EP3472098A1 - Lösliche eisenphosphate und verfahren zu deren herstellung - Google Patents
Lösliche eisenphosphate und verfahren zu deren herstellungInfo
- Publication number
- EP3472098A1 EP3472098A1 EP17730760.0A EP17730760A EP3472098A1 EP 3472098 A1 EP3472098 A1 EP 3472098A1 EP 17730760 A EP17730760 A EP 17730760A EP 3472098 A1 EP3472098 A1 EP 3472098A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- iron
- pyrophosphate
- alkali polyphosphate
- product
- iii
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/26—Compounds containing phosphorus
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/42—Pyrophosphates
Definitions
- the invention relates to an iron phosphate-containing product and a process for its preparation, wherein the iron phosphate-containing product is characterized by good water solubility and a high iron content.
- Iron is an essential trace element and therefore essential for the nutrition of humans, animals, plants and microorganisms. There is therefore a need to make iron available to biological systems via the nutrient supply.
- Phosphorus is also an essential mineral that is commonly present as a phosphate and is absorbed and is usually present in sufficient quantities in human and animal foods. In plants and microorganisms, growth can be promoted by the supplemental administration of phosphates. Since many phosphates are safe for health and are often approved as food additives for humans and animals, the phosphates are suitable as salt formers for the administration of metallic trace elements.
- iron (II) and iron (III) phosphates are generally poorly soluble in water under physiological conditions and pH. This makes it difficult to process them as part of food and nutrients and make them available to biological systems. Only at very low pH values the iron (II) and iron (III) phosphates become more soluble.
- iron pyrophosphates for the mineral enrichment by the addition of organic acids, in particular ascorbic acid.
- organic acids in particular ascorbic acid
- Increasing the solubility by acidification with organic acids has limits depending on the application and milieu.
- iron is an essential ingredient. Fertilizers therefore usually contain an iron source as a micronutrient (trace element).
- trace element a micronutrient
- the iron source is required in soluble form.
- the iron must also be in a bioavailable form.
- sparingly soluble iron salts are generally not suitable as iron sources for nutrient enrichment.
- the iron compounds are, for example, made much more acidic.
- this has disadvantages in terms of corrosion of the equipment used for plant fertilization and does not automatically increase the bioavailability of the iron source.
- Iron sources with organic complexing agents such as EDTA, HEDTA, DTPA or EDDHA are also available to improve water solubility. However, such solutions are very expensive due to the complexing agents used. In addition, the use of complexing agents, such as EDTA, HEDTA, DTPA or EDDHA, not uncontroversial, as they often also bind other important trace elements very strong, and thus in turn can significantly reduce their bioavailability. In addition, organic complexing agents can not be used without restriction in foods for humans and animals.
- WO 2014/056688 corresponding to US 2015/0259258, discloses an iron-containing solid composition containing at least one polyphosphate and at least one iron source as a micronutrient.
- the solid composition is prepared by mixing the respective solids of an iron source and a phosphate source.
- the iron content is in the range between 0.1 and 5 wt .-%, based on the total weight of the solid composition.
- the solid composition should have improved water solubility. After dissolution in water less than 0.2 wt .-% of insoluble constituents, based on the total composition, remain.
- the water solubility is also defined by a turbidity measurement. Within a dissolution time of less than 15 minutes at 20 ° C. while stirring with a magnetic stirrer at 400 rpm, turbidity of the solution of less than 50 nephelometric turbidity units NTU should be achieved at a standard concentration of 10 mmol Fe per kg solution.
- iron sources which are physically mixed as solids with a phosphate source also used as a solid
- sulfates, nitrites, chlorides, orthophosphates and pyrophosphates of iron are disclosed.
- polyphosphates sodium and potassium polyphosphates are preferably used.
- the solid composition has a ratio of phosphorus in the polyphosphate bonded form (P 0 i y ) to iron (Fe) between 5 and 50, preferably between 8 and 32.
- the method claimed in WO 2014/056688 or US 2015/0259 also comprises the preparation of an aqueous nutrient solution by dissolving the mixture of the iron source introduced as a solid and the phosphate source introduced as a solid. In a further step, the solution obtained can then be dried again to obtain a water-soluble solid.
- WO 2014/056690 corresponding to US 2015/0251963, essentially discloses the composition described in WO 2014/056688 or US 2015/0259 as an aqueous nutrient solution.
- the aqueous nutrient solution is prepared by dissolving the mixture of solid iron source and solid phosphate source in water or aqueous solution and, after a longer dissolution time, filtered to remove any undissolved constituents. If such a nutrient solution is to be applied, for example for plant nutrition, by spraying or fertigation, such a filtration step is necessary in order to prevent clogging of the nozzles or outlet openings of the used device by undissolved constituents. This additional process and filtration equipment increases the expense and expense of preparing such a nutrient solution.
- the iron content is limited in relation to the total amount of the solid and also in relation to the phosphorus content in favor of the water solubility. It has been found that increasing the amount of iron source in the composition according to WO 2014/056688 and WO 2014/056690 reduces the water solubility and thus also the amount of bioavailable iron.
- the provision of a desired amount of iron in a water-soluble composition to be used to prepare a bioavailable iron solution therefore requires a relatively large amount of product according to WO 2014/056688 and WO 2014/056690, along with high storage and storage costs Transport costs for both the source materials (iron source and phosphate source) and the mixed composition.
- the phosphate content in the composition according to WO 2014/056688 and WO 2014/056690 is high in relation to the iron content, but the interest lies in providing a high proportion of dissolved and bioavailable iron and less in providing a high amount Phosphate, which is provided by the food for humans and animals in any case usually in sufficient quantity.
- the administration of phosphate is indeed desired, but also here a higher proportion of the essential trace element iron would be desirable against the background of the problem of PhophatüberPHgung.
- the compositions according to WO 2014/056688 and WO 2014/056690 are described as being water-soluble, in fact their solubility is limited.
- the compositions go into solution only after a dissolution time of a few minutes with stirring at 20 ° C, indicating that they are in other conditions, for example lower temperature, again can precipitate or crystallize relatively early. This can, apart from the low iron content described above and the consequent high required amount required, especially when used as a liquid plant fertilizer, which is usually applied by means of spray nozzles, lead to clogging of the lines and nozzles of the agricultural equipment used for this purpose. A high and fast solubility would therefore be desirable.
- the object of the invention was to provide a product containing iron and phosphorus, which among other things is also suitable for supplying nutrients to biological systems and which has a fast and good water solubility compared to the prior art and a comparatively high Fe / P ratio or low Has P / Fe ratio and no organic complexing agents and / or acids required to improve the water solubility.
- the process according to the invention comprises the essential stages in which
- the inventors have found that the faster and better water solubility achievable according to the invention and the possibility of simultaneously setting a comparatively high Fe / P ratio are achieved with iron (III) pyrophosphate, but not with other iron sources, not even with other iron phosphates. such as iron phosphorates or higher iron polyphosphates, and also not with the pyrophosphate of bivalent iron, iron (II) pyrophosphate.
- the product containing iron phosphate produced or producible by the process according to the invention is characterized by a faster and better water solubility and a simultaneously higher Fe / P ratio than the prior art, in particular WO 2014/056688 and WO 2014/056690 ,
- alkali polyphosphates used in the process according to the invention serve as complexing agents. It is possible to use a single alkali polyphosphate or a mixture of alkali polyphosphates.
- alkali polyphosphate includes pyrophosphates as well as higher condensed phosphates.
- the aqueous alkali polyphosphate solution contains one or more alkali polyphosphates selected from the group consisting of potassium potassium pyrophosphate, potassium tripolyphosphate, tetrasodium pyrophosphate and sodium tripolyphosphate.
- TKPP alkali polyphosphates tetrapotassium pyrophosphate
- KTPP potassium tripolyphosphate
- K5P3O10 potassium tripolyphosphate
- the abovementioned corresponding sodium phosphate compounds are also suitable according to the invention, but the potassium phosphate compounds are better water-soluble and in higher concentrations and have better complexing properties and are therefore preferred over the sodium phosphate compounds.
- TKPP is very good and water soluble in high concentrations, significantly better than the corresponding sodium salt and better than KTPP.
- TKPP is therefore very well suited as a complexing agent of the present invention and is particularly preferred.
- the complexing agent of the present invention contains a mixture of TKPP and KTPP, which is advantageously used especially when calcium ions are present.
- the iron source used according to the invention is or consists at least predominantly of iron (III) pyrophosphate, which is also referred to as iron (III) diphosphate, Fe (III) 4 (P 2 O 3) 3 XH 2 O.
- iron (III) pyrophosphate which is also referred to as iron (III) diphosphate, Fe (III) 4 (P 2 O 3) 3 XH 2 O.
- ferrous pyrophosphate iron orthophosphates or higher-condensed iron phosphates, no satisfactory results were achieved in the sense of the present invention.
- the iron source is added as a solid or as a wet filter cake to the alkali polyphosphate solution, but not as a solution or suspension containing high water content.
- the addition of the iron source as a solid to the alkali polyphosphate solution has proven to be particularly advantageous and gave the best results.
- the inventors have found that not all iron (III) pyrophosphate preparations give the same good results, but the water solubility of the product according to the invention is influenced by the loss on ignition of the iron (III) pyrophosphate used.
- the loss on ignition is determined according to the invention by annealing 2 g of sample at 800 ° C for 30 min and determines the mass loss during annealing.
- the higher the loss on ignition of the sample the more bound and / or free water contains the sample and the more water is introduced in the production of the product according to the invention via the iron source.
- Too high an ignition loss surprisingly deteriorated the dissolution properties of the product according to the invention.
- precipitations and increased turbidity increasingly occur.
- the iron (III) pyrophosphate added to the alkali polyphosphate solution has an ignition loss of ⁇ 25%, preferably ⁇ 22%, particularly preferably ⁇ 20%. From a loss on ignition of 25% and higher significantly deteriorated solubility of the product according to the invention were found.
- the iron (III) pyrophosphate added to the alkali polyphosphate solution has an ignition loss of> 8%, preferably> 10%. It has surprisingly been found that the use of an iron (III) pyrophosphate with too low loss on ignition can lead to a sediment of Iron (III) pyrophosphate forms, which can not be solved later. Behind this observation, thermodynamic processes are suspected, but so far they have not been elucidated. Also surprisingly, the inventors have found that the rate at which the batch obtained from alkali polyphosphate solution and ferric pyrophosphate is dried in accordance with the invention to obtain a powder or granule influences the water solubility of the product according to the invention. Rapid drying improves the water solubility of the product according to the invention whereas too slow a drying or too slow removal of water worsens the water solubility of the product according to the invention.
- the mixture obtained from alkali polyphosphate solution and iron (III) pyrophosphate is dried to give a powder or granulate within a period of less than 20 minutes, preferably less than 15 minutes, more preferably less than 10 minutes. most preferably less than 7 minutes.
- the drying of the mixture obtained from alkali polyphosphate solution and iron (III) pyrophosphate is expediently carried out at a temperature in the range from 110 to 400 ° C., preferably 150 to 350 ° C., particularly preferably 200 to 300 ° C.
- the selection of the suitable drying temperature depends inter alia on the drying device, the drying process and not least on the water content of the approach.
- the drying step may entail with regard to the water solubility of the product according to the invention
- the person skilled in the art will determine the suitable drying temperature taking into account the drying apparatus, the drying method and the water content of the batch and also from the point of view of advantages short drying time can be easily determined.
- a product is considered in the context of the invention, when it is obtained a substantially free-flowing powder, which typically has a loss on ignition of less than 10%. Products dried according to the invention often have a loss on ignition of 5% or less.
- the loss on ignition is determined according to the invention by annealing 2 g of sample at 800 ° C for 30 min and determines the mass loss during annealing.
- the aqueous alkali polyphosphate solution comprises the alkali polyphosphate in a concentration of 10 to 80% by weight alkali polyphosphate, preferably 20 to 70% by weight alkali polyphosphate. If the concentration of the alkali polyphosphate in the receiver solution is too high, it is poorly soluble or insoluble. If, on the other hand, the concentration is too low, then the duration of the procedure is too long. A concentration in the range of 30 to 60 wt .-% alkali polyphosphate has been found to be particularly advantageous.
- the amount of alkali polyphosphate in the aqueous alkali polyphosphate solution and the amount of added iron (III) pyrophosphate are selected such that in the resulting suspension of alkali polyphosphate solution and iron (III) pyrophosphate the molar ratio of Fe: P is in the range of 1: 2.5 to 1:10.
- the rapid and good water solubility of the product prepared by the process according to the invention is manifested by its lucidity within a short time after the product has been combined with water.
- the lucidity is determined by turbidity measurement (nephelometry or Tyndallometrie) with a nephelometer (Merck Turbiquant 1500 IR without flow cuvette).
- the wavelength of the light source is in the range of 700-1 100 nm ("Herschel range").
- NTU Nephelometry Turbidity Units
- NTU is added 0.5 grams of product in 100 ml of water at 25 ° C.
- the amount of alkali polyphosphate in the aqueous alkali polyphosphate solution and the amount of added iron (III) pyrophosphate are selected such that the product obtained according to the invention becomes a clear solubilizer 1 minute after the product has been combined with water having a nephelometric haze value ⁇ 150 NTU, preferably ⁇ 100 NTU, more preferably ⁇ 50 NTU.
- the present invention also encompasses the use of the iron phosphate-containing product according to the invention as a means of nourishing biological systems, in particular of humans, animals, plants and microorganisms, with iron and phosphorus. Furthermore, the invention also encompasses the use of the product according to the invention containing iron phosphate as a nutrient enrichment agent for foods, animal feed, plant fertilizers and nutrient solutions for microorganisms containing iron and phosphorus, and as a dietary supplement, animal feed supplement and plant fertilizer.
- a significant advantage of the invention lies in the very good water solubility and bioavailability of the product according to the invention and the high recoverable iron content.
- Alkali polyphosphate was dissolved in water with stirring using an agitator (IKA EUROSTAR power, IKA-Werke GmbH & Co. KG, Staufen, Germany) using a paddle stirrer. The stirring speed was adapted to the medium and was between 100 and 1500 rpm.
- the iron source was added to iron (III) pyrophosphate as a solid, aqueous suspension or moist filter cake with stirring. Subsequently, the resulting mixture was heated to boiling. The approach became intense brown and its viscosity increased. In order to ensure the further processability of the batch against the background of the viscosity increase, it was diluted with water, if necessary. Drying (small scale)
- the prepared batch was dropped by means of a pipette into a commercially available, preheated to 200 ° C Teflon pan. The drying proceeded very fast within a few minutes ( ⁇ 5 min). Subsequently, the obtained powder was recovered from the pan with a scraper.
- the batch was introduced by means of a spray drier (fluidized-bed laboratory unit type WFP 8 Spec., DMR cilantro GmbH, Kaiseraugst, Switzerland) at a supply air flow temperature of 320 ° C., 180 m 3 air flow, bottom-up spray and a residence time ⁇ 5 minutes transferred fine powder.
- a spray drier fluidized-bed laboratory unit type WFP 8 Spec., DMR cilantro GmbH, Kaiseraugst, Switzerland
- NTU Nephelometric turbidity measurement
- Turbidity measurements were carried out with a nephelometer (Turbiquant 1500 IR, Merck KGaA, Darmstadt, Germany) without flow cuvette. 0.5 g of sample was weighed into a volumetric flask, 100 ml of water were added and shaken briefly. Then the measurement series was started by transferring it to the NTU container.
- Example 1 Iron QIQ pyrophosphates with different losses of ignition
- Example 2 varying concentrations of the alkali polyphosphate solution
- FePP iron (III) pyrophosphate
- FePP iron (III) pyrophosphate
- Example 4 Comparison of the preparation according to the method of the invention and the prior art by physical mixing
- the product according to the invention was prepared in the same way as Example 1.2 described above.
- iron (III) pyrophosphate and TKPP were mixed intensively in a powder mixer for 30 seconds. Subsequently, the solution properties of the powders obtained were determined by turbidity measurement after various dissolution times of 0.5 min to 120 min. Table 4 below gives the results of the turbidity measurements of the two batches.
- Figure 1 shows the solution behavior in the period of 0 to 120 minutes
- Figure 2 shows a section thereof for the period between 0 and 3.5 minutes. From Figure 2 it is clear that the product according to the invention is immediately soluble, whereas those from the Physically mixed composition consistently shows a very high turbidity and thus significantly poorer water solubility.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Mycology (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Fodder In General (AREA)
- Fertilizers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102016111335.2A DE102016111335A1 (de) | 2016-06-21 | 2016-06-21 | Lösliche Eisenphosphate und Verfahren zu deren Herstellung |
PCT/EP2017/064311 WO2017220366A1 (de) | 2016-06-21 | 2017-06-12 | Lösliche eisenphosphate und verfahren zu deren herstellung |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3472098A1 true EP3472098A1 (de) | 2019-04-24 |
Family
ID=59070644
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17730760.0A Withdrawn EP3472098A1 (de) | 2016-06-21 | 2017-06-12 | Lösliche eisenphosphate und verfahren zu deren herstellung |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3472098A1 (de) |
DE (1) | DE102016111335A1 (de) |
WO (1) | WO2017220366A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113975293B (zh) * | 2021-08-30 | 2022-12-16 | 中国海洋大学 | 多聚磷酸纳米铁补铁剂及其制备方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2357069A (en) * | 1941-04-07 | 1944-08-29 | Victor Chemical Works | Iron fortification of flour |
KR20140067137A (ko) | 2011-09-22 | 2014-06-03 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 배기 계통을 위한 열적으로 절연된 구성요소 |
DE102012100128A1 (de) * | 2012-01-10 | 2013-07-11 | Chemische Fabrik Budenheim Kg | Kondensierte Eisen(III)phosphate |
BE1021206B1 (fr) | 2012-10-10 | 2015-08-04 | Prayon | Composition nutritive |
BE1021212B1 (fr) | 2012-10-10 | 2015-08-11 | Prayon | Composition nutritive |
-
2016
- 2016-06-21 DE DE102016111335.2A patent/DE102016111335A1/de not_active Withdrawn
-
2017
- 2017-06-12 WO PCT/EP2017/064311 patent/WO2017220366A1/de active Search and Examination
- 2017-06-12 EP EP17730760.0A patent/EP3472098A1/de not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
DE102016111335A1 (de) | 2017-12-21 |
WO2017220366A1 (de) | 2017-12-28 |
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Inventor name: SIEGLING, SEBASTIAN Inventor name: SCHNEE, RAINER Inventor name: WISSING, ALBERTUS Inventor name: ENGERS, DAVID Inventor name: RATH, GIDEON Inventor name: WISSEMBORSKI, RUEDIGER |
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