DE2132846A1 - Soil treatment agents - Google Patents

Description

The invention relates to an improved soil treatment « conditioning agents.

In particular, it relates to improved soil management * improver, which is a hydrophilic, high-molecular, organic polymer and a condensed phosphoric acid holds. It also relates to an improved soil treatment agent that still contains inorganic salts have a fertilizing effect.

109882/1888

As used herein, the term "hydrophilic, high molecular weight organic polymer" is intended to encompass water-compatible, synthetic, high molecular weight organic substances including various nonionic, anionic and cationic substances. The term "condensed phosphoric acid" is intended to mean different phosphoric acids which are usually present in the form of a mixture of different polyphosphoric acids, which should preferably _{contain from 3 to 83% by weight of the acid, based on P 2} ⁰ C *,

fc The improved soil treatment agent of the invention converts transforms a soil with a structure of individual grains into a soil with a crumbly structure.

The agent also serves as a fertilizer. Therefore this is fictional appropriate means for the cultivation of plants particularly suitable.

To convert floors with individual grains in soils with a crumbly structure different soil treatment agents have already been vorgesehlagen * Examples of such known soil treatment agents are inorganic substances such as bentonite and zeolite organic substances of natural manufacturing W origin, such as pectin, various starches, sodium alginate and humic , as well as synthetic organic polymers such as polyvinyl alcohol and polyacrylic acid derivatives.

It has been shown that these synthetic * organic polymers Among other things, they are very suitable for converting a soil with individual grains into a crumbly soil. It was » de, however, found that these organic polymers, when applied to such soil from individual grains, have a tendency to gradually shrink too much of the granular structures formed in the treated soil to cause what is due to their inadequate water tolerance can be attributed to This will slow down the germination of the seeds and the growth of the plant roots. About that-

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in addition, a water-impermeable layer accelerates itself The granular structure gradually shrinks beneath the layer of cultivation soil. That way will significantly hinders plant growth.

It is also known that condensed phosphoric acids have a dispersing property. It is finally still known that condensed phosphoric acids can form water-soluble chelate compounds with various polyvalent metals.

It has now been found that the effect of the hydrophilic, high molecular weight, organic polymers on the conglomeration of the soil with a single-grain structure is significantly increased, when the polymer is used together with the condensed phosphoric acid. This observation is very surprising since the organic polymers and the condensed phosphoric acids show opposite properties with regard to the conglomerating and dispersing behavior towards the soil.

It has also been found that by using a mixture of the polymer and the condensed phosphoric acid obtained soil with a crumbly structure can be left to stand for prolonged periods of time without it becoming sealed Grains compacted.

As is well known, a productive land suitable for cultivation should have three phases in the correct distribution, viz solid, liquid and gaseous phases. Farther such a country should have the appropriate amounts of nitrogen, phosphorus and potassium along with small amounts of VerDincLun genes of Ca, Zn, Mn, Pe, Cu, Mo, etc. as required metals.

It is known that the commercially available phosphorus fertilizers contain orthophosphoric acid when applied to the soil have the disadvantage that they are poorly water-soluble phos-

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- Hm

form phates of metals that are commonly present in the soil sindo In these circumstances, both the metals as well as the phosphorus fertilizers for plant growth are no longer available. Such disadvantages occur in particular occurs when the soil contains a relatively large amount of such metals »

By using the new means according to the invention can a single-grain structure advantageously into a crumbly one Structure to be converted. At the same time, certain metals that are commonly found in soil can be in insoluble form ) are present, converted into the water-soluble chelate compounds which are available for the fertilizer elements. Another advantage obtained by using the invention Means can be obtained lies in the fact that if a soil is made of certain metals or metals responsible for vegetation are indispensable, is depleted, then the desired metals advantageously by means of a soil treatment agent according to the invention which contains the salts of the desired metals «

When fertilizing it is very important that the highest fertilizing effect is the phosphate component present in a given fertilizer is realized, since the vegetative nutritional effect of the potassium and nitrogen compounds strongly depends on the Fertilizer effectiveness depends on the phosphorus component. In addition, the vegetative growth in the plant depends heavily on the presence of small amounts of certain metals in their available form. For example, molybdenum has the available Form the function that the activity of the 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 considerably restricted. In such circumstances, a nitrogen substance that may affect the Soil is added in the form of ammonium salts, cannot be used effectively for plant growth in the first stage,

109882/1888

Such a disadvantage can easily be removed by using the agents according to the invention, because the phosphate " Part of the agent converts the molybdenum contained in the soil into the available chelate compound. In addition, however, can also a soil that is poor in molybdenum, e.g. aluminite soil, volcanic ash soil etc., can be made fertile by adding the agents according to the invention, to which a molybdenum salt beforehand has been given.

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

In general there is an unlimited variety of soils due the individual origins and with regard to the chemical components, the pH values, the physical properties etc.

For these reasons, it is difficult, if not impossible, to create an all-powerful or universal soil treatment agent that is suitable for any type of soil. In other words, a certain soil treatment *. agent that is suitable for a particular soil is not always equally suitable for conditioning another soil type can be used with different quality. There is therefore an urgent need to provide a soil treatment agent, which is suitable for all types of earth.

Such a means is now the means according to the invention.

Another advantage obtained by using the agent according to the invention is that due to the simultaneous If the condensed phosphoric acid is present in the mixture, it is possible to reduce the amount of the high molecular weight organic polymer, which is required to condition a poor soil with a granular structure.

109882/1888 ^ ⁶ "

WHERE "·

As already stated, can in which he be inventive agent phosphoric acid used is a mixture of a plurality of polyphosphoric acids, preferably about 73 to 86 weight. * # Of acids, based on P contains ₂ ⁰ Sf, or a partially neutralized product thereof be. Such condensed phosphoric acids are commercially available or. they can be prepared, for example, by polymerizing orthophosphoric acid (H-PO _1. ) or a mixture of orthophosphoric acid and phosphorus pentoxide (P ₂ Oc) with heating. For the purpose of partial neutralization of these condensed phosphoric w potassium hydroxide or potassium carbonate may, inter alia advantageously because of Düngemittelwir · "of the mixture prepared from 'are fsrwendet effect.

In practicing the invention, it should be noted that there is no critical limitation on the relative amounts between the hydrophilic, organic polymer and the condensed phosphoric acid. The two components can thus mixed together in equal parts by weight 'Ü7 © Pfl © n or they may be used in a one-sided excess WEF & .®n ₀ In most cases, the condensed phosphoric acid in the © domestic used to three-fold weight excess of the organic polymers.

The following examples describe the effects of conglomeration obtained by combining various hydrophilic, high molecular weight, organic polymers and condensed phosphoric acid. The soil was dispersed in water to investigate the ability of the soil to form a crumbly structure. The Erdgwurde from the area of Kumamote-prefecture _for Japan taken.

A condensed phosphoric acid with 83.0% by weight of acid, based on P ^ O c, was used, which had the following composition;

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Orthophosphoric acid H ~ PO ^ 5 »6O%

Pyrophosphoric acid H ₁ ^ P ₂ 0 ^ 18.7OJt

Tripolyphosphoric Acid HcPoO ₁₀ 17.80J <

Tetrapolyphosphoric ^{acid Η} 6 ^Ρ 4 · ° 13 1 ^, 70Ji

Pentapolyphosphoric acid ^Η 7 ^ ς ^ο ΐ6 12.00Ji

Hexapolyphosphoric acid ^H 8 ^ 6 ° 19 8.60%

Heptapolyphosphoric acid HgP "0 ₂₂ 7 _f 20%

Octapolyphosphoric acid ^H 10 ^P 8 ^ 26 5t10%

Nonapolyphosphoric acid ^H 11 ^P Q ^O 28 2.50%

High polymer phosphorus «H_ + οΡ ,, Ο.- + 1 7.80%

acids ⁿ (S £ W ⁿ

The following hydrophilic, organic polymers were used:

1. Polyacrylamide (n - 20,000 - 30,000)

2. Diaclear MA-2010 (liquid)

(Viarenzeichen Mitsubishi Chem. Ind. Go «, Japan) an anionic polymer, partially hydrolyzed polyacrylamide

3. Sunfloc C ~ if50 (powder)

(Trademark Froth Chem. Co., Japan, cationic Polymer)

^. Sunfloc N-50P (powder)

(Trademark of Froth Chem. Co., Japan, non-ionogenic Polymer)

5. Sunfloc AA-300D (powder)

(Trademark of Froth Chem · Co., Japan, cationic Polymer)

6. Sunfloc AH-.200D (powder)

(Trademark of Froth Chem. Co., Japan, anionic polymer)

7. Separan AP30 (powder)

(Trademark The Dow Chem. Co., USA, anionic polymer)

8. Konanfloc ZP-900 (liquid)

(Trademark Konan Chem. Co., Japan, anionic polymer)

9. Konanfloc 2000B (liquid)

(Trademark Konan Chem. Co., Japan, non-iono ~ genetic polymer)

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■ · ο -

10. Konanfloc 3000 (liquid)

(Trademark Konan Chem »Co ,, Japan, non-ionogenic Polymer)

11. Aronbis M (n »15,000-20,000 powder)

(Trademark Toagosei Chem. Ind. Co., Japan, anionic polymer)

Polymers 1 through 11 are hereinafter referred to as "PM-I" through "PM-II" designated·

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

P ₂ O ^ 15 wt.% K ₂ ~ ^ OI wt. '% H ₂ O 71 ~% by weight.,

2. Eleven organic polymer solutions (B) of the above-mentioned polymers 1 to 11 were prepared by adding 1 g each of the Powder in each 100 ecm of water were dissolved or by adding the corresponding liquids in fivefold Amount of water have been diluted.

3. Eleven solutions (C) were prepared separately by the The above solution (A) was mixed with the corresponding solutions (B) in a ratio of 1: 5 (volume). The resulting Solutions (C) were diluted with water to make a 1000-fold dilution (test solutions D).

It can be seen from the above that all test solutions (D) contained 15 # / 6ΟΟΟ β O, OO25 # P ₂ O <on the one hand and 1 ^ / 12000 = O, OOO83J6 of the respective polymer on the other.

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21328ΑΘ

k. A solution of the condensed phosphoric acid (B) was prepared as a control by diluting the above solution (A) with water to a 6000-fold dilution. The resulting solution (E) contained 0.0025 / f ^P 2 ° 5 ^#

5. Eleven solutions (F) to control the respective polymers 1 to 11 were prepared by mixing solutions (B) with what ser to make a 1200-fold dilution. Each of the control solutions (P) thus contained O, OOO83Ji of the polymers.

Using the above solutions (D), (E) and (F) we knew in the following manner sedimentation experiments of the specified Soils carried out:

In each case 20 g of soil were placed in Zk 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).

The solution (E) of the poly phosphoric acid added to make a total volume of 100 ecm and to give the control experiment (2).

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

At all remaining eleven cylinders each test solutions (D) were added (Test numbers ¹ to 12 · 3).

All 2k cylinders were shaken well to obtain the suspensions of the earth, left to stand and visually for the most occupied volume during each time period

of the earth.

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The results obtained are shown in the table below.

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Tabel

No. of the composition cylinder

Volume in ecm of the sedimenting earth

Seconds minutes

0 10 20 30 1 2 "3 4 5

10

60

SS "**

(Control
le 1) Water ^ + CPA ⁺⁺ 100 96 83 93 91 50 90 . .82 38 75 70 38 66 47 38 29 (Control.
Ie 2) Water λ + PM ⁺ -I 1
(Day)
31 76 2
(Days)
31 48 3
(Days)
30th 44 4th
(Days)
30th 44 (Days)
30th 43 1 Water H + PM-I 100 84 67 61 40 41 38 39 38 38 37 O
CO
OO 1" Water λ
+ CPA + PM-2 100 75 55 50 45 45 44 44 44 44 43 OO 2 Water H + PM-2 100 94 73 73 46 37 / 39 35 39 35 38 2 ' Water ^
+ CPA + PM-3 100 80 57 57 46 42 44 41 44 41 44 OO
OO 3 Water η + PM-3 100 90 85 62 45 39 36 38 35 37 35 OO V Water H
+ CPA + PM-4 100 72 70 49 45 44 41 43 41 43 40 4th Water η + PM-4 100 90 82 67 45 38 38 36 37 36 37 4 « Water -
+ CPA + PM-5 100 75 54 49 45 42 43 41 43 41 43 5 Water ■ + PM-5 100 80 45 37 36 36 5 ¹ Water :
+ CPA 100 59 43 42 41 41 • Earth ■ Earth - Earth - Earth η earth κ earth h earth (■ earth ν earth ν earth ι- earth "· Earth

.. FM Polymeres ... CPA condensed phosphoric acid

Superiority {%) of the constituents of the soil's end abatement volumes caused by the condensed phosphoric acid (CPA) plus the polymers (PM-I to PM-II) compared to the effects of the polymers (PM-I-to PM -Il) alone

16

16

14th

16

14th

co ro oo

-F-CD

Continuation of the table

f No. of
Cylinder composition + Vvt-b Volume in ecm
Seconds
0 10 20 82 69 the sedimenting
Minutes
30 1 -2 3 45 41 41 Earth
4th 5 10 60 ■%
Duration-
part ⁺⁺⁺ 6th Water + earth + PM-6 100 63 54 56 48 ' 47 47 41 40 40 40 6 · Water + earth
+ CPA ⁺⁺ + PM-7 100 80 59 50 39 37 36 47 47 47 47 18th 7th Water + earth + PM-7 100 60 48 49 43 42 42 36 36 35 35 7 ' Water + earth
+ CPA + PM-8 100 89 76 45 43 38 37 42 42 41 41 17th —Λ
43 8th Water + earth + PM-8 100 80 63 64 43 42 41 36 36 36 36 «Ο
OO
€ 0 8th' Water + earth
+ CPA + PM-9 100 80 62 51. 43 42 42 41 41 41 41 14th IO 9 Water + earth + PM-9 100 65 53 49 48 47 47 41 41 41 41 OO 9 ¹ Water + earth
+ CPA + PM-IO 100 67 43 49 38 38 38 47 47 47 47 15th CO
«Ο 10 Water + earth + PM-IO 100 53 49 40 45 45 45 38 38 37 37 10 · Water + earth
+ CPA + PM-Il 100 82 73 45 54 42 33 45 45 45 44 19 ^^
1 11 Water + earth + PM-Il 100 80 62 61 39 37 37 32 31 31 31 11 · Water + earth
+ CPA 100 4b 37 37 36 36 16

PM polymer

CPA condensed phosphoric acid

Superiority (%) of the constituents of the soil's final settling volumes which by
the condensed phosphoric acid (CPA) plus the polymers (PM-I to PM-II) was effected compared to the effects of the polymers (PM-I to PM-II) alone

The values in the table show:

a) The sedimentation rate of the soil in the aqueous suspension according to Control 1 is determined by would give the condensed phosphoric acid (control 2) he « considerably reduced. Furthermore, the final settling of the earth is condensed by the addition of the Phosphoric acid hardly affected.

b) The sedimentation velocities of the earth in comparison to the aqueous suspension (1) are determined by Addition of the respective hydrophilic polymers (test nos. 1 to 11) increases and the final settling volumes (ecm) of the soil in the aqueous medium are increased by adding the polymers. This fact says that the polymers themselves are effective in promoting the conglomeration of the fine particles of the earth, whereby Lumps with larger dimensions can be obtained. Finally it turns out that the efficiency for the Acceleration of conglomeration depending on the characteristic Properties of the individual polymers vary.

c) A marked increase in the final sedimentation volumes of the sedimented soil is caused by the simultaneous Additions of the hydrophilic, high molecular weight, organic polymers and the condensed phosphoric acid (test No. 1 »to 11»).

The agents according to the invention can of course be incorporated into fertilizers, such as conventional nitrogen fertilizers and also contain pesticides, herbicides and / or bactericides or are added to them.

The invention is described in more detail in the following examples.

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example 1

63.6 kg condensed phosphoric acid with 83 _f 0 wt .- # acid, based on Pp ^{O |} > * ^{WUR <ien mi} ^ ²⁰ ° S ^k water at room temperature diluted.

About 85/6 of the condensed phosphoric acid in the resulting Solutions were neutralized by slowly adding an aqueous solution of 63 kg of KOH. The whole thing then became adjusted to 350 kg by adding water.

With stirring, 450 kg of a 5% aqueous solution are added to the solution Given a solution of a polyacrylamide with an average degree of polymerization of approximately 30,000. The emotion the mixture obtained (80 kg) was continued at room temperature until a homogeneous solution was obtained. The solution had the following composition:

Condensed phosphoric acid ₉

based on Pg ⁰ ^ 7 »95 wt. <-%

KOH 7.6 wt. JfL

Polyacrylamide 2.8 wt. «#

H ₂ O 81.65 wt. JfL

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

The potassium and phosphorus it contains act as fertilizers.

Example 2

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

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Polyphosphoric acid 69 kg (as in example 1) 66 kg KOH 20 kg Additive A 220 kg water 375 kg All in all

110 kg of urea was then added to the mixture and the whole (1020 kg) was stirred for two hours.

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

Additive A Components Parts by weight Iron (III) nitrate 18.6 Copper (II) nitrate 5.0 Zinc nitrate 6.1 Manganese sulfate * 3.2 Magnesium sulphate 156.0 Ammonium molybdate 2.4 citric acid 7.2 Boric acid 9.0 water 352.5 lnsget, auit 600.0

If desired, the relative amounts of each Components are changed. Some of these can be replaced by other compounds. Finally still can further compounds are added.

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

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Example 3

An aqueous solution of potassium was prepared by adding 137 kg of a condensed phosphoric acid with 83 wt. ~ $ Of the acid, based on Pp ^ s ^»m ^ © into aqueous ³⁰ solution of 133 kg of KOH were treated. To 100 kg of the resulting solution were added 650 kg of water and then 100 kg of a 5% aqueous solution of polyacrylamide with an average degree of polymerization (n) of 30,000. The whole was stirred at room temperature for three hours. Sufficient ethanol was slowly added to the solution with stirring to form a precipitate. After the completion of the precipitation, the precipitate was removed by filtration and dried under a reduced pressure of about 1 mmHg. Thus, 35 kg of the desired composition was obtained in the form of a white powder.

When using the mass in 500 "to 5000 times Volume of water dissolved,

example b

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

Additive B Components 750 g Magnesium sulfate 83 g Manganese sulfate 21 g Copper (II) sulfate 26 g Zinc sulfate 6 g Ammonium molybdate 100 g Iron (III) nitrate 20,000 ml water

1098 8 2/1888

The resulting pale green solution was stirred for an additional hour and 11 kg of urea were then added to obtain a clear solution added. To the solution, alcohol was gradually added to form a precipitate. When finished Precipitation, the precipitate was filtered off and dried at about 1 mm Hg.

In this way 4-7 kg of a pale green powder was obtained. The product can be used as a soil treatment agent.

Try with the earth

The effects of the agent (Composition A) of Example 1 on Riverin Allovium soil, taken in the area of Kumamoto-prefecture, Japan, were a) in terms of conglomeration and b) in terms of distribution among the three Phases, i.e. the solid, liquid and gaseous phases, determined as follows:

In each case 35 kg of a soil sample, which passed through a sieve with a mesh size of 5 mm, were placed in two wooden boxes a) and b) filled with the same dimensions.

In box a) were 5 l of an aqueous soil treatment agent spread, which has been prepared by diluting the composition A with 150 times the volume of water was. The dilute aqueous soil treatment agent thus had a content of 2.856/150 of the polymer.

5 liters of tap water were added to box b) as a control.

The two boxes were left to stand under the same conditions for 10 days. The individual boxes became six

109882/1883

Samples of the earth were taken from various places. With these Samples were carried out the following examinations:

a) Separation of the conglomerated granules

The test was carried out according to the Yoder method. It was observed the following distribution of clods of earth:

Grain size (diameter. Earth from box a) Earth from box b) knife in mm) {%) (Control) {%) > 2 2.6 0.5 2-1 7.5 1.9 1 «0.5 17.5 4.4 0.5 ~ 0.25 21.1 8.6 0.25-0.1 18.2 10.1 <0.1 33.1 83.5 All in all $ 100.0 100.0 # b) Dre! «Phases» Distribution

The determination was carried out by the conventional method. The results obtained are summarized below. The total cavity is the sum of the fractions in % of the liquid and gaseous phases.

Earth from box a)

Earth from box b) (control)

Solid Liquid Gas «Total« Phase Phase Phase Void (% / v) (% / v) {% / v) content

(J6 / V)

56.9

40.6
35.0

18.2 58.8 8.1 43.1

From the above experiments it emerges that the use of the soil treatment agent according to the invention has an effective effect on

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plomeration of the soil particles, increased water uprightness preservation and an increase in the void volume and thus an increase in the overall appearance of the resulting earth clumps causes.

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Claims (1)

Claims 1, soil treatment agent, characterized in that it is condensed phosphoric acid, consisting of up to 87 wt .- #, based on ^ 2 ^{Q <} j ' " ³¹ ^ ^{- a n} y ^dr ° P ⁿⁱ l ^es f high molecular weight organic polymer with a contains conglomerating effect. 2, soil treatment agent according to claim 1, characterized in that « indicates that it also contains one or more salts of Pe, Gu, Zn, Mn, Mg and / or Mo. 3, soil treatment agent according to claim 1 or 2, characterized I denote that the condensed phosphoric acid with an alkali or alkaline earth compound is partially is neutralized. ^. Soil treatment agent according to one of the preceding claims, characterized in that it is in solid or liquid form. 5. Soil treatment agent according to one of the preceding claims, characterized in that the hydrophilic, high molecular weight, organic polymer is a hydrophilic, anionic, cationic or anionic polymer. 6. Soil treatment agent according to one of the preceding claims, characterized in that the hydrophilic, high molecular weight, organic polymers a polyacrylamide, a salt of polyacrylic acid or a partially hydrolyzed one Is a product of the polyacrylamide. 7. Soil treatment agent according to one of the preceding claims, characterized in that it furthermore contains a nitrogen fertilizer, a herbicide, insecticide and / or bactericide. 109882/1888 ORIGINAL INSPECTED