CC BY
25
7. Methods of analysis of phosphate rock, phosphate and compound fertilizers, feed phosphates./M. Vinnik, Er-banova LN etc. - M.: Chemistry. - 1975-218.
8. GOST 30181.4-94. Mineral fertilizer. Method for determination of total mass fraction of nitrogen in compound fertilizers and nitrate in ammonium and nitrate forms (Devarda method). - M.: Publisher IPC Standards, -
1996. - 8 p.
9. GOST 20851.2-75. Mineral fertilizer. Methods for determination of phosphate. - M.: Publisher IPC Standards, -
1997. - 37 p.
DOI: http://dx.doi.org/10.20534/AJT-16-9.10-95-100
Sobirov Mukhtorjon Mahammadjanovich, Junior scientific researcher Academy of Sciences Republic of Uzbekistan Institute of General and inorganic chemistry, Tashkent, Uzbekistan, E-mail: fcb-m-2011@mail.ru Tajiev Sayfuddin Muhitdinovich, PhD in chemistry, Head of laboratory of Complex fertilizers, Academy of Sciences Republic of Uzbekistan Institute of General and inorganic chemistry, Tashkent, Uzbekistan, E-mail: sayf49@rambler.ru Sultonov Bokhodir Elbekovich, PhD in technique, senior reseacher of Laboratory of Phosphorous fertilizers,
Academy of Sciences of the Republic of Uzbekistan, Institute of General and inorganic chemistry, Tashkent, Uzbekistan.
E-mail: bse-chemist-68@mail.ru
Obtainment of suspended phosphorus-potassium containing nitrate
Abstract: In this study, process of obtaining suspended phosphorus-potassium containing fertilizers based on decomposition phosphorite from Central Kyzylkum in nitric acid subsequence mixing potassium chloride and ammonium nitrate obtained by neutralization of nitric acid with gaseous ammonia, has been studied. It is determined that decomposition coefficient of phosphorite flour depending on the norm of nitric acid. Triple N: P2 O5: K2 O fertilizer was obtained when ratio from 1:0.5:0.5 to 1:1:2.
Keywords: phosphorite flour, nitric acid, potassium chloride, processing phosphorite, and ammonium nitrate.
Introduction. There are some ways of producing com- 21% P2 O5 and it is obtained by granulation method. The
plex fertilizers based on ammonium nitrate with phospho- resulting complex fertilizer contents 32-34% of nitrogen
rus additives [1], potassium [2] or sulfur [3]. A drawback and 2-6% P2 O5, but drawback of the method is limited
of known methods consists in using scarce and expensive possibility of expanding the range of produced fertilizers.
reagents such as thermal phosphoric acid and potassium Besides, the method can not produce a triple NPK-fertil-
nitrate, and fine-dispersed ammonium sulphate. izer with potassium component in form potassium chlo-
In [4] the way for producing complex fertilizer based ride that is available, as the introduction of the latter in
on ammonium nitrate containing, except nitrogen, has the ammonium nitrate melt with a temperature of170 °C
additionally another nutrient, namely phosphor com- will be result in decomposition of the explosive mixture.
prising mixing the ammonium nitrate melt with a phos- A new trend in the improvement of fertilizer is to
phorus reagent. For that way nitrogen-phosphate fertil- create suspended fertilizers, i. e. liquids, in which a su-
izer is used as component which contents from 13 to persaturated solution, the crystals of soluble salt nutri-
ent are in suspended condition. Application of fertilizers suspended allows obtaining any ratio of nutrients. The production does not require large capital investments, and can be as close as possible to the places of consumption. Using suspended fertilizer makes possible to organize individual providing nutrients to any particular field. Flexibility in the choice of the ratio between the nutrients components avoids making excessive doses of the mineral fertilizer, which not only reduces the cost of their purchase, but also improve the ecological environment clean and products.
Complex suspended fertilizers are convenient and profitable for farmers for several reasons. Advantage of fertilizers is complete absence of manual labor when using these fertilizers. There is the possibility of applying fertilizers with irrigation during preparation of soil for sowing, their combination with pesticides and other necessary ingredients. Farmers appreciate them for the benefits connected with uniformity of their application, and therefore, the synchronization of maturation of plant due to absence of caking and dissipation, characteristic for dry fertilizer mixtures.
Suspended fertilizer is also well-tested in the practice of the method and subsequent agrochemical effective for their application in various soils and for different crops. Notably it is widespread of this method has received in the United States and in countries Western Europe. Over 65% of liquid fertilizers are used in 10 leading agricultural states such as Iowa, Illinois, Nebraska, Californium, Texas, Indiana, Kansas, Ohio, Minnesota and Georgia [5].
It is well known that method of producing liquid nitrogen fertilizer by mixing urea, ammonium nitrate and the subsequent introduction in the composition of microelements [6]. The disadvantage of this fertilizer is the introduction of micronutrient is carried out by coarse dissolving them in a melt of ammonium nitrate, which complicates production technology. Moreover, it does not include other nutrients as phosphorus and potassium.
There is also a liquid nitrogen fertilizer, and its production method comprising urea, ammonium sulfate, ammonium nitrate and water. Fertilizer was created in order to maximize the use of ammonium sulfate solution, while maintaining the nitrogen content at a level that provides agrochemical efficiency of fertilizers and maintaining its properties during transportation and storage. The disadvantage of this fertilizer is that it contains only sulfur and nitrogen, does not include other macronutrients [7].
As it is from the above noted that development of rational technology of complex suspended nitrogen,
phosphorus, potassium, and calcium-containing fertilizers based on nitric acid decomposition of phosphorite flour from Central Kyzylkum at a reduced norm of acid, potassium chloride and ammonia is a topical object.
Objects and methods. Experiments were conducted in a laboratory apparatus consisting of a tubular glass reactor equipped with helical stirrer driven by an electric motor. In the synthesis of new types of suspended fertilizers high calcareous containing phosphorite flour was used with composition (weight.%.): 17.55 — P2O5; 43.68 — CaO; 14.83 — CO2; 1.68 — MgO; 2.472 — R2O3; 1.01 — SO3; 2.17 — F; 1.19 — H2O; 3.80 — insoluble residue, potassium chloride from Dehkanabad plant potassium fertilizers (K2O — 60%), gaseous ammonia and 58.50% of nitric acid. Norma of nitric acid was varied in the range of 30-70% of the stoichiometry on the decomposition of carbonate and phosphate minerals ofphosphorite flour to form calcium phosphate and calcium nitrate.
To obtain complex suspended phosphorus-potassium-nitrate the phosphorite flour was decomposed by first part of the nitric acid. The remainder of the nitric acid is neutralized with gaseous ammonia; this result in a 64.16% ammonium nitrate solution is formed. The decomposition process of phosphorite flour by acid is easily feasible. Interaction of the components is virtually completed within 15-20 min. The temperature of the process ranges at 30-45 °C according to the norm acid. To improve the quality and properties of the compound suspended fertilizer the calculated amount of 64.16% solution of ammonium nitrate and potassium chloride was added into obtained nitrogen phosphoric slurry under constant stirring. The water content of the slurry was maintained at 30% H2O.
The contents of all forms of P2O5 (total, acceptable, water-soluble) in the products obtained was determined by photocalorimetric as a yellow complex phosphorus-vanadium- molybdenum complex on photo calorimeter CPC-3 (A. = 440 nm) [8]. The nitrogen content is by the distillation of ammonia on Kjeldahl and chloramine method [9]. Determination of potassium content in the obtained samples was determined as described in [10]. Determination of the content of all forms of calcium was carried out by complexometric titration volume Trilon B in the presence of calcein or chrome dark blue indicators [11]. Expansion coefficient (Ec) was calculated using the formula, where - P2O5acc. is an acceptable form of 2% citric acid, P2O5tot. is a total phosphorus content of the fertilizer samples. The water content in the obtained fertilizer samples was determined by calculation.
Results and discussion. The suspended nitrogen-phosphorus-potassium-calcium-containing fertilizer (N: P2O5: K2O = 1: 1: 1) obtained at 30% norm of nitric acid contains 7.10% of total nitrogen, of which 35.07% is in the ammonium and the remainder of 64.93% is in the nitrate form, 7.11% of P2O5total., of which 34.88% is in acceptable form, 7.10% of K2O,
Table 1. - Chemical composition of suspended
17.67% of CaOtot. of which 34.52% of CaO is in acceptable form (Table. 1). It mainly consists of calcium nitrate - 12.46% ammonium nitrate - 14.21% of mono-and dicalcium phosphate, as well as phosphorite flour in activated form - 28.32% and potassium chloride -11.83%. The amount of nutrients N + P2O5 + K2O + CaO is 38.98%.
phosphorus-potassium-containing nitrate, %
N: P2O5: O N P2O5 CaO ° Ec
total nitrate ammonium total accep. total accep.
When norm of HNO, 30%
1:0.5:0.5 11.01 63, 4.68 5.5 1.99 U.70 4.79 5.50 27.25 ,6.18
1:0.7:0.5 9.29 5.61 ,.67 6.50 231 16.21 5.6, 4.64 27.68 ,5.54
1:0.7:0.7 9.02 5.46 ,.57 631 2.25 15.72 5.47 631 26.84 ,5.66
1:1:1 7.10 4.61 2.49 7.11 2.48 17.67 6.10 7.10 26.45 ,4.88
1:1:2 634 4.11 2.22 635 2.2, 15.80 5.46 12.69 2,.65 ,5.12
When norm of HNO, 40%
1:0.5:0.5 10.97 6.58 439 5.48 2.5, U.65 6.22 5.48 27.26 46.17
1:0.7:0.5 9.25 5.92 ,3, 6.48 2.96 16.1, 732 4.62 27.69 45.68
1:0.7:0.7 8.98 5.75 6.29 2.88 15.66 7.11 6.29 26.86 45.79
1:1:1 7.06 4.94 2.12 7.07 ,.19 17.59 7.94 7.07 26.47 45.12
1:1:2 632 4.41 1.89 632 2.86 15.74 7.11 12.6, 2,.68 45.25
When norm of HNO, 50%
1:0.5:0.5 10.9, 6.81 4.11 5.46 ,.11 U.60 7.66 5.46 27.27 56.96
1:0.7:0.5 9.21 6.22 2.99 6.45 16.06 9.04 4.60 27.70 56.28
1:0.7:0.7 8.94 6.04 2.91 6.26 15.59 8.77 6.26 26.87 5639
1:1:1 7.0, 5.27 1.76 7.02 ,.9 17.51 9.79 7.0, 26.48 55.56
1:1:2 6.29 4.71 1.57 6.29 ,.51 15.67 8.76 12.58 2,.71 55.80
When norm of HNO, 60%
1:0.5:0.5 10.94 7.11 ,.8, 5.46 ,.65 U.61 9.06 5.47 27.27 66.85
1:0.7:0.5 9.2, 6.54 2.67 6.46 4.28 16.08 10.66 4.61 27.69 66.25
1:0.7:0.7 8.96 635 2.60 6.27 4.16 15.61 1035 6.27 26.86 6635
1:1:1 6.66 532 6.65 436 16.58 10.96 6.66 26.67 65.56
1:1:2 5.99 4.78 1.20 5.99 ,.94 14.92 9.87 11.99 24.01 65.78
When norm of HNO, 70%
1:0.5:0.5 10.95 7.4 ,.55 5.47 4.1, U.6, 10.50 5.47 27.26 75.50
1:0.7:0.5 9.24 6.88 236 6.47 4.86 16.11 1234 4.62 27.69 75.12
1:0.7:0.7 8.97 6.68 2.29 6.28 4.72 15.6, 11.97 6.28 26.86 75.16
1:1:1 631 537 0.94 632 4.72 15.7, 12.07 631 26.84 74.68
1:1:2 5.70 4.85 0.85 5.71 4.27 14.2, 10.92 11.42 24.29 74.78
With increasing amounts of ammonium nitrate to the decomposition coefficient of phosphorite flour is in-26.75% in the composition of the slurry, i. e. with change creased from 34.88% to 36.18%. the ratio of N: P2O5: K2O of from 1: 1: 2 to 1: 0.5: 0.5,
With an increase the norm of nitric acid from 40% to 70%, the content of acceptable phosphorus and calcium raised from 2.86% to 4.27%, from 7.11% to 10.92% respectively. The decomposition coefficient of phosphate flour increased from 45.25% to 74.78%.
We have also studied the change of water-soluble forms of calcium and phosphorus in the resulting phosphorus-potassium containing suspended nitrate (Fig.
1) depending on the norms of nitric acid and the ratio of nutrients. It is found that with increasing nitric acid water-soluble form of calcium and phosphorus increases. For example, at a ratio of N: P2O5: K2O from 1: 1: 2 and a nitric acid norm of 30%, content water-soluble forms of phosphorus and calcium is 0.23% and 3.79% and the acid norm of 70% is equal to 1.23% and 8.04%, i. e. increased 5.35 and 2.12 times, respectively.
Figure 1. Changing water-soluble content of P2 05 (a) and CaO (b) depending on the norm of HNO3 and ratio of N: P2 O5. K2 O
Table 2. - Salt composition of suspended phosphorus-potassium -containing nitrate,%
N: P2O5: O NH NO, 4 3 Са (NO3)2 Mono-dical-cium phosphate Activated phosphorite KCI
1 2 3 4 5 6 7
When norm of HNO3 30%
1:0.5:0.5 26.75 9.63 3.75 21.95 27.25 9.16
1:0.7:0.5 21.00 11.44 4.36 25.98 27.68 7.74
1:0.7:0.7 20.37 11.06 4.25 25.20 26.84 10.52
1:1:1 14.21 12.46 4.68 28.32 26.45 11.83
1:1:2 12.71 11.12 4.21 25.32 23.65 21.15
When norm of HNO, 40%
1:0.5:0.5 25.09 12.81 4.73 18.75 27.26 9.13
1:0.7:0.5 19.07 15.15 5.53 22.17 27.69 7.71
1:0.7:0.7 18.5 14.70 5.38 21.50 26.86 10.48
1:1:1 12.14 16.52 5.96 24.16 26.47 11.78
1:1:2 10.86 14.77 5.34 21.62 23.68 21.05
When norm of HNO 50%
1:0.5:0.5 23.44 15.95 5.78 15.57 27.27 9.09
1:0.7:0.5 17.15 18.85 6.75 18.40 27.70 7.68
1:0.7:0.7 16.64 18.29 6.56 17.85 26.87 10.44
1:1:1 10.07 20.51 7.26 20.04 26.48 11.72
1:1:2 9.01 18.38 6.53 17.94 23.71 20.96
1 2 3 4 5 6 7
When norm of HNO, 60%
1:0.5:0.5 21.9 19.14 6.72 12.47 27.27 9.10
1:0.7:0.5 15.32 22.65 7.89 14.73 27.69 7.69
1:0.7:0.7 14.87 21.98 7.66 14.29 26.86 10.45
1:1:1 7.63 23.31 8.03 15.18 26.67 11.10
1:1:2 6.87 21.05 7.26 13.67 24.01 19.97
When norm of HNO3 70%
1:0.5:0.5 20.33 22.38 7.59 9.28 27.26 9.12
1:0.7:0.5 13.43 26.47 8.93 10.96 27.69 7.70
1:0.7:0.7 13.04 25.69 8.67 10.64 26.86 10.46
1:1:1 5.37 25.86 8.68 10.68 26.84 10.52
1:1:2 4.86 23.36 7.85 9.66 24.29 19.02
As it is seen from the tabulated data that with a change in a N: P2O5: K^O salt composition ofthe complex suspended fertilizer changed considerably. For example, at a ratio of N: P2O5: K2O = 1: 0.5: 0.5, and 30% norm of nitric acid, the suspended fertilizer composition is the following: calcium nitrate — 9.63% ammonium nitrate — 26.75% and mono- dicalcium phosphate — 3.75% and phosphorite flour in an activated form — 21.95% (Table 2.). By changing the ratio of N: P2O5: K2O from 1: 0.5: 0.5 to 1: 1: 2 in one and the same norm ofnitric acid in the obtained complex suspended fertilizer content ofthe main component is increased except the ammonium nitrate. For example, at a 50% norm of nitric acid with a change the ratio of N: P2O5: K2O from 1: 0.5: 0.5 to 1: 1: 2 content of calcium nitrate, mono- and dicalcium phosphate, phosphorite flour in activated form is increased from 15.95 to 20.51 from 5.78 to 7.26, and from 15.57 to 20.04%, respectively, ammonium nitrate content is decreased from 23.44 to 9.01%.
The rheological properties of the suspended fertilizer: density, viscosity, and crystallization temperature are important as they determine the conditions of production, storage, transportation and application into the soil. Therefore, we was studied the rheological properties of the suspended complex fertilizers. Research shows that with an increase the temperature, decrease of vis-
cosity and density of the fertilizer suspension are observed. The crystallization temperature of the suspended fertilizer varied from -6 to 7 °C. The suspended fertilizer containing higher concentrations of calcium nitrate, i. e. obtained at raised norm of nitric acid has higher crystallization temperature. pH of the suspended complex fertilizer depending on norm of acid and ratio of nutrients in the range 4.5-6.5.
Increasing the norm of nitric acid promotes increase of the acceptable forms of phosphorus and calcium, but it is unsuitable to increase the norm of acid from this point of view, since in this case there is overspending acid. Therefore, we consider that the optimal norm of nitric acid is 50-60%. The most common a N: P2O5: K2O in the complex fertilizer for the main crops — cereals, sugar beet, cotton, potatoes, vegetables, fodder root crops — are the following: 1: 0.7: 0.5; 1: 1: 1, 1: 1: 2 ratio and these are optimal.
Conclusion. The principal possibility of obtaining new effective forms of suspended fertilizer universal action on the basis of local raw materials experimental way has been obtained. The proposed suspended complex NPK-fertilizer in comparison with standard solid mineral fertilizer is characterized by simple production and meets the basic requirements established in agricultural production.
References:
1. Production of ammonium nitrate in aggregates with high unit capacity/under editor V. M. Olevsky, second ed., - M.: Chemistry, - 1990, - 130-164 p.
2. RF patent № 2182144, IPC 7 S05G 1/001, publ. 10, 05, - 2002.
3. RF Patent № 2279416, publ. 10.07.2006.
4. RF patent № 2253639, IPC 7 S05S 1/02, publ. 10.06.2005.
5. Levin BV On the state and prospects for the production of mixed mineral fertilizers (fertilizer mixtures) in Rus-sia//World of sulfur, N, P and K - 2009, - No3. 3-13 p.
6. Author's certificate USSR 1279982, MKI S05D 9/02 1983.
7. Patent RB TA (11) 3173 C1, S05S 9/00, S05S13/00, publ. 12.30. - 1999.
8. GOST 20851.2.75. Methods for determination of phosphorus content. - M.: Ed. standards, - 1983. - 22 p.
9. GOST 30181.4-94 Methods for determination of total mass fraction of nitrogen in compound fertilizers and nitrate in ammonium and nitrate forms (Devard method).//Intergovernmental Council for Standardization, Metrology and Certification - Minsk - 1996. - 7 p.
10. GOST 20851.3-93 Mineral fertilizers. Methods for determination of potassium. Intergovernmental Council for standarizatsii, Metrology and Certification - Minsk - 1995. - 11-18 p.
11. Vinnik M., Erbakova L. I., Zaitsev G. I. Methods for analysis of phosphate raw materials, phosphate and compound fertilizers, feed phosphates/ - M.: Chemistry, - 1975. - 218 p.
DOI: http://dx.doi.org/10.20534/AJT-16-9.10-100-104
Choriev Azimjon Uralovitch, Karshi State University, Senior Lecturer the Faculty of Natural Sciences, Department of Chemistry E-mail: azimjon-organik@mail.ru Abdushukurov Anvar Kabirovitch, National University of Uzbekistan named after Mirzo Ulug'bek, professor the Department of Organic Chemistry E-mail: abdushukurov-ximik@mail.ru
Synthesis of 4-hydroxy-w-chloracetophenones
Abstract: This paper reports a synthesis of 4-hydroxy-w-chloracetophenone as a catalyst using MoCI5, WCI6, SnCI4, VCI3 The mechanism has not been studied. It was studied the influence of the ratio of reactants, catalysts' concentration and the time ofsynthesis in the reaction of obtaining 4-hydroxy-w-chloracetophenone from phenol and chloride chloracetyl. The purified 4-hydroxy-w-chloracetophenone is characterized in terms of physical-chemical properties.
Keywords: 4-hydroxy-w-chloracetophenone, chloracetyl chloride, small quantities Lewis acids, IR spectrum.
4-Hydroxy-w-chloracetophenone is an aromatic ketone formula C8H7O2CI and an important photochemical reaction used in perfumery and as a reagent in organic chemistry. 4-Hydroxy-w-chloracetophenone acts as an optical filter being able to use the energy of UV radiation (promoting electrons into an excited state) and release this energy as heat to the environment (electrons returning to the initial state). This is possible because 4-hydroxy-w-chloracetophenone singlet and triplet have close states in terms of energy.
4-Hydroxy-w-chloracetophenone is used as a flavor ingredient, a flavor enhancer, perfume fixative in perfumery industry. In the composition of perfumes, cologne and scented soaps and UV light does not degrade the smell and color of these products. It is used as an additive for plastics, coatings and adhesive formulations [1, 5005-5010]. It is a component of sunscreen prod-
ucts and a plastic packaging can be added to block UV rays, protecting products within them [2, 3909-3916]. It is used in textile to protect them against degradation under the action of ultraviolete radiation [3, 53-62]. In preparations for solar protection, 4-hydroxy-w-chloracetophenone is intended to absorb UV-A and UV-B, protecting the skin from the negative effects of tanning (sun). It is known that structure is unstable in terms of photochemical because under the influence of sunlight it forms reactive radicals, aggressive, in which scientists associates with oxidative stress in human cells, skin damage, etc. 4-hydroxy-w-chloracetophenone and its derivatives are used as intermediates for dyes, in the manufacture of insecticides and pharmaceuticals, etc. [4, 145-149]. In the pharmaceutical industry are used for their anesthetic [5, 4818-4825] and anti-inflammatory properties [6, 3505-3514] etc. [7, 4046-4051]. It is a white solid
