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Progress on cleaner production of vinyl chloride monomers over non-mercury catalysts

Jinli ZHANG, Nan LIU, Wei LI, Bin DAI

《化学科学与工程前沿（英文）》 2011年第5卷第4期页码 514-520 doi: 10.1007/s11705-011-1114-z

摘要： Polyvinyl chloride (PVC) has become the third most used plastic after polyethylene and polypropylene and the worldwide demand continues to increase. Polyvinyl chloride is produced by polymerization of the vinyl chloride monomer (VCM), which is manufactured industrially via the dehydrochlorination of dichloroethane or the hydrochlorination of acetylene. Currently PVC production through the acetylene hydrochlorination method accounts for about 70% of the total PVC production capacity in China. However, the industrial production of VCM utilizes a mercuric chloride catalyst to promote the reaction of acetylene and hydrogen chloride. During the hydrochlorination, the highly toxic mercuric chloride tends to sublime, resulting in the deactivation of the catalyst and also in severe environmental pollution problems. Hence, for China, it is necessary to explore environmental friendly non-mercury catalysts for acetylene hydrochlorination as well as high efficiency novel reactors, with the aim of sustainable PVC production via the acetylene-based method. This paper presents a review of non-mercury heterogeneous and homogeneous catalysts as well as reactor designs, and recommends future work for developing cleaner processes to produce VCM over non-mercury catalysts with high activity and long stability.

关键词： polyvinyl chloride vinyl chloride monomer acetylene hydrochlorination non-mercury catalysts green chemical process

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A density functional theory study of the adsorption of Hg and HgCl2 on a CaO(001) surface

GUO Xin, ZHENG Chuguang, LU Nanxia

《能源前沿（英文）》 2007年第1卷第1期页码 101-104 doi: 10.1007/s11708-007-0011-0

摘要： The adsorption of mercury and mercury chloride on a CaO(001) surface was investigated by the density functional theory (DFT) by using CaO cluster embedded in an electrostatic field represented by 178 point charges at the crystal CaO lattice positions. For the mercury molecular axis normal to the surface, the mercury can only coordinate to the O anion and has a very weak binding energy of 19.649 kJ/mol. When the mercury chloride molecular axis is vertical to the surface, the Cl atom coordinates to the Ca cation and has a binding energy of 23.699 kJ/mol. When the mercury chloride molecular axis is parallel to the surface, the Hg atom coordinates to the O anion and has a binding energy of 87.829 kJ/mol, which means that the parallel geometry is more stable than the vertical one. The present calculations show that CaO injection could substantially reduce gaseous mercury chloride, but have no apparent effect on the mercury, which is compatible with the available experimental results. This research will provide valuable information for optimizing and selecting a sorbent for the trace element in flue gas.

关键词： mercury chloride mercury molecular surface cluster electrostatic

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Mercury enrichment in

Chunhao Dai, Pufeng Qin, Zhangwei Wang, Jian Chen, Xianshan Zhang, Si Luo

《环境科学与工程前沿（英文）》 2017年第11卷第1期 doi: 10.1007/s11783-017-0892-z

摘要： Mercury enrichment in response to elevated atmospheric mercury concentrations in the organs of rape ( ) was investigated. Elevated soil mercury content had significant impact on mercury accumulation in rape stems, roots, seeds and seed coats. Leaf mercury in the leaves was mostly affected by atmospheric input while the stems were mostly affected by soil concentrations. Mercury in the aboveground plant tissue mainly derived from atmospheric absorption, and atmospheric mercury absorption in leaves was higher than that in the stems. Mercury enrichment in response to elevated atmospheric mercury concentrations in the organs of rape ( ) was investigated using an open top chamber fumigation experiment and a soil mercury enriched cultivation experiment. Results indicate that the mercury concentration in leaves and stems showed a significant variation under different concentrations of mercury in atmospheric and soil experiments while the concentration of mercury in roots, seeds and seed coats showed no significant variation under different atmospheric mercury concentrations. Using the function relation established by the experiment, results for atmospheric mercury sources in rape field biomass showed that atmospheric sources accounted for at least 81.81% of mercury in rape leaves and 32.29% of mercury in the stems. Therefore, mercury in the aboveground biomass predominantly derives from the absorption of atmospheric mercury.

关键词： Open top chamber Gaseous elemental mercury (GEM) Soil Mercury Brassica napus

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Mercury removal from flue gas using nitrate as an electron acceptor in a membrane biofilm reactor

《环境科学与工程前沿（英文）》 2022年第16卷第2期 doi: 10.1007/s11783-021-1454-y

摘要：

Membrane bioreactor achieved mercury removal using nitrate as an electron acceptor.

关键词： Mercury removal Oxygen Ferrous sulfide Transformation of mercury Microbial community

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A review of atmospheric mercury emissions, pollution and control in China

Shuxiao WANG,Lei ZHANG,Long WANG,Qingru WU,Fengyang WANG,Jiming HAO

《环境科学与工程前沿（英文）》 2014年第8卷第5期页码 631-649 doi: 10.1007/s11783-014-0673-x

摘要： Mercury, as a global pollutant, has significant impacts on the environment and human health. The current state of atmospheric mercury emissions, pollution and control in China is comprehensively reviewed in this paper. With about 500–800 t of anthropogenic mercury emissions, China contributes 25%–40% to the global mercury emissions. The dominant mercury emission sources in China are coal combustion, non-ferrous metal smelting, cement production and iron and steel production. The mercury emissions from natural sources in China are equivalent to the anthropogenic mercury emissions. The atmospheric mercury concentration in China is about 2–10 times the background level of North Hemisphere. The mercury deposition fluxes in remote areas in China are usually in the range of 10–50 μg∙m ∙yr . To reduce mercury emissions, legislations have been enacted for power plants, non-ferrous metal smelters and waste incinerators. Currently mercury contented in the flue gas is mainly removed through existing air pollution control devices for sulfur dioxide, nitrogen oxides, and particles. Dedicated mercury control technologies are required in the future to further mitigate the mercury emissions in China.

关键词： atmospheric mercury emissions pollution control China

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Insight of chemical environmental risk and its management from the vinyl chloride accident

《环境科学与工程前沿（英文）》 2023年第17卷第4期 doi: 10.1007/s11783-023-1652-x

摘要： The combustion of vinyl chloride (VC) after the train derailment accident in Ohio, USA in February, 2023 has caused widespread concern around the world. This paper tried to analyze several issues concerning the accident, including the appropriateness of the VC combustion in the emergency response in this accident, the meanings of so-called “controlled combustion”, the potential environmental risks caused by VC and combustion by-products, and follow-up work. In our view, this accident had surely caused environmental and health risks to some extent. Hence, a comprehensive environmental risk assessment is necessary, and then the site with risk should be comprehensively remediated, hazardous waste should be harmlessly treated as soon as possible. Finally, this accident suggests that further efforts should be taken to bridge the gap between chemical safety management and their environmental risk management.

关键词： Vinyl chloride Combustion Chemical safety management Environmental risk Emerging contaminants

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New insights into mercury removal mechanism on CeO

Ling Li, Yu He, Xia Lu

《环境科学与工程前沿（英文）》 2018年第12卷第2期 doi: 10.1007/s11783-018-1007-1

摘要： First-principles calculations were performed to investigate the mechanism of Hg adsorption and oxidation on CeO (111). Surface oxygen activated by the reduction of Ce to Ce was vital to Hg adsorption and oxidation processes. Hg was fully oxidized by the surface lattice oxygen on CeO (111), without using any other oxidizing agents. HCl could dissociate and react with the Hg adatom on CeO (111) to form adsorbed Hg–Cl or Cl–Hg–Cl groups, which promoted the desorption of oxidized Hg and prevented CeO catalyst deactivation. In contrast, O–H and H–O–H groups formed during HCl adsorption consumed the active surface oxygen and prohibited Hg oxidation. The consumed surface oxygen was replenished by adding O into the flue gas. We proposed that oxidized Hg desorption and maintenance of sufficient active surface oxygen were the rate-determining steps of Hg removal on CeO -based catalysts. We believe that our thorough understanding and new insights into the mechanism of the Hg removal process will help provide guidelines for developing novel CeO -based catalysts and enhance the Hg removal efficiency.

关键词： Elemental mercury removal Surface adsorption Ceria First-principles calculations

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Removal of elemental mercury by KI-impregnated clay

Boxiong SHEN,Jianhong CHEN,Ji CAI

《环境科学与工程前沿（英文）》 2016年第10卷第2期页码 236-243 doi: 10.1007/s11783-014-0765-7

摘要： This study described the use of clay impregnated by KI in gas phase elemental mercury (Hg ) removal in flue gas. The effects of KI loading, temperature, O , SO and H O on Hg removal were investigated using a fixed bed reactor. The Hg removal efficiency of KI-clay with 3% KI loading could maintain at a high level (approximately 80 %) after 3 h. The KI-clay demonstrated to be a potential adsorbent for Hg removal when compared with activated carbon based adsorbent. O was found to be an important factor in improving the Hg removal. O was demonstrated to assist the transfer of KI to I on the surface of KI-clay, which could react with Hg directly. NO and SO could slightly improve Hg removal, while H O inhibited it greatly. The results indicated that after adsorption, most of the mercury escaped from the surface again. Some of the mercury may have been oxidized as it left the surface. The results demonstrated that the chemical reaction primarily occurred between KI and mercury on the surface of the KI-clay.

关键词： clay elemental mercury removal efficiency potassium iodide mechanism

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Biosorption of mercury and lead by aqueous

Pratibha SANJENBAM, Kumar SAURAV, Krishnan KANNABIRAN

《化学科学与工程前沿（英文）》 2012年第6卷第2期页码 198-202 doi: 10.1007/s11705-012-1285-2

摘要： Toxic heavy metals are increasingly accumulating in the environment worldwide and are considered to be life threatening contaminants. The biosorption of mercury and lead by marine actinomycetes isolated from marine sediment collected from the Bay of Bengal coast of Puducherry, India, was evaluated. The maximum tolerance concentration (MTC) of sp. was determined by a well diffusion method and a broth dilution method. The effects of the initial metal ion concentration, the pH and the biomass dosage on the biosorption of mercury and lead ions were investigated. The MTC of the isolate to metals was 200 mg·L for mercury and 1800 mg·L for lead. At neutral pH, the isolate had a maximum biosorption of metal ions of 200 mg·L and 150 mg·L for mercury and lead respectively. Fourier transform infrared (FTIR) absorption spectra showed the chemical interactions between the functional groups in the biomass such as hydroxyl (-OH), amine (-NH ), carboxyl (-COOH) and the metal ions. The isolate was further characterized by molecular taxonomy and identified as a member of the genus Based on the phenotypic and phylogenetic analysis, the strain was classified as a new species of the genus and designated as VITSVK9 sp. (HM137310). A blast search of the 16S rDNA sequence of the strain showed the most similarity (95%) with sp. A515 Ydz-FQ (EU384279). Based on the results, it can be concluded that this marine could be used as a biosorbent for the removal of heavy metal ions from aqueous environments.

关键词： mercury lead biosorption maximum tolerance concentration Streptomyces VITSVK9 sp.

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Mercury removal and recovery by immobilized

Meifang CHIEN, Ryo NAKAHATA, Tetsuya ONO, Keisuke MIYAUCHI, Ginro ENDO

《化学科学与工程前沿（英文）》 2012年第6卷第2期页码 192-197 doi: 10.1007/s11705-012-1284-3

摘要： From several mercury removing microorganisms, we selected MB1, which is non-pathogenic, broad-spectrum mercury resistant, mercuric ion reducing, heat tolerant, and spore-forming, as a useful bacterium for bioremediation of mercury pollution. In this study, mercury removal performance of the immobilized MB1 was investigated to develop safe, efficient and stable catalytic bio-agent for mercury bioremediation. The results showed that the alginate gel immobilized MB1 cells efficiently removed 80% of mercury from the solution containing 10 mg/L mercuric chloride within 24 h. These cells still had high activity of mercury removal even after mercuric ion loading was repeated for nine times. The analysis of mercury contents of the alginate beads with and without immobilized MB1 suggested that a large portion of reduced metallic mercury was trapped in the gel beads. It was concluded that the alginate gel immobilized MB1 cells have potential to remove and recover mercury from mercury-containing water.

关键词： mercury removal immobilized bacteria alginate gel bioremediation

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Evaluating effect of chloride attack and concrete cover on the probability of corrosion

Sanjeev Kumar VERMA, Sudhir Singh BHADAURIA, Saleem AKHTAR

《结构与土木工程前沿（英文）》 2013年第7卷第4期页码 379-390 doi: 10.1007/s11709-013-0223-9

摘要： Corrosion of reinforced concrete (RC) structures is one of the significant causes of deterioration of reinforced concrete (RC) structures. Chlorination is a major process governing the initiation and advancement of the injurious corrosion of steel bars. Now, several researches on the chlorination of concrete structures have been ongoing around the world. Present article reviews several recently performed chlorination studies, and from results of a field survey evaluates the effect of chloride content on the probability of corrosion and the influence of concrete compressive strength on the chloride content and penetration, also evaluates the effect of concrete cover over the chloride content of the RC structures at rebar depth and on the probability of corrosion.

关键词： concrete chloride reinforcement corrosion deterioration cover

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Source attribution for mercury deposition with an updated atmospheric mercury emission inventory in the

Jiajun Liu, Long Wang, Yun Zhu, Che-Jen Lin, Carey Jang, Shuxiao Wang, Jia Xing, Bin Yu, Hui Xu, Yuzhou Pan

《环境科学与工程前沿（英文）》 2019年第13卷第1期 doi: 10.1007/s11783-019-1087-6

摘要：

Estimated anthropogenic Hg emission was 11.9 tons in Pearl River Delta for 2014.

Quantifying contributions of emission sources helps to provide control strategies.

More attentions should be paid to Hg deposition around the large point sources.

Power plant, industrial source and waste incinerator were priorities for control.

A coordinated regional Hg emission control was important for controlling pollution.

关键词： Emission inventory Mercury deposition Pearl River Delta (PRD) Source attribution Control strategy

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Chloride binding and time-dependent surface chloride content models for fly ash concrete

S. MUTHULINGAM,B. N. RAO

《结构与土木工程前沿（英文）》 2016年第10卷第1期页码 112-120 doi: 10.1007/s11709-015-0322-x

摘要： Corrosion of embedded rebars is a classical deterioration mechanism of reinforced concrete structures exposed to chloride environments. Such environments can be attributed to the presence of seawater, deicing or sea-salts, which have high concentrations of chloride ion. Chloride ingress into concrete, essential for inducing rebar corrosion, is a complex interaction between many physical and chemical processes. The current study proposes two chloride ingress parameter models for fly ash concrete, namely: 1) surface chloride content under tidal exposure condition; and 2) chloride binding. First, inconsistencies in surface chloride content and chloride binding models reported in literature, due to them not being in line with past research studies, are pointed out. Secondly, to avoid such inconsistencies, surface chloride content and chloride binding models for fly ash concrete are proposed based upon the experimental work done by other researchers. It is observed that, proposed models are simple, consistent and in line with past research studies reported in literature.

关键词： binding isotherms chloride ingress concrete fly ash surface chloride content

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Removal of elemental mercury with Mn/Mo/Ru/Al

Yongfu GUO, Naiqiang YAN, Ping LIU, Shijian YANG, Juan WANG, Zan QU

《环境科学与工程前沿（英文）》 2013年第7卷第3期页码 464-473 doi: 10.1007/s11783-012-0430-y

摘要： In this work, a catalytic membrane using Mn/Mo/Ru/Al O as the catalyst was employed to remove elemental mercury (Hg ) from flue gas at low temperature. Compared with traditional catalytic oxidation (TCO) mode, Mn/Al O membrane catalytic system had much higher removal efficiency of Hg . After the incorporation of Mo and Ru, the production of Cl from the Deacon reaction and the retainability for oxidants over Mn/Al O membrane were greatly enhanced. As a result, the oxidization of Hg over Mn/Al O membrane was obviously promoted due to incorporation of Mo and Ru. In the presence of 8 ppmv HCl, the removal efficiency of Hg by Mn/Mo/Ru/Al O membrane reached 95% at 423 K. The influence of NO and SO on Hg removal were insignificant even if 200 ppmv NO and 1000 ppmv SO were used. Moreover, compared with the TCO mode, the Mn/Mo/Ru/Al O membrane catalytic system could remarkably reduce the demanded amount of oxidants for Hg removal. Therefore, the Mn/Mo/Ru/Al O membrane catalytic system may be a promising technology for the control of Hg emission.

关键词： flue gas elemental mercury membrane catalysis transition metal

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On corrosion to stainless steel by calcium chloride with different extender

Lv XU, Yuanyang HU, Liwei WANG, Ruzhu WANG,

《能源前沿（英文）》 2010年第4卷第2期页码 181-184 doi: 10.1007/s11708-009-0065-2

摘要： A calcium chloride solution with a different extender, which is made up of either pure calcium chloride, calcium chloride with expanded graphite, or calcium chloride with activated carbon, acts differently on stainless steel. The mass ratio between calcium chloride with expanded graphite or activated carbon is almost 4∶1, which is demonstrated to be the optimum ratio. The experimental research in this paper reveals that, of the three solutions, which are pure calcium chloride, calcium chloride with expanded graphite, and calcium chloride with activated carbon, the strongest oxidation creation and pitting corrosion happened in the solution of calcium chloride with expanded graphite, the weakest oxidation creation happened in the solution of calcium chloride with activated carbon, and pitting corrosion was stronger than oxidation creation in the solution of pure calcium chloride. This paper gives the reasons for these phenomena. Furthermore, based on theory analysis, multiple means and approaches are provided to prevent stainless steel from further corroding.

关键词： stainless steel corrosion calcium chloride expanded graphite activated carbon oxidation creation pitting corrosion