Synthesizing Copper and Cobalt Phthalocyanines on the Basis of Coke�Plant Wastes A

Synthesizing Copper and Cobalt Phthalocyanines on the Basis of Coke�Plant Wastes A

ISSN 1068364X, Coke and Chemistry, 2012, Vol. 55, No. 5, pp. 179–183. © Allerton Press, Inc., 2012. Original Russian Text © A.V. Velichko, L.B. Pavlovich, L.A. Samigulina, 2012, published in Koks i Khimiya, 2012, No. 5, pp. 25–30. CHEMISTRY Synthesizing Copper and Cobalt Phthalocyanines on the Basis of CokePlant Wastes A. V. Velichkoa, L. B. Pavlovichb, and L. A. Samigulinab aZAO NauchnoProizvodstvennaya Kompaniya TERMO, Novokuznetsk, Kemerovo Oblast, Russia email: [email protected] bSiberian State Industrial University, Novokuznetsk, Kemerovo Oblast, Russia email: [email protected], [email protected] Received April 11, 2012 Abstract—The synthesis of copper and cobalt phthalocyanines from cokeplant waste—specifically, the pri mary distillation fraction from phthalic anhydride—has been developed. The introduction of this process in the phthalicanhydride shop at coke plants provides the opportunity for resource and energy conservation. DOI: 10.3103/S1068364X12050109 The conservation of energy and materials is espe highly selective. Accordingly, they are widely used for cially important for coke production. In coking, the removal of sulfur compounds from gas emissions unique aromatic hydrocarbons accumulate, but they [6] and the removal of mercaptans from petroleum are not extracted or utilized. The construction of coke fractions [7]. In addition, metal phthalocyanine pig batteries without equipment for trapping and process ments are important disperse organic dyes. They are ing the coking byproducts cannot be regarded as an stable with respect to light and the atmosphere, with environmentally acceptable approach. pure and bright coloration, universal in application, In the past, pyridines, phenols, indene, couma and resistant to chemical reagents [8]. rone, anthracene, carbazole, and other materials were Metal phthalocyanines are of particular interest for extracted from the coking byproducts, and highly use in microelectronic, electrochemical, and opto effective technologies were used for the production of electronic systems [9]. Films of phthalocyanine and highpurity mesitylene, pseudocumene, naphthalene, copper phthalocyanine are used in gas sensors [10]; and benzene. That is no longer the case. The only Rus and cobalt phthalocyanine is used as a cathode catalyst sian phthalicanhydride shop, at OAO ZSMK, has in the manufacture of galvanic elements [11, 12]. The been closed. semiconductor characteristics of these materials may It would be expedient to create systems capable of be enhanced and modified by molecular modification utilizing cokeplant wastes and byproducts in the pro [9]. They have also been used in carbon fibers and duction of specific materials that are in high demand: nanomaterials [13]. powder paints for coating the inner surface of gas pipe There is no industrial production of phthalocya lines; glass plastics; electrical and thermal insulators; nine pigments in Russia. In our view, the development and metalphthalocyanine catalysts and pigments [1– of production facilities for phthalocyanine catalysts 3]. By siting such facilities at coke plants, we may and pigments should be a high priority. reduce transport costs and also energy costs in the In laboratory and industrial conditions, copper preparation of the raw materials. In addition, existing phthalocyanine and cobalt phthalocyanine may be cokeplant equipment may be used for the purification produced by dry sintering and also in the presence of of exhaust gases and wastewater, with considerable plasticizing agents. The synthesis of copper phthalo reduction in capital costs. cyanine is investigated on the basis of the reaction of In the present work, we address practical matters urea, phthalic anhydride, and metal salts—copper(II) relating to the synthesis of cobalt phthalocyanine and sulfate, copper(I) chloride, copper(II) chloride, cop copper phthalocyanine: the technological conditions, per(II) acetate, and copper(II) carbonate—in the the recipe, the catalyst, the cobalt or copper salt, and presence of ammoniummolybdate catalyst, by the the plasticizer. following reaction Transitionmetal phthalocyanines are active cata () ⋅ C6H4CO3 ++8NH2 2CO CuCl2 2H2O lysts of the redox removal of NOx from gases [4, 5], as well as the oxidation of mercaptans, hydrogen sulfide, (NH4)2MoO4 C H N Cu++ 8NH 8CO and sulfohydryl compounds. Such phthalocyanines 32 16 8 3 2 are stable in the presence of sulfur compounds and are + CuCl2 + 4H2O. 179 180 VELICHKO et al. Tests results for reagents used in the synthesis of metal phthalocyanines* Composition, wt % Results of synthesis Time for color of metal yield, wt % Reagent phthalic metal salt urea synthesis, h phthalocy anhydride copper phtha cobalt phtha anine locyanine locyanine CuCl ⋅ 2H2O (I) 9.6 55.0 35.0 4 Bright blue 69.3 – CuCl2 ⋅ 2H2O 9.8 55.5 34.3 4 Bright blue 37.5 – CuSO4 ⋅ 5H2O 12.2 53.1 34.3 4 Dark blue 43.4 – Cu(CH3COO)2 ⋅ H2O 9.6 55.7 34.3 4 Black 18.0 – Cu(CH3COO)2 ⋅ H2O 8.6 54.7 36.3 30 Blue 31.6 – (CuOH)2CO3 9.0 54.4 36.2 4 Black 18.6 – (CuOH)2CO3 9.0 54.4 36.2 30 Blue 37.2 – CoCl2 ⋅ 6H2O 13.2 53.4 33.0 4 Blue – 30.0 CoSO4 ⋅ 7H2O 13.2 53.4 33.0 4 Blue – 35.0 Co(NO3)2 ⋅ 6H2O 13.9 53.3 32.8 4 Blue – 29.0 * Mole ratio of phthalic anhydride and metal salt 4 : 1; mole ratio of phthalic anhydride and catalyst 1 : 0.1; temperature during synthesis 195°C. In laboratory conditions, the copper phthalocya We find that, when using copper sulfate and chlo nine is produced by two methods. The first is based on ride, the copper phthalocyanine is formed in 2 h; the dry sintering of the components at 180–225°C and process is slower when using copper carbonate or ace heating for 3–30 h. Stoichiometric proportions of tate. For CuCl, the color of the product is bright blue, phthalic anhydride, urea, the copper salt, and ammo as against dark violet for CuSO4 and a dirty greenish nium molybdate are placed in heatresistant crucibles, blue for the other salts. The yield is 18–69.3% for cop with careful preliminary crushing and mixing by per phthalocyanine and 29–35% for cobalt phthalocy means of a mortar and pestle, placed in a cold drying anine. chamber, heated at 1.5 deg/min to the required tem Comparison of the IR spectra of all the samples perature, and held for a specified time. indicates little difference, except that the spectral In the second method, the copper phthalocyanine structure for copper phthalocyanine produced from is synthesized in the presence of plasticizing agents. CuCl is characteristic of the α modification. Derivato Stoichiometric properties of phthalic anhydride, urea, graphic analysis of copper phthalocyanine in compar the copper salt, ammonium molybdate, and the plas ison with the Dutch pigment adopted as the standard ticizer are placed in a 0.5dm3 threeneck flask, fitted indicates that the relative mass loss of the synthesized with a thermometer, a mixer, and a tube; the propor samples is greater, on account of the inadequate puri tion of the dry components and the plasticizer is fication and roasting of the copper phthalocyanine. 1 : 0.5–0.7. Experiments are conducted in the range We now consider the suitability of petroleum prod 180–225°C. The plasticizer is placed in the flask and ucts and cokeplant byproducts as plasticizers. Such heated to 80–100°C. Then the dry components (after materials are readily available, inexpensive, chemi preliminary crushing and mixing) are introduced. The cally inert, nontoxic, and technologically convenient. mixture is heated to the required temperature at Their viscosity is minimal, and their boiling point is 1.5 deg/min and held with constant mixing. above the temperature used in synthesis of the copper The copper phthalocyanine obtained is purified by phthalocyanine. The petroleum products considered solution in sulfuric acid (density 1.84 g/cm3), with are AMT300 oil, transformer oil, compressor oil, tur subsequent neutralization, filtration, and washing in bine oil, axle oil, and kerosene. The cokeplant hot water. The paste of copper phthalocyanine settles byproduct is a solvent. in the plasticizer and is filtered out in vacuum. The Analysis of the results shows that transformer oil and residue is washed with hot water and also purified with kerosene are suitable plasticizers. In the other cases, the sulfuric acid. After drying, we obtain a finely crystal metal phthalocyanines obtained are not subjected to line bluish violet powder. washing and drying in purification. The yield of copper Various copper and cobalt compounds are tested by phthalocyanine depends on the quantity of plasticizer sintering, so as to select the reagent that is cheapest (Fig. 1). Experiments show that the temperature is sta and most available. The table summarizes the test ble, there is no thickening of the reaction mass, and the results. kerosene separates well from the product. COKE AND CHEMISTRY Vol. 55 No. 5 2012 SYNTHESIZING COPPER AND COBALT PHTHALOCYANINES 181 Yield, wt % Thus, with respect to phthalic anhydride, the con 100 sumption standards for urea, the copper salt, and 1 ammonium molybdate are 100, 35, and 1.7 wt %, 80 respectively. 2 Industrial trials are conducted in the phthalic 60 anhydride shop at OAO ZSMK (Fig. 2). The raw material employed is the waste from phthalicanhy 40 dride production: the primary distillation fraction, 10 5432 6 7 which consists of yellow, pink, gray or brown flakes or Kerosine content, wt % dark brown melt with 98.0% phthalic anhydride; the crystallization temperature is 128°C. By contrast, for phthalic anhydride of superior and first grade, its con Fig. 1. Yield of copper phthalocyanine as a function of the tent is 99.8% and the crystallization temperature is plasticizer (kerosene) content: (1) CuCl (I); (2) CuSO4. 130.8 and 130.6°C, respectively. In the industrial trials, the copper phthalocyanine To optimize the conditions, we consider the influ is produced in a periodic reactor at 210°C and very low pressure, in the presence of kerosene.

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