氧化钙对油基钻屑热脱附产物影响的研究

doi:10.11949/0438-1157.20211702

摘要/Abstract

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

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

中图分类号:

X 741

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.

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.

图/表 13

表1 实验用四川威远油基钻屑的工业分析和元素分析

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

图1 红外加热仪器实物图与流程图

Fig.1 Schematic diagram and picture of infrared heating instrument

图2 不同含量CaO油基钻屑热脱附产物分布

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

图3 CaO添加量对固相含油量影响

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

表2 不同CaO添加量残渣特性

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

图4 不同CaO添加量对油基钻屑气体影响

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

表3 不同CaO添加量回收油元素分析

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

图5 添加CaO前后油基钻屑热脱附产物分布

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

图6 添加CaO前后油基钻屑残渣含油量

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

图7 不同温度下添加CaO前后油基钻屑气体产量

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

图8 不同温度下添加CaO对油基钻屑气体总产量、热值和热量的影响

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

图9 添加CaO前后热脱附温度对油品馏程影响

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

表4 添加CaO前后不同温度回收油特性

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

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