PETROLEUM CONTAINING WASTEWATER PRODUCTS PURIFICATION BY CARBON-CONTAINING WASTES PYROLYSIS PRODUCTS

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1 PETROLEUM CONTAINING WASTEWATER PRODUCTS PURIFICATION BY CARBON-CONTAINING WASTES PYROLYSIS PRODUCTS Ilnar Abuzarovich Nasyrov, Aigul Ilgizovna Ahmadieva, Dinar Dilshatovich Fazullin, Gennady Vitalevich Mavrin, Mikhail Pavlovich Sokolov Kazan Federal University, Naberezhnye Chelny Institute ABSTRACT Due to the accumulation of production wastes and consumption and their annual environment in large volumes processing of production and solid municipal waste is urgent. Pyrolysis processing of carbonbearing waste, with receiving gaseous, liquid pyrolysis fuels and the firm rest containing a certain amount of carbon and being therefore a potential sorbent for sewage treatment from oil products is the alternative [1]. Research objects are firm products of carbon-bearing waste pyrolysis. Research objects are the indicators characterizing sorption properties of firm pyrolysis products in relation to the oil products which are contained in superficial and sewage-specific area, structure of a surface, efficiency of oil products sorption. The method of capillary condensation of nitrogen on the NOVA 4200e device of Quantachtrome determined the specific surface, volume and radius the pyrolysis products. The largest specific surface area at a pyrolysis wood sawdust - to 320 m2/g. The obtained data confirm existence of sorption properties that is confirmed with also sorption absorption of oil products. The method of the scanning electronic and x-ray microscopy studied element structure and structure of a surface of pyrolysis products. By means of the infrared KN-3 petro analyzer it is shown that the best sorption indicators in relation to oil products in model solutions are shown by a pyrolysis wood sawdust and waste of rubber. Isotherms of sorption of oil products are received. The maximum specific adsorption for toluene pyrolysis products of wood sawdust - is 10.9 mg/g and waste of rubber mg/g, hexane of 10.9 mg/g and 14.8 mg/g, the emulsified oil products of 27.1 mg/g and 20.1 mg/g - respectively. Thus, researches of sorption properties show prospects of use of pyrolysis products for cleaning natural and sewage from oil products. Keywords: pyrolysis, sorbent, activated carbon, wastewater, petroleum products, carbon-containing wastes. INTRODUCTION As research objects in the real hand the samples of pyrolysis products processing of carboniferous waste (USO) received on installation of low-temperature pyrolysis of a complex on processing of silt rainfall by method of continuous pyrolysis are taken. The following USO was exposed to pyrolysis processing: silt rainfall, wood waste (in particular, wood sawdust), rubber waste (worn-out automobile tires). The firm pyrolysis product received as a result of processing was studied as a potential sorbent for sewage treatment from oil products. It is known that, the adsorptive properties of sorbents depend on the size of a specific surface and on structure, i.e. on the size of a time and their distribution by the sizes [2]. The structure of the received carbonized influences adsorption process speed, defines forms of an isotherm and number of the absorbed molecules of various sizes. 1713

2 Researches of structure and properties of the potential sorbents received as a result of pyrolysis of USO are for this purpose conducted. METHODS Measurement of weight was taken on laboratory scales of RV 512 and analytical scales of RV 214. The ionometr ANION 4100 was applied to measurement of ph value of solutions. As an electrode of comparison the chlorsilver electrode, as a measuring electrode - a glass electrode of ESL was applied. The absolute error of measurement made 0,1 units рн. Hashing of solutions was carried out on a LAB-PU-02. For determination of bulk density the studied samples were located in previously weighed 20 ml cylinder and the volume occupied by coal before stirring was measured. Stirring time - 1 minute [3]. Definition of mass concentration of oil products was carried out by method IK-specter-photometry with application of a KN-3 concentration meter which principle of action is based on measurement by a photometer of optical density of solution of oil products in four-chloride carbon in infrared area of a range in the range of measurement from 0 to 100 mg/dm 3. The procedure of the analysis consists in extraction of the emulsified and dissolved oil components from water extraction by four-chloride carbon, chromatographic separation of oil products from the accompanying organic compounds of other classes on the column filled with oxide of aluminum and further measurement on the device. For assessment of sorption properties of the received sorbent through the columns filled with it with the set expense passed model water solutions a certain concentration of test substances. The sorbent was filled with height of 100 mm in number of 1 g in a glass column with an internal diameter of 10 mm, the 150 mm long and punched bottom. Adsorption was carried out on skilled filtering installation (fig. 1). Oil products in the received filtrate extracted four-chloride carbon and measured by method IK-specterphotometry (the device a KN-3 concentration meter) [4]. Figure 1. Scheme of skilled filtering installation 1- container with solution of test substance; 2-adjusting crane; 3-sorption column with a sample; 4 - withdrawal of a filtrate; 5-container 1714

3 For obtaining such characteristics as specific surface area, the size and volume of a time researches were conducted on sorption of gas on the Quantachrome 4200E device. Sorption desorption isotherms which are presented in figures 2 and 3 were received. Determination of specific surface area and porous structure was carried out with use of a method of the Brunauer - Emmett - Teller (BET). The t-method of Helsi was applied to scoping the micropores in the presence of a time of bigger diameter. Distribution meso- and macrotime by the size for a sample was determined by a method of Barret-Joiner- Halend (BJH). The BJH model applied to definition of porosity of a sample allows to calculate the volume of a time, as well as to construct the schedule of distribution of a time by the sizes in coordinates the radius of a time - the volume of the time corresponding to this radius [5,6,7]. RESULTS AND DISCUSSION Characteristics of the received pyrolysis products of silt rainfall, wood waste and waste of rubber are presented in table 1. Table 1. Characteristics of pyrolysis products sample color foreign substance surface area*, m^2/g pore volume, cc/g pore size, A solid pyrolysis sludge gray-black no solid pyrolysis wood waste solid pyrolysis rubber waste black no matt black no 49.0 [8] [9] - * - The specific surface area of pyrolysis products by the BET method 1715

4 Figure 2. Sorption-desorption isotherm (solid pyrolysis sludge) 1716

5 Figure 3. Sorption-desorption isotherm (solid pyrolysis wood waste) The result of processing of experimental data on the BET method shows that the specific surface area of a pyrolysis silt rainfall made 58.7 m2/g, wood waste m2/g. For comparison values of specific surface area of some sorbents are given in table 2. Table 2. Surface area of sorbents parameters fine-pored silica gel coarse-pored aluminosilicate activated carbon surface area*, m^2/g

6 As a result of processing of experimental data by a t-method received the following values: the volume of micropores of pyrolysis products of silt rainfall is equal to cm3/g, wood waste cm3/g. Results of processing of experimental data on the BJH method are presented in table 3. Table 3. Results of processing of experimental data on a t-method and BJH method parameters pyrolysis products sludge wood waste micropore volume, cc/g meso- and macropores volume, cc/g pore size, A For comparison indicators for some sorbents are given in table 4 [2]. Table 4. Volume and pore size parameters parameters fine-pored silica gel coarse-pored aluminosilicate activated carbon pore volume, cc/g pore size, A less than 70 The obtained data (specific surface area, volume and radius of a time) allow predicting presence at pyrolysis products of sorption properties in relation to oil products. According to the X-ray phase analysis the main components of a pyrolysis silt rainfall are carbon, oxygen and nitrogen. High content of organic compounds in solid of a silt deposit causes the total maintenance of these components about 83% of element structure of the analyzed pyrolysis product. Less than 17% of element structure is the share of a mineral part. The main components of a pyrolysis waste of wood are carbon and oxygen. The total maintenance of these components more than 99% of element structure of the analyzed pyrolysis product. The received results are presented in tables 5 and 6. Table 5. Elemental composition of the pyrolysis sludge 1718

7 Element Mass, % C N O Na 0.02 Mg 0.27 Al 1.46 Si 2.17 P 0.37 S 0.65 K 0.27 Ca 1.36 Ti 0.16 Fe 7.25 Zn 3.26 Table 6. Elemental composition of the pyrolysis wood waste Element Mass, % C O Mg 0.08 Al 0.16 Si 0.10 K 0.14 Ca 0.25 Results of measurements of bulk density of pyrolysis products are presented in table

8 Table 7. Bulk density of pyrolysis products and activated carbon sample bulk density, g/dm 3 solid pyrolysis sludge solid pyrolysis wood waste solid pyrolysis rubber waste activated carbon standard Preceding from the received results it is possible to draw the following conclusion: the bulk density of absorbent carbon of the BAU brand made g/dm 3, at standard value in accordance with GOST "Coal active wood shredded" g/dm 3. For comparison values of bulk density of the known adsorbents [2] are presented in tab. 8. Table 8. Bulk density of adsorbents parameters fine-pored silica gel coarse-pored aluminosilicate activated carbon bulk density, g/dm The values of bulk density of pyrolysis products received during definition do not concede in comparison with the known adsorbents. Also make for silt rainfall g/dm 3, wood waste g/dm 3, rubber waste g/dm 3. Mass content of oil products in a water extract of pyrolysis products was defined by method IK-specterphotometry. Table 9. Content of petroleum products sample mass concentration of petroleum products, mg/dm 3 solid pyrolysis sludge 2.36 solid pyrolysis wood waste 2.26 solid pyrolysis rubber waste 1.47 activated carbon 1.08 standard *

9 * The Government Act of the Russian Federation of November 3, 2016 N 1134 "About questions of implementation of cold water supply and water disposal". Content of oil products in a water extract of pyrolysis products of silt rainfall, waste of wood and rubber does not exceed maximum allowable concentration. Sorption properties of pyrolysis products in relation to oil products it was studied by method IK-specterphotometry on model solutions [10,11]. The results received during definition of sorption properties of pyrolysis products are presented in tables 10 and 11. Table 10. Mass content of petroleum products sample concentration, mg/dm 3 benzene hexane kerosene toluene epp * stock solution filtrate after the pyrolysis of the sludge filtrate after the pyrolysis of wood waste filtrate after the pyrolysis rubber waste filtrate after activated carbon * epp-emulsified petroleum products Table 11. Degree of sorption sample R, % benzene hexane kerosene toluene epp sludge wood waste rubber waste activated carbon Data on a commodity coal sorbent of the BAU brand are provided in tables 10 and 11 for comparison. The pyrolysis waste of rubber showed the best results from three examinees of pyrolysis products and almost does not concede on extent of sorption to a commodity sorbent of BAU. If in relation to kerosene extent of sorption made 88,4%, then for other studied model solutions varied from 33,7 to 85,7%. 1721

10 After studying of sorption properties of pyrolysis products sorbents with the best results were chosen. Further by a standard technique for determination of sorption capacity of a sorbent sorption isotherms were under construction under optimum conditions on oil products. Results are presented in tables On the basis of the received values (tab. 12,14,16), sorption capacity (and, mg/g) paid off [12]. Results are presented in tables 13,15,17. Table 12. Sorption of dissolved petroleum products (toluene) initial concentration, mg/l concentration after sorption, mg/l degree of sorption, % pyrolysis of the sludge pyrolysis of wood waste pyrolysis of the sludge pyrolysis of wood waste 2.07 ± ± ± ± ± ± ± Table 13. Sorption capacity initial concentration, mg/l а, mg/g pyrolysis of the sludge pyrolysis of wood waste Also the schedule in coordinates was under construction: "sorption capacity initial concentration" (fig. 4). 1722

11 Figure 4. Isotherms of sorption of dissolved petroleum products (by toluene) by pyrolysis products: rubber waste; b) wood waste (without saturation) Given according to the analysis of an isotherm (fig. 4) gives the grounds to claim that in a point of saturation of their projection to ordinate axis point to the size of the sorption capacity (SC) in relation to oil products. It is defined that the maximum sorption capacity on NP made for pyrolysis products of wood sawdust - 10,8 mg/g and pyrolysis products of waste of rubber - 10,6 mg/l. Table 14. Sorption of dissolved petroleum products (hexane) concentration after sorption, mg/l degree of sorption, % initial concentration, mg/l pyrolysis of the sludge pyrolysis of wood waste pyrolysis of the sludge pyrolysis of wood waste 1.37 ± ± ± ± ± ± ± ±

12 Table 15. Sorption capacity initial concentration, mg/l pyrolysis of the sludge а, mg/g pyrolysis of wood waste Figure 5. Isotherms of sorption of dissolved petroleum products (by hexane) by pyrolysis products: rubber waste; b) wood waste (without saturation) The analysis of the table showed that with increase in concentration of the dissolved NP (hexane) sorption capacity on oil products increases in solution. The largest sorption capacity on NP made for pyrolysis products of wood sawdust mg/g and pyrolysis products of waste of rubber mg/g. Table 16. Sorption of emulsified petroleum products initial concentration, mg/l concentration after sorption, mg/l degree of sorption, % 1724

13 pyrolysis of the sludge pyrolysis of wood waste pyrolysis of the sludge pyrolysis of wood waste 5 ± ± ± ± ± ± ± Table 17. Sorption capacity initial concentration, mg/l а, mg/g pyrolysis of the sludge pyrolysis of wood waste

14 Figure 6. Isotherms of sorption of emulsified petroleum products by pyrolysis products: rubber waste; b) wood waste (without saturation) The largest sorption capacity on the emulsified NP made for pyrolysis products of wood sawdust mg/g and pyrolysis products of waste of rubber mg/g. SUMMARY 1. By means of low-temperature pyrolysis samples of firm pyrolysis products of silt rainfall, wood waste and waste of rubber are under production conditions received. 2. According to the X-ray phase analysis the main components of a pyrolysis silt rainfall are carbon, oxygen and nitrogen. The total maintenance of these components about 83% of element structure of the analyzed pyrolysis product. Less than 17% of element structure is the share of a mineral part. The main components of a pyrolysis waste of wood are carbon and oxygen. The total maintenance of these components more than 99% of element structure of the analyzed pyrolysis product. 3. The specific surface area of a firm pyrolysis silt rainfall by the BET method made 58.7 m2/g, wood waste m2/g. The volume of a time by the BJH method made cm for a pyrolysis silt rainfall3/g, a pyrolysis waste of wood cm3/g. The obtained data confirm existence of sorption properties that is confirmed with also sorption absorption of oil products. 4. The values of bulk density of pyrolysis products received during definition do not concede in comparison with the known adsorbents. Also make for silt rainfall g/dm 3, wood waste - 295,2 g/dm 3, rubber waste g/dm Sorption properties of pyrolysis products in relation to oil products were studied by method IK-specterphotometry on model solutions. The pyrolysis waste of rubber showed the best sorption properties in relation to NP. For model solution of kerosene extent of sorption made 88.4%, for other studied model solutions varied from 33.7 to 85.7%. Isotherms of sorption of NP, the maximum specific adsorption of toluene by pyrolysis products of wood sawdust mg/g and pyrolysis products of waste of rubber mg/g, hexane of 10.9 mg/g and 14,8 mg/g, the emulsified oil products of 27.1 mg/g and 20.1 mg / г-respectively are received. 1726

15 CONCLUSIONS Thus, the conducted researches show prospects of use of pyrolysis products for cleaning natural and sewage from NP. Use of the offered sorption materials from pyrolysis products processing of USO will promote: - reduction of the saved-up ecological damage; - reduction of the areas under temporary and long storage of USO; - decrease in emission of harmful substances by production of sorbents from waste in comparison with technologies where are used natural mineral or organic raw materials; - development of technology of pyrolysis processing of carbon-bearing waste and technology of receiving new sorbents from production wastes and consumption; - extension of the nomenclature of sorption materials due to production of new effective and cheap sorbents from waste; - increase in volumes of the purified waste water from oil products in the region where production and use of such sorption materials can be organized; - increase in efficiency of works at emergency oil spills and oil products with use of the offered sorbents; - increase in production of the accompanying production of pyrolysis of USO - electro-and heat power that will allow to make manufacturing techniques of sorbents energetically self-sufficient; - decrease in logical costs for the treatment of carbon-bearing production wastes and consumption. ACKNOWLEDGEMENTS The work is performed according to the Russian Government Program of Competitive Growth of Kazan Federal University. REFERENCES The problem of disposal sludge treatment plants. Ilnar A. Nasyrov, Vilnus M. Ahmetov, Munir N. Miftahov, Gennady V. Mavrin and Mikhail P. Sokolov//International Journal Of Pharmacy & Technology. 8(2), 2016, pp Nikolsky B.P. Reference book by the chemist. Raw materials and products of the industry of inorganic substances. Processes and devices. Corrosion. Himiya publishing house, Moscow, vol. 5. part 2, pp. 973, GOST Coal the active clarifying wood powdery. Specifications. Removal of oil products and phenol from waste water by composite sorbents under dynamic conditions. Dinar D. Fazullin, Gennady V. Mavrin and Ruben G. Melkonyan Chemistry and Technology of fuels and Oils/" Springer Science + Business Media, Inc." Vol.50., No. 1, March, River Recent development in the treatment of oily sludge from petroleum industry: A review. Guangji Hua, Jianbing Li, Guangming Zeng//Journal of Hazardous Materials 261, 2013, pp Adsorption of Benzene on Activated Carbon from Agricultural Waste Materials. Akpa J.G.1 and Nmegbu C.G.J.//Research Journal of Chemical Sciences, Vol. 4(9), September, 2014, pp E.A. Taiwo, J.A. Otolorin, Oil recovery from petroleum sludge by solvent extraction, Petrol. Sci. Technol. 27, 2009, pp Novichkov Y.A., Petrenko T.V., Bratchun V.I. Investigation of the process of anoxic pyrolysis of worn automobile tires//bulletin of the Kharkov National Automobile and Highway University, 29,

16 Novichkov Y.A., Khazipov V.A., Petrenko T.V. High-quality carbon sorbent - a processing of automobile tires//the Bulletin of the Kharkov national motor-road university, 34-35, Modified PTFE-PANI Membranes for the Recovery of Oil Products from Aqueous Oil. Dinar D. Fazullin, Gennady V. Mavrin and Ildar G. Shaikhiev//Petroleum Chemistry, 2017, Vol. 57, No. 2, pp Distillation of petroleum products from water by hydrophobic membranes. Dinar D. Fazullin, Radif R. Zinnatov, Ilnar A. Nasyrov, Elvina V. Prytkova, Elena A. Kharitonova//Research Journal of Pharmaceutical, Biological and Chemical Sciences. No. 7(4), 2016-P Sorption properties of carbon waste pyrolysis product for biological wastewater treatment. Ilnar A. Nasyrov, Stanislav V. Dvoryak and Ildar G. Shaikhiev//Acta Technica. 61 (4B/2016), 2016, pp