO等碱性物质；青岛碱厂白泥含CaCO353.21％。
以赤泥白泥为原料,筛选添加剂,并优化各制备工艺参数,制得性能最佳的脱硫剂,制备的最佳配方为：主原料含量占90%,助剂含量共占10%。主原料的最佳配比为赤泥：白泥=2：1(wt%),即赤泥60%,白泥30%。主原料粉碎越细越好。助剂分别为粘结剂——Na；造孔剂——Za；润滑剂——R。按照上述优选的脱硫剂成分和含量添加适量水混匀,采用挤条机挤条成型,直径Φ3mm,长度为2～5cm。烘箱110℃6h烘干；马弗炉中焙烧温度600℃,焙烧时间在6h时脱硫效果最好。
考察了最佳脱硫剂的脱硫反应条件,结果表明：脱硫剂在中低温度下反应效果好,50～70℃温度范围内,脱硫效果很好；反应温度过高或过低都会对反应造成影响；空速对脱硫效果影响也很大,400～1200h-1空速范围内,脱硫剂在越小空速下反应脱硫效果越好；模拟燃气中含水量对脱硫效果的影响也较大,含水量过多过少均对脱硫效果不利,最佳含水量为7.28%；燃气中含O2量对脱硫效果也有较大影响,在工业燃气O2含量限度内越多,O2量越多,脱硫效果越好,当O2含量为2%时达到最大值。最佳工艺条件：反应温度：50℃,H2O含量：7.28%,O2含量：2%,400h-1时,穿透硫容可以达到25.3%。
XRD表征表明,制备脱硫剂时,600℃高温焙烧使得原料中FeO、Fe3O4向活性Fe2O3转变；在30～110℃温度范围内,反应温度越低,越有利于的脱硫反应进行。
本文利用钢厂赤泥和碱厂白泥联合烟气脱硫脱除燃气中H2S,实验证实脱硫效果很好。本课题“以废治废”,使经济与环保共赢,在我国具有非常现实的意义。
In this study, the desulfurizer prepared by red mud from Steel Plant and white mud from Soda Plant were conductded to purify the fuel gas contained hydrogen sulfide.The desulferization process was featured with high purification efficiency,simple preparation mehthod and low energy consumption,easy to regenerate.Also,the available adsorbents were suited to control H2S pollution.
H2S is a harmful impurity in the fuel gas.It can not only cause the pipeline and equipment to be corroded so as to influence the follow up processing(as leading to catalyst poisoning) but also seriously threaten the personal safety,belonging to one of the environmental pollution sources which must be controlled.
The preparation for a flue gas desulfurizer with red mud from Steel Plant and white mud from Soda Plant. Drying, crushing and sieving the red mud and white mud, joining a few body aids, to prepare molding desulfurizer which is strong, then Flue Gas Desulfurizion activity tests are carried out in fixed bed reactor. In order to improve the preparation technics of desulfurizer and H2S capacity, the ratio of red mud and white mud, body aids content and preparation methods et al are reviewed. XRD is studied to review desulfurizer components and thereby the desulfurizion mechanism is studied thoroughly.
The components and content of raw materials are analyzed:The red mud from Qingdao Steel Plant contains iron-oxide 66.57% in all, some CaCO3 and MgO as well;The white mud from Qingdao Soda Plant contains CaCO3 53.21%.
The main component of the adsorbents were red mud and white mud. the feasible content that main materials are 90% and the body aids are 10% is ascertained. The best ratio of main materials is red mud:white mud=2:1(wt%), that is to say, red mud 60%,white mud 30%.The main materials are the finer the better. The best components of body aids are binders, pore-making agents, lube. According to the above chosen desulfurizer components and content, desulfurizer is made intoφ3mm and 2-5cm in length after mixing well-proportioned in water and crushing it strip-shaped in extrusion press. The desulfurizer which dried at 110℃for 6h,then calcined at 600℃in muffle 6h, has best desulfurizion effect.
The optimal reaction conditions of desulfurizer were reviewed.Those show:the desulfurizer must react in a low temperature, the desulfurizion effect is very good in 50～70℃.The space velocity has a great effect on desulfurizion, the less the greater in 400～1200 h-1. The H2O content in fule gas also has a great influence on desulfurizion, the best content is7.28%, more or less is not well. The O2 content in fule gas has a great effect on desulfurizion too, according to the O2 Content in the fuel gas,the more the better, until 2% in best. The optimal conditions of H2S removal were desulfurization temperature:50℃, H2O content:7.28%, O2 content:2%, when space velocity is 400h-1, the sulfur capacity of the best desulfurizer reaction could get to 25.3%.
The aim of this paper is to purify the fuel gas contained hydrogen sulfide with red mud from Steel Plant, and white mud from Soda Plant, and the good effect is conformed. This task "treat waste by waste", makes the economy and environmental protection win-win. It has a very practical significance in China.
引文
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