Available online at ScienceDirect. Procedia Engineering 150 (2016 )

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1 Available online at ScienceDirect Procedia Engineering 150 (2016 ) International Conference on Industrial Engineering, ICIE 2016 Disposal of Synthetic Surfactants-Containing Wastewater Treatment Sludge in the Ceramic Brick Production S.V. Sverguzova, Zh.A. Sapronova, I.V. Starostina* Belgorod State Tecnological University n.a. V.G. Shukhov, Kostyukova Street, 46, Belgorod, , Russia Abstract The results of studies on the using the carbonate slurry purification surfactants-containing model solutions as the entrained additive in the production of wall ceramics are introduced here. For wastewater purification a thermally modified carbonated sediment formed in the production of sugar is used. It is found that at the firing temperature 950ºC there is a decomposition of CaCO3 contained in the sediment with the formation of CaO and CO2. Evolving vapor and gaseous products contribute to pore formation in the body of ceramic mass which leads to a decrease in the density of ceramic products and improve their heat and sound insulation properties. Products with the additive of the water treated sludge in the amount of 50% can be used for the construction of non-critical structures (internal walls), the compressive strength of which must not be lower than 2.5 MPa or M25 type The Authors. Published by Elsevier by Elsevier Ltd. Ltd. This is an open access article under the CC BY-NC-ND license ( Peer-review under responsibility of the organizing committee of ICIE Peer-review under responsibility of the organizing committee of ICIE 2016 Keywords: ceramic brick; thermally modified carbonated sediment; sludge water treatment; surfactant; clay; density; strength. 1. Intorduction Production of material goods and meeting the vital needs of mankind all over the world is associated with large quantities of waste formation [1, 2]. Thus, according to [3, 4] only solid waste is produced in amount around 7 billion tons in the world annually. One of the widespread and big-volume waste is sediment (sludge) generated during wastewater treatment. The sediment is formed at municipal, industrial, mixed and rainwater (melt) wastewater purification. Generally, sediments are used or sent for recycling only in small quantities, the * Corresponding author. Tel.: ; fax: address: starostinairinav@yandex.ru The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license ( Peer-review under responsibility of the organizing committee of ICIE 2016 doi: /j.proeng

2 S.V. Sverguzova et al. / Procedia Engineering 150 ( 2016 ) predominant mass of sediments are sent to industrial landfills for their long-term storage, to filtration fields or exported to dump [5]. Recently, a lot of attention is paid to recycling or disposal of various waste productions [6-14]. 2. The goal of research The paper presents the results of researches on sludge disposal, received during the purification of surfactant containing waters by burned waste production of sugar such as thermally modified saturated precipitate (TMSP). The saturation sediment is formed at the stage of beet juice purification with Ca(OH) 2 suspension, so it contains up 65 to 75 % CaCO 3. After dewatering in press-chamber filter the sludge has moisture content of about 30 %. As a result of heat treatment organic substance in the initial carbonation sediment carbonized to form carbon film on the surface of CaCO 3 grain (Fig. 1) and the TMSP becomes black [15]. TMSP obtained was used as a sorption material for purification of surfactant containing solutions with the initial concentration of 50 mg / dm 3. Additive TMSP was 2 g / dm 3. Fig.1. (a) X-ray diagram of TMSP: - CaCO 3; - carbon; - SiO 2; (b) Energy dispersive spectrum of TMSP At 85% efficiency of cleaning the content of synthetic surfactants in the filtrated sediment with a moisture content of 30% is approximately 0,6%. According to the energy dispersive researches results the elemental composition of wastewater treatment purification is presented in Fig. 1-b. This sediment was used by us as a poreforming additive in the clay mass in the ceramic red brick manufacture. Ceramics industry has been in existence for thousands of years [16]. Currently, building ceramics industry is one of the leading branches of building materials industry [17]. In the Russian Federation there are several thousands of building ceramics companies, mainly of wall ceramics. According Rosstat [18] in 2014 in Russia there were produced 7365,1 million of conventional bricks. In the beginning of 2015 the total production capacity of the existing manufacturers of ceramic wall materials with the exception of small businesses and individual entrepreneurs amounted to about 9.2 billion units conventional bricks, of which capacity introduced only in million conventional bricks, which exceeded the value of 2013 by 70% [19]. At the same time, the literature indicates that the growth of the ceramic piece wall materials production declined slightly compared with the production of silicate materials of dense and cellular structure [20]. Depending on the needs of the market there are produced bricks of the following types: solid brick with density of kg / m 3 ; hollow (perforated) brick with density of kg / m 3 ; clay facing bricks (density from 1300 to 1450 kg / m 3 ); glazed brick for lining with density of kg/m 3 ; clinker brick with increased frost resistance with density kg/m3; fireclay brick (density from 1700 to 1900 kg / m3).

3 1612 S.V. Sverguzova et al. / Procedia Engineering 150 ( 2016 ) For the internal finishing works it s more rational to use lightweight brick, having a large number of pores and high thermal and sound insulating properties. It is known that calcium carbonate, being in a finely divided state, increases the porosity of the finished products and reduces their density. Therefore the sediment of wastewater purification with TMSO, finely divided and containing particles of CaCO3 with an average size of about 150 microns, may serve as pore-forming additive to clay mixtures. 3. The main part In the experiments there were used the clays from Ternovka, Tavrovo, Rakitnoe and Volokonovka deposits of Belgorod region, at the X-ray patterns of which (Fig.2) there were detected illite (d = 10,069); kaolinite (d = 7,202; 4,482; 2,567; 2,497; 2,336); montmorillonite (d = 5,001; 3,259; 3,097); impurities of quartz (d = 3,352; 2,286); calcite (d = 3,3871) and anorthite (d = 4,270). Clay deposits of Tavrovo are represented by illite (d = 10,050; 7,112); kaolinite (d = 2,659; 2,495; 2,399); montmorillonite (d = 5,016; 3,253; 3,039); quartz impurities have also been observed (d = 4,270; 3,352; 2,285). In the clay deposits of Rakitnoe and Volokonovka there have been found illite, montmorillonite, kaolinite; impurities of quartz and anorthite. Fig. 2. XRD of clay deposits a- Ternovka, b Tavrovo, c - Rakitnoe, d - Volokonovka. Legend: - illite, - kaolinite, - montmorillonite; - quartz, - calcite, anorthite

4 S.V. Sverguzova et al. / Procedia Engineering 150 ( 2016 ) For determining rational utilization process conditions, water treatment sludge with moisture content of 30% was introduced into the raw batch in an amount of from 5 to 25% by weight. Samples- cylinders with diameter and height of 20mm were molded by the method of plastic press. Drying of the molded samples was made at the ºC-ture to constant weight; firing was made in muffle furnace at for 1 hour. The chosen firing range was defined by the features of raw materials. As the used TMSP consists of CaCO3 and adsorbed surfactants, then in the process of sintering clay mass there can be the emission of gaseous substances. In the range of temperatures ºC there are reaction of dehydration and decomposition of the main clay minerals of montmorillonite and kaolinite [21]: Al3 4SiO2 H Al3 4SiO2 H Al3 2SiO2 2H Al3 2SiO2 2H K 3Al3 6SiO2 K Al3 4SiO2 2Al3 2SiO2 K 3Al3 6SiO2 K Al3 6SiO2 2Al3 The firing temperature of 950ºC promotes the decomposition of CaCO3 with formation of CaO and CO2. The resulting CaO, in spite of a high melting point, in clay containing masses is strong flux due to the formation with Al3 and SiO2 relatively low-melting compounds. With the appearance of liquid phase in the samples sintering process of ceramic materials begins. CaO is also involved in the formation of a stable modification scheme anorthite: CaO Al O 2SiO CaO Al O 2SiO which as mullite improves the physico-mechanical parameters of products. Evolving vapor and gaseous products improve pore formation in the body of the ceramic mass, which leads to a decrease in the density of ceramic products and improve their heat and sound insulation properties. From the results given in Fig.3 it is shown that the additive of precipitate to the raw clay mixture leads to the significant reduction in the density of the finished products. Thus, with the addition of the sludge in an amount of 12.5% the density is reduced by approximately 20% and with the addition of sludge 25% the density reduction is about 40%. Fig. 3. Reduction of density of brick samples, depending on the amount of wastewater treatment sludge added to the clays of deposits: 1 Tavrovo, 2 Ternovka, 3 Rakitnoe, 4 - Volokonovka Since the sludge addition to the raw clay mixtures may reduce the strength of the finished product, we have researched the dependence of the samples R compression strength from the mass fraction of the sludge additives. The tests were conducted on a laboratory hydraulic press "PGM -100MG4".

5 1614 S.V. Sverguzova et al. / Procedia Engineering 150 ( 2016 ) The test results shown in Fig.3 show that with addition of the sludge in an amount of 10.0% the strength reduction is insignificant in comparison with the strength of control samples containing no addition of the sludge. Thus in the ceramic samples of the control composition not containing precipitates the changes of special phase don t occur except for the appearance of the liquid phase, hematite, magnetite, and anorthite. Sludge containing of purification in an amount of 5-10% in the composition of the ceramic samples has no significant effect on the strength properties. With this waste content there is no significant gas evolution during thermal decomposition of the components included in the precipitate. As a result of the samples firing the forming liquid phase on the surface of the raw grain mixture enters the capillaries, formed as a result of a slight gas evolution, and serves as a cement binder forming a thin film on the contact phases. There are also gases melt gripping and pore securing. The increase in the mass fraction of sludge to 25% leads to the intensification of the processes of gas evolution as a result of the CaCO3 decarbonization. However, the volume of the resulting liquid phase is insufficient holding the gaseous products and hardening the forming pores (Fig.4), which eventually leads to porosity increase, lower density and compressive strength of ceramic materials with 20 MPa in the control to 13 MPa when the content of the slurry is 25 %. Fig.4. The micrographs of ceramic samples: a - a control composition without the water treatment sludge; b - water treatment sludge with the addition of 25%

6 S.V. Sverguzova et al. / Procedia Engineering 150 ( 2016 ) Fig.5-a shows the compressive strength dependence of bricks mark with additives based on water treatment sludge on the amount of added sludge with strength conversion coefficient k = 2 at the transition from small samples (2: 2) to bricks of standard sizes. As can be seen from Fig.5-b, product even with the 50% addition of water treatment sludge can be used for the non-structural construction (internal walls), which compressive strength should not be less than 2.5 MPa or M25 grade. Fig.5. (a) Dependence of the samples strength on the amount of water purification sediment additives to clays from deposits: 1 Volokonovka, 2 - Rakitnoe, 3 - Ternovka, 4 Tavrovo; (b) Strength of the samples in accordance with the brick mark by GOST : M75 - internal walls of 2-storey buildings; M50 - internal walls of single-storey buildings; M35 and M25 - outbuildings and partitions 4. Conclusions It has been determined that adding the sediment, consisting mostly of 3, to the clay raw mass in amount up to 10% doesn t have a noticeable influence on the strength properties of bricks. As a result of samples baking the liquid phase, formed on the surface of raw mixture grains, penetrates to the capillars, formed as a result of slight gas development, and acts as a cement binder, forming thin films at the phase contact. Gases are also get entrapped with fusion and pores are fixed. The effervescing vapourous and gaseous products contribute to the pore formation in the bulk of ceramic mixture, which reduces the density of ceramic products and improves their heat-insulating and sound-proofing properties. It was demonstrated that the products containing the highest content of water treatment sludge (50%) can be used for constructing non-critical structures. Acknowledgements The research work is carried out with financial support from Ministry of Education and Science of Russian Federation within the framework of Strategic Development Program of BSTU named after V.G. Shukhov for ( 2011-PR-146). References [1] N.. Kuvykin,.G. Bubnov, V.I. Grinevich, Hazardous waste, Ivanovo State University of Chemistry and Technology, Ivanovo, (In Russ.). [2] P.P. Palchunov,.V. Sumarokov, Industrial waste utilization, Stroyizdat, Moscow, [3] Information on [4] Europes Environment,Copenhagen: Europen Environment Agency, [5] N.. Schegolnikova, Sediment of water treatment plants: problem or business? Water Magazine. 9 (2015) (In Russ.). [6] I.V. Starostina, S.V. Sverguzova, I.V. Ovcharova, P.V. Besedin, E.A. Pendurin, E.M. Kuzina, Recycling of microbiological industry waste with the obtaining of foaming agents for building industry, International Journal of Applied Engineering Research. 21 (2015)

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