氧化铁脱硫剂的制备、改性及回收利用研究
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摘要
本课题进行了以钢铁厂炼钢转炉泥为原料制备氧化铁脱硫剂的研究,通过对脱硫剂的改性,提高了脱硫剂脱除硫化氢(H2S)和羰基硫(COS)的效果,脱硫失效后的废脱硫剂可以用来制备氧化铁红。
在氧化铁脱硫剂制备过程中,转炉泥酸浸的最佳实验操作条件是:硫酸浓度为70%,反应时间为2小时,反应温度为120℃,盐酸用量为15 mL/10 g原料(干料),助溶剂用量为10.5 g/10 g原料(干料),最高铁浸出率可达96.20%。制得的普通脱硫剂为黄色的条状颗粒,强度大于50 N/cm,堆密度为0.70~0.80 g/ml,比表面积为100 ~ 120 m2/g,孔隙率为42%,颗粒大小为φ(3~5)×(5~15) mm;在原料气中H2S浓度为50 mg/m3,温度为室温(25℃),压力为常压,空速为1000 h-1,水汽含量为1%以及无氧的条件下,脱硫剂的一次平均有效硫容大于10%。
通过浸渍碳酸盐活性组分对脱硫剂进行改性,提高了脱硫剂的脱硫能力。结果表明,改性后的脱硫剂在室温(10～30℃),常压,空速为1000 h-1,原料气中水汽含量1%以及无氧的条件下,COS硫容达到3%,对硫化氢的脱除能力也有一定程度的提高;改性后脱硫剂的FT-IR分析表明,COS在脱除过程中被氧化生成硫酸盐,逐渐毒化了催化剂表面起催化水解作用的碱性羟基活性中心,这是造成脱硫剂失活的直接原因。
废脱硫剂的后续处理工艺简单,利用废脱硫剂铁含量高的特点来制备氧化铁红,所得氧化铁红产品纯度>99%。
In this thesis, the iron oxide desulfurizer was prepared from converter steel-making mud, and it had a greater capacity of removing hydrogen sulfide (H2S) and carbonly sulfide(COS) from coking gas by modification. After the desulfurizer becomes invalid, it could be prepared into iron oxide red.
In the process of desulfurizer preparation, the optimal operational conditions were: sulfur acid concentration 70%, reaction time 2 h, temperature 120℃, the dosage of hydrochloric acid 15 mL/10 g material(dry) and the dosage of assistant-solution agent 10.5 g/10 g material(dry). The highest iron extraction yield was 96.20%. The unmodified desulfurizer particles were yellow slender cylindrical, and they were characterized: strength greater than 50 N/cm, bulk density 0.70~0.80 g/ml, specific surface area 100~120 m2/g, porosity 42% and the size of the desulfurizer particleφ(3~5)×(5~15) mm. Under the conditions: H2S concentration in the feed gas 50 mg/m3, room temperature(25℃), 1 atm, space velocity 1000 h-1, moisture content 1% and oxygen free, the average effective sulfur capacity of the desulfurizer per one time was more than 10%.
In order to improve the capacity of sulphurization from coking gas, the iron oxide desulfurizer was modified by immerging carbonate. Results showed that, under the conditions: H2S concentration in the feed gas 50 mg/m3, room temperature(10～30℃) , normal atmospheric pressure, space velocity 1000 h-1, moisture content 1% and oxygen free, the modified desulfurizer’s capacity on COS was 3%, and that the desulfurizer could also remove more H2S. The alkaline hydroxy group on the active center surface could catalyze and hydrolyze COS into hydrogen sulfide, but FT-IR of modified desulfurizer showed that it was poisoned by sulfate which was oxided in the process of removing, and then it lose activity completely.
The inactive desulfurizer could be recycled and prepared into iron oxide red. The technology was simple, and the purity of iron oxide red exceeded 99%.
在氧化铁脱硫剂制备过程中,转炉泥酸浸的最佳实验操作条件是:硫酸浓度为70%,反应时间为2小时,反应温度为120℃,盐酸用量为15 mL/10 g原料(干料),助溶剂用量为10.5 g/10 g原料(干料),最高铁浸出率可达96.20%。制得的普通脱硫剂为黄色的条状颗粒,强度大于50 N/cm,堆密度为0.70~0.80 g/ml,比表面积为100 ~ 120 m2/g,孔隙率为42%,颗粒大小为φ(3~5)×(5~15) mm;在原料气中H2S浓度为50 mg/m3,温度为室温(25℃),压力为常压,空速为1000 h-1,水汽含量为1%以及无氧的条件下,脱硫剂的一次平均有效硫容大于10%。
通过浸渍碳酸盐活性组分对脱硫剂进行改性,提高了脱硫剂的脱硫能力。结果表明,改性后的脱硫剂在室温(10～30℃),常压,空速为1000 h-1,原料气中水汽含量1%以及无氧的条件下,COS硫容达到3%,对硫化氢的脱除能力也有一定程度的提高;改性后脱硫剂的FT-IR分析表明,COS在脱除过程中被氧化生成硫酸盐,逐渐毒化了催化剂表面起催化水解作用的碱性羟基活性中心,这是造成脱硫剂失活的直接原因。
废脱硫剂的后续处理工艺简单,利用废脱硫剂铁含量高的特点来制备氧化铁红,所得氧化铁红产品纯度>99%。
In this thesis, the iron oxide desulfurizer was prepared from converter steel-making mud, and it had a greater capacity of removing hydrogen sulfide (H2S) and carbonly sulfide(COS) from coking gas by modification. After the desulfurizer becomes invalid, it could be prepared into iron oxide red.
In the process of desulfurizer preparation, the optimal operational conditions were: sulfur acid concentration 70%, reaction time 2 h, temperature 120℃, the dosage of hydrochloric acid 15 mL/10 g material(dry) and the dosage of assistant-solution agent 10.5 g/10 g material(dry). The highest iron extraction yield was 96.20%. The unmodified desulfurizer particles were yellow slender cylindrical, and they were characterized: strength greater than 50 N/cm, bulk density 0.70~0.80 g/ml, specific surface area 100~120 m2/g, porosity 42% and the size of the desulfurizer particleφ(3~5)×(5~15) mm. Under the conditions: H2S concentration in the feed gas 50 mg/m3, room temperature(25℃), 1 atm, space velocity 1000 h-1, moisture content 1% and oxygen free, the average effective sulfur capacity of the desulfurizer per one time was more than 10%.
In order to improve the capacity of sulphurization from coking gas, the iron oxide desulfurizer was modified by immerging carbonate. Results showed that, under the conditions: H2S concentration in the feed gas 50 mg/m3, room temperature(10～30℃) , normal atmospheric pressure, space velocity 1000 h-1, moisture content 1% and oxygen free, the modified desulfurizer’s capacity on COS was 3%, and that the desulfurizer could also remove more H2S. The alkaline hydroxy group on the active center surface could catalyze and hydrolyze COS into hydrogen sulfide, but FT-IR of modified desulfurizer showed that it was poisoned by sulfate which was oxided in the process of removing, and then it lose activity completely.
The inactive desulfurizer could be recycled and prepared into iron oxide red. The technology was simple, and the purity of iron oxide red exceeded 99%.
引文
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