DE2001251A1 - Process for the production of phosphorus-potash fertilizers from phosphoric acid and minerals of the mica group - Google Patents

Description

9 Π Π 1 9 R 1 Andrejewski & Honke patent attorneys

Physicist Dr. Walter Andrejewski

Graduate engineer Lawyer files: ^ _{928 / You} " _Df _ _{| ng}

Essen, May 14, 1970 Kettwiger Strasse 36

Patent application of the

Rikkihappo Oy

Malminkatu 50, Helsinki 10 / Pinnland

Process for the production of Phosphor-Kall-DUngemlttel from phosphoric acid and minerals of the mica group

The present invention relates to a simple process for the production of phosphorus-potash fertilizers or the phosphorus-kai ! -Components of fertilizers from phosphoric acid and minerals the mica group. According to the process according to the invention, a magnesium-containing product with a high content can be obtained of nutrients, the solubility of which can be regulated by varying the production conditions. The method according to the invention can also be used

009835/1711

Patent attorneys Dr. W. Andrejewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse

a considerable part of that contained in the mica minerals Convert the potash into a form that is accessible to the plants.

In the manufacture of fertilizers, efforts are made to convert the nutrients into a form in which their solubility properties be consistent with the purpose pursued by the fertilization concerned. Usually used For the field fertilization to be repeated every year, fertilizers with easily soluble nutrients. For forest fertilization purposes due to the technical difficulties associated with the application of the fertilizer, highly concentrated, Sustainable products are needed, especially in Finland because of the very frequent mossy forest soils Phosphorus potash fertilizer. The most expedient turns out to be the fertilizer with a lasting effect, the nutrients of which are partly in easily soluble, partly in slowly disintegrating form are stored, because it is able to immediately remedy the acute nutrient deficiency existing at the time of fertilization as well as the nutritional requirements that arise later.

In fertilizer analysis, nutrients are used to dissolve Water (abbreviation WL) and, as more effective, sustainable media, citric acid solution (abbreviation ZL) or ammoniacal ammonium citrate solution (abbreviation AZL) is used.

about the production of magnesium-containing phosphorus fertilizers presented a number of patents and publications. As magnesium

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Patent attorneys Dr. W. Andrejewski, Dr. M. Honice, 43 Essen, Kettwiger Strasse 36

-Ziepender are dolomite, magnesium chloride and magnesium carbonate (US Pat. No. 5,291,594), which are mixed with rock phosphate. After acidification with phosphoric acid, the mixture at temperatures of 260 ° is - 36O ⁰ C calcined. There are also patents for the processing of carnallite (German patent 1 257 8OO) and magnesium sulfate (German Democratic Republic, patent 59 715). Of the silicate group, the hydrous magnesium silicate serpentine (Chemical Abstracts 51 (1957) 116401, 51 (1957) 15054g, £ 4 (1960) 18854g) was used as a magnesium donor. Another example of the processing of silicates into fertilizers is described in German patent 1 257 212, according to which synthetic potash silicate is suitable as a potash fertilizer with a lasting effect. However, all prior publications and patents cited in this paragraph differ in essential points from the present invention.

The most common minerals of the mica group are Biotlt and its Phlogopite as well as muscovite and its fine-leaved variant serecite should be mentioned with a strong magnesia-rich variant. Biotite is potassium-magnesium-iron-aluminum-silicate, the name muscovite stands for potassium-aluminum-silicate. Put the mica the main minerals of the most common types of rock in Finland. They are also accompanying rocks for many Ore types that are sent to waste dumps during processing. The minerals of the mica group, in a very special way Dimensions of the most easily soluble biotite, represent the

009835/1711

Patent attorneys Dr. W. Andrejewtki, Dr. M. Honk, 43 Essen, Kettwiger Strasse 36

the most important source of potash for wild plants. In spite of this, the fertilizer industry has not been able to to process these minerals as potash raw material, as a suitable one There was no process to bring the potash contained in them into a form in which it has real value.

In the method according to the invention, a nutrient-rich phosphorus-potash fertilizer is produced by heating a mixture of phosphoric acid and minerals of the mica group at temperatures between the boiling point of phosphoric acid and 600 ° C. The duration of this heat treatment is 15 minutes to 6 hours. The one based on the present invention Method allows the solubility properties of the nutrients of the fertilizer to be produced with the help to control the heating temperature and tent as well as the concentration of the phosphoric acid to be processed. Is made possible this regulation of the solubility by the complicated composition of the phosphoric acid-mica mixture, which the Construction of a large number of compounds that differ significantly in terms of their solubility is guaranteed. This is the point in which the present invention differs significantly from those previously published Investigations differentiate, which all have in common, that with them the formation of magnesium phosphate is aimed at will. The possibility of controlling the solubility is increased by the fact that the phosphoric acid-mica mixture Any additives that may be added can be added both before and after heating. To get the phosphorus potash

009835/1711

Patent Attorney Dr. W. Andrejewski, Dr. M. Honk ·, 43 Essen, Kettwiger Strasse · 36

Potash (potassium chloride or potassium sulfate) depending on the desired solubility properties can be reduced either before heating, with the added potash partly in water-soluble form, partly in ammonium citrate-soluble form, or in a mechanical manner after heating, with it then being exclusively in water-soluble form occurs, be added. Likewise, the other nutrients and trace elements such as sulfur, boron, copper, manganese, zinc and molybdenum can be added to the mixture both before and after heating. According to the method according to the invention, even a considerable part of the nutrients of the acid-insoluble mica minerals, such as part of the potassium contained in the sericite and, when processing mica of the biotite group, also a sufficiently large part of the magnesium into a form usable for the plants convict. The product obtained according to the present invention is also suitable as a raw material for the production of nitrogen-phosphorus-potash fertilizer. The ammonia addition can be done%, for example in the form that is left free acid during the heating of the mixture in this, an excess which is then neutralized in a known per se manner with ammonia.

In order to convey a clear picture of the present invention, and in order to particularly clarify the possibilities for regulating the solubility properties, the following are presented some examples are given:

009835/1711

Patent attorneys Dr. W. Andrejewski, Dr. M. Honk ·, 43 Essen, Kettwlger Strasse

example 1

50.0 g of biotite with a content of

10.4 % K ₂ O 22.3 % MgO 11.1 % Pe ₂ O, 7.3 * Al ₂ O

and a degree of grinding that 90 % passed through an 80 Tyler mesh sieve and 54 passed a 250 Tyler mesh sieve, with 200.0 g of phosphoric acid, the P ₃ O, content of which was 32.0 % (dilute acid), mixed. A further 50.0 g of the same biotite were mixed with 118.5 g of phosphoric acid, the PpO content of which was 54.0 % (concentrated acid). After drying by evaporation, the two mixtures were kept at a temperature of 300 for one hour C. The batch to which the dilute acid was added yielded a residue of 116.7 g after handling, and the batch to which concentrated acid was added a residue of 114.8 g Data of the second batch are compiled in Table 1b The term "free acid" appearing in the tables denotes the unconverted amount of phosphoric acid in the mixture.

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Patent attorneys Dr. W. Andrejewslri, Dr. M. Honk ·, 43 Essen, Kettwiger Strasse

Table la

free acid

total quantity Table Ib

P ₂ O ₅ 6.3 of the total P ₂ O ₅ 10.0 from the total 0.5 K ₂ O K ₂ O MgO 1.7 amount of phosphorus 3.3 amount of phosphorus of the total of the total 33.8 11th 48.0 18.0 1.7 amount of potash calimen quantity 54.8 55.7 4.5 11th 11th 0.5 61.7 86.2 38 56 2.7 9.6 0.5 MgO 2.5 * 4.5 1.2 6.6 9.7

free acid

total quantity

If 81.0 g of potassium chloride are added mechanically to the products obtained above, a substance is obtained whose P ₃ O ₅ -KgO ratio is 17: 15. The yield amounts to 197.7 g and 195.8 g, respectively. The nutrient

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Patent Attorney Dr. W. Anclrejewtki, Dr. M. Honke, 43 Essen, Kettwiger Strasse 36

Content and potential values are compiled in Table 2a (dilute acid) and in Table 2b (concentrated acid).

Table 2a

total quantity

P ₂ O ₅ % of the total
amount of phosphorus K ₂ O % from the Oesamt-
amount of potash NgO 3.7
20.0
52.4 11th
61.7 26.2
26.9
28.5 91.9
94.4 % 0.3
1.6
5.6

Table 2b

total quantity

P ₂ O ₅ % of the total
.phosphorus amount K ₂ O % of the total
amount of potash MgO 5.9
28.2
32.7 18th
86.2 * .5
27.6
28.8 92.0
95.8 % 0.7
3.9
5.7

If the mixture of 50.0 g Biotit, 200.0 g phosphoric acid (P ₂ 0 ₅ content 32.0 %) and 8l.0 g potassium chloride and the mixture 50.0 g biotite, 118.5 g phosphoric acid (PgO ^ Content 54.0 %) and

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Patent Attorney Dr. W. Andrejewski, Dr. M. Honk ·, 43 EsMn, Kettwig «r StraB ·

8l, 0 g of potassium chloride dried by evaporation and then a When exposed to a temperature of 300 ° C. for an hour, 188.0 g and 185.4 g of end products were obtained (cf. Tables 3a and 3b).

Tabel

free acid

total quantity

P ₂ O ₅ % of the total
amount of phosphorus K ₂ O % of the total
kai imenge MgO 21.8
2.0
30.9
34.0 64.1
90.9 22.8
25.2
30.0 76.0
84.0 % 0.2
1.6
5.9

Table 3b

P ₂ O ₅ % of the total
amount of phosphorus K ₂ O % of the total
kai imenge MgO 4.8
0.7
28.8
3 ^ .5 14th
83.5 19.1
26.5
30.4 62.8
87.2 % 0.4
3.6
6.0

free acid

total quantity Were the aforementioned ffiotit-phosphoric acid-potassium chloride

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Patent Attorney Dr. W. Andrafcwikl, Or.

43

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If the mixture was heated at 400 ° C. instead of 300 ° C., the yield was 185.5 β or 180.2 g (cf. Tables 4a and 4b).

Table 4a

free acid

total quantity

Table 4b

P ₂ O ₅ % of the total
amount of phosphorus K ₂ O % of the total
amount of potash MgO 1.3
27.1
34.5 3.8
78.6 16.5
25.7
30.4 54.3
84.5 % 0.1
3.2
6.0

1.1 r-ä P ₂ O ₅ 18th ,8th K ₂ O the Oesamt- NgO 1 - 5 of the total from amount of potash Λ 21 amount of phosphorus 26th , 5 A. 6th WL 35. 3.1 31 , 3 0, 2 ' free acid AZL 59.4 2, total quantity 6O ₁ 6, 84, ,1 »7

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Patent attorneys Dr. W. Andrefewski, Dr. M. Honke, 43 Essen, Kettwiger Strasse

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Example 2

50.0 g of blctite of the same composition as in Example 1 were mixed with 300.0 g of phosphoric acid (PgO ^ content 32.0 %) . After drying by evaporation, the mixture was heated at 300 ° C for two hours. The product obtained had 21.4 # free phosphoric acid, ie 15.5%? 2 ° ^to 5 * If the above-mentioned mixture of two Sunden at 400 ° C heated eo SiOH yielded 141.2 g of a product whose solubility in Nähretoff- and Table 5 are compiled.

Table 5

^p a ° 5 * of the total
amount of phosphorus K ₂ O * of the total
amount of potash MgO 5.0
0.6
27.3
68.0 7.4
40.1 0.4
2.5
3.7 11th
68 * 0.3
1.2
7.9

free acid

total quantity

If 93.0 g of potassium chloride are added mechanically to the product obtained above, the result is 24.2 g of a substance whose P ₂ O ₅ - K ₂ O ratio is 3: 2 (see Table 6).

009835/1711

Patent attorneys Dr. W. Andrejewski, Dr. M. Honice, 43 Essen, Kettwiger Strasse 36

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Table 6

P ₂ O ₅ % of the total
amount of phosphorus K ₂ O % of the total
amount of potash MgO 3.0
16.4
41.0 7.4
40.1 25.3
26.6
27.3 92.7
97.4 % 0.2
0.7
4.8

total quantity

If the mixture of 50.0 g of Blotlt, 300.0 g of phosphoric acid (PgOc content 32.0 %) and 93.0 g of potassium chloride was dried by evaporation and then heated at 300 ° C. for two hours, the yield was 229 , 0 g (see Table 7). If the heating time was reduced to one hour, but the temperature was increased to 400 ° C., the yield was 227.3 g (cf. Table 8).

Table 7 • % of the total
amount of phosphorus K ₂ O % of the total
cal! amount MgO P ₂ O ₅ 18.3
0.7
37.8
41.9 43.7
90.2 18.4
24.2
27.9 65.9
86.7 *. 1.1
2.3
4.9 WL
free acid
AZL
total quantity

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Patent attorneys Dr. W. Andrejewski, Dr. M. Honk ·, 43 Essen, Kettwiger Strasse Table 8

free slur

total quantity example

P ₂ O ₅ * from the Gesarat
phoBphor amount K ₂ O * of the total
amount of potash MgO 2.0
30.6
42.2 4.7
72.5 13.6
23.9
28.1 48.4
85.1 % 0.1
1.8
4.9

50.0 g of serezite concentrate with a content of

9.2 % K ₂ O and 24.6 % Al ₂ O ₃

and a degree of grinding that 90 pounds passed through an 80 Tyler meah sieve, 200.0 g of phosphoric acid (PgOc content 32.0 %) were added. After drying by evaporation, the mixture was heated at 400 ° C. for one hour. The result was 112.8 g of a substance, the nutrient and solubility values of which are listed in Table 9.

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Patent Attorney Dr. W. Andwfrkl, Dr. M. Honk ·, 43 EtMn ₁ KeMwIgM * StraB ·

Table 9

free acid

total quantity

. ^P 2 ° 5 % from the Oesaat-
phoephor quantity V % from the Oeeaat-
kallaenge 4.3
0.9
27.5
56.7 7.6
48.5 0.3
1.1
4.1 7th
27

Claims

Claims (2)

Patent Attorney Dr. W. Andrejewskl, Dr. M. Honk ·, 43 Essen, Kettwiger Strasse 36 patent claims 1. A process for the production of phosphorus-potash-DUnger or the Phoephor-Kali components of fertilizers from minerals of the Qlinmergruppe and phosphoric acid are characterized by the fact that the fertilizer is produced by heating a mixture of phosphoric acid and minerals of the mica group either with the addition of additives such as potassium salt, boron, copper, manganese, zinc, Miybdenum and sulfur compounds or even without Admixture of aoloher aggregates is produced. 2. The method according to claim 1, characterized in that the heat treatment lasts 15 minutes to six hours and the Heating temperature between the boiling point of phosphoric acid and 600 ° C. YY. Method according to claim 1, characterized in that that the free acid reacted with the heat treatment xloht Ammonia is neutralized. PAe Dr Andreevskl, Dr Honke 009835/1711