Organochlorine Waste Research Articles

Copolymerization of Industrial Organochlorine Waste with Wood Pyrolysis Products for Bitumen Compositions

The work presents a new approach to the copolymerization and co-processing of industrial organochlorine waste (OCW) resulted in the production of vinyl chloride at Karpatnaftochim LLC, Kalush, Ukraine, and liquid wood pyrolysis products (LWPP) generated by the activated charcoal production at Perechyn Forestry and Chemical Plant, LLC. Kalush, Ukraine. This article highlights studies of the composition of the raw materials and the properties of the resulting products. Through the use of infrared spectroscopy and DTA analysis, the primary structure and properties of copolymers, oligomers, asphalt and bitumen products obtained from OCW and LWPP were determined. It describes the trial of the liquid products of wood pyrolysis in bitumen compositions with OCW.

Feasibility study of organochlorine waste processing and recycling in the vinyl chloride production unit: techno-economic assessment and emission estimation

Feasibility study of organochlorine waste processing and recycling in the vinyl chloride production unit: techno-economic assessment and emission estimation

Determination of the composition and study of the extraction of iron compounds from organochlorine wastes of vinyl chloride production

Sources of organochlorine waste (OCW) generation in the production of vinyl chloride, their toxicity and impact on the environment were analyzed. A comparative analysis of methods of waste disposal was performed. It was established that the method of thermal decontamination has gained the widest application. Methods of identification of organochlorine compounds and methods of separation and concentration of substances were considered. It was determined that one of the effective methods of their extraction is liquid extraction using oxalic and hydrochloric acids as extractants. As a result of the analysis of the composition of insoluble compounds in the cubic residues of the vinyl chloride rectification stage before submitting them to incineration, the presence of two following compounds was established: Fe2O3 and Fe3O4 with a predominant content of the Fe3O4 phase. The rational conditions for the extraction of iron compounds from OCW have been established: the type of extractant (chloric acid), the ratio of OCW:extractant; number of extraction cycles, and temperature. The rational concentration of hydrochloric acid as an extractant is 1%. Reduction of the content of iron compounds in OCW will contribute to increasing the operational life of the incineration plant from 20 days to three or more months.

Molecular Research of Lipid Peroxidation and Antioxidant Enzyme Activity of Comamonas testosteroni Bacterial Cells under the Hexachlorobenzene Impact.

The species of Comamonas testosteroni is the most common human pathogen of the genus, which can be associated with acute appendicitis, infections of the bloodstream, the peritoneal cavity, cerebrospinal fluid, inflammatory bowel disease, and in general, bacteremia. According to the literature, Comamonas testosteroni has destructive activity to a wide range of toxic chemical compounds, including chlorobenzenes. The specified strains were isolated from the soil of the organochlorine waste landfill, where hexachlorobenzene (HCB) was predominant. These strains were expected to be capable of degrading HCB. Microbiological (bacterial enrichment and cultivating, bacterial biomass obtaining), molecular biology, biochemical (enzymatic activities, malondialdehyde measuring, peroxidation lipid products measuring), and statistical methods were carried out in this research. The reaction of both strains (UCM B-400 and UCM B-401) to the hexachlorobenzene presence differed in the content of diene and triene conjugates and malondialdehyde, as well as different catalase and peroxidase activity levels. In terms of primary peroxidation products, diene conjugates were lower, except conditions with 20 mg/L HCB, where these were higher up to two times, than the pure control. Malondialdehyde in strain B-400 cells decreased up to five times, in B-401, but increased up to two times, compared to the pure control. Schiff bases in strain B-400 cells were 2–3 times lower than the pure control. However, in B-401 cells Schiff bases under higher HCB dose were in the same level with the pure control. Catalase activity was 1.5 times higher in all experimental variants, compared to the pure control (in the strain B-401 cells), but in the B-400 strain, cells were 2 times lower, compared to the pure control. The response of the two strains to hexachlorobenzene was similar only in peroxidase activity terms, which was slightly higher compared to the pure control. The physiological response of Comamonas testosteroni strains to hexachlorobenzene has a typical strain reaction. The physiological response level of these strains to hexachlorobenzene confirms its tolerance, and indirectly, the ability to destroy the specified toxic compound.

Scaling up the Process of Catalytic Decomposition of Chlorinated Hydrocarbons with the Formation of Carbon Nanostructures

Catalytic processing of organochlorine wastes is considered an eco-friendly technology. Moreover, it allows us to obtain a value-added product—nanostructured carbon materials. However, the realization of this process is complicated by the aggressiveness of the reaction medium due to the presence of active chlorine species. The present research is focused on the characteristics of the carbon product obtained over the Ni-Pd catalyst containing 5 wt% of palladium in various quartz reactors: from a lab-scale reactor equipped with McBain balance to scaled-up reactors producing hundreds of grams. 1,2-dichloroethane was used as a model chlorine-substituted organic compound. The characterization of the materials was performed using scanning and transmission electron microscopies, Raman spectroscopy, and low-temperature nitrogen adsorption. Depending on the reactor type, the carbon yield varied from 14.0 to 24.2 g/g(cat). The resulting carbon nanofibers possess a segmented structure with disordered packaging of the graphene layers. It is shown that the carbon deposits are also different in density, structure, and morphology, depending on the type of reactor. Thus, the specific surface area changed from 405 to 262 and 286 m2/g for the products from reactor #1, #2, and #3, correspondingly. The main condition providing the growth of a fluffy carbon product is found to be its ability to grow in any direction. If the reactor walls limit the carbon growing process, the carbon product is represented by very dense fibers that can finally crack the reactor.

Development of polyfunctional sorbents based on zeolites for wastewater treatment

The article presents technological approaches to solving the problem of involving production waste in the technology of sorption treatment of wastewater by component composition. Zeolites of the Holinsky deposit of Eastern Transbaikalia of the klinoptilolite type were taken as the initial matrix for creating a sorbent. We propose to use chloroanic wastes as an adsorbent of heavy metal ions, as which we propose to consider epichlorohydrin. The analysis of existing technologies for the disposal of organochlorine wastes, as well as known sorption materials, using sulfur as one of the modifier components. As a result of the deposition of a sulfur-containing polymer network on the surface of natural zeolite, not only its hydrophobization occurs. Sulfur atoms appear in its composition, which contributes to an increase in the selective ability to heavy metal ions, while copper ions are sorbed most rapidly. Previously, we proposed a method for modifying natural zeolites with highly organosilicon compounds, which made it possible to effectively neutralize oily wastewater.

АДСОРБЦИОННАЯ ОЧИСТКА СТОЧНЫХ ВОД, ОБРАЗУЮЩИХСЯ ПРИ ДЕМЕРКУРИЗАЦИИ РТУТЬЗАГРЯЗНЕННЫХ ПОЧВ

The soils of industrial enterprises operating plants for the production of chlorine and 
 alkali with a mercury cathode are contaminated with mercury. Demercurization of the soil leads to the 
 formation of mercury-containing wastewater. To remove mercury from wastewater, an adsorption 
 method is proposed using a sorbent based on lignin, organochlorine waste, and sodium polysulfide

Development of a coating based on zirconium dioxide to improve the chemical resistance of refractories in thermal decontamination of organochlorine waste

Development of a coating based on zirconium dioxide to improve the chemical resistance of refractories in thermal decontamination of organochlorine waste

Склад шламу від спалювання хлорорганічних відходів виробництва 1,2-дихлоретану

During organochlorine wastes thermal utilization formed at direct chlorination of ethylene to 1,2-dichloroethane in the production of vinyl chloride at Karpatnaftohim LLC, the ash is formed, which clogs gas pipelines and heat exchange elements of the steam generator, causes disruption of normal technological process and leads to emergency shutdowns.The composition of this ash was determined by chemical methods of quantitative analysis and flame photometry for such macrocomponents as Fe2O3 (28%) and FeCl3 (5%), as well as magnesium chlorides (30%) and sodium (4%), the rest (about 32% ) probably resinous highly chlorinated unburned components of VAT residues, carbon particles and nitric acid-insoluble iron compounds. Utilization methods and possible ways to reduce the amount of ash from the organochlorine waste combustion formed at the production of vinyl chloride are briefly considered.

Extraction of iron-containing catalyst from chlororganic wastes generated by ethylene chlorination

The technologies for extracting an iron-containing catalyst from process streams of direct chlorination of ethylene, as well as methods for the disposal of organochlorine wastes from vinyl chloride production, are considered. Problems arising from thermal waste disposal necessitate studies on the extraction of iron compounds from organochlorine by-products of the ethylene chlorination process. X-ray fluorescence analysis found that the composition of the burning sludge, as the main elements, includes iron – 33.52% and chlorine – 32.69%. The extraction of iron compounds with aqueous and aqueous acidic media under mechanical stirring is studied. It is shown that the addition of hydrochloric acid to the solution does not contribute to an increase in the degree of extraction of iron compounds. It is found that an increase in the duration of extraction and the temperature of this process provides a degree of extraction of iron compounds of more than 80%. The process of separation of an aqueous-organic emulsion, which is formed during extraction, by sedimentation, filtration and centrifugation, is investigated. It is found that at a temperature of about 80 °C there is an effective and rapid separation of the aqueous and organic phases as a result of sedimentation. Based on the obtained experimental results of the extraction study, a functional scheme for the extraction of an iron-containing catalyst is proposed, as well as ways to solve technological and environmental problems that arise during the combustion of organochlorine wastes from vinyl chloride production. The scheme provides for the use of the heat of hot organochlorine wastes for the extraction of iron compounds with industrial water. In addition, the use of the heat of the gases generated during the combustion of organochlorine wastes is provided for heating air, which low-boiling components from these wastes are blown off. In the future, this air is used to burn organochlorine wastes purified from iron compounds

X-ray fluorescence determination of the composition of ash from incineration of organochlorine wastes from direct chlorination of ethylene to 1,2-dichloroethane

X-ray fluorescence determination of the composition of ash from incineration of organochlorine wastes from direct chlorination of ethylene to 1,2-dichloroethane

Remediation of organic halogen- contaminated wetland soils using biochar

Organochlorine waste from papermaking has polluted soils worldwide, and the addition of biochar will improve polluted soils in a variety of scenarios. A field study (2014 to 2016) was conducted to investigate the application of wheat (Triticum aestivum L.) straw biochar (0, 20, 40, 60 Mg ha−1) to organic halogen-contaminated saline-alkali soil. The addition of biochar reduced the concentrations of adsorbable organic halogens (AOX) in the soil and extractable organic halogens (EOX) in reeds (Phragmites communis) by 9–94% and 14%–51%, respectively, and subsequently increased reed biomass by 1%–25%; these changes were related to the changes in different soil properties. Soil properties, such as the organic functional groups, surface properties, and pH, were improved following the addition of biochar, and some changes were maintained at heightened levels over time. The activity of urease, alkaline phosphatase, and sucrase enzymes in soil increased by 14 to 57%, 2 to 147%, and 1 to 75% as a function of increasing biochar amendment, respectively, while that of dehydrogenase decreased by 13% to 60%, which may have aided in the acceleration of AOX decomposition. The diversity of the bacterial community also increased due to biochar application, and is likely a key indicator of halogen degradation. The addition of biochar likely decreased the bioavailability of organic halogens by improving the function and structure of the microbial community, reducing their transfer to reeds grown in papermaking organochlorine-contaminated soils. Biochar may play an important role in reducing environmental contamination by organic halogens.

Моделирование процесса адсорбции в системе жидкость – твердое тело: регрессионный анализ извлечения меди из водных растворов цеолитом Холинского месторождения, модифицированным серосодержащим полимером

This article describes the formation of an effective sorbent for heavy metal ions by modifying natural zeolite (clinoptilolite type, Kholinskoye deposit). The modification was carried out by applying the network of a sulphur-containing polymer on the zeolite surface. For the formation of a polymer network, elemental sulphur was dissolved in the hydrasine hydrate–monoethanolamine system to generate polysulphide anions (in particular, S2 2- ). During the contact of the obtained sulphur solution with zeolite, polysulphide anions and the monoethanolamine entering the zeolite pores were concentrated on the surface. Further polycondensation of S2 2- anions with 1,2,3-trichloropropane (epichlorohydrine production waste) resulted in the formation of a reticulated sulphur-containing polymer covering the zeolite surface. Such a sorbent provides immediate solution to the problems concerned with utilisation of organochlorine wastes and purification of technological media containing heavy metals. Extraction of metals by the obtained sorbent was studied using model solutions with a metal concentration of 5000 mg/L. Encouraging results were obtained for five metals. Detailed information on the extraction of copper ions from aqueous solutions is presented. Experimental data was obtained on the effect of pH on the sorption efficiency of copper ions, as well as on the thermodynamic and kinetic characteristics of adsorption under static and dynamic conditions. The complex coordination mechanism of Cu (II) sorption by modified zeolite was confirmed using IR-spectroscopy. Since the thermodynamic and kinetic dependencies frequently deviate from the classical laws during sorption by the complex coordination mechanism, regression analysis was used to process the experimental data. As the result, nonlinear models were obtained fairly accurately describing experimental data on the extraction of copper ions by modified zeolite. The obtained regression models can be applied in further research of the new sorbent and in designing installations for extracting copper compounds from technological media.

HCH air levels derived from Bailín dumpsite dismantling (Sabiñánigo, Spain)

Remediation and management of dumpsites is a worldwide problem that must be addressed to protect human health and the environment. Aragon Government long-term objective is the control of air quality related to landfills used to dump organochlorine waste. The present study evaluated the influence of dismantling works performed in Bailín landfill, an hexachlorocyclohexane (1,2,3,4,5,6-hexaclorohexane; HCH) dumpsite located in the city of Sabiñánigo, Spain. A total of 65,000 t of HCH solid waste and 342,000 t of polluted soil were transferred to a new cell with additional isolating measures going beyond the Spanish legal requirements. To evaluate influence of excavation of the old cell, transfer of waste and the state once the works in Bailín area had finished, levels of α-, β-, γ-, δ- and ɛ- HCH isomers were analyzed in 112 air samples obtained from summer 2014 to autumn 2016 by using passive air samplers. Results showed that: i) the existence of the old landfill and/or the works performed during its dismantling were a source of HCH air contamination, ii) old landfill represented an HCH source even after dismantling work was completed, iii) other sources, tentatively associated to Sardas dumpsite and HCH production site (INQUINOSA Factory) were identified in the surroundings, where management should be addressed. Data comparison reflected a heavier contamination caused by the production, storage, and waste disposal than the corresponding to application of lindane and/or technical HCH in Spain. Meteorological dependence (temperature, solar radiation and relative humidity), α-/γ-HCH ratios and isomer profiles of HCH air concentrations were evaluated for temporal trends and geographic distribution.

ПРИМЕНЕНИЕ СЕРОСОДЕРЖАЩЕГО СОРБЕНТА НА ОСНОВЕ ЛИГНИНА ДЛЯ ИЗВЛЕЧЕНИЯ РТУТИ ИЗ ВОДНЫХ РАСТВОРОВ

The article presents data on the use of sulfur-containing sorbent obtained on the basis of tonnage of waste lignin, as well as on the basis of organochlorine wastes from epichlorohydrin production, for the extraction of mercury and mercury salts from aqueous solutions. For obtaining of sorbents lignin previously had been subjected to chlorination by the action of chlorine water (chlorine content of 3.5 - 5.7 per cent). The obtained powders of sorbents differ in sulphur content and content of residual chlorine in the finished product. The results of investigations of sorption properties of the sorbent, as well as its kinetic and thermodynamic characteristics. The sorption activity of this sorbent, while the extraction of mercuric ions from solutions at room temperature has a good performance. Kinetic studies are consistent with the comprehensive coordination mechanism of absorption of mercury ions. These studies will help to solve some global environmental problems, including wastewater treatment from heavy metals, recycling organochloride wastes from epichlorohydrin production and also utilization of large-tonnage waste of pulp and paper industry and hydrolytic lignin.

Synthesis of bimodal carbon structures via metal dusting of Ni-based alloys

A prospect of using metal dusting as an approach to synthesize self-organizing Ni-based catalysts for production of bimodal carbon materials has been discussed. Forced metal dusting of bulk Ni-M alloys driven by decomposition of chlorinated hydrocarbons led to a rapid and full disintegration of alloyed Ni-M precursors with spontaneous formation of active catalytic particles responsible for the growth of carbon filaments. Self-organizing catalysts were shown to be effective for utilization of organochlorine waste, processing of freons and various hydrocarbons into carbon nanomaterials. Secondary disintegration of metal particles resulted in the appearance of bimodal structures. The structural and morphological peculiarities of carbon nanomaterials obtained have been described.

Preparation of carbon nanomaterials in the process of organochlorine waste utilization

A method for the catalytic processing of chlorine-substituted hydrocarbons with the production of a fibrous carbon material is considered. This method is suitable for the utilization of organochlorine chemical industry wastes. The method is based on the carbide cycle mechanism, which was described earlier for the process of hydrocarbon decomposition with the formation of the base structures of carbon nanomaterials. Depending on temperature and hydrogen concentration, the process is performed in two regimes: by the carbide cycle mechanism with the deposition of carbon or by the mechanism of hydrodechlorination with the production of corresponding hydrocarbons. It was found that the presence of chlorine in the system changed the character of carbon diffusion through a catalyst particle, which is responsible for the formation of highly defective filaments with a featherlike morphology and a developed surface area (to 400 m2/g). A demonstration retrofit for the conversion of liquid organochlorine wastes with the production of featherlike carbon was developed. The use of massive alloys as catalyst precursors made it possible to obtain a high yield of carbon product (to 500 g/(g Ni)).

Green technology recycling highly toxic industrial waste

Recently, due to the increasing environmental problems in the process of industrial chemical production, there is a need to increase the conversion of raw materials into the finished products. This prevents the formation of by-products and especially toxic waste. This dramatically reduces the cost for selection and utilization toxic industrial waste. In this paper we describe a several of new policy decisions more effective ways of processing and recycling of industrial organochlorine waste (OCW) in the production of dichloroethane and vinyl chloride monomer, returning — recycling of raw materials. The study on chlorination of unsaturated chlorinated wastes showed that the additional treatment with chlorine to reduce the amount of unsaturated OCW and to increase the content of 1,2-dichloroethane in chlororganic waste at 9-15% reduced the loss of 1,2-dichloroethane when burned. The study optimized the conditions of the process of alkali dehydrochlorination, using a freshly prepared suspension of Ca(OH) 2 in NaOH, which allows to process the 1,2-dichloroethane and 1,1,2-trichloroethane with a total conversion of 95-96% of trade vinyl chloride and vinylidene chloride to the outputs of the last 25-70%. This method can reduce the amount of waste incinerated chlororganic 2-5 times.

Environmentally-friendly organochlorine waste processing and recycling

Due to environmental concerns, there is a need to enhance conversion to product and to prevent generation of wasteful byproducts and loss of organochlorine compounds in chemical production processes. The paper focuses on making vinyl chloride monomer production more efficient, and on possible ways of industrial organochlorine waste recycling. Environmentally-friendly processing and recycling methods of organochlorine waste are considered. Typical waste products are 1,2-dichloroethane, 1,1,2-trichloroethane, vinylidene chloride, and vinyl chloride monomer. Polymerization and copolymerization of typical waste with and without the C5–C9 fraction resulted in non-toxic polymer products that can be used in the construction industry. The possibility of joint chlorine and sulfide-containing chemical waste recycling into polysulfide oligomeric products (Thiokol) is discussed. This comprehensive recycling allows utilizing 80–90% of all waste, generated during synthesis of chlorinated products. The results of this study aim to improve vinyl chloride monomer yield and minimize the formation of organochlorine waste by processing and recycling of byproducts into useful products, including vinyl chloride monomers, vinylidene chloride, and other oligomers and polymers.

Processing of organochlorine waste components on bulk metal catalysts

A method for destroying chloroorganic waste components on catalysts, particularly bulk metal nickel (99.99%), nichrome (80% Ni and 20% Cr), and chromel (90% Ni and 10% Cr) is proposed. The process is accompanied by the formation of carbon nanofibers (CNFs) with feathery morphology. Catalytic destruction of 1,2-dichloroethane on bulk nickel catalysts is characterized by a long induction period (∼3 h) with spontaneous activation of the alloy’s surface. Preactivation of the catalyst with acids or by alternative treatment in oxidizing and reducing environments shortens the induction period by one order of magnitude. The state of the surface before and after activation is studied by SEM, TEM, and EDX. The activity of catalysts is determined for the decomposition of 1,2-dichloroethane at temperatures of 500 to 700°C. Nichrome exhibited the greatest activity (yield of CNFs, 400 g/g of catalyst); the yield of CNFs on catalysts prepared by coprecipitation and mechanical activation was considerably lower. The proposed approach combines organochlorine waste disposal with the production of a useful product (CNFs). The use of bulk metal catalysts is promising since it simplifies the technology for their preparation, and the absence of carriers makes it easy to cleanse CNFs of impurities of catalyst fragments.