Study on influence of CaO during thermal desorption products of oil-based drilling cuttings

doi:10.11949/0438-1157.20211702

Abstract

Abstract:

Calcium oxide(CaO) was used as additive to regulate the thermal desorption process of oil-based drilling cuttings to reduce the low quality and severe smell of oil and gas. The results showed that: (1) The higher CaO addition ratio, the higher yield of oil and the lower yield of water and gas. The yield of residue increased at first and then decreased. (2) Higher desorption temperature resulted in lower yield of residue and higher yield of oil, water, and gas. (3) The addition of CaO significantly increased oil yield and decreased the yield of oil and gas by different degrees under every temperature. (4) The yield and saturation of hydrocarbons of oil increased, the sulfur content in oil decreased after adding CaO. Therefore adding CaO improved the additional economic value of recycled oil and reduced the water and gas yield, especially the yield of CO₂ and H₂S. The introduction of CaO as an additive reduces the atmospheric pollution of the thermal desorption process to the operating environment, as well as the desulfurization burden of the subsequent process, reduces the high energy consumption caused by water evaporation, and creates favorable conditions for the reuse of oil products and non-condensable gas.

Key words: fixed-bed, oil-based drilling cuttings, desorption, waste treatment, recovery, environment

摘要：

针对油基钻屑热脱附过程中能耗高、气味刺鼻和油气品质较低等问题，选用氧化钙（CaO）作为添加剂对油基钻屑热解过程调控，考察了不同CaO添加量和温度对反应工况、产物分布及性质的影响。研究结果表明：（1）随着CaO添加量的上升，油收率上升，水和气收率下降，固相收率先升后降。（2）随着热脱附温度的升高，热脱附固体残渣收率逐渐降低，热脱附油、水、气的收率都有不同程度的上升。（3）添加CaO后，所有温度下，均存在热脱附后油收率有明显的上升，而油气收率明显下降现象。（4）CaO的添加提升了油收率和油中脂肪烃的饱和度，降低了油中硫元素的含量，提升了回收油的附加经济值，降低了水和气收率，尤其是CO₂和H₂S的产率。引用CaO作为添加剂降低了热脱附工艺对操作环境的大气污染，以及后续流程的脱硫负担，降低了水分蒸发导致的高能耗，为油品与不凝气的再利用创造了有利条件。

关键词: 固定床, 油基钻屑, 脱附, 废物处理, 回收, 环境

CLC Number:

X 741

Shipei XU, Chao WANG, Qingyuan LI, Bingkang ZHANG, Shiwei XU, Xueqin ZHANG, Shiying WANG, Mengxiao CONG. Study on influence of CaO during thermal desorption products of oil-based drilling cuttings[J]. CIESC Journal, 2022, 73(4): 1724-1731.

许世佩, 王超, 李庆远, 张炳康, 许世伟, 张雪琴, 王诗颖, 丛梦晓. 氧化钙对油基钻屑热脱附产物影响的研究[J]. 化工学报, 2022, 73(4): 1724-1731.

Figures/Tables 13

Table 1 Industrial analysis and element analysis of oil-based drilling cuttings from Weiyuan Sichuan province

样品	工业分析/%（质量，干基）			元素分析/%（质量，干基）
样品	挥发分	灰分	固定碳	C	H	N	S
油基钻屑	20.38	76.94	2.68	13.76	1.32	0.15	4.05

Fig.1 Schematic diagram and picture of infrared heating instrument

Fig.2 Products distribution of OBDC co-desorption with different proportion of CaO

Fig.3 The influence of CaO proportion on the oil content of residue

Table 2 Residue characteristics with different CaO proportion

CaO添加比例/%	灰分/%（质量，干基）	元素分析/%（质量，干基）
CaO添加比例/%	灰分/%（质量，干基）	C	H	N	S
0	83.86	7.54	0.29	0.15	3.90
2.5	83.99	7.66	0.22	0.34	3.57
5.0	84.20	7.30	0.20	0.15	3.34
7.5	84.25	7.08	0.20	0.13	3.35
10.0	84.39	6.69	0.48	0.34	3.00

Fig.4 The influence of CaO proportion on OBDC thermal desorption

Table 3 Ultimate analysis of oil with different CaO proportion

CaO添加比例/%	元素分析/%（质量，干基）				氢碳比
CaO添加比例/%	C	H	N	S	氢碳比
0	85.04	14.19	0.57	0.20	2.00
2.5	85.01	14.45	0.45	0.09	2.04
5.0	84.98	14.45	0.46	0.11	2.04
7.5	85.05	14.48	0.39	0.08	2.04
10.0	84.82	14.46	0.61	0.11	2.05

Fig.5 Products distribution of OBDC thermal co-desorption with and without CaO

Fig.6 Effect of thermal desorption temperature on oil content of residue with and without CaO

Fig.7 Gas yield of OBDC co-desorption with and without CaO under different temperatures

Fig.8 Total gas, HHV and heat quantity of OBDC co-desorption with and without CaO under different temperatures

Fig.9 Effect of thermal desorption temperature on distillation range with and without CaO

Table 4 Characteristics of oil under different temperatures with and without CaO

是否添加CaO	温度/℃	元素分析/%（质量，干基）				氢碳比
是否添加CaO	温度/℃	C	H	N	S	氢碳比
未添加CaO	250	84.93	14.46	0.39	0.23	2.04
	300	84.98	14.46	0.39	0.18	2.04
	350	85.02	14.08	0.60	0.30	1.99
	400	85.35	14.08	0.37	0.20	1.98
	450	85.04	14.19	0.57	0.20	2.00
添加CaO	250	85.04	14.19	0.57	0.20	2.08
	300	85.01	14.45	0.45	0.09	2.10
	350	84.98	14.45	0.46	0.11	2.08
	400	85.05	14.48	0.39	0.08	2.09
	450	84.82	14.46	0.61	0.11	2.05

References 31

1	何敏, 张思兰, 王丹, 等. 油基钻屑热解处理技术[J]. 环境科学导刊, 2017, 36(S1): 57-60.
	He M, Zhang S L, Wang D, et al. Pyrolysis technology of oil-based drill cuttings[J]. Environmental Science Survey, 2017, 36(S1): 57-60.
2	王晓琦, 翟增强, 金旭, 等. 页岩气及其吸附与扩散的研究进展[J]. 化工学报, 2015, 66(8): 2838-2845.
	Wang X Q, Zhai Z Q, Jin X, et al. Progress in adsorption and diffusion of shale gas[J]. CIESC Journal, 2015, 66(8): 2838-2845.
3	杨飞, 岳长涛, 李术元, 等. 四川盆地志留系页岩CH₄和CO₂吸附特征[J]. 化工学报, 2017, 68(10): 3851-3859.
	Yang F, Yue C T, Li S Y, et al. Adsorption characteristics of CH₄ and CO₂ on Silurian shale in Sichuan basin[J]. CIESC Journal, 2017, 68(10): 3851-3859.
4	单海霞, 何焕杰, 袁华玉, 等. 油基钻屑处理技术研究进展[J]. 河南化工, 2012, 29(15): 26-29.
	Shan H X, He H J, Yuan H Y, et al. Research progress of treatment technology for oil-based drilling cuttings[J]. Henan Chemical Industry, 2012, 29(15): 26-29.
5	李学庆, 杨金荣, 尹志亮, 等. 油基钻井液含油钻屑无害化处理工艺技术[J]. 钻井液与完井液, 2013, 30(4): 81-83, 98.
	Li X Q, Yang J R, Yin Z L, et al. Novel harmless treating technology of oily cuttings[J]. Drilling Fluid & Completion Fluid, 2013, 30(4): 81-83, 98.
6	Yan P, Lu M, Guan Y M, et al. Remediation of oil-based drill cuttings through a biosurfactant-based washing followed by a biodegradation treatment[J]. Bioresource Technology, 2011, 102(22): 10252-10259.
7	王思凡, 胡东锋, 李前春. 超临界CO₂萃取法处理油基钻屑工艺实验[J]. 石油钻采工艺, 2019, 41(5): 597-602.
	Wang S F, Hu D F, Li Q C. Experimental study on the oil-based drilling cuttings treatment technology based on supercritical CO₂ extraction method[J]. Oil Drilling & Production Technology, 2019, 41(5): 597-602.
8	郑婷婷, 涂妹, 刘莎丽, 等. 含油钻屑热解析及焚烧处理技术研究[J]. 化工管理, 2015(4): 146-147.
	Zheng T T, Tu M, Liu S L, et al. Study of thermal desorption and incineration technology of oil-based drilling cuttings[J]. Chemical Enterprise Management, 2015(4): 146-147.
9	张珂, 朱建华, 周勇, 等. 含油污泥的废油置换脱水特性[J]. 化工学报, 2013, 64(9): 3396-3403.
	Zhang K, Zhu J H, Zhou Y, et al. Fry-drying of oily sludge via spent lubricating oil of vehicle[J]. CIESC Journal, 2013, 64(9): 3396-3403.
10	温宏炎, 张玉明, 纪德馨, 等. 油泥焦与褐煤共燃特性及动力学[J]. 化工学报, 2020, 71(2): 755-765.
	Wen H Y, Zhang Y M, Ji D X, et al. Co-combustion of oil sludge char and brown coal: characteristics and kinetics[J]. CIESC Journal, 2020, 71(2): 755-765.
11	石艺. 塔里木油田应用LRET技术回收油基钻井液[J]. 石油钻采工艺, 2014, 36(3): 6.
	Shi Y. Tarim Oilfield uses LRET technology to recover oil-based drilling fluid[J]. Oil Drilling & Production Technology, 2014, 36(3): 6.
12	单海霞, 何焕杰, 刘晓宇, 等. 油基钻屑的生物处理[J]. 江南大学学报(自然科学版), 2013, 12(4): 470-474.
	Shan H X, He H J, Liu X Y, et al. Study on biological treatment of oil-based drilling cuttings[J]. Journal of Jiangnan University (Natural Science Edition), 2013, 12(4): 470-474.
13	余勇刚, 代家林, 朱战兵, 等. 钻屑回注技术[J]. 天然气勘探与开发, 2009, 32(4): 60-64, 87.
	Yu Y G, Dai J L, Zhu Z B, et al. Cuttings reinjection technology[J]. Natural Gas Exploration and Development, 2009, 32(4): 60-64, 87.
14	蔡浩, 姚晓, 华苏东, 等. 页岩气井油基钻屑固化处理技术[J]. 环境工程学报, 2017, 11(5): 3120-3127.
	Cai H, Yao X, Hua S D, et al. Solidification treatment technology of oil-based drilling cuttings in shale gas well[J]. Chinese Journal of Environmental Engineering, 2017, 11(5): 3120-3127.
15	章骅, 鲁文涛, 邵立明, 等. 轧钢含油污泥湿式减压蒸馏处理工艺优化[J]. 化工学报, 2017, 68(12): 4649-4657.
	Zhang H, Lu W T, Shao L M, et al. Separation of oil and residue from rolling oil sludge by wet vacuum distillation[J]. CIESC Journal, 2017, 68(12): 4649-4657.
16	王天宇, 蒋文明, 刘杨. 含油污泥阴燃处理技术研究与进展[J]. 化工学报, 2020, 71(4): 1411-1423.
	Wang T Y, Jiang W M, Liu Y. Research and progress of smoldering combustion technology for oily sludge[J]. CIESC Journal, 2020, 71(4): 1411-1423.
17	邵志国, 史志鹏, 许毓, 等. 氧化钙在油基钻屑热脱附中的协同作用[J]. 天然气工业, 2020, 40(10): 148-155.
	Shao Z G, Shi Z P, Xu Y, et al. Synergistic effect of calcium oxide in thermal desorption of oil-based drilling cuttings[J]. Natural Gas Industry, 2020, 40(10): 148-155.
18	张哲娜, 金兆迪, 林传钢, 等. 油基钻屑低温热脱附处理工艺模拟[J]. 油气田环境保护, 2020, 30(6): 29-32, 68.
	Zhang Z N, Jin Z D, Lin C G, et al. Simulation study on low temperature thermal desorption of oil-based drilling cuttings[J]. Environmental Protection of Oil & Gas Fields, 2020, 30(6): 29-32, 68.
19	王帮林. 油基钻屑热脱附处理后回收柴油的再利用技术[J]. 江汉石油职工大学学报, 2020, 33(5): 49-51.
	Wang B L. Recycling technology for diesel oil recovered from thermal desorption treatment of oil-based drilling cuttings[J]. Journal of Jianghan Petroleum University of Staff and Workers, 2020, 33(5): 49-51.
20	王君, 刘天璐, 黄群星, 等. 储运含油污泥慢速热解特性分析[J]. 化工学报, 2017, 68(3): 1138-1145.
	Wang J, Liu T L, Huang Q X, et al. Slow pyrolysis characteristics of petroleum sludge[J]. CIESC Journal, 2017, 68(3): 1138-1145.
21	史志鹏, 许毓, 邵志国, 等. 热脱附处理页岩气油基钻屑的研究与应用[J]. 油气田环境保护, 2019, 29(6): 37-40, 65.
	Shi Z P, Xu Y, Shao Z G, et al. Research and application of thermal-desorption treatment of oil-based cuttings from shale gas production[J]. Environmental Protection of Oil & Gas Fields, 2019, 29(6): 37-40, 65.
22	邵志国, 印涛, 裴明东, 等. 基于电磁加热式油基钻屑热脱附装置控制系统[J]. 中国仪器仪表, 2019(6): 45-48.
	Shao Z G, Yin T, Pei M D, et al. Control system of the oil-based drilling cuttings thermal desorption device based on electromagnetic heating[J]. China Instrumentation, 2019(6): 45-48.
23	郭文辉, 孟祥海, 肖超, 等. 热脱附技术处理油基钻屑实验研究[J]. 油气田环境保护, 2018, 28(4): 38-41, 62.
	Guo W H, Meng X H, Xiao C, et al. Experimental study on the oil-based drill cuttings treatment by thermal desorption[J]. Environmental Protection of Oil & Gas Fields, 2018, 28(4): 38-41, 62.
24	周浩, 汪根宝, 李蒙, 等. 含油钻屑的热解特性[J]. 环境工程学报, 2017, 11(12): 6421-6428.
	Zhou H, Wang G B, Li M, et al. Investigation of pyrolysis characteristics of oil-contaminated drill cuttings[J]. Chinese Journal of Environmental Engineering, 2017, 11(12): 6421-6428.
25	范海宏, 张鹏, 李斌斌. 石灰污泥共热法在水泥煅烧中的应用[J]. 环境工程学报, 2013, 7(2): 689-694.
	Fan H H, Zhang P, Li B B. Application of sludge drying heat with lime in cement burning[J]. Chinese Journal of Environmental Engineering, 2013, 7(2): 689-694.
26	张鹏. CaO处理污泥干化臭气的实验研究[D]. 西安: 西安建筑科技大学, 2012.
	Zhang P. The test research of using CaO from cement kiln waste to treat sludge drying exhaust gas[D]. Xi'an: Xi'an University of Architecture and Technology, 2012.
27	纪秀俊. CaO调质城市污泥热干化过程及其建模研究[D]. 兰州: 兰州理工大学, 2018.
	Ji X J. The research of CaO treatment municipal sludge effects on sludge thermal drying and mathematical modeling[D]. Lanzhou: Lanzhou University of Technology, 2018.
28	许世佩. 红外快速加热与反应分级调控煤热解制油气研究[D]. 北京: 中国科学院大学(中国科学院过程工程研究所), 2019.
	Xu S P. Coal pyrolysis for oil and gas with infrared quick heating and staged reaction control [D]. Beijing: University of Chinese Academy of Sciences (Institute of Process Engineering, Chinese Academy of Sciences), 2019.
29	蒋卷涛. 煤焦加氢制甲烷的CaO-Fe催化作用研究和热力学分析[D]. 北京: 北京化工大学, 2016.
	Jiang J T. Study on catalysis of CaO-Fe and thermodynamic analysis in hydrogasification of char for methane[D]. Beijing: Beijing University of Chemical Technology, 2016.
30	赖登国. 内构件移动床固体热载体油页岩热解技术研究[D]. 北京: 中国科学院大学(中国科学院过程工程研究所), 2017.
	Lai D G. Pyrolysis of oil shale by solid heat carrier in moving bed with internals[D]. Beijing: University of Chinese Academy of Sciences (Institute of Process Engineering, Chinese Academy of Sciences), 2017.
31	Liu H, Yi L L, Hu H Y, et al. Emission control of NO _x precursors during sewage sludge pyrolysis using an integrated pretreatment of Fenton peroxidation and CaO conditioning[J]. Fuel, 2017, 195: 208-216.

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