TW201609609A - Sulfur fertilizer - Google Patents

Abstract

The present invention refers to a sulfur fertilizer composition, the process for preparing the same and its use.

Description

Sulfur fertilizer

The present invention relates to a sulfur fertilizer composition, a process for the preparation thereof, and uses thereof.

Sulfur (S) is an important plant nutrient. The demand for sulfur in plants is similar to the demand for phosphorus (P). Therefore, sulfur and nitrogen (N), potassium (K) and P are aggregated into the four main nutrients of plants. Sulfur is an important component of several essential amino acids, so sulfur is important for the quality and quantity of protein. It also involves the metabolism and photosynthesis of nitrogen, the oil synthesis in oilseed crops such as mustard, the synthesis and function of enzymes, amino acids and other organic compounds.

Since the amount of sulphide removal from exhaust gases (especially from power plants, waste and biomass incineration plants) has increased, the amount of sulphur compounds in the soil has been significantly reduced in many areas over the last three decades. For example, the release of SO ₂ in Germany has dropped from approximately 5 million metric tons per year to 500,000 metric tons per year. Therefore, the average intake of S in the soil has changed from about 500 kg S/(ha*a) to less than 50 kg S/(ha*a).

Sulfur deficiency has a major impact on crop yield and quality. Sulfur deficiency occurs mainly in acidic sandy soils where sulfur has been filtered out, especially in areas with large amounts of winter rain. Area.

Naturally, sulfur deficiency occurs mainly in cultures with high sulfur demand, such as alfalfa, canola (canola), cotton, clover, alfalfa, alfalfa, wheat, barley, corn, sunflower, soybean, navy beans, sorghum. , oats and triticale, as well as cruciferous plants like canola, turnip, arugula and onion garlic crops like onions and garlic.

Sulfur deficiency can result in low yields and poor quality of the culture. Fertilization with sulfur can overcome these problems. Fertilization with sulfur not only affects the sulfur content of the plant but also positively affects the shelfability of the product (eg garlic).

The most commonly used sulfur fertilizers are: ammonium sulfate, potassium sulfate, magnesium sulfate, gypsum or elemental sulfur.

Elemental sulfur and ammonium sulfate cause soil acidification, so it can only be used in soils with high pH without negative effects. On the other hand, NH ₃ evaporation is a problem in the use of ammonium sulfate in high pH soils.

Ammonium sulfate, potassium sulfate, and magnesium sulfate have very high solubility and sulfate can be washed away in case of heavy rain. Elemental sulfur has a very low degree of melting. The elemental sulfur applied during the winter is not effective in overcoming the sulfur deficiency because the soil microorganisms oxidize S too slowly. Gypsum exhibits useful solubility, but is generally not available in stable particulate form and does not increase the pH of the soil.

Other sources of sulfur may be ferrous sulfate from by-products of TiO ₂ production. Heretofore, the use of ferrous sulfate has been known as waste water treatment, iron oxide coloring, or as a chromate reducing agent.

In advanced technology, iron sulphate has not been mentioned or recommended as a sulphur fertilizer. Some applications mention iron sulphate as a moss-killing agent; or as a source of Fe - if there is a deficiency of Fe (discoloration) situation; or as a phosphorus and heavy metal absorber in contaminated soil. However, the use of iron sulphate causes acidification of the soil.

The agricultural use of ferric sulphate is described in several patent applications.

GB 1 473 403 discloses a process for the preparation of a composition as a soil amendment or fertilizer by using iron sulfate heptahydrate (ferrous sulfate) with an oxide, hydroxide or carbonic acid selected from alkali or alkaline earth elements The salt compound is thoroughly mixed to obtain a reaction product containing an alkali or alkaline earth element sulfate and iron hydroxide. Immediately thereafter, the ferrous hydroxide is converted to ferric hydroxide by oxidation with oxygen or air. The use as a sulphur fertilizer is not disclosed in GB 1 473 403.

DE 42 19 351 discloses an agricultural additive derived from ferrous sulfate (not ferrous sulfate heptahydrate!) which is obtained as a by-product of the manufacture of titanium dioxide, optionally blended with an alkaline earth compound and an organic substance. The use of this substance is to treat the deficiency of Fe, Mn and Zn. The use as a sulphur fertilizer is not disclosed in DE 42 19 351.

EP 0 093 204 discloses a process for granulating a mixture of iron-containing fertilizers comprising ferrous sulphate and a fertilizer agent with a hydrophilic additive. It also discloses a method of mixing other fertilizer agents such as ammonium sulfate, NPK compounds, micronutrients or natural fertilizers. The use as a sulphur fertilizer is not disclosed in EP 0 093 204.

EP 2 165 976 discloses a process for pressurizing a composition based on ferrous sulfate heptahydrate. The use of this substance is as a source of Fe for agriculture. The use as a sulphur fertilizer is not disclosed in EP 2 165 976.

In advanced technology, it is still necessary to provide soil when the composition is applied to the soil. A modified sulfur fertilizer composition with sufficient sulfur in the soil.

In order to solve the problems of the present invention, the inventors have considered the disadvantages of the compositions of the prior art and achieved the solution of the present invention to provide a sulfur fertilizer which is harmless to soil and plant nutrition, preferably in the form of stable particles, and without Expensive addition or agglomeration process, as well as its preparation and its use as a fertilizer.

Accordingly, the present invention is directed to a method of making a fertilizer composition comprising S, Fe and one or more than one alkaline earth element (including calcium and magnesium) suitable for application to sulfur-deficient soil, wherein The substance comprising Fe and sulfate ions is admixed with at least one of the following components in the form of a solid salt, filter cake, paste, slurry or solution selected from or comprising oxides of alkaline earth elements including Ca and Mg. , hydroxide or carbonate, preferably CaCO ₃ , MgCO ₃ , dolomite (Ca, Mg) CO ₃ , MgO, sintered dolomite (Ca, Mg) O, CaO, semi-hydrated dolomite Ca(OH) ₂ MgO, or Ca(OH) ₂ or a mixture thereof, mixed at a molar ratio of (Ca + Mg) / Fe = 2 to 200, preferably 2.5 to 25, more preferably 10 to 25, and the blend is Conversion is the form of administration.

The blending and conversion to the application form can be carried out simultaneously or continuously, such that the reaction mixture is in the form of a granulated, pelletized or powder, depending on the ratio of ingredients used. Thus, the process of the invention can be practiced in a device which can also be compressed, granulated and/or pelletized.

Blending and/or converting can be in any water, diluted sulfuric acid, preferably diluted CaSO ₄ , elemental sulfur or other S-containing compounds, other compounds used as fertilizers, such as micronutrients, preferably boron compounds , binders or granule auxiliaries or mixtures thereof may also be employed to assist in obtaining the desired product form.

In the method of the present invention, the substance containing Fe and sulfate ions is preferably FeSO ₄ which may contain water of crystallization, such as Fe(II)SO ₄ heptahydrate, which is preferably obtained from the titanium dioxide production method.

Generally, at least one oxide, hydroxide or carbonate component containing an alkaline earth element for neutralizing any acid (such as adhered sulfuric acid) and increasing the pH is preferably limestone, which is a kind for agricultural applications. A natural substance that does not contain a critical amount of harmful substances. In order to provide appropriate reactive blending in the process of FeSO ₄ and to provide appropriate responses, the activity and effectiveness in the soil, which may contain fine particles of limestone 95% <0.09mm, and containing> 95% CaCO _3.

The component of the oxide, hydroxide or carbonate of the alkaline earth element containing the oxide, hydroxide or carbonate of the alkaline earth element may also be a slag derived from steel or a reaction product derived from such slag. . The slag is highly alkaline and more reactive than CaCO ₃ .

In order to be applied to a more acidic soil or if a faster effect is required, the oxide, hydroxide or carbonate component of the alkaline earth element comprising an oxide, hydroxide or carbonate of an alkaline earth element may be sinter or Sintered dolomite or hydrated lime, which provides higher neutralization capacity and higher reactivity than CaCO ₃ and slag.

According to the DIN EN 12945:2014-07 standard, the neutralization value of the at least one component selected from the group consisting of oxides, hydroxides or carbonates of alkaline earth elements containing oxides, hydroxides or carbonates of alkaline earth elements may be 1 to 55% (e.g., CaO), preferably 20 to 55%, more preferably 33 to 48%.

In addition, starch, magnesium sulfate, citric acid, clay, mortar binder, cellulose coating, glucoside binders such as starch, molasses, lignosulfonate, water, water At least one of a combination of lime, water glass, bentonite, cellulose fibers, stearate, urea, or a combination of these materials may be used as a binder or a granulation aid relative to the Fe and sulfate ions and at least One of the components selected from the group consisting of oxide, hydroxide or carbonate components of the alkaline earth elements Ca and Mg is 0.1 to 10% by weight, preferably 0.3 to 5% by weight, more preferably 0.8 to 3 The weight percentage of weight is used.

In a specific embodiment, the method of the present invention is carried out by blending the following materials: - a substance comprising Fe and a sulfate ion, - a substance comprising an alkaline earth element Ca and/or a carbonate of Mg, preferably CaCO ₃ , MgCO ₃ , or dolomite, and - a substance comprising an oxide or hydroxide of an alkaline earth element, preferably MgO, CaO, Mg(OH) ₂ , or Ca(OH) ₂ , in powder form without any Water is added and these materials react when mixed and granulated in the same apparatus to form a granulated composition.

The invention also targets a fertilizer composition comprising S, Fe and at least one alkaline earth element comprising at least one of Ca and/or Mg, wherein the molar ratio of (Ca+Mg)/Fe is in the range of 2 to 200, It is preferably from 2.5 to 25, more preferably from 10 to 25.

In the fertilizer composition of the present invention, the molar ratio of Fe to S in the fertilizer composition of the present invention may be from 0.3 to 6, preferably from 0.5 to 2, more preferably from 0.8 to 1.2.

The main reaction product of the process of the invention or the main reaction product in the composition of the invention are calcium sulphate, iron hydroxide and unreacted alkaline earth compounds. The obtained iron hydroxide has two important functions: the first function is a particle binder with effect and efficiency, and the second function is to retain sulfate and micro by adsorption. The amount of elemental ions. Therefore, a sulfur fertilizer comprising iron hydroxide (or a reaction product of iron sulfate and a basic compound) has improved properties compared to a substance not containing iron hydroxide because sulfate is not easily washed away from the soil. In addition to the reaction product during mixing, calcium sulphate can be additionally added.

As explained above, the iron sulfate in the composition has been mostly or completely converted into an alkaline earth sulfate. Since the crystal structure is usually measured by X-ray diffraction (XRD), and the quantitative relationship between the XRD peaks and the exact crystal structure may be somewhat different, the ratio of the XRD signal rather than the crystal structure is compared. For analysis and definition of the fertilizer composition of the invention. Therefore, the ratio of (P*Q)/(I*J) is >8, preferably greater than 5, and most preferably greater than 2, where P is the integral area of the X-ray diffraction spike between 2θ = 20.0 and 21.5°. , Q is the integral area of the XRD spike between 2θ=29.0 and 30.5°, I is the integral area of the XRD spike between 2θ=16.0 and 20.0°, and J is the integral area of the XRD spike between 2θ=23.4 and 28.0. (Measured by Cu-K-ray diffraction spikes).

Alternatively, the fertilizer composition of the present invention may have a ratio of A/B > 1, preferably > 5, preferably > 10, and A is the integral area of the X-ray diffraction peak between 2θ = 20.2 and 21.5 ° and B is the integrated area of the X-ray diffraction spike between 2θ = 25.0 and 28.0.

The invention also relates to a method of fertilizing S and one or more than one alkaline earth element, preferably Ca and/or Mg, wherein the above fertilizer composition of the invention is applied (preferably in the form of agglomerates) to In farmed sulfur-deficient soils, it is preferred to fertilize sulfur to plants supplying amino acids, proteins and/or oils, especially alfalfa, mustard (canola), cotton, clover, alfalfa, alfalfa, wheat. , barley, corn, sunflower, soybeans, navy beans, sorghum, oats and triticale, also There are cruciferous plants like canola, turnip, arugula and onion garlic crops like onions, leeks and garlic.

The advantages of this method are that the fertilized S and the fertilized C (and Mg as needed), and the increase in soil pH are achieved simultaneously in a single step. Therefore, the cost and labor required for separate fertilization steps can be eliminated.

Another advantage is that part of the Ca (and optionally Mg) can be obtained in the form of a solution, whereas Ca (and optionally Mg) derived from conventional limestone or dolomite is not soluble and must be dissolved by contact with an acidic environment. A fertilizer composition that provides both Ca (and optionally Mg) solubility while providing a relatively alkaline fertilizer composition has clear advantages over conventional fertilizer types. There are even soluble sulfur (as sulfate), valuable trace elements such as Mn and Zn (and optionally B), and low levels of unwanted elements (such as As, Hg, Cd, Pb) and toxic organic compounds. Will produce highly valuable fertilizer types.

Preferably, the application of the farmland between summer and winter is for the application of alkali fertilizer, that is, before the start of the plant growth period, respectively, the area north of the equator is between August and December, or The area south of the equator is between February and June.

In general, (acidic) ferrous sulfate and (alkaline) Ca and/or Mg compounds may vary with the pH of the soil.

For slightly acidic soils, the molar ratio of (Ca+Mg)/S>2 may be appropriate, while for more acidic soils, the molar ratio of (Ca+Mg)/S>>2 may be appropriate.

Typical data were re-fertilized with calcium 300-600 kg Ca/(ha*a) and 30 kg S/(ha*a) => molar fraction Ca/S = 7.5-15.

By applying the fertilizer composition of the present invention, the pH of the soil can be increased above 5.8, preferably above > 6.0, preferably > 6.2.

In general, the sulfur in the fertilizer of the present invention can be obtained in the form of sulfate, but the sulfur is actually represented by S for the purpose of calculation.

The invention also provides the use of a solution comprising iron sulphate or the use of crystalline ferric sulphate having more than 3 moles of water of crystallization, preferably ferrous sulphate heptahydrate, more preferably sulphuric acid obtained from the manufacture of titanium dioxide. A ferrous by-product for the preparation of a sulfur fertilizer composition and/or for wetting and/or agglomerating a powdered fertilizer material.

The advantages of the products and methods of the invention are: - the supply of bioavailable sulfur in large quantities and at low cost.

- The compound of the invention or the product of the process of the invention exhibits the best sulfur solubility: but not too high.

- => Long-term supply of sulfur and calcium/magnesium improves the structural porosity of the soil.

- Highly alkaline => also useful for neutralizing acidic soils. The bioavailability of such other applied fertilizer materials is thus enhanced.

- Preferred are particulate free fluids and dust free forms of fertilizer.

- Ferric hydroxide exhibits excellent stabilizing properties for the resulting particles. At the same time, iron hydroxide can avoid the micro-nutrient present in the fertilizer of the present invention being washed away due to its high absorption capacity for trace elements.

If the iron sulfate is removed from the by-products of the titanium dioxide production process, the fertilizer of the present invention additionally contains valuable plant nutrients and micronutrients such as Mg, Mn, and Zn. At the same time, the product does not contain Hg, Cd, As, Pb, Cr. The composition of the present invention can be used in all cultures, preferably those having a high sulfur demand, such as alfalfa, mustard (canola), cotton, clover, alfalfa, alfalfa. Earthworms, wheat, barley, corn, sunflower, soybeans, navy beans, sorghum, oats and triticale, as well as cruciferous plants like canola, turnip, arugula and onion garlic crops like onions, leeks and garlic, especially Suitable for canola and rapeseed and preferably during the winter months.

The fertilizer may have a pH of 5.5 to 13, and for most applications it is preferably 6.0 to 11, preferably 6.5 to 8.5. When calcium oxide or calcium hydroxide is contained for stronger and more rapid neutralization, the pH of the fertilizer is preferably 8.5 to 13. Therefore, no acidification of the soil is observed; both S and Ca are applied in combination; the iron sulfate completely or almost completely reacts and gives the particles good stability.

The invention also relates to:

A composition of the present invention which comprises a mass ratio of Zn, Zn/Fe of 0.0001 to 0.003, preferably 0.0002 to 0.0015, and/or a mass ratio of Mn, Mn/Fe of 0.00001 to 0.01, preferably 0.00001 to 0.001; these elements are valuable micronutrients and therefore do not require the independent application of Zn and Mn.

- The composition of the present invention, wherein the mass ratio of Cr/Fe is from 0.0000001 to 0.0001, preferably from 0.0000001 to 0.00005, preferably from 0.1 to 0.00002; the concentration of Cr is sufficiently low to avoid harmful effects.

- the composition of the present invention, wherein the mass ratio of Ti/Fe is from 0.001 to 0.03, preferably from 0.002 to 0.02, more preferably from 0.003 to 0.015; - the composition of the present invention, wherein the pH is according to the ISO standard 5.5 to 13, preferably from 6.0 to 11, more preferably from 6.5 to 8.5 for most applications, but preferably from 8.5 to the composition comprising calcium oxide or titanium hydroxide. 13. The pH is determined in accordance with DIN EN ISO 787 Part 3, wherein the pH is measured no earlier than five days prior to sample preparation, and wherein the sample is ground prior to pH measurement.

- The composition of the invention wherein the neutralization value according to the DIN EN 12945:2014-07 standard is from 1 to 55% (e.g. CaO), preferably from 20 to 55%, preferably from 33 to 48%.

- the composition of the present invention, wherein the fertilizer is formed into granules having an average particle size according to volume of from 1 to 8 mm, preferably from 2 to 6, more preferably from 2 to 4 mm; - the composition of the present invention, wherein The composition is agglomerated in a disc granulator, or a granulation drum or intensive mixer.

- The composition of the present invention, wherein the composition is granulated in a disc granulator, or a granulation drum or an intensive mixer, and no water is added to aid in granulation.

- The composition of the present invention, wherein the composition is agglomerated using a dense mixer in combination with a granulator such as a pan-shaped granulator or a granulation drum.

- The composition of the present invention, wherein the fertilizer composition can be obtained by blending.

o Ca and / or Mg compound, preferably CaCO ₃ or dolomite (Ca, Mg) CO ₃

○ ferric sulfate, preferably Fe(II)SO ₄ heptahydrate, ○ CaSO ₄ as needed; ○ requires CaO, (Ca, Mg)O or Ca(OH) ₂

○As needed, iron sulfate monohydrate, o depending on the iron sulphate monohydrate obtained from the TiO2 manufacturing process, which has previously been reacted with lime or limestone or aged lime or sinter lime to produce a reaction product having a typical pH of about 4; o the composition of the invention Wherein the fertilizer comprises iron oxide, and/or a product of neutralization from iron oxide with at least one calcium and/or magnesium compound, and/or a reaction product of iron sulfate with calcium and/or magnesium compounds; The composition is used as alfalfa, mustard (canola), cotton, clover, alfalfa, alfalfa, wheat, barley, corn, sunflower, soybean, navy bean, sorghum, oat and black wheat, and cruciferous plants like alfalfa Moss, turnips, arugula and onion garlic crops are like sulfur fertilizers for onions, leeks and garlic:

○ Use the composition between summer and winter, that is, the area north of the equator is between August and December, and the area south of the equator is between February and June; ○ The composition is used as a calcium-sulfur fertilizer in the following manner: the pH of the soil is increased to >5.8, preferably >6.0, preferably >6.2;

Further improvements of the invention may include:

- Adding other elements for fertilization purposes, such as micronutrients like boron, copper, molybdenum; - additional elemental sulfur can be used; the presence of basic compounds can avoid acidification of the soil.

- Preferably, the calcium and/or magnesium compound has a pH > 8, such as slag, sintered or hydrated lime/dolomite obtained from steel.

- Low content of Sr or As.

- Passivate the surface of the particles during the agglomeration with limestone.

- in the monohydrate with ferric sulfate (already in advance and limestone, or lime, or cooked The lime or burned lime is reacted to passivate the surface of the particles during the granulation.

- Heat treatment / drying.

- Compact with a roller former or pelletizer to make it compact.

The invention is illustrated by the following examples.

Example 1a - Preparation of a compacted Ca-S-fertilizer having a neutralization value of 2.4% S and 45% CaO equivalent and having a low compressive strength

Two batches of each batch containing 2 kg of ferrous sulfate from the production of titanium dioxide by the sulphate process, and 8 kg of pulverized limestone were added together and mixed in a plowshare mixer for about 2 minutes. The molar ratio of (Ca + Mg) / Fe is 12. These mixtures were fed to a roller of a pair of roller compactors through a hopper having a screw feeder at room temperature and compressed into a crucible. The contact pressure during the increase in the density is about 9.5 N/mm ² . According to the Archimedes principle, the mash was measured in paraffin oil to a density of about 2070 kg/m ³ . The crucible was crushed and the resulting portion of the sieved portion collected between 2 and 5 mm was collected. The granules had a residual moisture content and were measured to dryness at 105 ° C to be 8.2% by weight.

From this part of the collection, 10 fresh granules were arbitrarily taken out and crushed by applying pressure, and the average compressive strength was 1.6 kg. The test was repeated in exactly the same manner using ferrous sulfate and limestone powder. The fresh particles have a compressive strength of 1.3 kg. Ten particles were dried overnight at 105 ° C and found to have a compressive strength of 1.5 kg.

Example 1b - Preparation of a compacted Ca-S-fertilizer having a neutralization value of 2.4% S and 45% CaO equivalent and having a low compressive strength

Two batches of each batch containing 2 kg of ferrous sulfate from the production of titanium dioxide by the sulphate process and 8 kg of pulverized limestone, which have been aged by hand mixing and aged by manual mixing for one week, have The molar ratio of Ca + Mg) / Fe was 12, and these mixtures were fed to a roller of a pair of roller compactors through a hopper having a screw feeder at room temperature and compressed into a crucible. The contact pressure during the increase in the density is about 8.0 N/mn ² . According to the Archimedes principle, the mash was measured in paraffin oil to a density of about 2320 kg/m ³ . The crucible was crushed and the resulting portion of the sieved portion collected between 2 and 5 mm was collected. The granules had a residual moisture content and were measured to dryness at 105 ° C to be 8.5% by weight.

Ten fresh granules were arbitrarily removed from this portion of the collection and pressure was applied to crush it. The average compressive strength is 2.2 kg. Aging the mixture prior to compaction results in a moderately improved compressive strength.

Example 1c - Preparation of a compacted Ca-S-fertilizer having a neutralization value of 6% S and 22% CaO equivalent and having a low compressive strength

Two batches of each batch containing 5 kg of ferrous sulfate from the production of titanium dioxide by the sulphate process, and 5 kg of pulverized limestone were added together and mixed in a plowshare mixer for about 2 minutes. The molar ratio of (Ca + Mg) / Fe is 3. These mixtures were fed to a roller of a pair of roller compactors through a hopper having a screw feeder at room temperature and compressed into a crucible. The specific applied force is about 9.0 N/mm ² during the increase in the density. According to the Archimedes principle, the mash was measured in paraffin oil to a density of about 1840 kg/m ³ . The crucible was crushed and the resulting portion of the sieved portion collected between 2 and 5 mm was collected. The granules had a residual moisture content which was measured to dryness at 105 ° C and found to be 21.6% by weight.

From this part of the collection, 10 fresh particles were arbitrarily taken out and crushed by applying pressure, and the average compressive strength was 0.3 kg. Particles with high residual humidity exhibit low compressive strength.

Example 1d - Preparation of a compacted Ca-S-fertilizer having a neutralization value of 6% S and 22% CaO equivalent and having a high compressive strength

Each of the two batches contains 5 kg of ferrous sulfate and 5 kg of pulverized limestone from the sulphate process, which have been aged by hand mixing and aged by manual mixing for one week. The molar ratio of Ca + Mg) / Fe was 3, and these mixtures were fed to a roller of a pair of roller compactors through a hopper having a screw feeder at room temperature and compressed into a crucible. The contact pressure during the increase in the density is about 8.0 N/mm ² . According to the Archimedes principle, the mash was measured in paraffin oil to a density of about 2220 kg/m ³ . The crucible was crushed and the resulting portion of the sieved portion collected between 2 and 5 mm was collected. The granules had a residual moisture content and were found to be 7.9% by weight when dried at 105 °C.

Ten fresh granules were arbitrarily removed from this portion of the collection and pressure was applied to crush it. The average compressive strength is 3.5 kg. After drying 10 granules at 105 ° C overnight, it was found that the compressive strength was 8.9 kg. Aging the mixture prior to pressing results in improved compressive strength.

Example 2a - Preparation of a compacted Ca-S-fertilizer with a neutralization value of 5% S and 28% CaO equivalent and high compressive strength

50 kg of limestone powder, 50 kg of ferrous sulfate obtained from the production of titanium dioxide by the sulphate method in a 150 liter, specially arranged high-speed mixing tool and a fixed inner wall scraper in a rolling and inclined (30°) mixing tank And 6 kg of water was thoroughly mixed for 2 minutes in the same mode. The rotation speed of the mixing tool was 16.5 m/s, and the container was rotated at 1 m/s. This mixing process forms microparticles which are granulated on a rolling and tilting disc agglomerator (1 m diameter) with a fixed flow altering device and a rolling scraper. During the granulation, approximately 20 kg of limestone was added for the purpose of drying. The final composition had a molar ratio of (Ca + Mg) / Fe of 4. The resulting granules are round. 80% of the volume of these particles is between 2 and 6 mm.

Ten particles were arbitrarily taken out from the volume fraction of 3.15 to 5 mm, dried at 40 ° C overnight and pressure applied to pulverize. The average compressive strength is 7.4 kg. The immediate slow dry granulation produces good compressive strength.

Example 2b - Preparation of Ca-S-fertilizer with 5% S and 28% CaO equivalent neutralization and high compressive strength agglomeration

In a rolling and inclined (30°) mixing tank with a capacity of 150 liters and a specially arranged high-speed mixing tool and a fixed inner wall scraper, 50 kg of limestone powder and 50 kg of sulphate produced by the method of sulfate production are obtained. 1 kg of lignosulfonate and 4.5 kg of water were thoroughly mixed in the same mode for 1.5 minutes. The speed of the mixing tool was 16.5 m/s and the container was rotated at 1 m/s. This mixing process forms microparticles which are granulated on a rolling and tilting disc agglomerator (1 m diameter) with a fixed flow altering device and a rolling scraper. During the granulation, approximately 17.5 kg of lime was added for the purpose of drying. The final composition had a molar ratio of (Ca + Mg) / Fe of 4. The resulting granules are round. 90% of the volume of these particles is between 2 and 6 mm.

Ten particles were arbitrarily taken out from the volume fraction of 3.15 to 5 mm, dried at 40 ° C overnight and pressure applied to pulverize. The average compressive strength was 3.0 kg.

The use of lignosulfonates results in a lower amount of water required for granulation.

Example 2c

50 kg of limestone powder, 50 kg of ferrous sulfate obtained by producing titanium dioxide by a sulfate method, and 5 kg of water were thoroughly mixed in the same manner as in Example 2b.

It is not possible to granulate this mixture on the disc agglomerator of Example 2b because the water content is too low for the effect of the granulation.

Example 2d - Preparation of Ca-S-fertilizer with agglomeration of 2% S and 46% CaO equivalent neutralization

In a rolling and inclined (30°) mixing tank with a capacity of 150 liters and a specially arranged high-speed mixing tool and a fixed inner wall scraper, 80 kg of limestone powder and 20 kg of sulphate produced by the method of sulfate production are obtained. Mix thoroughly with 8 kg of water in the same pattern for 2 minutes. The speed of the mixing tool was 16.5 m/s and the container was rotated at 1 m/s. This mixing process forms microparticles which are granulated on a rolling and tilting disc agglomerator (1 m diameter) with a fixed flow altering device and a rolling scraper. During the granulation, approximately 20 kg of lime was added for the purpose of drying. The final composition had a molar ratio of (Ca + Mg) / Fe of 15. The resulting granules are round. 80% of the volume of these particles is between 2 and 6 mm.

Ten particles were arbitrarily taken out from the volume fraction of 3.15 to 5 mm, dried at 40 ° C overnight and pressure applied to pulverize. The average compressive strength is 5.3 kg. The immediate slow dry granulation produces good compressive strength.

Example 2e - Preparation of Ca-S-fertilizer with agglomeration of 6% S and 22% CaO equivalent neutralization

45 kg of limestone powder, 5 kg of sinter lime and 50 kg of titanium dioxide produced by the sulphate method in a 150 liter, specially arranged high-speed mixing tool and a fixed inner wall scraper in a rolling and tilting (30°) mixing tank. The ferrous sulfate was thoroughly mixed in the same mode for 30 minutes. The molar ratio of (Ca + Mg) / Fe was 3. The speed of the mixing tool was 4 m/s and the container was rotated at 1 m/s. The chemical reaction of the component during the mixing process caused a temperature increase of approximately 50 °C.

This mixing process produces a black particulate product with good handling properties. The resulting particles are round.

Example 3 - Determination of alkali content of fertilizer

The alkali content of the fertilizer of the present invention is determined by acid-base titration. For this assay, 1 g of a representative product sample was reacted with a 1 M hydrochloric acid solution in a beaker. The reaction of calcium carbonate and hydrochloric acid produces carbon dioxide. The sample was left overnight until the reaction was complete and a large amount of carbon dioxide was emitted from the beaker. The next day, the beaker was briefly heated to just below the boiling point of water to dissipate any remaining carbon dioxide. Immediately thereafter, excess hydrochloric acid was back-titrated with a 1 M sodium hydroxide solution. The extent of the titration is monitored by measuring the pH of the liquid, for example by means of a potential difference, and measuring the consumption of sodium hydroxide solution at the equivalent point. The amount of the base material is then expressed as percent CaCO ₃ equivalents.

A 1.501 g of the fertilizer sample was reacted with 25 ml of 1 M hydrochloric acid having a titration concentration of 0.9921 in one beaker. The reaction mixture was allowed to stand overnight and then an excess of the hydrochloride salt was then titrated with &lt;RTI ID=0.0&gt;&gt; The sample contained 39.6% by weight of CaCO ₃ .

The calculation procedure is as follows: 100%*{[(25ml HCl * 0.9921)-(12.8726ml NaOH * 1.0031)] * 0.001L/ml * 100.087g/mol CaCO ₃ * 0.5mol H+/mol CaCO ₃ }/[1.501g] = 39.6 wt.-% CaCO ₃ .

CaCO _{3, which} accounts for 39.6% by weight, is equal to 22.2% by weight of CaO.

Example 4 - Rushing test of soil nutrients filled with sulfur fertilizer

The effect of the limestone/FeSO ₄ mixture on the pH of the two soils was analyzed in two soil incubation experiments. The application of lime and the limestone/FeSO ₄ preparation caused an increase in pH in both soils one week after fertilization, with reference to the pH data of Table 1.

The pH of the soil was measured in 1 part of soil plus 2.5 parts of a suspension of 0.01 M CaCl ₂ solution. The effect of limestone/FeSO4 preparation on pH is greater than the effect of pure limestone!

Example 5 - Plant Nutrition Test with Sulfur Fertilizer (Pot Test)

The effect of the limestone/FeSO ₄ mixture on plant growth was studied under natural conditions in a pot experiment with summer rapeseed and alfalfa in a small Mitscherlich pot containing 6 kg of soil per pot. The experimental soil was leached soil [luvisol] subsoil (0.4-0.8 m deep) derived from loess [Loess] with a total S concentration of 0.027%. Summer rapeseed (Brassica napus L, cv.Belinda) and alfalfa (Medicago sativa L) were cultured in treatment conditions without lime and sulfur fertilizer (control group); treatment conditions with lime but no sulfur fertilizer, and various limestones The /FeSO ₄ mixture was applied with 50 mg S kg ^-1 soil (= 0.3 g S per pot). For each of the rapeseed and clams, each treatment contains four copies. The soil in the pot is treated with nitrogen (1 g N/per pot, added as NH ₄ NO ₃ ), phosphorus and potassium (0.6 g P and 1.6 g K per pot, added as K ₂ HPO ₄ and KCl), magnesium (0.3 g Mg per pot, added as Mg(NO ₃ ) ₂ ; boron (3 mg B per pot in the form of H ₃ BO ₃ ), copper (30 mg Cu per pot in the form of CuCl ₂ ), manganese ( 120 mg Mn per pot in the form of MnCl ₂ ), molybdenum (0.6 mg Mo per pot in the form of ammonium molybdate) and zinc (60 mg Zn per pot in the form of ZnCl ₂ ). The fertilizer is mixed with the soil and 60% saturated water After a week of incubation, rapeseed and alfalfa are sown. The seeds of alfalfa are inoculated with Rhizobium melilotii. After germination, the rapeseed plants are sparse to 3 plants per pot and 20 plants per pot. The potted plants were then fertilized with NH ₄ NO ₃ in liquid form at 0.5 g per pot. Compared to summer rapeseed, no further application of mineral nitrogen was carried out to analyze the effect of S fertilizer applied as a novel product on nitrogen fixation. .

After three months of sowing, the summer rapeseed plants were harvested and the alfalfa was harvested three times during the growth period. After the first and second harvests, the mash was fertilized with 0.5 g K per pot of K ₂ HPO ₄ in liquid form. The following table shows the effect of applying sulfur fertilizer on the yield of summer rapeseed with gypsum and various limestone/FeSO ₄ mixtures.

Sulfur fertilization with a limestone/FeSO ₄ mixture enhances the growth of summer rapeseed. Canola plants that were not treated with S fertilizer showed typical S deficiency symptoms on older leaves. This symptom was not seen on the leaves treated with sulphur fertilized with lime/FeSO4. The sulfur deficiency was so severe that summer rapeseed could not produce any seeds in the control group without sulfur treatment, as can be seen from Table 2.

The results of the influence of the lime/FeSO ₄ mixture are presented herein to show that the product of the invention is suitable for use as a mineral sulfur and lime fertilizer for agricultural plants.

In yet another experiment, we have tested the effect of S fertilization in the form of various limestone/FeSO ₄ mixtures on the yield of alfalfa. Compared to summer rapeseed, S fertilization did not result in an initial significant increase in harvest rate. The soil has sufficient sulfur supply for the first growth of the mites. However, increasing the CaCO ₃ fraction will result in a decrease in the biomass of the shoots during the first harvest, see Table 3.

This is because of the sensitivity of strontium to "free lime" in soil solutions, which may cause OH ion toxicity. However, at the second and third harvests, we found a clear positive effect on the limestone/FeSO ₄ mixture. The highest cumulative shoot biomass is produced when treated with an alkaline slag lime/FeSO ₄ mixture.

Conclusion: The effect of the limestone/FeSO ₄ mixture proposed here indicates that the product is suitable for use as a mineral sulfur and limestone fertilizer for agricultural plants. The limestone/FeSO ₄ mixture should not be applied to legumes at a ratio greater than 1:1.

Claims (25)

A method of making a fertilizer composition comprising S, Fe and one or more than one alkaline earth element (including Ca and/or Mg), suitable for application to a sulfur-deficient soil, which will comprise Fe and sulfate ions a substance in the form of a solid salt, a filter cake, a paste, a slurry or a solution and at least one oxide, hydroxide or carbonate selected from or containing an alkaline earth element (including at least one of Ca and Mg), preferably CaCO. ₃ , MgCO ₃ , dolomite (Ca, Mg) CO ₃ , MgO, sintered dolomite (Ca, Mg) O, CaO, semi-hydrated dolomite Ca(OH) ₂ MgO or Ca(OH) ₂ or a mixture thereof The ingredients are blended in a molar ratio of (Ca + Mg) / Fe = 2 to 200, preferably 2.5 to 25, more preferably 10 to 25, and the blend is converted into an applied form. A method of producing a fertilizer composition according to the first aspect of the patent application, wherein the blending and converting are carried out simultaneously. A method of producing a fertilizer composition according to any one of claims 1 or 2, wherein the blending and/or converting is in the presence of water, dilute sulfuric acid, preferably diluted CaSO ₄ , elemental sulfur or other S-containing The compound, other compound for fertilizer, such as a micronutrient, preferably a boron compound, a binder or a granule adjuvant, or a mixture thereof, is used. The method of producing a fertilizer composition according to any one of claims 1 to 3, wherein the Fe and sulfate ion-containing substance is FeSO _{4 which} may contain water of crystallization. A method of producing a fertilizer composition according to the fourth aspect of the invention, wherein FeSO ₄ is Fe(II)SO ₄ heptahydrate, preferably obtained from a titanium dioxide production method. The method of producing a fertilizer composition according to any one of claims 1 to 5, wherein the at least one component comprising an oxide, hydroxide or carbonate of an alkaline earth element is limestone, which is 95% < 0.09 mm It consists of fine particles and it contains >95% CaCO ₃ . The method of producing a fertilizer composition according to any one of claims 1 to 5, wherein the at least one component comprising an oxide, hydroxide or carbonate of an alkaline earth element is sintered lime, sintered dolomite or hydrated lime. The method of producing a fertilizer composition according to any one of claims 1 to 5, wherein the at least one component comprising an oxide, hydroxide or carbonate of an alkaline earth element is derived from slag produced by steel or obtained from The reaction product of such slag. The method for producing a fertilizer composition according to any one of claims 1 to 8, wherein starch, magnesium sulfate, citric acid, clay, mortar binder, cellulose gum, glucoside binder such as starch, molasses are used. , a combination of lignosulfonate, water, hydrated lime, water glass, bentonite, cellulose fibers, stearate, urea, or a combination of such materials as a binder or a granule adjuvant, relative to the a composition comprising Fe and sulfate ions and at least one selected from the group consisting of oxides, hydroxides or carbonates comprising alkaline earth elements Ca and Mg In other words, it is used in a weight ratio of 0.1 to 10% by weight, preferably 0.3 to 5% by weight, more preferably 0.8 to 3% by weight. The method of producing a fertilizer composition according to any one of claims 1 to 9, wherein the method is carried out in a device capable of compacting, granulating and/or pelletizing the reaction product. The method for producing a fertilizer composition according to claim 10, wherein the granulating is carried out by blending: a. a substance containing Fe and a sulfate ion, b. containing an alkaline earth element Ca and/or Mg. The carbonate material is preferably CaCO3, MgCO3, or dolomite, and c. a substance containing an alkaline earth element Ca and/or Mg oxide or hydroxide, preferably MgO, CaO, Mg(OH)2. Or Ca(OH)2, without adding any water, reacting these materials in the form of a powder, and mixing and granulating in the same apparatus. The method of producing a fertilizer composition according to any one of claims 1 to 11, wherein the at least one member is selected from or contains an alkaline earth element oxide, hydroxide or carbonate according to DIN EN 12945:2014-07. The neutralization value of the ingredients is from 1 to 55% (e.g., CaO), preferably from 20 to 55%, and most preferably from 33 to 48%. A fertilizer composition comprising S, Fe and at least one alkaline earth element (including at least one of Ca and/or Mg), wherein a molar ratio of (Ca+Mg)/Fe is in the range of 2 to 200, preferably It is 2.5 to 25, more preferably 10 to 25. The fertilizer composition according to claim 13 wherein the molar ratio of Fe to S is from 0.3 to 6, preferably from 0.5 to 2, more preferably from 0.8 to 1.2. The fertilizer composition according to any one of claims 13 and 14, wherein the peak area ratio (P*Q) / (I*J) of P, Q, I and J in the XRD spectrum is greater than 8, Preferably, it is greater than 5, more preferably greater than 2, P is the integral area of the X-ray diffraction peak between 2 θ = 20.0 and 21.5 °, and Q is between X θ around 2 θ = 29.0 and 30.5 °. The integrated area of the shot peak, I is the integrated area of the X-ray diffraction spike between 2 θ = 16.0 and 20.0 °, and J is the integrated area of the X-ray diffraction spike between 2 θ = 23.4 and 28.0. The fertilizer composition according to any one of claims 13 to 15, wherein the peak area ratio A/B is greater than 1, preferably greater than 5, more preferably greater than 10, and A is between 2θ = 20.2 and 21.5. The integral area of the X-ray diffraction spike between ° and B is the integrated area of the X-ray diffraction spike between 2 θ = 25.0 and 28.0. The fertilizer composition according to any one of claims 13 to 16, wherein the Zn/Fe mass ratio is 0.0001 to 0.003 Zn, preferably 0.0002 to 0.0015, and/or the Mn/Fe mass ratio is 0.00001 to 0.01. The Mn is preferably 0.00001 to 0.001. The fertilizer composition according to any one of claims 13 to 17, wherein the fertilizer is in the form of granules having a volume of from 1 to 8 mm, preferably from 2 to 7 mm, more preferably 3, based on the average particle size. To the range of 6mm. A fertilizer composition, which is obtained according to any one of claims 13 to 18, which can be obtained according to the method of any one of claims 1 to 12. A method of applying S and or one or more alkaline earth elements (preferably Ca and/or Mg) fertilizer, wherein the fertilizer composition according to claim 19 of the patent application is applied, preferably in the form of granules, for application to agricultural sulfur deficiency In soil, it is preferred to apply sulfur fertilizer to plants supplying amino acids, proteins and/or oils, especially alfalfa, mustard (canola), cotton, clover, alfalfa, alfalfa, wheat, barley, corn. Sunflowers, soybeans, navy beans, sorghum, oats and triticale, as well as cruciferous plants like canola, turnip, arugula and onion garlic crops like onions, leeks and garlic. According to the method of claim 20, the application to the sulfur-deficient soil is carried out for alkaline fertilization between summer and winter. The method according to claim 20 or 21, wherein the fertilizer composition according to claim 19 of the patent application is applied to the soil which is deficient in sulfur, and the application amount thereof increases the pH of the soil to 5.8 or more, preferably > 6.0 or more, preferably >6.2. A use of the composition of claim 19 as a sulfur fertilizer for applying a sulfur fertilizer to plants supplying amino acids, proteins and/or oils, in particular, alfalfa, mustard (canola), cotton, clover, Valerian, alfalfa, wheat, barley, corn, sunflower, soybean, navy beans, sorghum, oats and triticale, as well as cruciferous plants like canola, turnip, arugula and onion garlic crops like onions, leeks And garlic. A ferric sulfate is preferably iron (II) sulfate heptahydrate, more preferably a by-product ferrous sulfate obtained from the production of titanium dioxide for the preparation of a sulfur fertilizer composition. Use of a solution containing iron sulfate or iron sulfate crystals having more than three molecules of crystal water, preferably iron (II) sulfate heptahydrate, more preferably by-product sulfuric acid obtained from the production of titanium dioxide The use of iron is used as an aid for wetting and/or granulating the powdered fertilizer material.