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Jumaeva Dilnoza Jurayevna, Ph. D., senior scientist of the laboratory "Colloid Chemistry" doctoral institute of General and Inorganic Chemistry Institute of the Academy of Sciences of Uzbekistan
E-mail: [email protected] Toirov Olimjon Zuvurovich, Ph. D., Senior scientist of the Institute of Power Engineering and Automation of the Academy of Science of Uzbekistan
E-mail: [email protected]
The obtainment of carbon adsorbents and their compositions for cleaning industrial wastewater
Abstract: The novel coal adsorbents based on Angren coal have been elaborated. They are the following: a) composite material obtained by addition in coal carbonates of alkaline-earth metals, allowing to rise sorption capacity adsorbent by 70-80% and use it can be used for sewage purification from some ions of inorganic impurities and decreasing of the water rigidity from 16.4 to 0.5 mg-eq/l; b) heat-treated at 550 °C, with hydrophobic properties (wetting angle a = 99°), a porosity of 30%, capacity to kerosene to 25% and the specific surface to 150 m 2/g which are suitable for purification of waste surface from oil-products; c) the activated coal, obtained by treatment of granular coal by water vapor at 800 °C, with the activity by the methylene blue is not less than 225 mg/g, the specific surface more 700 m 2/g and they can be used in the processes of waste purification from some dissolved organic impurities; d) oxidized by air at 180-200 °C (pre-heated Angren coal at 550 °C) with a high ion selectivity, capacity of 1.8 mg-eq/g and these adsorbents can be used for waste purification from some inorganic micro impurities.
Keywords: coal, adsorbent, industrial wastewater, treatment, hardness, softening, thermal activation.
Introduction the development of obtain methods of new eeffective
Coal adsorbents are widely used for purification and adsorbents based on brown coals of Angren deposit of
hardness decreasing of sewage in the metallurgy, oil- Uzbekistan by their thermal and steam-gas activation will
industry, chemical-industry and other fields of national promote to solution of some actual problems. economy. In connection with the increasing of their Analysis of investigations devoted to obtain and
necessity it is advisable to organize their production on using of the activated coal adsorbents for purification
the base of local raw materials [1-3]. The problem of in- of wastewater from some dissolved inorganic salts has
dustrial wastewater purification and reducing of their ri- showed that the problems of purification of industrial
gidity, has solved not only some environmental and also wastewater by activated coals are widely studied in litera-
economical problems but will promote to saving of raw ture. It is necessary to note that the decisive role at this is
materials and some other material resources. Therefore, devoted to microporesty of activated coals. However, at
present the purification of wastewater by the method of ion — exchanging has a great significance as this method has allowed to utilize some valuable impurities and to purify water to the required standards — maximum permissible concentration (MPC). Therefore, in literature it is proposed to oxidize activated coals with aim to impart them the ion-exchange properties. However, the expenditures on the oxidation of activated coals have raised their cost and decreased the profitableness of their using. It is known that many sorts of brown coals have natural cation-exchanging properties, due to the presence some humic components with carboxyl groups in their structure. The using of the adsorbents obtained on the base ofAngren coals will reduce not only the rigidity of water and purification from inorganic impurities, as well as to utilize some of heavy metals heaving in their composition. We have established the possibility of using of obtained coal adsorbents for the purification of flowing of the mine JSC "Koch-Bulak" JSC "Almalyk MMC" and also the waste ofJSC "Uzmetkombinat".
Results and discussion. In present study the following types of coal adsorbents on the base of brown coal of the Angren deposits were obtained for the first time for the effective purification of wastewater from the dissolved ions of inorganic impurities and petroleum products: a) composites with the addition of carbonates of alkaline-earth metals allowing enhance the sorption capacity of the adsorbents by 70-80%, they can be used for purification and reducing of their hardness from 16.4 to 0.5 mg-eq/l; b) the coal heat-treated at 550 °C with hydrophobic properties (wetting angle a = 99°, the porosity 30%, capacity to kerosene to 25%, and the specific surface to s = 150 m 2/g) suitable for the cleaning of surface of wastes from oil-products; c) the activated by water vapor treatment at 800 °C with the activity by methylene blue not less than 225 mg/g, with the specific surface more 700 m 2/g, which can be used for purification of wastewater from dissolved organic impurities; d) oxidized air at 180-200 °C (pre-heat-treated of Angren coals at 550 °C) with a high ion-changing selectivity and the capacity to 1.8 mg-eq/g.
In this paper we have investigated the composition of brown coals from Angren deposit of Uzbekistan Republic, their physic-chemical properties, the amount of humic acids (their amount was varied from 30 to 50%) and the total sum of carboxylic, hydroxyl and phenol groups. New methods of the coals activation and obtain on their base effective adsorbents and compositions used for waste purification were elaborated. The nature of the surface and changes occurring at the surface reactions
on Angren coal were investigated by methods of infrared spectroscopy (IRS), electron paramagnetic resonance (EPR) and thermograph. In particular it was shown the disappearance in IR- spectrum of bands of functional groups during heat treatment in the temperature range 200-800oC which increased the hydrophobicity of coal; and by EPR method the increasing of unpaired electrons concentration during heat treatment in the range 200-550oC was determined and also it was shown the formation of the "oxygen complex" on the surface of thermo-coal, which partly increased its hydrophilic-ity. The works by the investigation of ion exchange of cations of different charge (valence) at using of Angren coals have shown that the values of individual sorption of cations from aqueous solutions were significantly different and they can be carried out to the following series by their adsorption strength NH4+<Na+<Mg 2+<Cd 2+, Mn 2+, Sn 2+<Sr2+<Ca2+, Zn 2+, Fe 2+<Co 2+<Ni 2+, Al 3+<Ba 2+< <Cr 3+<Pb 2+<Cu 2+< Hg 2+<Fe 3+
which has differed from such obtained on strongly acid cationic exchangers of the type KU-2, but it is closer to series typical for the weak acid cationic exchangers of the type KB-4 [1].
These obtained data have suggested that Angren coals are typical weak-acid ion exchangers.
The initial local coals and obtained on their base adsorbents have been used at wastewater purification at JSC "Uzmetkombinat" and at the mine "Koch-Bulak", JSC "Almalyk MMC" (Uzbekistan). In mine waters of "Koch-Bulak" the content of cations Ca 2 +, Na + and anions SO42 -, Cl- and also the water rigidity have varied in wide ranges and in some months their content has exceeded the norms of the MPC. Series of experiments by wastewater purification of "Koch-Bulak" by Angren coal of the sort BSSH and also by the obtained composite coal adsorbent were carried out and obtained results are presented in Table 1.
From the data of Table I it is shown that the initial Angren coal and composite adsorbent obtained on its base have decreased in waste of mine "Koch-Bulak" the cations content: Ca 2+ from 230.42 to 24.25 mg/l; Na+ from 156.0 to 6.2 mg/l and anions: Cl- from 153.17 to 20.10 mg/l; SO42- from 2249.80 to 214.5 mg/l. The total rigidity ofwater has decreased from 16.4 to 8.1 mg.ekv/l. Thus, the rigidity of the mine waters has decreased in two time and content of such ions as Ca2+, Mg 2+, Na+, Cl- and SO 2- — to level of the MPC.
4
For purification of wastewater of the "Uzmetkombinat" from some contaminations the heat-treated, activated coals and some composite adsorbent obtained
on the base of Angren coal were tested. The heat treat- out by treatment with water vapor at 800 °C for 60 min.; ment of coal was carried out at temperature 550oC for composite adsorbents were synthesized by addition of 30 min. without of air; the activation of coal was carried alkaline earth metals salts to coal.
Table 1. - Wastewater purification of the mine "Koch-Bulak" JSC of the "Almalyk MMC" (Republic of Uzbekistan) by Angren coal and composite adsorbent, obtained on the it's base
№ Ingredients, mg/l Flowing of mine water of the "Koch-Bulak" Flowing purified by the initial coal of the sort BSSH Flowing purified by the composition on the base of the initial coal
1 Potassium, 9.30 6.8 3.0
2 Sodium 156.00 6.4 6.2
3 Calcium 230.42 105.45 24.25
4 Chlorides 153.17 29.58 20.10
5 Sulfates 2249.80 349.37 214.58
6 pH 8.0 8.0 7.8
7 CO^ 2.46 2.82 Not detected
8 The dry residue 3931.0 846.0 766.0
9 Total rigidity, mg.ekv./l 16.4 8.4 8.1
It was determined that at the thermal treatment of coal were obtained the hydrophobic (wetting angle was a > 99 °), high-porosity (pores volume was 30%) adsorbents with the capacity according to kerosene 25%.
New type of the activated coal adsorbents was obtained at treatment of Angren coal by water vapors which characterized by the micro porous structure with an activity by the methylene blue not less than 225 mg/g and the specific surface was over 700 m 2/g.
The obtained adsorbents were tested for wastewa-ter purification from dissolved inorganic impurities and oil- products at the JSC "Uzmetkombinat". Purification was carried out in three stages under static and dynamic
Table 2. - The results of wastewater purification of
conditions. The first stage was carried out in static conditions at using of thermo-treatment Angren coal; the second and third stages in dynamic conditions by activated coal and composite adsorbent. The obtained results are presented in Table 2.
From the data of this table it is shown that at wastewater purification of "Uzmetkombinat" by heat-treated and activated coals and also some composite adsorbents the purification degree has achieved norms of MPC.
It was found that petroleum products have adsorbed on the heat-treated and activated coals; but the composite adsorbent has adsorbed some cations of dissolved inorganic impurities and has decreased the water rigidity.
JSC "Uzmetkombinat" by some coal adsorbents
№ Name of the contamination The composition of wastewater of "Uzmetkombinat", mg/l After purification by heat-treated coal, mg/l (i-stage) After purification by activated coal, mg/l (II — stage) After purification by composite adsorbent, mg/l (ill-stage)
1 Oil products 12.9 2.5 - -
2 Potassium 3.0 2.8 2.6 1.0
3 Sodium 40.0 38.6 34.5 17.3
4 Calcium 100.4 95.6 90.2 26.2
5 Magnesium 22.7 22.6 21.0 8.2
6 Chlorides 53.2 52.0 48.7 8.4
7 Sulfates 169.8 167.0 158.0 42.0
8 PH 7.9 8.0 8.1 8.0
9 CO2 2.5 2.4 1.5 Not detected
10 The dry residue 531.0 490.6 418.8 188.6
11 Total rigidity, mg.ekv./l 8.9 8.4 8.0 0.5
Conclusion. Thus, some new methods of obtain of [2-7]: a) composite, obtained by addition to coal carbon-coal adsorbents on the base ofAngren coal were elaborated ates of alkaline-earth metals, with high sorption capacity
which can be used for sewage purification from some ions of inorganic impurities and decreasing of the water rigidity from 16.4 to 0.5 mg-eq/l; b) heat-treated at 550 °C, with hydrophobic properties (wetting angle a = 99°), a porosity of 30%, capacity to kerosene to 25% and the specific surface 150 m 2/g which are suitable for purification of wastewater surface from oil-products; c) the activated, obtained by treatment of granular coal by water vapor at 800 °C, with the activity by the methylene blue is not less than 225 mg/g, the specific surface is over 700 m 2/g and they can be used in the processes of wastewater purification from some dissolved organic impurities; d) oxidized by air at 180-200 °C (pre-heated Angren coal at 550 °C) with a high ion selectivity, capacity of 1.8 mg-eq/g and these adsorbents can be used for wastewater purification from some inorganic micro impurities.
The industrial tests were curried out by waste purification of the mine "Koch-Bulak" by composite adsor-
bents. The decreasing of cations: Ca 2+ from 230.42 to 24.25 mg/l; Na+ — from 156.0 to 6.2 mg/l and anions: Cl- from 153.17 to 20.10 mg/l; SO42- from 2249.80 to 214.5 mg/l was determined. Total rigidity of water decreased from 16.4 to 8.1 mg.ekv/l. Obtained results of waste purification of the abovementioned mine by content of some cations and anions have corresponded to norms of the MPC. It was proposed the three-stage purification of wastewater containing dissolved inorganic impurities and oil-products. It was shown that on the first stage of purification by the heat-treated Angren coal the degree of purification has reached 90%. On the second and third stages of purification at using of activated Angren coal and the composite adsorbent the degree of purification of wastewater has met the norms of the MPC. Industrial tests of the proposed adsorbents for wastewater purification at JSC "Uzmetkombinat" have yielded positive results.
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Zatuchny Dmitry Aleksandrovich, Doktor der technischen Wissenschaften Dozent Moskauer Staatliche Technische Universitätfür Zivilluftfahrt Dozent des Lehrstihles "Technischer Betrieb der elektronischen Ausstattung vom Lufttransport"
E-mail: [email protected]
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