不锈钢酸洗废混酸流化床焙烧再生特性的实验研究

doi:10.11949/0438-1157.20211775

摘要/Abstract

摘要：

废酸流化床法再生技术可高效回收酸和金属离子，具有广阔的应用前景。利用自行搭建的流化床热态实验装置，并结合SEM、离子色谱和XPS等表征手段研究了密相区温度、初始床料粒径对废混酸（HNO₃+HF）中酸与金属离子再生回收特性的影响规律。结果表明：流化床法可有效实现废混酸中酸和金属元素再生回收，金属氧化物在床料表面附着量随流化床密相区温度的升高而增加，850℃时达到峰值，继续升温后附着量小幅降低，同时增大床料初始粒径，金属氧化物在床料表面附着量将大幅提高；NO _x 、HF生成量随流化床密相区温度的升高而增加，750℃时达到峰值，继续升温后大幅回落，同时随着床料初始粒径增大，NO _x 生成量将小幅降低，而HF生成量峰值对应的密相区温度变化到800℃。

关键词: 废混酸, 再生, 流化床, 焙烧, 不锈钢酸洗

Abstract:

The waste acid fluidized bed regeneration technology can efficiently recover acid and metal ions, and has a broad application prospect. The effect of temperature in the dense phase zone and initial bed size on the regeneration and recovery characteristics of acid and metal ions in waste mixed acid (HNO₃+HF) was investigated by using a self-built fluidized bed thermal state experimental setup and combining SEM, ion chromatography and XPS characterization methods. The results show that the fluidized bed method can effectively achieve the regenerative recovery of acid and metal elements in waste mixed acid, and the amount of metal oxide adhered to the surface of the bed material increases with the increase in temperature of the fluidized bed dense phase zone, reaching a peak at 850℃. The amount of adherence decreases slightly as the temperature continues to rise. By increasing the initial particle size of the bed material, the amount of metal oxide adhered to the surface of the bed material will be significantly increased. The amount of NO _x and HF generation increases with the increase of temperature in the dense phase zone of the fluidized bed, reaching a peak at 750℃, and then decreases significantly after continuing to increase the temperature, while the amount of NO _x generation will decrease slightly as the initial particle size of the bed material increases, and the temperature in the dense phase zone corresponding to the peak of HF generation is delayed to 800℃.

Key words: waste mixed acid, regeneration, fluidized bed, roasting, stainless steel pickling

中图分类号:

TK 09

徐劲松, 林敏, 陈晓平, 马吉亮, 耿鹏飞, 鲍学兵, 刘道银, 梁财. 不锈钢酸洗废混酸流化床焙烧再生特性的实验研究[J]. 化工学报, 2022, 73(5): 2242-2250.

Jinsong XU, Min LIN, Xiaoping CHEN, Jiliang MA, Pengfei GENG, Xuebing BAO, Daoyin LIU, Cai LIANG. Experimental study on regeneration characteristics of stainless steel pickling waste mixed acid by fluidized bed roaster[J]. CIESC Journal, 2022, 73(5): 2242-2250.

图/表 12

图1 废混酸流化床焙烧法再生实验系统示意图1—空气压缩机;2—冷干机;3—制氮机;4—氮气钢瓶;5—氧气钢瓶;6—预热器;7—喷枪;8—废混酸罐;9—电磁泵;10—密相区电加热器;11—料罐;12—流化床反应炉;13—稀相区电加热器;14—电加热带;15—烟气分析仪;16—流量计;17—真空泵;18—去离子水;19—NaOH溶液;20—旋风分离器;21—灰斗;22—冷却器;23—布袋除尘器;24—碱洗装置

Fig.1 Schematic diagram of the experimental system for regeneration of waste mixed acid by fluidized bed method1—air compressor;2—cold dryer;3—nitrogen generator;4—nitrogen cylinder;5—oxygen cylinder;6—preheater;7—spray gun;8—waste mixed acid tank;9—electromagnetic pump;10—electric heater in the dense phase zone;11—canister;12—fluidized bed reactor;13—electric heaters in the thin phase zone;14—electric heating belt;15—flue gas analyser;16—flow meter;17—vacuum pump;18—deionised water;19—NaOH solution;20—cyclone separator;21—grey bucket;22—cooler;23—bag filter;24—alkaline washing unit

表1 废混酸理化特性和成分分析

Table 1 Physicochemical characteristics and composition analysis of waste mixed acid

化学组成/(g/L)

密度/

(g/ml)

F^-

3 -

H⁺

表1 废混酸理化特性和成分分析

Table 1 Physicochemical characteristics and composition analysis of waste mixed acid

化学组成/(g/L)

密度/

(g/ml)

F^-

3 -

H⁺

28.8

55.5

2.66

4.13

3.26

50.75

0.78

0.0436

1.1141

0.68

图2 氧化铁床料粒径分布

Fig.2 Iron oxide bed material particle size distribution

表2 氧化铁床料元素分析

Table 2 Elemental analysis of iron oxide bed material

样品	元素分析/%（质量）
样品	Fe	Al	Cu	Ni	Ca	Zn	Cr	Mn
床料	92.61	3.59	1.06	0.71	0.59	0.50	0.47	0.47

图3 床料表观形貌变化（750℃下5 h后取样分析）

Fig.3 Changes in the apparent morphology of the bed material (analysis of samples taken after 5 h at 750℃)

图4 喷酸5 h床料粒径分布及累积分布

Fig.4 Particle size distribution of bed material for 5 h of acid spraying

图5 喷酸5 h床料颗粒粒径增加量变化

Fig.5 Change in particle size increase of bed material for 5 h of acid spraying

图6 喷酸5 h床料颗粒平均体积增加量变化

Fig.6 Change in the average volume increase of bed material particles for 5 h of acid spraying

图7 床料表面主要金属元素含量占比变化

Fig.7 Changes in the percentage of major metal elements on the surface of the bed material

图8 烟气中NO x 生成量与密相区温度的关系

Fig.8 RelationshipbetweenNO x generation in flue gas and temperature in dense phase zone

图9 烟气中HF生成量与密相区温度的关系

Fig.9 Relationship between HF generation in flue gas and temperature in dense phase zone

图10 0.4 mm初始粒径床料喷酸5 h XRD谱图（850℃）

Fig.10 XRD pattern of 0.4 mm initial particle size bed material sprayed with acid for 5 h (850℃)

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