The way to improve the functional properties of liquid nitrogen fertilizers based on urea and ammonium nitrate

 

(57) Abstract:

Usage: the technology of mineral fertilizers, and more particularly liquid nitrogen fertilizers to improve their performance properties, in particular for the preservation of colorless, transparent and prevent sediment during storage of fertilizers in contact with carbon steel. Improvement of operational properties of liquid nitrogen fertilizer reaches an introduction to him as a corrosion inhibiting additive mixture of ammonium orthophosphate and alkylphosphates - salts of mono - and dialkylated esters of orthophosphoric acid, 1 wt.h. alkylphosphates have 2-30 wt. including orthophosphate ammonium in terms of P2O5. Need a mass ratio of ammonium orthophosphate and alkylphosphate provide mixing in appropriate proportions of the two parties of liquid nitrogen fertilizer, one of which ingibirovany the ammonium orthophosphate, and the other alkylphosphate. 1 C.p. f-crystals.

The invention relates to the technology of mineral Debreceni and, more specifically, liquid nitrogen fertilizer, and can be used to improve their performance properties, in particular to save biscotti steel.

As liquid nitrogen fertilizers based on urea and ammonium nitrate are widely used mixed aqueous solutions of urea and ammonium nitrate. When storing these solutions in tanks made of carbon steel last corrode at a rate of about 1 mm per year. Thus the solution becomes brownish in color and becomes practically unusable due to the formation and accumulation of corrosion products causing clouding of the solution and the deposition volume of sediments. In the end worsen the conditions of storage, transportation and making udobreniya in the soil, clogged communication and capacity.

There are ways to improve the functional properties of liquid nitrogen udobreniya on the basis of urea and ammonium nitrate by introducing various additives, such as ammonia (Lukashev, A. I., Fanfaron F. I., Nisai C. M. , Leshukov B. C. Liquid nitrogen odobrenje - Plav. Book publishers. Stavropol, 1969) or 0.2% of thiocyanate ammonium (Yakovlev, L. M., N. Pakhomova.M. and other Corrosion of carbon steel in liquid nitrogen udobreniya. Chemistry in agriculture, 1985, No. 9, S. 78-80). However, the corrosion rate decreases slightly, and the operational properties of RA is amental processes, resulting in poor appearance of the product. For example, a known method for improving the performance properties of liquid nitrogen fertilizers based on urea and ammonium nitrate by introducing as corrosion inhibiting additives derived phosphoric acids (ibid, S. 78-80). In the role of derivatives of phosphoric acids using liquid complex fertilizer (brand HCS 10-34-0) containing a mixture of ortho-, pyro-, Tripoli, metropolitanates. When this utility is added to the mixed aqueous solution of urea and ammonium nitrate in the amount of 0.2% (in terms of P2O5). The corrosion rate of carbon steel welded samples does not exceed 0.1 mm. Due to a sharp reduction in the volume of sediment corrosion products liquid nitrogen odobrenje becomes more suitable for practical use.

However, a mixed aqueous solution of urea and ammonium nitrate after adding thereto a liquid complex Debreceni (HCS 10-34-0) gets dirty grey and cloudy. In addition, when defending udobreniya on the bottom of the tank, carbon steel still accumulates a lot of bottom sediment, including along with the residual products of q is

On a set of attributes and the technical nature of the proposed method closest known method for improving the performance properties of liquid nitrogen udobreniya on the basis of urea and ammonium nitrate by introducing an additive, inhibiting corrosion, derivatives of phosphoric acid. As such, use of inorganic orthophosphate ammonium (U.S. patent N 2 855 286, CL 71-29, 1958) or orthophosphate in combination with ammonium sulfate (GDR patent N 208143, class C 05 C 1/00 C 05 C 9/00, 11.12.81), or alkylphosphate (salts of mono - and dialkylated esters of orthophosphoric acid) (patent GDR N 271900, class C 05 C 1/00 C 23 F 11/117, 20.09.89). Patent GDR N 271900 adopted as the closest analogue. Alkylphosphate and inorganic orthophosphate different effects on the performance properties of liquid nitrogen fertilizer.

Inorganic orthophosphate (often use ammonium orthophosphate) is injected into a mixed aqueous solution of urea and ammonium nitrate in the amount of 0.02-2 wt. % in terms of P2O5. After they are added to a solution of the latter retains its transparency and transparency when stored in contact with carbon steel When this sediment is formed even less than ispolzovat beige color and gel-like structure and gradually settles to the bottom of the tank. In narrow gaps (if any inside the tank) formed structures resembling in appearance fluffy mold and contributing to crevice corrosion.

Adding ammonium sulfate to the orthophosphate does not preclude accumulation in narrow gaps such structures, indicating the beginning of crevice corrosion.

In the case of the use as an additive, inhibiting corrosion, alkylphosphates the latter is most often used in support of surface-active substances. According to the patent GDR N 271900 in a mixed aqueous solution of urea and ammonium nitrate is administered a composition containing in addition to 30-90% of alkylphosphates (ammonium salts monoalkyl esters of orthophosphoric acid with C6-C12-alkyl) also 3-20% of the sulfates of fatty acids with C17-C24the alkyl and 3-20% sodium soap. Such composition is administered in fertilizer in quantities of 0.001 to 0.05 wt. %, which corresponds to the contents of alkylphosphates in the fertilizer in the number 0,0003-0,0475 wt.%. Alkylphosphate in this composition directly inhibit corrosion (ed. mon. USSR N 173571, CL C 25 F 11/12, 28.09.65), and sulfates of fatty acids and sodium Soaps are essentially conditioning additives, so as not possessing the properties of inhibi solution.

The lack of alkylphosphates as corrosion inhibitor is that containing liquid nitrogen odobrenje during storage in contact with the carbon steel acquires a yellow colour, which gradually increases with the transition to a brown color, apparently due to oxidation of organic alkyl radicals as corrosion processes, while at the bottom of the tank appear yellow-brown flakes, education which contribute & conditioning additives, which by their nature are surfactants with longer alkyl chains.

Despite the fact that adding alkylphosphates to the mixed aqueous solution of urea and ammonium nitrate in contact with carbon steel, leads to the formation of sediment, even more dense than in the case of the use of ammonium orthophosphate, alkylphosphate have the advantage that they reduce the likelihood of crevice corrosion, which is not inhibited by orthophosphate.

The main object of the invention is the improvement of operational properties of liquid nitrogen udobreniya on the basis of urea and ammonium nitrate is to maintain transparency and bescot the C carbon steels.

The task is solved in that in the known method to improve the functional properties of liquid nitrogen fertilizers based on urea and ammonium nitrate by introducing as corrosion inhibiting additives alkylphosphates - salts of mono - and dialkylated esters of orthophosphoric acid, according to the invention the ammonium and orthophosphate salts of mono - and dialkylated esters of phosphoric acid are used together in a mass ratio of 2-30 wt.h. orthophosphate ammonium (in terms of P2O51 wt.h. salts of mono - and dialkylated esters of orthophosphoric acid.

In addition, the required mass ratio of ammonium orthophosphate and alkylphosphate carried out by mixing in appropriate proportions of the two parties of liquid nitrogen fertilizer, one of which ingibirovany the ammonium orthophosphate, and the other alkylphosphate.

The combined use of ammonium orthophosphate and alkylphosphates as an additive, inhibiting corrosion, and provides a corresponding decrease in the concentration of each of these substances in fertilizer due to the presence of another substance. This provides the same level of corrosion protection, which is achieved by separately applied to the tion of each of these components (in comparison, and the concentration of the particular application component) decreases in proportion and its negative impact on the appearance of fertilizers, contact with carbon steel. For example, when reducing the concentration of alkylphosphates twice, respectively, attenuated the intensity of yellowing of the solution and decreases the formation of a brown precipitate in the tank. Also, when reducing the concentration of orthophosphate ammonium decreases the mass of gel-like beige sediment. In addition, in a joint application of orthophosphate and alkylphosphates occurs an unexpected effect of the interaction between these substances in solution, leading to almost complete prevention of sediment while maintaining colorless and transparent solution. In other words, the combined use as a corrosion inhibitor orthophosphate ammonium and alkylphosphates eliminates their disadvantages and to preserve the advantages, reflected in their separate use.

In the end, improve operational properties of liquid nitrogen fertilizer: transparency and transparency fertilizer is stored, and the bottom sediment is practically absent.

Production of liquid nitrogen fertilizers, which jointly applied ammonium orthophosphate and alkylphosphate may be made by mixing batches of fertilizer, poluchaemaya - alkylphosphate.

This invention is explained below in more detail at some examples.

In all experiments (examples 1-7) as the background environment used a mixed aqueous solution of urea (35 wt.%) and ammonium nitrate (45 wt. %), which corresponds to the liquid nitrogen fertilizer, containing 32% nitrogen (mark UAN-32). The solution was made by one or another corrosion inhibitor, after which ammonia brought the pH of the solution to 7.5. Then the solution was filled half a glass beaker, which was placed elongated rectangular plate made of carbon steel. When this plate relied bottom end into the bottom of the flask, and the upper half of the plate above the level of the solution. The flask was closed with a stopper and set on prolonged storage at room temperature. After 4 months. the experience was stopped, made the necessary observations and measurements. The weight loss of the sample during the entire 4-month test period was determined by the average corrosion rate.

Examples 1-5 are used to compare and characterize the known state of the art. Examples 6 and 7 show the benefits of the combination of inhibitors in accordance with the invention.

Example 1. In a mixed aqueous solution of urea and ammonium salitral phosphate 0.1 wt.% in terms of P2O5.

After 4 months. at the bottom of the flask appeared small scattered clumps. The solution remained clear and colorless. In a narrow gap between the bottom end of the metal plate and the glass-bottomed flask was formed light touch of the solid phase, resembling the appearance of downy mildew, while the bottom plate is blackened, which is a sign of education hearth crevice corrosion.

The average corrosion rate of the sample of carbon steel was 0,006 mm/year.

Example 2. In a solution made DAP and map in a mass ratio of 2:1, having a total concentration of orthophosphate 0.1 wt.% in terms of P2O5(as in example 1). Then to the solution was added ammonium sulfate in the amount of 0.04 wt. %.

After 4 months. at the bottom of the flask appeared small scattered clumps. The solution remained clear and colorless. In a narrow gap between the bottom end of the metal plate and the glass-bottomed flask was formed light touch of the solid phase, resembling the appearance of downy mildew, while the bottom plate is blackened, which is a sign of education hearth crevice corrosion.

The average corrosion rate was 0,004 mm/year.

Example 3. In plants which received ammonium orthophosphate with a total concentration of 0.2 wt.% in terms of P2O5(the relationship between DAP and map is not defined).

After 4 months. at the bottom of the flask appeared small scattered clumps. The solution remained clear and colorless. In a narrow gap between the bottom end of the metal plate and the glass-bottomed flask was formed light touch of the solid phase, resembling the appearance of downy mildew, while the bottom plate is blackened, which is a sign of education hearth crevice corrosion.

The average corrosion rate of the metal sample constituted 0.004 mm/year.

Example 4. In a solution made alkylphosphate is a mixture of mono - and dimethyl esters of orthophosphoric acid in an amount of 0.1 wt.%.

After 4 months. at the bottom of the flask appeared a thin layer of brown sludge. The solution is slightly yellow. The initially clear solution with shaking flask became turbid. In a narrow gap between the bottom end of the metal plate and the glass-bottomed flask was no accumulation of sediment, the bottom end plate remained brilliant, indicating the absence of crevice corrosion.

The average corrosion rate of the metal specimen was 0,006 mm/year.

Example 5. For corrosion inhibiting solution icollage of domestic plants in the production of liquid nitrogen fertilizers containing mainly alkylphosphate with long alkyl chains (C6-C8and surfactants. Water inhibitor "Conbloc" contained about 50%. The concentration of the inhibitor in the fertilizer was reduced to 0.02 wt.%.

After 4 months. at the bottom of the flask appeared a thin layer of light brown solid. The solution is slightly yellow. The initially clear solution with shaking flask became turbid. In a narrow gap between the bottom end of the metal plate and the glass-bottomed flask was no accumulation of sediment, the bottom end plate remained brilliant, indicating the absence of crevice corrosion.

The average corrosion rate of the metal specimen was 0.005 mm/year.

Example 6. Into the solution was introduced DAP and map in a mass ratio of 2:1, having a total concentration of orthophosphate in solution of 0.1 wt.% in terms of P2O5. Additionally, the solution made of 0.05 wt.% a mixture of mono - and dimethyl esters of orthophosphoric acid. Thus in a solution of 1 wt.h. alkylphosphates have 2 Mac.h. orthophosphate ammonium.

After 4 months. storage metal sample in a solution of the latter remained clear and colorless. No sediment in the flask was not. The lower end plate remained brilliant. Signs slit Yaya corrosion rate of the metal sample constituted 0.004 mm/year.

Example 7. Have ready 2 party solution. One solution made of orthophosphoric acid in an amount of 0.2% P2O5neutralized its ammonia and received an ammonium orthophosphate with a total concentration of 0.2 wt.% P2O5. In the solution of another party added organic corrosion inhibitor brand "Conbloc" (see example 5) in an amount of 0.02 wt.%.

The solutions were mixed in a mass ratio of 3:2, resulting in a mixed aqueous solution of urea and ammonium nitrate containing ammonium orthophosphate in the amount of 0.12% and organic inhibitor "Conbloc" in the amount of 0,008%. Thus, by 1 wt.h. inhibitor "Conbloc" have 15 wt.h. orthophosphate ammonium. Because the inhibitor "conbloc represents an approximately 50% aqueous solution of alkylphosphates, the prepared mixture of fertilizers from different parties on 1 Mac.h. alkylphosphates accounts for 30 wt.h. orthophosphate ammonium.

After 4 months. storage metal sample in a solution of the latter remained clear and colorless. No sediment in the flask was not. The lower end plate remained brilliant. Signs of crevice corrosion was absent. With shaking flask, the solution remained clear and colorless. the provide operational properties of liquid nitrogen fertilizers based on urea and ammonium nitrate by introducing him as a corrosion inhibiting additive salts of mono - and dialkylated esters of orthophosphoric acid, characterized in that it further as an additive injected ammonium orthophosphate in a mass ratio of 2 to 30 wt.h. orthophosphate ammonium in terms of P2O51 wt.h salts of mono - and dialkylated esters of orthophosphoric acid.

2. The method according to p. 1, characterized in that the required mass ratio between the additives provide by mixing appropriate proportions of the two parties of liquid nitrogen fertilizer, one of which ingibirovany the orthophosphate ammonium and other salts of mono - and dialkylated esters of orthophosphoric acid.

 

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