碱性无机盐-表面活性剂协同处理炼化油泥

doi:10.16085/j.issn.1000-6613.2021-0364

摘要/Abstract

摘要：

针对炼油厂含油废水处理过程中产生大量炼化油泥处置难题，采用化学热洗法对炼化油泥进行热洗除油处理试验，考察了不同类型的碱性无机盐和表面活性剂复配后对炼化油泥的除油效果的影响，并对热洗工艺条件进行了优化。结果表明，单一热洗药剂中硅酸钠（Na₂SiO₃）除油效果最佳，除油率为40.3%；复配药剂中硅酸钠-脂肪醇聚氧乙烯醚硫酸钠（AES）-辛基酚聚氧乙烯醚（OP-10）除油效果最好，除油率达58.2%。正交实验结果显示，化学热洗各工艺条件对除油率的影响程度依次为：药剂浓度>热洗温度>热洗时间>泥液比>搅拌速率。最优工艺条件为：药剂浓度3g/L、热洗温度80℃、热洗时间60min、搅拌速率300r/min、泥液比1∶6。在此条件下，对炼化油泥的除油率达75.1%；气相色谱分析表明炼化油泥热洗前后的原油组分显著降低，较短组分（C₁₂~C₂₀）、中等长度组分（C₂₁~C₃₀）和较长组分（C₃₁~C₃₆）去除率分别为57.8%、86.2%和98.0%，长碳链烷烃（C₃₁~C₃₆）去除效果最好。热洗药剂重复利用3次，除油率仍大于40.8%。

关键词: 炼化油泥, 化学热洗法, 表面活性剂, 界面张力, 气相色谱

Abstract:

In order to solve a large amount of refining sludge produced in the process of oily wastewater treatment in refinery, the refining sludge was treated by thermochemical-washing, the effects of different types of alkaline inorganic salts and surfactants on the oil removal efficiency of refining sludge were investigated, and the hot washing process conditions were optimized. The results showed that sodium silicate (Na₂SiO₃) has the best degreasing effect in single hot washing agent, and the degreasing rate was up to 40.3%. Sodium silicate sodium fatty alcohol polyoxyethylene ether sulfate (AES)?-octylphenol polyoxyethylene ether (OP-10) had the best oil removal rate of 58.2%. The results of orthogonal experiment showed that the influence of chemical hot washing process conditions on oil removal rate was as follows: reagent concentration>hot washing temperature>hot washing time>sludge-water ratio>stirring rate. The optimum operating condition was agent concentration 3g/L, washing temperature 80℃, thermal washing time 60min, stirring speed 300r/min and sludge-water ratio 1∶6, the oil removal rate was 75.1%. Gas chromatography analysis showed that the composition of crude oil decreased significantly before and after hot washing, shorter component(C₁₂—C₂₀), medium length component(C₂₁—C₃₀), and longer components(C₃₁—C₃₆)removal rates were 57.8%, 86.2% and 98.0%, respectively. The removal efficiency of long chain alkanes(C₃₁—C₃₆)was the best. After the hot washing agent was reused for 3 times, the oil removal rate was still more than 40.8%.

Key words: refining sludge, chemical hot washing method, surface active agent, interfacial tension, gas chromatography

中图分类号:

张大山, 陈慧娴, 毛林强, 张文艺. 碱性无机盐-表面活性剂协同处理炼化油泥[J]. 化工进展, 2022, 41(1): 468-475.

ZHANG Dashan, CHEN Huixian, MAO Linqiang, ZHANG Wenyi. Refining sludge treatment with alkaline inorganic salt and surfactant[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 468-475.

图/表 12

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药剂	英文缩写	规格	类型
失水酸梨醇单油酸酯聚氧乙烯醚	Tween	分析纯	阳离子表面活性剂
十二烷基二甲苯芐基氯化铵	CAS	分析纯	阳离子表面活性剂
十六烷基三甲基氯化铵	CTAC	分析纯	阳离子表面活性剂
十二烷基苯磺酸钠	LAS	分析纯	阴离子表面活性剂
脂肪醇聚氧乙烯醚硫酸钠	AES	分析纯	阴离子表面活性剂
聚丙烯酰胺	PAM	分析纯	阴离子表面活性剂
辛基酚聚氧乙烯醚	OP-10	分析纯	非离子表面活性剂
烷基酚聚氧乙烯醚	APEO	分析纯	非离子表面活性剂
碳酸钠	Na₂CO₃	分析纯	碱性无机盐
磷酸钠	Na₃PO₄	分析纯	碱性无机盐
硅酸钠	Na₂SiO₃	分析纯	碱性无机盐

药剂	英文缩写	规格	类型
失水酸梨醇单油酸酯聚氧乙烯醚	Tween	分析纯	阳离子表面活性剂
十二烷基二甲苯芐基氯化铵	CAS	分析纯	阳离子表面活性剂
十六烷基三甲基氯化铵	CTAC	分析纯	阳离子表面活性剂
十二烷基苯磺酸钠	LAS	分析纯	阴离子表面活性剂
脂肪醇聚氧乙烯醚硫酸钠	AES	分析纯	阴离子表面活性剂
聚丙烯酰胺	PAM	分析纯	阴离子表面活性剂
辛基酚聚氧乙烯醚	OP-10	分析纯	非离子表面活性剂
烷基酚聚氧乙烯醚	APEO	分析纯	非离子表面活性剂
碳酸钠	Na₂CO₃	分析纯	碱性无机盐
磷酸钠	Na₃PO₄	分析纯	碱性无机盐
硅酸钠	Na₂SiO₃	分析纯	碱性无机盐

序号	复配药剂	表面活性剂组合类型	界面张力/mN·m^-1	除油率%
1	Na₂SiO₃+LAS+OP-10	阴离子型+非离子型	32.9	54.95
2	Na₂SiO₃+AES+OP-10	阴离子型+非离子型	29.9	58.20
3	Na₂SiO₃+PAM+OP-10	阴离子型+非离子型	32.2	55.71
4	Na₂SiO₃+LAS+APEO	阴离子型+非离子型	39.6	47.55
5	Na₂SiO₃+AES+APEO	阴离子型+非离子型	40.3	46.83
6	Na₂SiO₃+PAM+APEO	阴离子型+非离子型	54.5	31.18
7	Na₂SiO₃+Tween+OP-10	阳离子型+非离子型	39.1	48.19
8	Na₂SiO₃+CAS+OP-10	阳离子型+非离子型	34.0	53.72
9	Na₂SiO₃+CTAC+OP-10	阳离子型+非离子型	37.9	49.42
10	Na₂SiO₃+Tween+APEO	阳离子型+非离子型	35.3	52.31
11	Na₂SiO₃+CAS+APEO	阳离子型+非离子型	43.4	43.32
12	Na₂SiO₃+CTAC+APEO	阳离子型+非离子型	42.4	44.41

序号	复配药剂	表面活性剂组合类型	界面张力/mN·m^-1	除油率%
1	Na₂SiO₃+LAS+OP-10	阴离子型+非离子型	32.9	54.95
2	Na₂SiO₃+AES+OP-10	阴离子型+非离子型	29.9	58.20
3	Na₂SiO₃+PAM+OP-10	阴离子型+非离子型	32.2	55.71
4	Na₂SiO₃+LAS+APEO	阴离子型+非离子型	39.6	47.55
5	Na₂SiO₃+AES+APEO	阴离子型+非离子型	40.3	46.83
6	Na₂SiO₃+PAM+APEO	阴离子型+非离子型	54.5	31.18
7	Na₂SiO₃+Tween+OP-10	阳离子型+非离子型	39.1	48.19
8	Na₂SiO₃+CAS+OP-10	阳离子型+非离子型	34.0	53.72
9	Na₂SiO₃+CTAC+OP-10	阳离子型+非离子型	37.9	49.42
10	Na₂SiO₃+Tween+APEO	阳离子型+非离子型	35.3	52.31
11	Na₂SiO₃+CAS+APEO	阳离子型+非离子型	43.4	43.32
12	Na₂SiO₃+CTAC+APEO	阳离子型+非离子型	42.4	44.41

水平	因素
水平	热洗温度 /℃	热洗时间 /min	泥液比	药剂浓度 /g·L^-1	搅拌速率 /r·min^-1
1	50	20	1∶4	1	100
2	60	30	1∶5	2	200
3	70	40	1∶6	3	300
4	80	50	1∶7	4	400
5	90	60	1∶8	5	500