DE2132846B2 - SOIL TREATMENT PRODUCTS - Google Patents

Description

The invention relates to a soil treatment agent with a content of a condensed Phosphate and an organic polymer.

The invention relates to a soil treatment agent with a content of a condensed phosphate and an organic polymer, which is characterized. that it contains partially neutralized with an alkali or alkaline earth compound, condensed phosphoric acid with a P ₂ O ₅ content of 73 to 87% by weight and polyacrylamide or a partially hydrolyzed polyacrylamide.

The soil treatment agent can also be a nitrogen fertilizer, a herbicide, an insecticide and or contain bactericide.

The improved soil treatment agent of the invention converts a soil with a structure of individual grains into a soil with a crumbly one Structure around.

To convert soils with single grains into soils with a crumbly structure are already various soil treatment agents known. Examples of such known soil treatment agents are inorganic substances such as bentonite and zeolite, organic substances of natural origin. such as pectin, various starches, sodium alginate and humin, as well as synthetic organic polymers such as Polyvinyl alcohol and polyacrylic acid derivatives c. For example, one method is to improve the Irrigation of surface soil of high permeability by applying an aqueous solution of partially hydrolyzed polyacrylamide has been described in US Pat. No. 3,633,310.

^l: .s has been found that these synthetic, organic polymers are very suitable, among other things, to a bottom with a / a grain in a crumbly soil convert However, these organic S_S polymers have, when applied to such a floor of individual grains be applied. the tendency to. gradually increasing the shrinkage of the granular structures formed in the treated soil as a result of their inadequate water tolerance. This will slow down the germination of the seeds and the growth of the plant roots. In addition, a water-impermeable layer, which gradually forms below the layer of the cultivation soil, accelerates the shrinkage of the granular structures. The addition of small amounts of orthophosphoric acid to irrigation fluids is known from US Pat. No. 2,163,065, while the use of fluids obtained from potassium hydroxide and orthophosphoric and polyphosphoric acids as fertilizers is described in US Pat. No. 3,022,154 became. Plant nutrient concentrates made from aqueous phosphoric acid solutions and specific clays are also known from US Pat. No. 3,160,495. However, these plant nutrient liquids are not suitable for conditioning the soil, such as, for example, the formation and maintenance of a crumbly structure, but merely serve to supply the plants "with the necessary nutrients in a suitable form.

It is also known that commercial phosphorus fertilizers containing orthophosphoric acid if they are used on the ground, they have the disadvantage that they are poorly water-soluble phosphates of metals usually present in the soil. Under these circumstances Both the metals and the phosphorus fertilizers for plant growth are no longer available Such disadvantages occur in particular. when the soil has a relatively large amount of such metals contains.

Finally, in FR-PS 20 16 727 and US-PS 26 26471 and 27 03 276 fertilizers or Soil conditioning agents have been described which, in addition to phytonutrients, contain phosphate compounds and organic polymer components. As in these known conditioning agents, however it does not contain any free phosphoric acid, which can be achieved with the use of these agents Results not yet satisfactory.

However, it has now been found that the effect of polyacrylamide or a partially hydrolyzed polyacrylamide on the conglomerate of the soil with a single-grain structure is significantly increased if the polymer is used together with the above-mentioned condensed phosphoric acid is used. This fact is surprising given the organic Polymers and condensed phosphoric acid with regard to conglomerating and dispersing Behavior towards the soil show opposite properties.

It was also found that the by using a mixture of the polymer and the condensed phosphoric acid obtained soil with a crumbly structure over prolonged periods of time can be left standing without him to compose himself Grains compacted.

As is well known, a productive land suitable for cultivation should have three phases in the right one Distribution, namely solid, liquid and gaseous phases contain. Furthermore, such a country should the appropriate amounts of nitrogen. Phosphorus and Potassium along with small amounts of Connections of Ca. Zn, Mn. Fc. Cu. Mon etc. as contain required metals.

By using the new agent according to the invention, a single-grain structure can be transformed will. At the same time, certain metals that are commonly found in soil can be insoluble Form are present in the water-soluble ("helal compounds which are available for the fertilizer elements. Another advantage, by using the agents according to the invention

; r can be maintained is that if a stalls of certain metals or metals, the "If the vegetation is indispensable, is impoverished, then the desired metals advantageously by a soil treatment agents according to the invention can be supplied, which the salts of the desired Contains metals. For example, one or more salts of can also be used in the soil treatment agent Fe. Cu, Zn, Mn, Mg and / or Mo may be included.

When fertilizing it is very important that the highest fertilizing effect of the phosphate component, contained in a certain fertilizer. is realized because the vegetative nutritional effect of the Potassium and nitrogen compounds greatly depend on the fertilizer effectiveness of the Phosphorkompor.ente depends. In addition, the vegetative growth in the plant depends heavily on its presence small amounts of certain metals in their available form. For example, B. Molybdenum in the available form the function that the activity of nitrate assimilating bacteria in the soil is increased.

In an acidic soil, however, the molybdenum is inactivated, so that the activity of the bacteria is considerable is restricted. In such circumstances, a nitrogen substance can form the soil in the Ammonium salts are added, not effectively utilized for plant growth in the first stage will. Such a disadvantage can be easily removed by using the present invention Agent used because the phosphate portion of the agent converts the molybdenum contained in the soil into the available Chelate compound converts. In addition, a bottom that is low in molybdenum, such. B. Aluminite soil, volcanic ash soil, etc. fertile be made by adding the agent according to the invention, to which a Mclybdänsal / has been given.

The soil treatment agent according to the invention is therefore suitable for a single-grain soil in to convert a crumbly soil and also as a source of phosphorus and as a source of necessary metallic elements to function.

In general there is an unlimited variety of soils due to individual origins and in terms of chemical constituents, pH values, physical properties, etc.

For these reasons, it is difficult to find a universal one To create soil treatment agents that are suitable for all types of soil In other words, that a certain soil treatment agent, that is suitable for a particular soil. not always the same for conditioning a different soil type with different! Quality can be used. Fs therefore an urgent one Need to provide a soil treatment agent that is suitable for all types of soil

Such a means is now provided by the crfindunesucn'äUt Vn Me! there.-.

Another advantage of \ erwenduu; de is obtained according to the invention is the because it is due to the availability of the approved i'i phosphoric acid in the mixture m-iniich in the. the Mem'.e of the high-molecular, organic ioiymeren. you · / ur conditioning a worse one Soil mn a come structure required lsi. / u decrease.

The condensed phosphoric acids used in iM-lindunusuomiiß are commercially available, or they can be prepared, for example, by polymerizing orthophosphoric acid (H ₃ PO ₄ ) or a mixture of orthophosphoric acid and phosphorus pentoxide (P ₂ O ₅ ) with heating. For the purpose of a partial neutralization of the condensed phosphoric acids mentioned, an alkali or alkaline earth compound is added to the soil treatment agent. z. B. advantageously potassium hydroxide or potassium carbonate due to the fertilizer effect of the mixture made therefrom added.

In practicing the invention, it should be noted that there is no critical limitation on the relative amounts between the polyacrylamide and the condensed phosphoric acid. the both components can thus be mixed with one another in equal parts by weight, or they can be used in a one-sided excess. In most cases it will be phosphoric acid used in one to three times the weight excess over the polyacrylamide.

The examples below describe the effects of conglomeration brought about by the combination from various polyacrylamides and the condensed phosphoric acid. Of the Soil was dispersed in water in order to have the ability to form a crumbly structure of the soil to investigate. The soil was taken from the area of Kumamoto Prefecture, Japan.

A condensed phosphoric acid containing 83.0% by weight of the acid, based on P ₂ O _{5, was} used. which had the following composition:

Orthophosphor- H., PO _-1 5.60 ",,

acid

Pyrophosphorus- H ₄ P ₂ O ₄ 18.70 "»

acid

Tripolyphosphor- H ₅ P ₃ O ₁₀ 17.80 ". Η

acid

Tetrapolyphosphor- H ₁₁ P ₄ A, 14.70 ",,

acid

Pentapolyphos- H ₇ P ₅ O ₁₁ , 12.00 "»

phosphoric acid
Hexapolyphos- H _S P "O ₁₉ S.60" »

phosphoric acid

Heptapolyphos- H ₄ P ₇ O ₂₂ 7.20 "»

phosphoric acid
_so Oclapolyphosphor- H ₁₀ PsO ₂₅ 5.10 ",,

acid

Nonapolyphos- H _n P ₄ O ₂ H -> 0 ⁿ .>

phosphoric acid

High polymer H "..," + PO., "+ 1 7.80".,

^ Phosphorsäliren (»S: IOl

The following polyacrylamides or their commercially available solutions containing them were used :

1. Polyacrylamide In = 20,000 = .- = 30,000).

2. Fin anionic, liquid product obtained by partial hydrolysis of polyacrylamide (molecular weight 10,000,0001.

3. Polyacrylamide ■ Nainumaerjlat (molecular weight 5,000,000 10,000,000) in a cationic liquid wedge! Viscosity of the 1 ″ aqueous solution approx. HK) cP).

It is assumed that it contains a mixture of the substances of the following formulas (x, y ,: do not give exactly known degrees of polymerization).

^L CH, - -CH-
j O - - I.
C =
I. V I.
NH, X

CH - CH

COONa

Polymers 1 through 11 are hereinafter referred to as "PM-I" to "PM-11".

(1) A solution (A) of the condensed phosphoric acid was prepared by adding about 85% of the neutralized condensed phosphoric acid with the appropriate amount of an aqueous KOH solution became. The resulting solution (A) had the following composition:

P, 0 ₅ 15 wt. ",

j <f O ... 14% by weight
Here Υ '''.'.'.'.'.'.'.'. 71 Weight .- <\,

h CH, - <

CH— ^! CH ₂ - C = O NH, -CH-
ι C = O
I. 0 "Well

4. Polyacrylamide. Sodium acrylate (molecular weight 5,000,000-10,000,000) as a cationic, iscose Liquid (viscosity of the 1% aqueous solution approx. 2CX) OcP).

It is assumed that a mixture of the substances of the formulas shown under 3 is present.

5. Polyacrylamide ■ Sodium acrylate as anionic, white powdery substance (viscosity of the 1% aqueous solution about 5000 cP). It is believed, that a mixture of the substances of the formulas shown under 3 is present.

6. Polyacrylamide Sodium acrylate as a cationic, white powdery substance (viscosity of the 1% aqueous solution about 6000 cP). It is assumed that a mixture of the substances shown under 3 Formulas.

7. Polyacrylamide ■ Sodium acrylate as anionic, powdery substance (average molecular weight 2,000,000- ■■ 3,000,000). It is believed that a Polymer of the formulas below is present.

CH, - CH -

C = O

NH ₂

CH ₁

CH

C = O

O "Na ⁺

8. Polyacrylamide resin (average molecular weight 5,000,000). Anionic liquid.

9. Polyacrylamide resin (medium molecular weight

5,000,000). Non-ionic liquid.

10. Polyacrylamide resin (average molecular weight

6,000,000). Non-ionic polymer.

11. Sodium polyacrylate. Anionic polymer.

is (2) 11 organic polymer solutions (B) of the above Polymers 1 through 11 were made. by adding 1 g of the powder in each 100 ecm of water have been dissolved or by diluting the corresponding liquids in five times the amount of water

^ o were.

(3) Eleven solutions (C) were prepared separately by mixing the above solution (A) with the corresponding solutions (B) in a ratio of 1: 5 (volume)! became. The resulting solutions (C) were mn

zs water diluted by a 100-fold dilution to achieve (test solutions D).

It can be seen from the above that all of the Tcst solutions (ID) contained 15% / 6000 = 0.0025% P ₂ O, on the one hand and 1% 12,000 = 0.00083% of the respective polymer on the other.

(4) A solution of the condensed phosphoric acid (E) was prepared for control by following the above Solution (A) with water to a 600 () fold dilution has been diluted. The resulting solution?

(E) contained 0.0025% P ₂ O ₅ .

(5) Eleven solutions (F) for controlling the respective polymers 1 to 11 were prepared by using the Solutions (B) have been diluted with water to make a 1200-fold dilution. Each of the Control solutions (F) thus contained 0.00083% of the polymers.

Using the above solutions (D). (Egg and (F) were sedimentation experiments in the following manner of the specified soils:

In each case 20 g of soil were placed in 24 measuring cylinders with a capacity of 100 ecm of the same size.

Tap water was added to one to make a total volume of 100 cc as a control (1) result.

To another of the cylinders, the solution (E) of polyphosphoric acid was added to make up a total volume of 100 ecm and to give the control experiment (2).

For all of the other eleven cylinders, the individual solutions (F) were added to a total volume of 100 ecm given (test numbers 3 to 12).

The individual test solutions (D) (test numbers 3 'to 12').

All 24 cylinders were shaken well to get the

Suspensions of the earth are left to stand and visually imprinted during each period of time

f> 5 with regard to the occupied volume of the earth considered.

The results obtained are summarized in the table below.

No, des
/ vlindeis

/ iis; iniiiK'nsel / unu

Volume in ecm dei SL'ilimeniating I-rilc

Seconds
Il 10

20th

M)

Minutes I 2

Main part **)

IO W)

(Control 1)
(Control 2)

Water + earth

Water + earth
+ CPA **)

\ 00 96

(Day)
31
100 83

93

91

90

70

(Days) 31

(Days) 30 40 38

(Days) 30 38

41 38 43 37 42 41 47 36 42 37 41 42 47 38 45 33 37

44 39 44 35 41 38 43 36 41 41 47 36 42 36 41 41 47 38 45 32 37

66

(Days) 30 38

44 39

44 35 41 37 43 36

Water + earth 100 83 67 50 ■ + ■ PM -! *)

Water + earth 100 76 55 48 45 44 + PM-I + CPA

Water + earth 100 84 73 6i 46 4 'l PM-2

Water + earth 100 75 57 50 46 45 + PM-2 + CPA

Water + earth 100 94 85 71 45 37 + PM-3

Water + earth 100 80 70 ^ 7 45 42 + PM-3 + CPA
Water + earth 100 90 82 62 45 39 f PM-4

Water + earth 100 72 54 49 45 44 + PM-4 + CPA

Water + earth 100 90 SO 67 45 38 + PM-5

Water 4- earth 100 75 59 -η 43 42 ■ f PM-5 + CPA

Water + earth 100 82 69 56 45 41 - + - PM-6 * j

Water + earth 100 63 54 50 48 47 + PM-6 + CPA ** I

Water + earth 100 80 59 44 39 37 + PM-7

Water -f- earth HK) 60 48 45 43 42 + PM-7 + CPA

Water -f earth 100 89 76 64 43 38 + PM-8

Water + Earth HXI 80 63 51 43 42

+ PM-8 + CPA

Water + earth 100 80 62 49 43 42 + PM -9

9 water + earth 100 65 53 49 48 47

+ PM-9 + CPA

Water + earth 100 67 43 40 38 38 + PM-10

10 'water + earth HX) 53 49 45 45 45

+ PM-10 + CPA

Water + earth 100 82 73 61 54 42 + PM-Il

ir water + earth 100 80 62 48 39 37

+ PM-II + CPA

"I PM Polymer.

** »CPA condensed phosphoric acid.

***) Superiority Tot of the constituents of the end abattoir volumes of the earth, which was caused by the condensed phosphoric acid (CP-- ι plus the PoU mers (PM-I to PM-111) in comparison 7U the effects of the polymers IPM-I to ³ M -) 11 alone

From the values in the table it can be seen: t ^ trolle 2) considerably reduced. Furthermore, the

a) The rate of sedimentation of the soil final sedimentation of the soil by adding the

In the aqueous suspension according to Control 1, condensed phosphoric acid is hardly affected

by adding the condensed phosphoric acid (con-b).

009 543/45

40

47

36

42

36

41

41

47

38

45

31

37

47

38

43 43 38

44 44 Ki

35

41 40

37

43 43 Id

36

41 41

40

47 47 IS

35

41 41

36

41 41

41

47 47

37

45 44 31

36 36

21 9

compared to the aqueous suspension (1) by adding the respective hydrophilic polymer (Tesi No. 1 to 11) increased, and the final deposition volumes (ecm) the frees in the aqueous medium are increased by adding the polymers. This fact suggests that the polymers themselves promote the conglomeration of fine particles of the earth are effective, giving lumps of larger dimensions. In the end It turns out that the efficiency for the acceleration The tendency of the conglomerates to vary depending on the characteristic properties of the polymer.

c) A marked increase in the final settling volumes of the sedimented soil is achieved, _s (through the simultaneous addition of the hydrophilic, high molecular weight organic polymers and the condensed phosphoric acid (test no. Γ to 11) (.

The compositions of the invention may _{naturally, n} in fertilizers, such as conventional nitrogen fertilizers, are incorporated and also Pesticide. Herbicides and / or bactericides contain or are added to them.

In the following examples, the invention _, described in more detail.

example 1

63 kg of condensed phosphoric acid with 83.0% by weight of acid, based on PiO ₅ . were diluted with 200 kg ₍₀ water at room temperature.

About 85 "µ of the condensed phosphoric acid in the resulting solution was neutralized by adding an aqueous solution of C3 kg of KOH was slowly added. The whole thing was then to 350 kg by ^ ? Uiiabe of water discontinued.

With stirring, 450 kg of a 5 "., Aqueous solution of a polyacrylamide were added to the solution an average degree of polymerization of given about 30,000. The stirring of the mixture obtained (80 kg) was further stirred at room temperature, until a homogeneous solution was obtained. The solution had the following composition:

Condensed phosphoric acid. ^{4 <i}

bezoy.cn on P, O _S 7.95 wt. ""

KOH ".. 7.6 wt .-" ο

Polyacrylamide 2.8 wt. "Η

H, Ö. . ' 81.65% by weight

The agent is usually applied to the floor after dilution with 100 to 1000 times the amount of water upset.

The potassium and phosphorus contained therein act as fertilizers. ^

Example 2

560 kg of the 5% strength aqueous solution of the same polyacrylamide as in Example 1 were stirred with stirring added at room temperature to 350 kg of an aqueous solution with the following composition:

Polyphosphoric acid

(as in example 1) 69 ka

KOH 66 kg

Additive A 20 kg ^

Water 220 kg

A total of 375 kg

846

10 kg of urea was then added to the mixture and the whole (1020 kg) was allowed to last for 2 hours touched.

The additive A used in this example has the following composition:

Additive A (ieu.ie Components lK.fi lisen (lll) nitrate 5.0 Copper! I ll nitrate (\1 Zinc nitrate 43.8 Manganese sulfate 156.0 Magnesium sulfate 2.4 Aminonium molybda ' 7.2 citric acid ^ .0 Boic acid 352.5 water 6 (X) .0 All in all

If desired, the relative quantities ■ - ■ 'of the individual components can be changed. 1 :: - r ^{L of} these can be replaced by other connections /:. Finally, other compounds can also be added.

The resulting mixture can after dilution only: be used with the appropriate amount of water to condition the soil.

Example 3

An aqueous solution of potassium polyphosphate was prepared by adding 137 kg of a condensed phosphoric acid with S3 weight- ":: of the acid,!" • ■ - • / •. »Λ. ¹ !; aul P ₂ O ₅ . were treated with an aqueous solution of 3 ^ kg of KOH. To 100 kg of the resulting solution, 650 kg of water and then 100 kg of a y'uigen aqueous solution of polyacrylamide with an average degree of polymerization iTv of 30 (X) O were added. The whole was stirred at room temperature for 3 hours. Sufficient ethanol was slowly added to the solution with stirring to form a precipitate. When the precipitation was complete, the precipitate was removed by filtration and dried under a reduced pressure of about 1 mm Hg. In this way, 35 kg of the desired composition was obtained in the form of a white powder.

When used, the mass is in the 500- to Dissolved SOOO times the volume of water.

Example 4

To the same aqueous mixture of potassium polyphosphate and polyacrylamide as in Example 3 The additive B with the following composition was gradually added while stirring: Additive B

Components

Magnesium sulfate

Manganese sulfate

Copper III sulfate

750 g 83 g

components

/ inksulfate

■ \ mmonium molybdiite
Eisenil Ill nitrate

water

26 g
6 μ
HH) μ
20 (KK) ml

The resulting pale green solution became a “Stirred for another hour, and 11 kg of urea were lost then / to add a clear solution to Lirhall / t. Alcohol gradually formed into the solution given a downfall. When the removal is complete the lowering was filtered off and dried at ftwa i mm Hg.

Thus 47 kg of a pale green powder was obtained. The product can be used as a soil treatment agent can be used.

a) Separation of the conglomerated granules

The test was carried out according to the Yoder method. The following distribution of the terrestrial ^ lump observed:

Control! Diameter in mmI

> 2

1 0.5
0.5 0.25
0.25 0.1
<0, l
All in all

Knee from KnMen;

I "oil

2.6

7.5
17.5
21.1
18.2
33.1

100.0

i.rde vom KaMen h | iKonlrollei

0.5

1.9

4.4

8.6

10.1

83.5

HXU)

Try with the earth

The effects of the agent (Composition A) of Example 1 on Riverin Allovium soil. taken «η the area of Kumamoto Prefecture. Japan, a) in terms of conglomeration and b) in terms of distribution / gave way to the three phases. <d. H. the solid, liquid and gaseous phases, "as follows:

35 kg each of a soil sample that passed through a sieve with a mesh size of 5 mm, were filled into two wooden boxes al and b) with the same dimensions.

In box a) were 5 l of an aqueous Bodenbehandkingsmitte'.s spread, which by diluting the composition A 150 times \ V; i> «. Cr \ olumen had been made that diluted The aqueous soil treatment agent thus had a content of 2.8% of the polymer.

In the box bl were to the Konirolle 5 1 line vv ater given.

The two boxes were left to stand under the same conditions for 10 days. From the A box was sampled from six different places on the soil. With these Samples were carried out the following examinations:

b) Three-phase distribution

The determination was carried out by the conventional method. The results obtained are compiled below. The total cavity is the sum of the fractions in "« the liquid and light phases.

resie
phase Hiissme
Phase* Cias
phase tiesami
cavity
echo I "(I Vl I "(. Vl I "ο Vl I "O Vl Earth from
Box a) 41.2 40.6 1S.2 5X.X Earth from
Box b)
(Control) 56.9 43.1

From the above experiments it can be seen that you are using the floor hack according to the invention effective conglomeration of the soil particles, increased water retention, and the like an increase in void volume and hence an increase in the overall appearance of the result causes the clod of earth.

Claims (1)

Claim: Soil treatment agent with a content of a condensed phosphate and an organic polymer, characterized in that it is partially neutralized with an alkali or alkaline earth compound, condensed phosphoric acid with a P ₂ O ₅ content of 73 to 87% by weight and Contains polyacrylamide or a partially hydrolyzed polyacrylamide.