Release characteristics of polycyclic aromatic hydrocarbons and dioxins during co-processing multi-source organic wastes in a coal-water slurry gasifier
CUI Chang-hao1, ZHANG Lei2, LIU Mei-jia1, LI Li1, CHEN Chao1, WANG Hao-xiang2, YAN Da-hai1, MA Xiao-feng2
1. Research Institute of Solid Waste Management, Chinese Research Academy of Environmental Sciences, Beijing 100012, China; 2. Shaoxing Fengdeng Environmental Protection Co., LTD, Shaoxing 312300, China
Abstract：Field studies were conducted to investigate the release characteristics of polycyclic aromatic hydrocarbons (PAHs) and dioxins (PCDD/Fs) during the co-processing of anthraquinone dye, distillation residue, waste activated carbon and waste organic solvents in a coal water slurry gasifier. Results indicate that co-processing organic wastes showed minimal impact on gasification parameters but altered the gas composition of CO and CO2 in syngas, in which the gas composition of CO decreased from 40.9% to 31.5%, while the gas composition of CO2 increased from 23.4% to 31.0%. The reason may attribute to the enhanced combustion facilitated by the addition of organic wastes. Naphthalene and low-chlorinated PCDD/Fs were predominant in the gaseous samples under blank and co-processing condition. Under co-processing condition, the TEQ levels of PAHs and PCDD/Fs are in the range of 0.12-0.49ng-TEQ/m3 and 1.22~3.82pg-TEQ/m3, respectively, which showed marginal increases compared to the blank conditions (0.06~0.11ng-TEQ/m3 for PAHs and 1.34~2.97ng-TEQ/m3 for PCDD/Fs), and also well below the relevant standard limits. Under co-processing condition, PAHs and PCDD/Fs in solid samples are predominantly low, medium-ring and low-chlorinated congeners. The TEQ levels of PAHs, including sulfur (0.49ng-TEQ/kg) and carbon black (0.37ng-TEQ/kg), as well as the TEQ levels of PCDD/Fs, including ammonium bicarbonate (8.3pg-TEQ/kg), are higher than those of other solid samples. Moreover, the TEQ levels of PAHs and PCDD/Fs does not significantly increase compared to blank condition, indicating lower environmental risk.
崔长颢, 章磊, 刘美佳, 李丽, 陈超, 王浩祥, 闫大海, 马晓烽. 水煤浆气化炉协同处理过程中有机物排放特征——以多环芳烃和二噁英为例[J]. 中国环境科学, 2024, 44(9): 5053-5062.
CUI Chang-hao, ZHANG Lei, LIU Mei-jia, LI Li, CHEN Chao, WANG Hao-xiang, YAN Da-hai, MA Xiao-feng. Release characteristics of polycyclic aromatic hydrocarbons and dioxins during co-processing multi-source organic wastes in a coal-water slurry gasifier. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(9): 5053-5062.
[1] 国家统计局.中国统计年鉴2023[EB/OL]. https://www.stats.gov. cn/sj/ndsj/2023/indexch.htm 2023-09-01/2023-12-29. National Bureau of Statistics. China Statistical Yearbook 2003[EB/OL] https://www.stats.gov.cn/sj/ndsj/2023/indexch.htm, 2023-09-01/2023-12-29. [2] 张朝龙,杨丽亚,董欣宜,等.合成氨行业CO2与大气污染物排放清单及减污降碳潜力研究:以河南省为例[J]. 环境科学研究, 2023, 36(11):2126–2137. Zhang C L, Yang L Y, Dong X Y, et al. Research on CO2 and air pollutant emission inventory and potential for pollution reduction and carbon reduction in synthetic ammonia industry: Taking Henan province as an example [J]. Research of Environmental Sciences, 2023,36(11):2126–2137. [3] Midilli A, Kucuk H, Topal M E, et al. A comprehensive review on hydrogen production from coal gasification: Challenges and opportunities [J]. International Journal of Hydrogen Energy, 2021,46: 25385–25412. [4] 李雪冰.德士古气化炉协同处置危险废物的污染物降解与排放研究[D]. 北京:中国环境科学研究院, 2018. Li X B. Degradation and emission of pollutants during co-processing of hazardous waste in Texaco gasifier [D]. Beijing: Chinese Research Academy of Environmental Sciences, 2018. [5] Gu S Q, Xu Z Q, Dai Y X, et al. The resource utilization of coal gasification wastewater by co-slurry with lignite: Slurryability, dispersion/aggregation behavior, and co-slurrying mechanisms [J]. Fuel, 2023,352:129114. [6] 张国庆,杜善周,黄涌波,等.水煤浆制备工艺现状及发展趋势[J]. 洁净煤技术, 2023,29(5):133–142. Zhang G Q, Du S Z, Huang Y B, et al. Current situation and development trend of coal water slurry preparation technology [J]. Clean Coal Technology, 2023,29(5):133–142. [7] Wang Y W, Wang Z, Li S G, et al. Experimental study of rheological behavior and steam gasification of coal bio-oil slurry [J]. Energy & Fuels, 2010,24:5210–5214. [8] 宋银涛,李学琴,池亮,等.生物质水煤浆的制备工艺及成浆特性[J]. 洁净煤技术, 2023,29(2):671–675. Song Y T, Li X Q, Chi L, et al. Preparation technology and slurry forming property of biomass coal water slurry [J]. Clean Coal Technology, 2023,29(2):671–675. [9] 李雪冰,李丽,黄泽春,等.水煤浆气化炉协同处置煤液化残渣的PAHs排放特征[J]. 中国环境科学, 2017,37(10):3845–3852. Li X B, Li L, Huang Z C, et al. Emission characteristics of polycyclic aromatic hydrocarbons during co-processing of coal liquefaction residue in coal-water slurry gasifier [J]. China Environmental Science, 2017,37(10):3845–3852. [10] 董子平,闫大海,何洁,等.煤直接液化残渣掺烧的燃烧特性及其苯系物的排放特征[J]. 环境科学研究, 2015,28(8):1253–1259. Dong Z P, Yan D H, He J, et al. Combustion properties and benzene compound emission characteristics of coal liquefaction residual co-combustion [J]. Research of Environmental Sciences, 2015,28(8): 1253–1259. [11] Yin Y J, Liu J, Yang J J, et al. Energetic-environmental-economic assessment of utilizing weak black liquor to produce syngas for replacing evaporation based on coal water slurry gasification [J]. Energy, 2023,283:129203. [12] 殷惠民,海颖,周北海.黑液水煤浆技术在造纸黑液处理中的应用[J]. 环境科学研究, 2000,13(3):55–57. Yin H M, Hai Y, Zhou B H. Application of CBLM to treat black liquid of paper making industry [J]. Research of Environmental Sciences, 2000,13(3):55–57. [13] Wang J B, Liu J Z, Chen G, et al. Prediction of the ash melting behavior and mineral phase transformation during the co-gasification of waste activated carbon and coal water slurry [J]. Fuel, 2023,340: 127522. [14] Li D D, Liu J Z, Wang S N, et al. Study on coal water slurries prepared from coal chemical wastewater and their industrial application [J]. Applied Energy, 2020,268:114976. [15] Li L, Ma C D, Li X T, et al. Study on the preparation of coal wastewater slurry from salt/alkali wastewater [J]. Fuel, 2022,318: 123612. [16] Dmitrienko M A, Strizhak P A. Coal-water slurries containing petrochemicals to solve problems of air pollution by coal thermal power stations and boiler plants: An introductory review [J]. Science of the Total Environment, 2018,613–614:1117–1129. [17] 杨东元,王亚红,扈广法,等.污水处理污泥掺配水煤浆气化重金属迁移研究及灰渣排放评价[J]. 应用化工, 2021,50(7):1826–1837. Yang D Y, Wang Y H, Hu G F, et al. Study on heavy metal migration of wastewater sludge-coal water slurry gasification process and ash emission [J]. Applied Chemical Industry, 2021,50(7):1826–1837 [18] Wang J B, Liu J Z, Li D D, et al. Geochemical distribution and mineralogy of heavy metals in the gasification residue of coal-waste activated carbon-slurry: Insights into leaching behavior [J]. Journal of Hazardous Materials, 2023,451:131146. [19] 王建斌,陈云,王可华,等.工业窑炉协同处置固废研究进展[J]. 化工进展, 2022,41(3):1494–1502. Wang J B, Chen Y, Wang K H, et al. Co-processing of solid waste in industrial kilns: a review [J]. Chemical Industry and Engineering Progress, 2022,41(3):1494–1502. [20] 周学双,赵东风,王新乐,等.炼厂含油污泥与石油焦共成浆性及其影响因素[J]. 环境科学研究, 2014,27(5):520–526. Zhou X S, Zhao D F, Wang X L, et al. Slurry forming ability and influencing factors of refinery oily sludge-petroleum coke [J]. Research of Environmental Sciences, 2014,27(5):520–526. [21] 张亦雯,丁路,杨明明,等.玉米秸秆水热炭化预处理制备水煤浆及其成浆特性研究[J/OL]. 洁净煤技术, https://doi.org/10.13226/j.issn.1006-6772.23031303. Zhang Y W, Ding L, Yang M M, et al. Preparation and slurry ability of coal water slurry with hydrothermal carbonization pretreatment of corn straw [J/OL]. Clean Coal Technology, https://doi.org/10.13226/j.issn.1006-6772.23031303. [22] Jiang P, Xie C R, Luo C L, et al. Distribution and modes of occurrence of heavy metals in opposed multi-burner coal-water-slurry gasification plants [J]. Fuel, 2021,303:121163. [23] Du Y Y, Li L, Huang Q F, et al. Partitioning of arsenic in slurry feed entrained-flow gasifier with wet gas cooling cleaning system [J]. Journal of Cleaner Production, 2019,239:117979. [24] 王伟成,吴昊,王兴军,等.水煤浆气化过程中元素的迁移与富集特性[J/OL]. 化工进展, https://doi.org/10.16085/j.issn.1000-6613. 2023-1673. Wang W C, Wu H, Wang X J, et al. Characteristics of migration and enrichment of elements during coal water slurry gasification [J/OL]. Chemical Industry and Engineering Progress. https://doi.org/10.16085/j.issn.1000-6613.2023-1673. [25] HJ 646–2013环境空气和废气气相和颗粒物中多环芳烃的测定气相色谱-质谱法[S]. HJ 646–2013 Ambient air and stationary source emissions– Determination of gas and particle-phase polycyclic aromatic hydrocarbons with gas chromatography/mass spectrometry [S]. [26] HJ 77.2–2008环境空气和废气二噁英类的测定同位素稀释高分辨气相色谱-高分辨质谱法[S]. HJ 77.2–2008 Ambient air and flue gas Determination of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) Isotope dilution HRGC–HRMS [S]. [27] HJ 950–2018固体废物多环芳烃的测定气相色谱-质谱法[S]. HJ 950–2018 Solid waste–Determination of polycyclic aromatic hydrocarbon–Gas chromatography mass spectrometry [S]. [28] HJ 77.3–2008固体废物二噁英类的测定同位素稀释高分辨气相色谱-高分辨质谱法[S]. HJ 77.3–2008 Solid waste Determination of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) Isotope dilution HRGC–HRMS [S]. [29] HJ 1024–2019固体废物热灼减率的测定重量法[S]. HJ 1024–2019 Solid waste–Determination of loss on ignition– Gravimetric method [S]. [30] Nisbet I C T, Lagoy P K. Toxic equivalency factors (TEFs) for polycyclic aromatic hydrocarbons (PAHs) [J]. Regulatory Toxicology and Pharmacology, 1992,16(3):290–300. [31] Kutz F W, Barnes D G, Bottimore D P, et al. The international toxicity equivalency factor (I-TEF) method of risk assessment for complex mixtures of dioxins and related compounds [J]. Chemosphere, 1990, 20(7–9):751–757. [32] Li X B, Li L, Du Y Y, et al. Chemical industrial kilns used for co-processing of hazardous waste: Low environmental risks of polycyclic aromatic hydrocarbons (PAHs) [J]. Journal of Environmental Chemical Engineering, 2020,8:104312. [33] Reizer E, Viskolcz B, Fiser B. Formation and growth mechanisms of polycyclic aromatic hydrocarbons: A mini-review [J]. Chemosphere, 2022,291:132793. [34] 刘定超,金伟,惠希东,等.石油焦燃烧过程中影响多环芳烃生成的因素分析[J]. 华东理工大学学报(自然科学版), 2018,44(5):631– 637. Liu D C, Jin W, Hui X D, et al. Influencing factors of polycyclic aromatic hydrocarbons formation during petroleum coke combustion [J]. Journal of East China University of Science and Technology (Natural Science Edition), 2018,44(5):631–637. [35] Yan D H, Li L, Cui C H, et al. A field study of dioxins during co–processing of hazardous waste in multicomponent slurry gasifier [J]. Journal of Environmental Management, 2021,299:113584. [36] 周宏仓,薛鸿斌,张翠翠,等.低环多环芳烃(萘、苊)在活性炭上的热脱附行为[J]. 中国环境科学, 2011,31(9):1497–1502. Zhou H B, Xue H B, Zhang C C, et al. The thermal desorption behavior of low-ring PAHs (naphthalene and acenaphthene) adsorbed by the activated carbon [J]. China Environmental Science, 2011,31(9): 1497–1502. [37] Thorsen W, Cope W, Shea D. Bioavailability of PAHs: effects of soot carbon and PAH source [J]. Environmental Science & Technology, 2004,38(7):2029–2037. [38] GB 31571–2015石油化学工业污染物排放标准[S]. GB 31571–2015 Emission standard of pollutants for petroleum chemistry industry [S]. [39] GB 16297–1996大气污染物综合排放标准[S]. GB 16297–1996 Integrated emission standard of air pollutants [S]. [40] GB 36600–2018土壤环境质量建设用地土壤污染风险管控标准(试行) [S]. GB 36600–2018 Soil environmental quality Risk control standard for soil contamination of development land [S]. [41] GB 18484–2020危险废物焚烧污染控制标准[S]. GB 18484–2020 Standard for pollution control on hazardous waste incineration [S].
