油基岩屑焚烧过程中钡的转化与环境风险研究

黄祥; 彭晓曦; 郭卫广; 韩雨岐; 张力; 侯江; 雍毅

doi:10.13198/j.issn.1001-6929.2023.02.21

油基岩屑焚烧过程中钡的转化与环境风险研究

doi: 10.13198/j.issn.1001-6929.2023.02.21

黄祥^{1, 2, 3,},
彭晓曦^{1, 2, 3},
郭卫广^{1, 2, 3},
韩雨岐^{1, 2, 3},
张力^{1, 2, 3},
侯江^{1, 2, 3},
雍毅^{1, 2, 3, ,}

1.
四川省生态环境科学研究院，四川成都　610041
2.
四川省环境保护重金属污染防治重点实验室，四川成都　610041
3.
四川省环境保护固体废物处理处置工程技术中心，四川成都　610041

基金项目: 四川省科技厅基本科研业务费项目(页岩气开采油基岩屑热脱附回收油品质及污染特征研究)；四川省科技厅重点研发计划项目(No.2021YFS0287)

详细信息

作者简介:
黄祥（1988-），男，湖南娄底人，高级工程师，硕士，主要从事重金属污染防治与固体废物污染控制及利用技术研究，444084189@qq.com

通讯作者:
雍毅(1963-)，男，四川成都人，研究员，主要从事重金属污染防治与固体废物污染控制及利用技术研究，81127158@qq.com

中图分类号: X741
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出版历程
- 收稿日期: 2022-12-26
- 修回日期: 2023-02-26

Study on Barium Transformation and Environmental Risk during Oil-Based Drill Cuttings Incineration

HUANG Xiang^{1, 2, 3
,},
PENG Xiaoxi^{1, 2, 3},
GUO Weiguang^{1, 2, 3},
HAN Yuqi^{1, 2, 3},
ZHANG Li^{1, 2, 3},
HOU Jiang^{1, 2, 3},
YONG Yi^{1, 2, 3
, ,}

1.
Sichuan Academy of Environmental Sciences, Chengdu 610041, China
2.
Sichuan Key Laboratory of Pollution Control for Heavy Metals, Chengdu 610041, China
3.
Sichuan Environmental Protection Engineering Centre of Solid Waste Treatment & Disposal, Chengdu 610041, China

Funds: Basic Scientific Research Business Cost Project of Sichuan Provincial Science and Technology Department (Study on Quality and Pollution Characteristics of Oil Recovered by Thermal Desorption from Oil-Based Drill Cuttings in Shale Gas Exploitation), China; Key Research and Development Projects of Sichuan Provincial Department of Science and Technology , China (No.2021YFS0287)

摘要

摘要: 油基岩屑焚烧处置技术已被广泛应用，为探究油基岩屑焚烧尾渣的主要环境风险及其形成机制，有效防控油基岩屑利用处置环境风险，通过实际样品采集和实验室模拟等方式，结合XRD、SEM-EDS、同步热分析等多种表征方法，针对四川省天然气开采油基岩屑典型回转窑焚烧处置过程中钡的转化以及焚烧尾渣的环境风险特征开展了研究. 结果表明：钡是油基岩屑中的主要重金属，油基岩屑经焚烧后，尾渣中钡的酸浸浸出毒性水平大幅上升，平均值达到333.0 mg/L，超过《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3—2007)标准限值；在还原气氛下，800 ℃时模拟焚烧尾渣可交换态钡含量和钡的酸浸浸出毒性水平出现大幅上升，平均值分别达到8 675.74 mg/kg和244.38 mg/L，并在1 100 ℃时进一步上升，不同油基岩屑的浸出毒性发生这种跃升的温度条件存在差异. 这种现象产生的主要原因是油基岩屑中的硫酸钡在800 ℃以上会发生碳热还原反应生成硫化钡，并与氯化氢等反应产生氯化钡，这种还原转化过程主要发生在硫酸钡晶体颗粒表面，并最终形成了被可溶性钡外壳包裹的硫酸钡晶体颗粒. 研究显示，可溶性钡是油基岩屑焚烧尾渣的主要环境风险，其产生主要与硫酸钡的碳热还原反应有关，钻井岩屑还原性高温热处理过程产生的可溶性钡环境风险应得到广泛关注和有效防控，建议从标准政策制定、风险源头防控和尾渣末端治理等方面进行控制.
- 油基岩屑 /
- 焚烧 /
- 钡 /
- 碳热还原
Abstract: The incineration technology of oil-based drill cuttings has been widely used. In order to effectively control the environmental risks in the utilization and disposal of oil-based drill cuttings, the main environmental risks and formation mechanisms of the incineration tailings of oil-based drill cuttings were explored. This study investigated the conversion of barium and the environmental risk characteristics of incineration tailings in typical rotary kiln incineration disposal process of oil-based drill cuttings from natural gas exploitation in Sichuan Province. Various characterization methods such as XRD, SEM-EDS, and simultaneous thermal analysis were used, including actual sample collection and laboratory simulations. The results indicated that barium was the main heavy metal in oil-based drill cuttings. After incineration of oil-based drill cuttings, the acid leaching toxicity of barium in the tailings increased significantly, with an average value of 333.0 mg/L, which exceeded the corresponding limit. In reducing atmosphere, the exchangeable state and extraction toxicity by acid leaching of barium from simulated incineration tailings increased significantly at 800 ℃, with the average values reaching 8675.74 mg/kg and 244.38 mg/L, respectively. These values further increased at 1100 ℃. The temperature conditions under which this extraction toxicity jump occurs varied among different oil-based drill cuttings. The main reason for this phenomenon was that the barium sulfate in oil-based drill cuttings was transformed into barium sulfide through carbothermic reduction reaction above 800 ℃, and reacted with hydrogen chloride to form barium chloride. This reduction conversion process mainly occurred on the surface of barium sulfate crystal particles, and eventually formed barium sulfate crystal particles with soluble barium shells. The research shows the soluble barium is the main environmental risk of incineration tailings of oil-based drill cuttings, which is mainly related to the carbothermal reduction reaction of barium sulfate. The environmental risk of soluble barium from the reductive high-temperature heat treatment processes of drilling cuttings should be widely concerned and effectively prevented. It is recommended that standard policy development, risk source prevention and tailing end treatment should be used for control.
- oil-based drill cutting /
- incineration /
- barium /
- carbothermic reduction

HTML全文

图 1 焚烧工艺流程及样品采集位置示意

Figure 1. Incineration process flow and sample collection location

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图 2 四川省典型油基岩屑和焚烧尾渣中主要重金属的总量及重金属的酸浸、水浸浸出毒性水平

Figure 2. The amount of major heavy metals and the extraction toxicity by acid and water leaching in typical oil-based drill cuttings and incineration tailings in Sichuan Province

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图 3 几种重晶石的XRD图谱

Figure 3. XRD analysis of several barites

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图 4 油基岩屑在还原和非还原气氛下不同温度模拟焚烧尾渣和实际焚烧尾渣中钡的分级形态含量

注：图中小写字母表示组内差异显著性 (P<0.05).

Figure 4. BCR graded forms content of barium in actual incineration tailings and simulated incineration tailings of oil-based drill cuttings simulated at different temperatures in reducing and non-reducing atmospheres

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图 5 油基岩屑在还原和非还原气氛下不同温度模拟焚烧尾渣中钡的酸浸浸出毒性水平

注：小写字母表示组内差异显著性(P<0.05).

Figure 5. Extraction toxicity by acid leaching of barium in simulated incineration tailings of oil-based drill cuttings at different temperatures in reducing and non-reducing atmospheres

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图 6 典型油基岩屑与重晶石、硫酸钡热重-差热曲线(TG-DSC)

Figure 6. TG-DSC curve of typical oil-based drill cuttings, barite and barium sulfate

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图 7 典型油基岩屑在还原和非还原气氛下不同温度模拟焚烧尾渣及实际焚烧尾渣XRD图谱

Figure 7. XRD analysis of actual incineration tailing and simulated incineration tailings of typical oil-based drill cuttings at different temperatures in reducing and non-reducing atmospheres

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图 8 典型油基岩屑在非还原和还原气氛下1 100 ℃模拟焚烧尾渣与实际焚烧尾渣扫描电镜图像

Figure 8. SEM images of actual incineration tailings and simulated incineration tailings of typical oil-based drill cuttings at 1100 ℃ in non-reducing and reducing atmospheres

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图 9 图8中图a1、b1、c1对应区域的能谱图

Figure 9. EDS of the corresponding regions of Fig. a1, b1 and c1 in Fig. 8

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表 1 模拟焚烧试验用典型油基岩屑重金属含量

Table 1. Heavy metal content of typical oil-based drill cuttings for simulated incineration experiments

样品名称	含量/(mg/kg)
样品名称	Ba	As	Mn	Ni	Zn	V	Cr	Cu	Pb	Cd
油基岩屑A	64 783.0±596.5	17.3±0.6	576.5±18.0	32.3±0.2	517.5±31.0	51.7±1.0	29.0±1.7	40.7±1.9	721.2±6.5	ND
油基岩屑B	69 183.4±4 720.8	24.3±1.0	509.9±7.2	68.9±1.5	283.6±7.9	434.4±3.6	55.7±0.6	58.1±0.9	275.6±3.7	ND
注：ND表示未检出.

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表 2 几种重晶石中钡总量、酸可溶钡含量和钡浸出毒性水平

Table 2. The total barium content, acid-soluble barium content and extraction toxicity by acid and water leaching in several barites

指标	平均值	标准差	中位数	最大值	最小值
钡总量(XRF检测法)/(mg/kg)	529 675.0	23 706.7	525 800.0	563 700.0	503 400.0
酸可溶钡含量/(mg/kg)	13 516.2	16 957.2	6 243.9	41 548.0	29.2
钡酸浸浸出毒性水平/(mg/L)	18.9	11.1	20.2	31.4	3.8
钡水浸浸出毒性水平/(mg/L)	17.8	9.1	18.1	27.8	7.3

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表 3 油基岩屑在还原和非还原气氛下不同温度模拟焚烧尾渣中钡的BCR分级形态及酸浸浸出毒性水平浓度显著性差异分析

Table 3. Analysis of significant differences of BCR graded forms and extraction toxicity by acid leaching of barium of oil-based drill cuttings in simulated incineration tailings at different temperatures in reducing and non-reducing atmospheres

指标	温度/℃	t值	P值
可交换态钡	300	2.564^*	0.047
	500	−0.491	0.643
	800	−2.198	0.079
	1 100	−2.646^*	0.046
可还原态钡	300	1.486	0.168
	500	2.012	0.072
	800	−1.011	0.336
	1 100	−6.081^**	0.000
可氧化态钡	300	0.916	0.398
	500	7.351^**	0.001
	800	5.064^**	0.004
	1 100	7.881^**	0.001
钡的酸浸浸出毒性水平	300	1.237	0.254
	500	0.025	0.980
	800	−2.133	0.086
	1 100	−2.691^*	0.043
注：表示在P<0.05下差异显著；*表示在P<0.01下差异显著.

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表 4 油基岩屑实际焚烧尾渣元素组成分析

Table 4. Elemental composition analysis of actual incineration tailing of oil-based drill cuttings

氧化物形式(不代表实际物相组成)	含量/%	相对标准偏差/%
BaO	29.76	0.29
CaO	29.55	0.16
SiO₂	16.59	0.35
SO₃	13.86	0.26
Al₂O₃	4.38	0.71
Fe₂O₃	2.29	0.42
MgO	2.17	0.89
Cl	1.22	0.75
F	0.68	11.30
SrO	0.49	0.29
Na₂O	0.40	3.82
K₂O	0.34	1.47
TiO₂	0.21	6.14
P₂O₅	0.11	4.41
MnO	0.05	4.59
ZnO	0.02	3.57
PbO	0.02	7.70

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