罐底油泥热解产物高附加值利用途径

High value-added utilization approach of pyrolysis products generated by tank bottom oily sludge

为探讨罐底油泥热解产物的高附加值利用途径,利用GC-MS、XRF、XRD、SEM-EDS等方法对罐底油泥热解产物进行了详细的性能分析。在此基础上,选择3种典型阴离子Cr(Ⅵ)、PO4^(3-)和F−和3种典型阳离子Cd^(2+)、Pb^(2+)和Cu^(2+)进行了吸附去除实验。结果表明:罐底油泥热解得到的油品,其烷烃化合物含量高达50.91%,碳数主要分布在(n-C12)~(n-C30),与矿物浮选药剂制备原料的性能类似;热解得到的残渣具有疏松多孔的结构,其结构骨架由元素C、S、Fe、Ca、Al、Si、O等共同构成,且以FeS、Fe_(1−x)S、Fe_(7)S_(8)、CaS、CaAl_(2)Si_(2)O_(8)晶体矿物及非晶态物相形式镶嵌在其中,在水中可起到还原剂、硫化物沉淀剂和钙盐沉淀剂的作用;热解渣对水中阴、阳离子均有很高的去除率,在热解渣用量分别为3、10、12、1、0.8和0.8 g·L^(−1)时,Cr(Ⅵ)、PO4^(3-)、F^(−)、Cd^(2+)、Pb^(2+)和Cu^(2+)去除率分别达到99.6%、98.9%、96.8%、99.3%、98.9%和99.4%。XRD分析结果表明,上述污染离子的去除是通过在热解渣表面生成FeCr_(2)O_(4)、Ca_(3)(PO_(4))_(2)、CaF_(2)、CdS、Cd(OH)_(2)、CdAl_(2)Si_(2)O_(8)、PbS、Pb(OH)_(2)、PbAl_(2)Si_(2)O_(8)、CuS、Cu(OH)_(2)、CuAl_(2)Si_(2)O_(8)沉淀而实现的。本实验结果可为罐底油泥热解产物尤其热解渣的高附加值利用途径提供参考。

In order to discuss the high value-added utilization approach of the pyrolysis products,generated by tank bottom oily sludge,the properties of pyrolysis products were carefully analyzed by GC-MS,XRF,XRD and SEM-EDS techniques.On this basis,the adsorption removal experiments of three typical anions Cr(Ⅵ),PO4^(3-)and F(−)and three typical cations Cd^(2+),Pb^(2+)and Cu^(2+)were carried out.The results showed the alkane content of the oils received by pyrolysis of tank bottom oily sludge was as high as 50.91%,and the carbon number was mainly distributed between n-C12 and n-C30,which was similar to the carbon number of the raw material for the preparation of mineral flotation agent.The structural framework of the pyrolysis residue with a loose porous structure was composed of elements C,S,Fe,Ca,Al,Si,O,etc.,and the crystal minerals such as FeS,Fe_(1−x)S,Fe_(7)S_(8),CaS,CaAl_(2)Si_(2)O_(8)and the amorphous phase forms were embedded in it.And the pyrolysis residue in water could act as reducing agent,sulfide precipitator and calcium salt precipitator.It was found that pyrolysis residue was of the high removal efficiency on those anions and cations in water.When the dosage of pyrolysis residue was 3,10,12,1,0.8 and 0.8 g·L^(−1),the removal efficiencies of Cr(Ⅵ),PO4^(3-),F−,Cd^(2+),Pb^(2+)and Cu^(2+)reached 99.6%,98.9%,96.8%,99.3%,98.9%and 99.4%,respectively.XRD analysis revealed that the removal of those pollution ions was achieved by precipitation of FeCr_(2)O_(4),Ca_(3)(PO_(4))_(2),CaF_(2),CdS,Cd(OH)_(2),CdAl_(2)Si_(2)O_(8),PbS,Pb(OH)_(2),PbAl_(2)Si_(2)O_(8),CuS,Cu(OH)_(2),CuAl_(2)Si_(2)O_(8)on the surface of pyrolysis residue.The experimental results provided a reference for the high value-added utilization of pyrolysis products,especially pyrolysis residue.