Refining sludge treatment with alkaline inorganic salt and surfactant

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

Abstract

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

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

CLC Number:

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.

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.

Figures/Tables 12

References 25

1	陈忠喜. 含油污泥处理工艺技术现状及其展望[J]. 油气田地面工程, 2020, 39(10): 1-7.
	CHEN Zhongxi. Present situation and prospect of oily sludge treatment technology[J]. Oil-Gas Field Surface Engineering, 2020, 39(10): 1-7.
2	REN H Y, ZHOU S Y, WANG B, et al. Treatment mechanism of sludge containing highly viscous heavy oil using biosurfactant[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020, 585: 124117.
3	LI Y, CHEN X, WANG Y H, et al. Application of chemical hot washing method for oily solid waste treatment[J]. IOP Conference Series: Earth and Environmental Science, 2018, 199: 042040.
4	宋相和, 纪怡璞. 干化-焚烧联运技术在含油污泥处理中的应用[J]. 安全、健康和环境, 2020, 20(6): 22-26.
	SONG Xianghe, JI Yipu. Application of drying-incineration combined technology in oily sludge treatment[J]. Safety Health & Environment, 2020, 20(6): 22-26.
5	SIVAGAMI K, TAMIZHDURAI P, MUJAHED S, et al. Process optimization for the recovery of oil from tank bottom sludge using microwave pyrolysis[J]. Process Safety and Environmental Protection, 2021, 148: 392-399.
6	KE C Y, QIN F L, YANG Z G, et al. Bioremediation of oily sludge by solid complex bacterial agent with a combined two-step process[J]. Ecotoxicology and Environmental Safety, 2021, 208: 111673.
7	OBI L, ATAGANA H, ADELEKE R, et al. Potential microbial drivers of biodegradation of polycyclic aromatic hydrocarbons in crude oil sludge using a composting technique[J]. Journal of Chemical Technology & Biotechnology, 2020, 95(5): 1569-1579.
8	TENG Q, ZHANG D M, YANG C P. A review of the application of different treatment processes for oily sludge[J]. Environmental Science and Pollution Research, 2021, 28(1): 121-132.
9	白羽, 程远鹏, 胡九江, 等. 含油污泥热清洗处理技术研究现状与展望[J]. 应用化工, 2020, 49(6): 1498-1501, 1507.
	BAI Yu, CHENG Yuanpeng, HU Jiujiang, et al. Progress and prospects of thermal cleaning and treatment of oily sludge[J]. Applied Chemical Industry, 2020, 49(6): 1498-1501, 1507.
10	陈红硕, 刘佳驹, 付正辉, 等. 热化学清洗-逆流提取联合处理高含油含聚油泥工艺试验[J]. 环境工程技术学报, 2019, 9(3): 294-301.
	CHEN Hongshuo, LIU Jiaju, FU Zhenghui, et al. Experimental study on treatment of high-oil sludge containing polymer by thermochemical cleaning and countercurrent extraction[J]. Journal of Environmental Engineering Technology, 2019, 9(3): 294-301.
11	RAMIREZ D, SHAW L J, COLLINS C D. Oil sludge washing with surfactants and co-solvents: oil recovery from different types of oil sludges[J]. Environmental Science and Pollution Research, 2021, 28(5): 5867-5879.
12	姜勇, 赵萍, 董铁有, 等. 含油污泥油含量测定方法[J]. 环境科学与管理, 2008, 33(2): 115-117.
	JIANG Yong, ZHAO Ping, DONG Tieyou, et al. Determination methods for oil concentration in the oily sludge[J]. Environmental Science and Management, 2008, 33(2): 115-117.
13	焦龙, 程超, 闫昕, 等. 表面活性剂-碱协同处理老化油泥工艺[J]. 油田化学, 2019, 36(3): 535-539.
	JIAO Long, CHENG Chao, YAN Xin, et al. Study on synergistic treatment of aged oil sludge with surfactant and alkali[J]. Oilfield Chemistry, 2019, 36(3): 535-539.
14	王开泉. 几种表面活性剂对不同油污清洗能力的对比[J]. 中国洗涤用品工业, 2018(9): 60-65.
	WANG Kaiquan. A comparative study on the oil cleaning performance of several surfactants[J]. China Cleaning Industry, 2018(9): 60-65.
15	黄朝琦, 秦志文, 尚绪敏, 等. 含油污泥化学热洗的药剂配方及工艺优化[J]. 化工进展, 2020, 39(4): 1478-1484.
	HUANG Zhaoqi, QIN Zhiwen, SHANG Xumin, et al. Formulation and process optimization of chemical thermal washing of oily sludge[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1478-1484.
16	TACKIE-OTOO B N, AYOUB MOHAMMED M A, YEKEEN N, et al. Alternative chemical agents for alkalis, surfactants and polymers for enhanced oil recovery: research trend and prospects[J]. Journal of Petroleum Science and Engineering, 2020, 187: 106828.
17	王鹏, 刘金河, 耿春香, 等. 新疆风城油砂水洗分离研究[J]. 广东化工, 2017, 44(1): 1-2, 8.
	WANG Peng, LIU Jinhe, GENG Chunxiang, et al. Hot water extraction of Fengcheng Xinjiang oil sands[J]. Guangdong Chemical Industry, 2017, 44(1): 1-2, 8.
18	张海燕, 陈光莹, 张海波, 等. 碱与表面活性剂在油水界面上的协同作用[J]. 湖南大学学报(自然科学版), 2016, 43(6): 93-98.
	ZHANG Haiyan, CHEN Guangying, ZHANG Haibo, et al. Synergism between alkali and surfactant at oil/water interface[J]. Journal of Hunan University (Natural Sciences), 2016, 43(6): 93-98.
19	SUN X Y, ZENG H B, TANG T. Effect of non-ionic surfactants on the adsorption of polycyclic aromatic compounds at water/oil interface: a molecular simulation study[J]. Journal of Colloid and Interface Science, 2021, 586: 766-777.
20	AHMADI M A, SHADIZADEH S R. Spotlight on the new natural surfactant flooding in carbonate rock samples in low salinity condition[J]. Scientific Reports, 2018, 8: 10985.
21	刁潘, 刘静, 张永奎, 等. 阴离子/非离子表面活性剂体系洗涤含油污泥[J]. 化工进展, 2014, 33(10): 2753-2757.
	DIAO Pan, LIU Jing, ZHANG Yongkui, et al. Experiment on enhanced washing of oily sludge by anionic/nonionic mixed surfactant[J]. Chemical Industry and Engineering Progress, 2014, 33(10): 2753-2757.
22	XU B. Influencing factors governing paraffin wax deposition of heavy oil and research on wellbore paraffin remover[J]. Petroleum Science and Technology, 2018, 36(20): 1635-1641.
23	LIU J W, WEI K H, XU S W, et al. Surfactant-enhanced remediation of oil-contaminated soil and groundwater: a review[J]. Science of the Total Environment, 2021, 756: 144142.
24	张玉才, 艾力江·吐尔地, 孙艳美, 等. 聚醚有机硅表面活性剂的制备及对油污的清洗作用研究[J]. 中国胶粘剂, 2020, 29(11): 26-30.
	ZHANG Yucai, AILIJIANG Tuerdi, SUN Yanmei, et al. Preparation of polyether organosilicon surfactant and its cleaning effect on oil stain[J]. China Adhesives, 2020, 29(11): 26-30.
25	蔡烈刚, 沈婷, 李智民, 等. 原位生物修复过程中石油烃降解特征研究[J]. 资源环境与工程, 2018, 32(4): 606-610.
	CAI Liegang, SHEN Ting, LI Zhimin, et al. Study on degradation characteristics of petroleum hydrocarbons during in situ bioremediation[J]. Resources Environment & Engineering, 2018, 32(4): 606-610.

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