WO2008069676A2

WO2008069676A2 - Production of npk or np material containing polyphosphates

Info

Publication number: WO2008069676A2
Application number: PCT/NO2007/000423
Authority: WO
Inventors: Torstein Obrestad; Arne Oksvik
Original assignee: Yara International ASA
Current assignee: Yara International ASA
Priority date: 2006-12-05
Filing date: 2007-11-28
Publication date: 2008-06-12
Anticipated expiration: 2009-06-05
Also published as: NO332851B1; CN101595078A; EP2091891A2; PL2091891T3; EP2091891B1; RU2439039C2; NO20065594L; ES2390612T3; CN101595078B; RU2009124418A; PT2091891E; WO2008069676A3

Abstract

It is disclosed a method for the nitrosphate process to produce NPK or NP material with polyphosphates by reducing the pressure in the evaporation stage and / or increasing the temperature in the evaporation stage and/or controlling the temperature in the crystallization stage wherein a material is produced containing a mixture of MAP, DAP, DCP and optionally apatite and a controlled amount of condensed phosphates (polyphosphates), and N/P and Ca/P ratios of the NPK material are N/P ≥ 0.95 and 1.0 ≥ Ca/P ≥ 0.2 and products thereof.

Description

Production of NPK or NP material containing polyphosphates

The present invention relates to a NPK or NP material containing polyphosphates and a method for producing the same. Said material has a specific composition of different phosphates obtained by using nitrophosphate process according to the present invention.

BACKGROUND

Water-soluble phosphates in fertilizers tend to become immobile in the soil due to precipitation of sparingly soluble phosphate-containing compounds. This occasionally leads to a quite low uptake of phosphates of conventional fertilizers. The phosphate efficiency could be increased if the phosphate-containing sources had better mobility or if the tendency of the phosphate sources to react with metal ions in the soil was less. This requires phosphate forms that are not precipitating as easily and that are not adsorbed as quickly and strongly by soil particles. Various types of polyphosphates and metaphosphates are claimed to have the described advantages, and in this context Soil Sci. Soc. Am. J., Vol. 46, 1982, Agronomic Effectiveness of Pyrophosphates as an Additive to Monocalcium Phosphate and Diammonium Phosphate in Calcareous soils are referred to as prior art. It is also known that calcium phosphate (CaHPO₄), which is considered to be water insoluble and therefore reacts much slower in soil than water-soluble phosphates, has a significant solubility when the ion strength is high, like for instance in the soil liquid. It is therefore believed that the advantages are the same for polyphosphate as for calcium phosphate by providing a sustained release of phosphates.

Liquid ammonium polyphosphate fertilizer is well known from prior art, and several documents disclose the production of this material, e.g., US 4011300 (Union Oil Company of California),US 3947261 (Agrico Chemical Company) and ES A

2033198 (Agrar Fertilizantes SA). The presence of polyphosphate in the fertilizers is claimed to reduce the precipitation of impurities like iron and aluminium salts which is a problem in liquid fertilizers.

The production of solid NPK fertilizers is also well known from prior art and several documents disclose its production, e.g. US 3617235 (Hydro) and US 5098461 (Tennessee Valley Auth).

None of the NPK fertilizers available on the market today comprises polyphosphates. This is supported by the prevailing market situation. 7 products were analysed for their contents of polyphosphates which have been found to be zero, see table 1. Tab. 1 : Polyphosphate analyses on several NPK types

So far known NPK producing processes do not directly result in formation of polyphosphate containing fertilizers.

The only known method to include polyphosphates is by adding polyphosphates separately as an additive.

It is well known from prior art that the orthophosphate ion (PO₄) can polymerize according to reaction 2: Reaction 2: nPO₄ + heat → P_nO_3n+1 + nH₂O.

As n moves towards indefinitely, the condensed formula moves towards (POa)_n . Condensed phosphates (polyphosphates) are defined to be phosphates in a non-ortho phosphate form. The normal procedure for producing polyphosphates is by wet process route where phosphoric acid is concentrated by heating to above 300 ⁰C or by starting from elemental phosphorous (the furnace process route). Yet another method for producing polyphosphates is by heating metal-hydrogen phosphates (MeHPO₄). The term "Me" relates to a single valent ion as NH₄, K or another in a phosphate compound.

None of these processes is directly applicable in a nitrophosphate process.

OBJECTIVE

The object of the invention is to obtain a solid NPK fertilizers comprising polyphosphate in order to increase the uptake of phosphate in the soil. Another object is to find a method for producing that material in the nitrophosphate process. Another object of the invention is to obtain a NPK fertilizer with polyphosphates and comprising a controlled amount of water soluble phosphates and a high amount of citrate-soluble phosphates.

The present invention provides a method for the preparation of solid NPK fertilizer comprising polyphosphates. The present invention further provides a NPK fertilizer produced according to said process.

These and other objectives may be obtained by the features as set forth in the following description of the invention and/or in the appended patent claims.

DESCRIPTION

The nitrophosphate process comprises the steps digestion of apatite in nitric acid, crystallization, filtration of calcium nitrate, neutralization with ammonia, evaporation before granulation.

In order to obtain polyphosphates, the present inventors have surprisingly found that this is achieved by reduction of the pressure in the evaporation stage and optionally as well increasing the temperature in the evaporation stage and optionally controlling the temperature in the crystallization stage. By controlling these conditions according to the present invention the content of water in the NPK fertilizer is lowered and thereby the content of polyphosphates increased.

The product according to present method comprises polyphosphates in contradiction to NPK fertilizers of prior art.

Abbreviations

AN ammonium nitrate

DAP di ammonium phosphate DCP phosphates sparingly soluble in water but soluble in neutralizes citrate acid solution

K potassium

MAP mono ammonium phosphate

MOP muriate of potash N nitrogen

NP nitrogen phosphor containing

NPK nitrogen phosphor potassium containing

P phosphor

SOP sulphate of potash

Description of the figure

Figure 1 describes schematically the NPK production by the nitrophosphate process. DETAILED DESCRIPTION

As shown in figure 1 raw phosphate is digested in nitric acid in the digestion stage 1.

In the crystallization stage 2, calcium nitrate tetrahydrate crystals are produced by cooling the digested solution and the crystals are removed by filtration. Typically, the temperature in the crystallisation stage 2 in the process according to the present invention is in the range of -10 ⁰C to + 10 ⁰C. The amount of soluble Ca left in the liquor will depend on the final cooling temperature. By varying the cooling temperature, the Ca/P ratio in the mother liquid is varied, and this ratio will determine the amount of water-soluble phosphates (mainly MAP/DAP) and the amount of phosphate compounds not soluble in water but soluble in a neutralized citric acid solution (DCP) formed in the neutralization stage 3. Typically, if the final cooling temperature is -5°C, the Ca/P ratio will be close to 0.3, and water- soluble phosphates in the final product will be 80-85 % by weight. If final cooling temperature is 0°C, the Ca/P ratio will be about 0.45, and water-soluble phosphates in the final product will be between 70 and 75 % by weight (varies with phosphorous content of the rock phosphate). Correspondingly, a crystallizer temperature of + 5 ⁰C will give a formation of 26 % polyphosphates of total phosphates in finished NPK when the pressure is 0.085 bar and temperature is 190 ⁰C in the evaporation stage 4, as one example for useful conditions for formation of polyphosphates. For example, a crystallizer temperature of -5 ⁰C gives a formation of 29 % polyphosphates of total phosphates in finished NPK when the pressure is 0.085 bar and temperature is 185 ⁰C in the evaporation stage 4, as another example of the process of the present invention. The resulting mixture of nitric acid, phosphoric acid and Ca (mother liquid) is transferred to a neutralization stage 3 and reacted with ammonia wherein ammonium nitrate, calcium and ammonium phosphates are produced according to reaction 1.

Reaction 1 : Ca(NOs)₂ + HNO₃ + H₃(PO₄)₃ + NH₃ + water → NH₄NO₃ + (NH₄)_(3-x)H_xPO₄ + CaHPO₄ + water (NP solution)

Finely divided hydroxyapatite may form in the neutralization reaction if the Ca concentration or the pH becomes too high. The specific composition of the NP solution being produced in the neutralization stage 3 depends on N/P and Ca/P ratios of the mother liquid and varies according to grade of NPK material. The term N/P ratio relates to the ratio of nitrogen and phosphorous as measured as weight percentages of the elements, e.g. N [g] / P [g] in a specific sample (e.g. 100 g sample). The N/P ratio for the product according to the present invention is > 0.95. The term Ca/P ratio relates to the ratio of calcium and phosphor measured as weight percentages of the elements. The Ca/P ratio for the product according to the present invention is 1.0 > Ca/P > 0.2, preferably 0.7 > Ca/P > 0.25.

Evaporation of water is carried out in the evaporation stage 4. The formation of polyphosphates in NPK material may be controlled by adjusting the pressure and optionally increasing the temperature in the evaporation stage 4. Preferably, the pressure in the process according to the present invention is decreased to < 0.8 bar and the temperature is increased to > 170 ⁰C, preferably to > 185 ⁰C. A pressure of 0.09 bar and temperature at 180 ⁰C will give the formation of 20 % polyphosphates of total phosphates in finished NPK, as one example of useful conditions for formation of polyphosphates. A pressure of 0.08 bar and temperature at 190 ⁰C in the evaporation stage 4 will give the formation of 27 % polyphosphates of total phosphates in finished NPK, as another aspect of the present invention. After evaporation stage 4 the water content of the evaporated NP liquor will be less than 1.0 %, preferably less than 0.6 % by weight. After stage 4, potassium salt in the form of muriate or sulphate of potash may be mixed into the NP liquor just prior to granulation or prilling, such that K originates thereof. After mixing the melt/slurry is launched out in droplets that solidify as they fall through counter flowing air in a prilling tower.

The present invention is therefore related to both NP and NPK material, since the addition of potassium is optional. Although the examples are related to NPK material, the person skilled in the art will acknowledge that the present invention is applicable on NP material and processes as well.

The term prilling relates to formation of solids according to US3617235 where the product from the evaporation stage 4 is in the next stage mixed with potassium chloride or sulphate in a high speed mixer by optionally addition of recycled material. The term granulation relates to all other types of formations of solids after a NPK process for formation of solid NPK fertilizers including addition of potassium salt which is either mixed with NP liquor in a granulator or in a separate mixer. Finally, the granulated/prilled product is dried and optionally further treated such as with screening and surface treatment.

The skilled person will by following the teachings of the present invention easily find a large set of variations in the NPK process relating to pressures and/or temperatures in the evaporation stage 4 and/or the temperature in the crystallization stage 2 in order to produce controlled amounts of polyphosphates.

The NPK or NP material according to the present invention comprises according to one embodiment at least about > 5 % by weight of phosphates as condensed phosphates (polyphosphates), preferably at least about 8 % by weight and more preferably at least about 10 % by weight. According to the method of the present invention a NPK or NP material is provided which contains 5-40 % by weight of condensed phosphates of the total amount of P containing compounds, according to yet another aspect of the invention, it contains 8-38 % and according to yet another aspect it contains 10-20 %. The phosphates comprise 50-95 % by weight of water-soluble phosphates, preferably 60-95 % by weight. The phosphates of the NPK material comprises as well > 93 % by weight of citrate-soluble phosphates, preferably > 95 % by weight.

Other types of phosphates are also comprised in the NPK or NP material of the present invention. Non-limiting examples of such other types of phosphates are citrate-soluble pyrophosphates (P₂O₇ ^2"), tripolyphosphates (P₃O₁₀ ^4") and phosphate- containing compounds of the formula Me^₂)P_nO_3n+! and Me(POs)_n . According to one embodiment of the present invention, the NPK or NP material comprises at least 10 % by weight of phosphates as citrate-soluble pyrophosphates (P₂O₇ ^2"), tripolyphosphates (PsO₁₀ ^4") or phosphate-containing compounds of the formula Me(_H+2)P_nO₃^₁ and/or Me(POs)_n, where in one aspect Me substantially is NH₄, K, or another single valent ion.

The amount of citrate-soluble is seeked to be as high as possible as citric soluble P is considered to be plant available P and is defined as solubles in neutral citric acid and measured by official method.

EXAMPLES

Formation of polyphosphates in a melt of AN + MAP

Pure ammonium nitrate (10 % by weight of NH₄NO₃) and mono-ammonium phosphate (90 % by weight OfNH₄H₂PO₄) was thoroughly mixed and melted at 190⁰C. The melt was stored at 200°C for 2 hours. The mixture was analysed for orthophosphate and polyphosphate components before and after heating:

Results:

Compounds At melting After 2 hours

Orthopho sphates 98.9% 61.3 %

Pyro dipho sphates traces only 32.0 %

Tripolyphosphates 1.1% 4.9 %

Trimetapho sphates traces 1.8 %

The results of this experiment show that condensed phosphates (polyphosphates) are formed in an ammonium nitrate -mono- ammonium phosphate melt. Experiment 1. Formation of polyphosphates in a neutral NP solution from NPK plant

A neutral NP (AN + MAP/DAP + DCP) solution from NPK plant was in the laboratory evaporated to dryness at low pressure and room temperature. The chemical content of the NP material is shown in table 2.

Table 2. Starting NP material; analyses.

Total NO₃- NH₄- Water Acid Acid Ortho Citrate

N [%] N [%] N [%] sol P [%] sol P [%] sol Ca form [%] sol. [%] [%]

22.7 8.85 13.85 8.5 10.7 3.73 100 99.95

About 10 grams of the dry material was heated and kept at various temperatures for 10 and 30 minutes (ambient pressure). Subsequently, a water extract was made, and the extract analysed regarding the amounts of different phosphates (paper chr omato graphy) .

The results are given in table 3.

Table 3. Distribution of condensed phosphates in heat treated NP material prodμced from NP solution from NPK plant

Retention times of 10 and 30 minutes at the temperature levels gave no significant difference in the distribution of phosphate-containing compounds, and the values of table 3 are averages of the values obtained at 10 and 30 minutes.

The solubility of phosphates in neutralized citric acid solution has been determined after the heat treatment and is shown in table 4. Table 4. Solubility of phosphates in a neutral ammonium citrate solution

Experiment 1 shows that orthophosphates of a neutral NP solution produced in a NPK plant and consisting of AN + MAP + DAP + CaHPO4 + water, will partly convert into polyphosphates by heat treatment. A heat treatment up to 300⁰C is not considered to influence the solubility of phosphates in a neutral ammonium citrate solution.

Experiment 2. Samples from the nitrophosphate plant Experiment 1 shows that condensed phosphates (polyphosphates) are produced when NP solutions are heated at atmospheric pressure.

In the nitrophosphate plant, a neutral NP water solution is evaporated at high temperatures to an low water content prior to mixing with potassium salt and granulation or prilling. According to experiment 1, polyphosphates could be produced in a nitrophosphate plant during evaporation of the NP solution.

To verify this, a series of NP/NPK samples were discharged from the plant and analysed for orthophosphates and polyphosphates.

Table 5 provides the result of this experiment.

Conclusion of experiment no 2: Despite of heating the NP solution up to 185°C, polyphosphates could not be detected neither in the concentrated NP liquor nor in the final NPK product.

Based on the results from experiment 1 and reactions 2, 3, it is reasonable to believe that the water content of the NP liquor (obtained by using the mentioned evaporation conditions) of table 5 is too high for the condensing reactions 2, 3 to take place.

Experiment 3. Reduction of pressure

In order to reduce the water content of the evaporated NP liquor significantly, the conditions (temperature and/or pressure) of the evaporator in the evaporation stage 4 must be adjusted. The temperature of the crystallizer in the crystallization stage 2 was held constant and within the scope of the present invention.

A new series of plant trials were therefore carried out, aiming to substantially reduce the water content of the NP liquor. Since too high temperature in the evaporator strongly will enhance the release of ammonia, the best way to reduce the water content is considered to be lowering of the evaporating pressure.

During the production of NPK 3*16, the composition of the NP base solution entering the evaporator was as follows, in weight percent: 52% AN + 2.5% DAP + 20% MAP + 10% CaHPO₄ + 3.5% others + 12% water. This NP solution was evaporated into an NP melt, then 27% MOP was added together with 3% filler to produce NPK 3* 16.

Similarly, NPK 12-11-18 + Mg + S+ micronutrients have been produced by evaporating the corresponding NP solution having the following composition, in weight percent:

51.6% AN + 2.4% DAP + 19.1% MAP + 10% CaHPO₄ + 2.8% others + 14% water.

After evaporation of this solution into a NP melt, SOP, kieseritte, dolime and micronutrients are added to produce NPK 12-11-18 with Mg and micronutrients.

A corresponding trial with NPK 24-6-12 was carried out as well.

To remove maximum amount of water from the NP solution without increasing temperature too much (to avoid loss of NH₃), the pressure of the evaporator was lowered to between 0.1 and 0.08 bar. The influence on the production of polyphosphates is shown in table 6.

Table 6. Results of experiment 3

It is evident from this example that condensed polyphosphates can be produced in the nitrophosphate process by evaporating the NP solution in the evaporation stage 4 to a melt almost free of water. This is obtained in a very short time if the evaporation is carried out at a very low pressure and at a temperature between 170 and 200⁰C.

It is also clear that with rock phosphate (from Kola) used as a phosphate source, the portion of citrate-soluble phosphates (phosphates available for plant) remains close to 100%.

Experiment 4. Variation of crystallizer temperature in crystallization stage Table 6 shows that NPK material containing polyphosphates can be produced in the nitrophosphate plant by adjusting the evaporator in the evaporation stage 4 to the right conditions. By varying the cooling temperature in the crystallizer in the crystallization stage 2, the amount of Ca can be varied and thereby the Ca/P ratio and the amount of water-soluble phosphates. Cooling temperature between -5°C and +5°C

Starting with rock phosphate (from Kola) in the digester, NPK 3*16 and NPK 24-6- 12 are produced with cooling temperature in the crystallizer close to -5 and +1°C, samples are discharged and measured for water-soluble phosphates, polyphosphates and total citrate-soluble phosphates. Results are given in table 7.

Table 7: Results of experiment 4

It is evident from this example that the Ca content of the NP solution can be varied by varying the final cooling temperature of the crystallizer in the nitrophosphate process such that the amount of water-soluble phosphates and amount of citrate soluble phosphates can be controlled in the final product. By using the correct evaporation conditions in the evaporation stage 4, a substantial amount of condensed phosphates (polyphosphates) is obtained as well.

Claims

1. A NPK or NP material from a nitrophosphate process, characterized in that it comprises condensed phosphates (polyphosphates).

2. A material according to claim 1, characterized in that the total amount of P containing compounds in the NPK or NP material comprises at least

5 % by weight of condensed phosphates (polyphosphates), preferably at least 8 % and more preferably at least 10 % by weight of phosphates as condensed phosphates (polyphosphates).

3. A material according to claim 1, characterized in that the total amount of P containing compounds in the NPK or NP material contains 5 % - 40 % by weight of condensed phosphates (polyphosphates).

4. A material according to claim 1, characterized in that the total amount of P containing compounds in the NPK or NP material contains 8 % - 35 % by weight of phosphates as condensed phosphates (polyphosphates).

5. A material according to claim 1 , characterized in that the total amount of P containing compounds in the NPK or NP material contains 10 % - 20% by weight of condensed phosphates (polyphosphates).

6. A material according to any of the claims Ito5, characterized in that the P containing compounds in the NPK or NP material produced comprise a mixture of MAP, DAP, DCP and optionally apatite.

7. A material according to any of claim Ito6, characterized in that the N/P and Ca/P ratios of the NPK or NP material are N/P > 0.95 and 1.0 > Ca/P > 0.2, and optionally K originates from SOP and MOP.

8. A material according to claim 7, characterized in that the Ca/P ratio is 0.7 > Ca/P > 0.25.

9. A material according to any of claim Ito8, characterized in that the total amount of P containing compounds in the NPK or NP material comprises 50-95 % by weight of water-soluble phosphates.

10. A material according to claim 9, characterized in that the NPK or NP material comprises 60-95 % by weight of water-soluble phosphates.

11. A material according to any of claim lto lO, characterized in that the total amount of P containing compounds in the NPK or NP material comprises > 93 % by weight of citrate-soluble phosphates.

12. A material according to claim 11, characterized in that the NPK or NP material comprises > 95 % by weight of citrate-soluble phosphates.

13. A material according to any of claim 1 to 12, characterized in that the NPK or NP material comprises at least 10 % by weight of phosphates as citrate-soluble pyrophosphates (P₂O₇ ^2"), tripolyphosphates (PsO₁₀) or phosphate- containing compounds of the formula Me(_n+2)P_nO3_n+i and/or Me(PO₃)_n.

14. A material according to claim 13, characterized in that Me substantially is NH₄, K, or another single valent ion.

15. A NPK or NP material containing condensed phosphates (polyphosphates) which may be obtained by a method characterized in that it utilizes a nitrophosphate process comprising the steps digestion of apatite in nitric acid (1), crystallization (2), filtration of calcium nitrate, neutralization with ammonia (3) and evaporation (4) where the pressure is reduced in the evaporation stage (4) and the temperature is optionally increased in (4) and the temperature is optionally controlled in the crystallization stage (2) resulting in formation of polyphosphates and optionally adding potassium after stage (4).

16. A material according to claim 15, characterized in that the NPK or NP material comprises at least 5 % by weight of condensed phosphates (polyphosphates), preferably at least 8 % and more preferably at least 10 % by weight of phosphates as condensed phosphates (polyphosphates).

17. A material according to claim 15, characterized in that the total amount of P containing compounds in the NPK or NP material contains 5 % - 40 % by weight of condensed phosphates (polyphosphates).

18. A material according to claim 15, characterized in that the total amount of P containing compounds in the NPK or NP material contains 8 % - 35 % by weight of phosphates as condensed phosphates (polyphosphates).

19. A material according to claim 15, characterized in that the total amount of P containing compounds in the NPK or NP material contains 10 % - 20% by weight of condensed phosphates (polyphosphates).

20. A material according to any of claim 15 to 19, characterized in that the P containing compounds in the NPK or NP material produced comprise a mixture of MAP, DAP, DCP and optionally apatite.

21. A material according to any of claim 15 to 20, characterized in that the N/P and Ca/P ratios of the NPK or NP material are N/P > 0.95 and 1.0 > Ca/P > 0.2, and optionally K originates from SOP and MOP.

22. A material according to claim 21, characterized in that the Ca/P ratio is 0.7 ≥ Ca/P > 0.25.

23. A material according to any of claim 15 to 22, characterized in that the water content of neutral NP solution is evaporated to a water content about < 1 % by weight at a temperature > 170°C.

24. A material according to claim 23, characterized in that the water content is about < 0.6 % by weight.

25. A material according to any of claim 15 to 22, characterized in that the pressure in the evaporation stage (4) is decreased such that the water content in the evaporated NP liquor is about < 1.0 % by weight.

26. A material according to any of claim 15 to 25, characterized in that the temperature in the evaporation stage (4) is increased to > 170°C.

27. A material according to any of claim 15 to 26, characterized in that the temperature in the crystallization stage (2) is in the range of -10 to + 10⁰C.

28. A material according to any of claim 15 to 27, characterized in that the total amount of P containing compounds in the NPK or NP material comprises 50-95 % by weight of water-soluble phosphates.

29. A material according to any of claim 15 to 27, characterized in that the total amount of P containing compounds in the NPK or NP material comprises 60-95 % by weight of water-soluble phosphates.

30. A material according to any of claim 15 to 27, characterized in that the total amount of P containing compounds in the NPK or NP material comprises > 93 % by weight of citrate-soluble phosphates.

31. A material according to claim 30, characterized in that the NPK or NP material comprises > 95 % by weight of citrate-soluble phosphates.

32. A material according to any of claim 15 to 31, characterized in that the NPK or NP material comprises at least 10 % by weight of phosphates as citrate-soluble pyrophosphates (P₂O₇ ^2"), tripolyphosphates (P₃O₁₀) or phosphate- containing compounds of the formula Me^₊₂₎P_nO_3n+1 and/or Me(POs)_n.

33. A material according to claim 32, characterized in that Me substantially is NH₄, K, or another single valent ion.

34. A method for the preparation of NPK and NP material, characterized by utilization of a nitrophosphate process comprising the steps digestion of apatite in nitric acid (1), crystallization (2), filtration of calcium nitrate, neutralization with ammonia (3) and evaporation (4) where the pressure is reduced in the evaporation stage (4), and wherein the temperature is optionally increased in (4), and wherein the temperature is optionally controlled in the crystallization stage (2), resulting in formation of polyphosphate and optionally adding potassium after stage (4).

35. A method according to claim 34, characterized in that the total amount of P containing compounds in the material comprises at least 5 % by weight of condensed phosphates (polyphosphates), preferably at least 8 % and more preferably at least 10 % by weight of phosphates as condensed phosphates (polypho sphates) .

36. A method according to claim 34, characterized in that the total amount of P containing compounds in the NPK or NP material contains 5 % - 40 % by weight of condensed phosphates (polyphosphates).

37. A method according to claim 34, characterized in that the total amount of P containing compounds in the NPK or NP material contains 8 % - 35 % by weight of phosphates as condensed phosphates (polyphosphates).

38. A method according to claim 34, characterized in that the total amount of P containing compounds in the NPK or NP material contains 10 % - 20% by weight of condensed phosphates (polyphosphates).

39. A method according to any of claim 34 to 38, characterized in that it may be produced by a method where the pressure in the evaporation stage (4) is decreased such that the water content in the evaporated NP liquor is about < 1.0 % by weight.

40. A method according to any of claim 34 to 39, characterized in that it may be produced by a method where the pressure in the evaporation stage (4) is decreased to < 0.8 bar.

41. A method according to any of claim 34 to 39, characterized in that the pressure in the evaporation stage (4) is decreased such that the water content in the evaporated NP liquor is about < 1.0 % by weight.

42. A method according to any of claim 34 to 41, characterized in that it may be produced by a method where the temperature in the evaporation stage (4) is increased to > 170°C.

43. A method according to any of claim 34 to 42, characterized in that it may be produced by a method where the temperature in the crystallization stage (2) is controlled in the range of -10 to + 10⁰C.