EP3142990A1 - Schwefeldünger - Google Patents

Schwefeldünger

Info

Publication number
EP3142990A1
EP3142990A1 EP15725542.3A EP15725542A EP3142990A1 EP 3142990 A1 EP3142990 A1 EP 3142990A1 EP 15725542 A EP15725542 A EP 15725542A EP 3142990 A1 EP3142990 A1 EP 3142990A1
Authority
EP
European Patent Office
Prior art keywords
composition according
fertilizer composition
sulfur
fertilizer
manufacturing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15725542.3A
Other languages
English (en)
French (fr)
Inventor
Gerhard Auer
Winfried GRUNDMANN
Jakob MAASSEN
Maurits Van Den Berg
Johann Adam VAN DER MAREL
Diedrich Steffens
Martin VERFÜRDEN
Johannes Pfeifer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Venator Germany GmbH
Venator Uerdingen GmbH
Original Assignee
Huntsman P&A Uerdingen GmbH
Huntsman P&A Germany GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman P&A Uerdingen GmbH, Huntsman P&A Germany GmbH filed Critical Huntsman P&A Uerdingen GmbH
Publication of EP3142990A1 publication Critical patent/EP3142990A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D3/00—Calcareous fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D5/00—Fertilisers containing magnesium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
    • C05F7/005—Waste water from industrial processing material neither of agricultural nor of animal origin
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/80—Soil conditioners

Definitions

  • the present invention refers to a sulfur fertilizer composition, the process for preparing the same and its use.
  • S Sulfur
  • N nitrogen
  • K potassium
  • P P
  • Sulfur is an important component of several essential amino acids and thus, sulfur is important for both protein quality and quantity. It is also involved in nitrogen metabolism, photosynthesis, synthesis of oils in oilseed crops such as canola, and in synthesis and function of enzymes, amino acids and other organic compounds.
  • Sulfur deficiencies can have a major impact on crop yield and quality. Sulfur deficiencies mainly arise on acid sandy soils where sulfate has been leached, especially in such areas with high winter rainfall. Naturally, deficiencies of sulfur mainly occur for cultures with high demand for sulfur, like alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale, furthermore cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic.
  • Fertilizing with sulfur may overcome those problems. Fertilizing with sulfur may not only affect sulfur content of plants but also positively affect the storability of the products (e.g. garlic).
  • sulfur fertilizers are: Ammonium sulfate, potassium sulfate, magnesium sulfate, gypsum or elemental sulfur.
  • Elemental sulfur and ammonium sulfate result in acidification of soil and therefore, they can be used without negative impact on soils with high pH only.
  • NH 3 volatilization can be a problem with ammonium sulfate in case of high pH of soil.
  • Ammonium sulfate, potassium sulfate, magnesium sulfate have very high solubilities and sulfate may be washed out in case of strong rainfall. Elemental sulfur has a very low solubility. Elemental sulfur applied during winter is ineffective for overcoming sulfur deficiency because the S is oxidized too slowly by soil microorganisms. Gypsum exhibits a useful solubility, but usually is not available in form of stable granulates and does not raise soil pH.
  • ferrous sulfate obtained as by-product from ⁇ 2 production. So far, the use of ferrous sulfate is known for waste water treatment, for iron oxide pigments, or as chromate reducing agent.
  • iron sulfate has not been mentioned or suggested as sulfur fertilizer. Some applications mention iron sulfate as moss killer or as Fe source in case of Fe deficiency (chlorosis) or as phosphorus and heavy metal absorber in polluted soils. However, the use of iron sulfate results in acidification of soil.
  • GB 1 473 403 discloses a method for preparing compositions useful as soil modifiers or fertilizers by thoroughly mixing ferrous sulfate heptahydrate
  • DE 42 19 351 discloses an additive for agriculture obtained from ferrous sulfate (not ferrous sulfate heptahydrate!) obtained as by-product from titanium dioxide manufacture optionally blended with earth alkaline compounds and an organic material. Use of this material is for treating Fe, Mn and Zn deficiencies. No application as sulfur fertilizer is disclosed in DE 42 19 351 .
  • EP 0 093 204 discloses a process for granulating Fe containing fertilizing mixtures comprising ferrous sulfate and fertilizing agents by use of hydrophilic additives. Also admixing of other fertilizing agents like ammonium sulfate, NPK compounds, micronutrients or natural fertilizers is disclosed. No application as sulfur fertilizer is disclosed in EP 0 093 204.
  • EP 2 165 976 discloses a method for pressure compacting of compositions based on ferrous sulfate heptahydrate. Use of this material is as Fe source for
  • the inventors have considered the disadvantages of the prior art compositions and came to the inventive solution by providing a sulfur fertilizer without detrimental impact on soil pH and plant nutrition, preferably in form of stable granulates, without expensive additives or processes for granulation, and a process for preparing the same as well as its use as fertilizer.
  • the present invention is directed to a process for manufacturing a fertilizer composition comprising S, Fe and one or more earth alkaline elements, including Ca and/or Mg, being suitable for administration onto a sulfur deficient soil wherein a material, comprising Fe and sulfate ions, in form of a solid salt, filter cake, paste, slurry, or solution, is blended with at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements including at least one of Ca and Mg, preferably CaCO3, MgCO3, dolomite (Ca,Mg)CO 3 , MgO, burnt dolomite (Ca,Mg)O, CaO, semi-hydrated dolomite
  • Blending and converting into an administration form may be carried out
  • the inventive process can be carried out in an apparatus which can also serve for compaction, granulation and/or pelletizing the reaction product
  • Blending and/or converting may be carried out in the presence of any of water, dilute sulfuric acid, preferably diluted, CaSO 4 , elemental sulfur or other S
  • micronutrients preferably a boron compound, binder or granulation aids, or mixtures thereof, also assisting in obtaining the required form of the product.
  • the material comprising Fe and sulfate ions may preferably be FeSO 4 which may contain crystal water, such as Fe(ll)SO 4
  • heptahydrate preferably obtained from the titanium dioxide production process.
  • the at least one component comprising oxides, hydroxides or carbonates of earth alkaline elements which is generally used for neutralizing any acid such as any adhering sulfuric acid and also for increasing the pH-value may preferably be limestone, limestone, which is a natural material without critical contents of harmful substances with respect to agricultural applications.
  • the limestone may consist of fine particles 95 % ⁇ 0,09 mm, and comprise >95 % CaCO 3 .
  • the component comprising oxides, hydroxides or carbonates of earth alkaline elements can also be a slag from steel manufacturing or a reaction product from such a slag.
  • the slag has a high basicity and is more reactive than CaCO3.
  • the component comprising oxides, hydroxides or carbonates of earth alkaline elements can be burnt lime or burnt dolomite or hydrated lime, providing a higher neutralization potential and higher reactivity than CaCO3 and slag.
  • the neutralizing value of said at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements according to DIN EN 12945:2014-07 standard may be 1 to 55% (as CaO), preferably 20 to 55%, most preferably 33 to 48%.
  • At least one of starch, magnesium sulfates, citric acid, clay, mortar binder, cellulose glue, glucosidic binder such as starch, molasses, lignosulfonate, water, hydrated lime, water glass, bentonite, cellulose fibres, stearates, urea or combinations of these materials may be used as binder or granulation aid in a weight ratio of 0.1 to 10 weight-%, preferably 0.3 to 5 weight-%, most preferably 0.8 to 3 weight-%, related to the total mass of the composition comprising Fe and sulfate ions and the at least one component being chosen from or comprising oxides, hydroxides or carbonates of the earth alkaline elements Ca and Mg.
  • the inventive process is carried out by blending:
  • a material comprising carbonates of the earth alkaline elements Ca and/or Mg, preferably CaCO3, MgCO3, or dolomite, and
  • the present invention is also directed to a fertilizer composition
  • a fertilizer composition comprising S, Fe and at least one earth alkaline element including at least one of Ca and/or Mg, wherein the molar ratio of (Ca+Mg)/Fe is in the range of 2 to 200, preferably 2.5 to 25, most preferably 10 to 25.
  • the molar ratio of Fe to S in the inventive fertilizer composition may be 0.3 to 6, preferably 0.5 to 2, most preferably 0.8 to 1 .2.
  • compositions are calcium sulfate, iron hydroxide and unreacted earth alkaline compounds.
  • the iron hydroxide obtained has two important functions: The first function is an effective and efficient binder for granulates; and the second function is partial retention of sulfate and trace element ions by adsorption. Therefore, a sulfur fertilizer comprising iron hydroxide (or reaction products of iron sulfate with alkaline compounds) has improved properties compared to a material without iron hydroxide as the sulfate is not washed out of the soil so easily.
  • calcium sulfate may also be added additionally.
  • iron sulfate has been converted mainly or completely into earth alkaline sulfates in the composition.
  • crystal structures generally are determined by x-ray diffraction (XRD) and quantitative relation of XRD peaks with actual relation of crystal structures can be somewhat ambiguous, the ratio of XRD signals are compared rather than ratio of crystal structures for analyzing and defining the inventive fertilizer composition.
  • XRD x-ray diffraction
  • the invention also concerns a process for fertilizing S and one or more earth alkaline elements, preferably Ca and/or Mg wherein the above inventive fertilizer composition is applied, preferably in form of granulates, onto a sulfur deficient soil used for agriculture, preferably for fertilizing sulfur to plants supplying amino acids, proteins and/or oil, in particular cultures of alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats, triticale, cruciferous plants like brassicas, radish, rocket and allium crops like onion, leek and garlic.
  • Advantage of this process is that fertilizing S and fertilizing Ca (and optionally Mg), and raising the soil pH is achieved at the same time with one single step.
  • Another advantage is that part of Ca (and optionally Mg) is available in soluble form (as CaSO4), whereas Ca (and optionally Mg) from conventional limestone or dolomite fertilizers is not soluble but has to get leached by contact with an acidic environment.
  • a fertilizer composition offering both Ca (and optionally Mg) solubility and at the same time considerable alkaline character has a clear advantage over conventional fertilizer types. Even more, the content of soluble sulfur (as sulfate), valuable trace elements like Mn and Zn (and optionally B) and the low content of unwanted elements (e.g. As, Hg, Cd, Pb) and toxic organic compounds results in a highly valuable fertilizer type.
  • said application on fields used for agriculture is made for base fertilization between summer and winter time, i.e. between August and December for areas north of the equator or between February and June for areas south of the equator, respectively, before the growth phase of the plants start.
  • the ratio of the (acidic) Fe(ll)sulfate and the (alkaline) Ca and/or Mg compound may vary depending on soil pH:
  • a molar ratio (Ca+Mg)/S of >2 may be appropriate, whereas for more acidic soils a molar ratio (Ca+Mg)/S of »2 may be appropriate.
  • Ca/S 7.5 - 15.
  • the pH of the soil may be raised to above 5.8, preferably above >6.0, most preferably >6.2.
  • sulfur in the inventive fertilizer is available in the form of sulfate, but for calculation purpose sulfur virtually is expressed as S.
  • the present invention also provides the use of a solution comprising iron sulfate or the use of crystalline iron sulfate with more than 3 molecules of crystal water, preferably iron(ll)sulfate heptahydrate, more preferably copperas as obtained as by-product from titanium dioxide manufacturing, for preparing a sulfur fertilizing composition and/or for moistening and/or granulating of powderous fertilizer materials.
  • - Preferred is a granular free flowing and dust free form of the fertilizer.
  • iron hydroxide due to its high capability for absorption of trace elements is able to avoid the micronut ents present in the inventive fertilizer (Mn, Zn) to be washed out.
  • the inventive fertilizer additionally comprises valuable plant nutrients and
  • micronutrients e.g. Mg, Mn, Zn.
  • the product is free of Hg, Cd, As, Pb, Cr.
  • the inventive composition can be used for all cultures, preferably those with high sulfur demand, e.g. alfalfa, canola (rapeseed), cotton, clovers, phalaris, barrel medic, lucerne, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale; furthermore cruciferous plants like Brassicas, radish, rocket and allium crops like onion, leek and garlic, especially suitable for canola and rapeseed and most preferably during winter time.
  • canola canola
  • cotton clovers, phalaris, barrel medic, lucerne, wheat, barley, maize, sunflowers, soybean, navy beans, sorghum, oats and triticale
  • cruciferous plants like Brassicas, radish, rocket and allium crops like
  • the pH of the fertilizer can be 5.5 to 13, for most applications preferably 6.0 to 1 1 , most preferably 6.5 to 8.5.
  • the pH of the fertilizer is preferably 8.5 to 13.
  • the present invention also concerns:
  • An inventive composition wherein it contains Zn with mass ratio of Zn/Fe 0.0001 to 0.003, preferably 0.0002 to 0.0015, and/or Mn with the mass ratio of Mn/Fe 0.00001 to 0.01 , preferably 0.00001 to 0.001 ; these elements are valuable micronutrients and therefore no separate application of Zn and Mn is necessary.
  • Said inventive composition wherein the pH according to ISO standard is 5.5 to 13, for most application preferably 6.0 to 1 1 , most preferably 6.5 to 8.5, but preferably 8.5 to 13 for compositions comprising calcium oxide or calcium dihydroxide.
  • the pH is determined according to DIN EN ISO 787 part 3, whereby the pH measurement is made no earlier than 5 days after preparation of the sample and whereby the sample is ground prior to pH measurement.
  • Said inventive composition wherein the neutralizing value according to DIN EN 12945:2014-07 standard is 1 to 55% (as CaO), preferably 20 to 55%, most preferably 33 to 48%.
  • Said inventive composition wherein the fertilizer is granulated with volume based average granule size is 1 - 8 mm, preferably 2 - 6, most preferably 2 - 4 mm;
  • Said inventive composition wherein it is granulated in a pan granulator, or a granulation drum, or an intensive mixer.
  • Said inventive composition wherein it is granulated in a pan granulator, or a granulation drum, or an intensive mixer, without the addition of water to aid granulation.
  • Said inventive composition wherein it is granulated in a combination of an intensive mixer and a granulator such as a pan granulator or a granulation drum.
  • Ca and/or Mg compound preferably CaCO 3 or dolomite (Ca,Mg)CO 3 o iron sulfate, preferably Fe(ll)SO 4 heptahydrate,
  • the fertilizer comprises iron sulfate and/or products obtained from neutralization of iron sulfate and at least one calcium and/or magnesium compound and/or the reaction products of iron sulfate and calcium and/or magnesium compounds; o Use of the composition as a sulfur fertilizer for alfalfa, canola
  • composition between summer and winter time, i.e. between
  • composition as a calcium-sulfur fertilizer in such way that he pH of the soil is raised to >5.8, preferably >6.0, most preferably >6.2;
  • trace element nutrients like boron, copper, molybdenum
  • the calcium and/or magnesium compound has a pH >8, e.g. slag from steel manufacturing, burnt or hydrated lime / dolomite
  • the present invention is further illustrated by the following Examples.
  • Example 1 a - Preparation of compacted Ca-S-fertilizer with 2.4% S and
  • the granules had a residual moisture content determined by drying at 105 ° C of 21 .6 wt.%. From this fraction, 10 fresh granules were arbitrarily taken out and crushed by applying a pressing force. The average crushing strength was 0.3 kg. Granules with a high residual moisture exhibit low crushing strength.
  • Example 2d Preparation of granulated Ca-S-fertilizer with 2% S and
  • the alkaline content of the inventive fertilizer is determined by an acid-base titration.
  • an acid-base titration For this analytical method, about 1 g of a representative sample of the product is reacted in a beaker with 25 ml of a hydrochloric acid solution of a concentration of 1 mol per liter. The reaction of the calcium carbonate and hydrochloric acid produces carbon dioxide. The sample is left overnight in order for the reaction to complete and the bulk of the carbon dioxide to be emitted from the beaker. The next day, the beaker is briefly heated to just below the boiling point of water to emit any remaining carbon dioxide. Subsequently, the excess
  • hydrochloric acid is back-titrated with a solution of sodium hydroxide of a concentration of 1 mol per liter. The extent of the titration is monitored by measuring the pH of the liquid, for example potentiometrically, and determining the consumption of sodium hydroxide solution at the equivalence point. The amount of alkaline substance is then expressed as equivalent percentage of CaCO3. 1 .501 g of a fertilizer sample is reacted with 25 ml of 1 M hydrochloric acid with a titer of 0.9921 in a beaker.
  • the soil pH was measured in a suspension of 1 part soil with 2.5 parts of a solution of 0.01 M CaCI 2
  • the effect of the limestone / FeSO4 preparations on pH is stronger than the effect of pure limestone!

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fertilizers (AREA)
EP15725542.3A 2014-05-16 2015-05-15 Schwefeldünger Withdrawn EP3142990A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014106980 2014-05-16
PCT/EP2015/060769 WO2015173396A1 (en) 2014-05-16 2015-05-15 Sulfur fertilizer

Publications (1)

Publication Number Publication Date
EP3142990A1 true EP3142990A1 (de) 2017-03-22

Family

ID=53274507

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15725542.3A Withdrawn EP3142990A1 (de) 2014-05-16 2015-05-15 Schwefeldünger

Country Status (5)

Country Link
EP (1) EP3142990A1 (de)
CN (1) CN106536453A (de)
BR (1) BR112016026684A2 (de)
TW (1) TWI555721B (de)
WO (1) WO2015173396A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015119480A1 (de) * 2015-11-11 2017-05-11 Fels-Werke Gmbh Düngemittelmischung und Verfahren zu deren Herstellung
CN108440185A (zh) * 2018-04-20 2018-08-24 浙江省农业科学院 一种生物营养型保水剂及其制备方法
TWI783312B (zh) * 2020-12-01 2022-11-11 國立屏東科技大學 含硫化物之有機肥材料及其製造方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB356195A (en) * 1929-06-01 1931-08-31 Eduard Dedolph Composition serving as a fertilizer and agricultural pest destroyer
IT995512B (it) 1973-09-26 1975-11-20 Sir Soc Italiana Resine Spa Composizioni adatte ad esse re utilizzate in agricoltura come modificatori di terreni e come fertilizzanti
US4264570A (en) * 1979-02-27 1981-04-28 Sokolov Igor D Method of producing magnesium sulphate
ATE15028T1 (de) 1982-04-29 1985-09-15 Norddeutsche Affinerie Verfahren zum granulieren von eisen-(ii)-sulfat enthaltenden duengergemischen.
US4455161A (en) * 1982-09-13 1984-06-19 The O.M. Scott & Sons Company Trace element fertilizer composition
ES2049127B1 (es) 1991-06-13 1994-10-01 Tioxide Espa A S A Corrector de carencias de microelementos para suelos agricolas y procedimiento para su preparacion.
ES2036949B1 (es) * 1991-11-21 1994-02-01 Tioxide Europ Corrector de carencias de microelementos a base de sulfato de magnesio y hierro para suelos agricolas y procedimiento para su preparacion.
ES2111458B1 (es) * 1995-05-22 1999-07-01 Turol Trading S L Abono fosfatado con azufre y oligoelementos para su uso agricola e industrial y procedimiento para su preparacion.
CN1434004A (zh) * 2003-03-11 2003-08-06 赵鹏 一种生物有机无机复混肥料及其生产方法
ES2302296T3 (es) * 2006-06-28 2008-07-01 Kemira Pigments Oy Procedimiento de tratamiento de un precipitado que comprende sulfato de hierro (ii) monohidratado, una instalacion, un material granular y sus utilizaciones.
EP2041032A1 (de) * 2006-06-28 2009-04-01 Sachtleben Pigments Oy Verfahren zur behandlung eines eisen(ii)-sulfatmonohydrat umfassenden niederschlags, vorrichtung, granulat und verwendungen davon
ES2658566T3 (es) 2007-07-02 2018-03-12 Fertinagro Biotech, S.L. Método de compactación de composiciones basadas en heptahidrato de sulfato ferroso y producto obtenido a partir de ellas
WO2010058425A2 (en) * 2008-11-20 2010-05-27 Chetan Navnithlal Shah Soil conditioner
CN103153915B (zh) * 2010-08-10 2015-06-03 艾戈泰克创新股份有限公司 聚磷酸盐肥料组合

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015173396A1 *

Also Published As

Publication number Publication date
WO2015173396A1 (en) 2015-11-19
TW201609609A (zh) 2016-03-16
TWI555721B (zh) 2016-11-01
CN106536453A (zh) 2017-03-22
BR112016026684A2 (pt) 2017-08-15

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