EP1196368A1 - Formiate de calcium exempt de poussiere - Google Patents

Formiate de calcium exempt de poussiere

Info

Publication number
EP1196368A1
EP1196368A1 EP00942057A EP00942057A EP1196368A1 EP 1196368 A1 EP1196368 A1 EP 1196368A1 EP 00942057 A EP00942057 A EP 00942057A EP 00942057 A EP00942057 A EP 00942057A EP 1196368 A1 EP1196368 A1 EP 1196368A1
Authority
EP
European Patent Office
Prior art keywords
agglomeration
calcium formate
dust
auxiliaries
particles
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Withdrawn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
EP00942057A
Other languages
German (de)
English (en)
Inventor
Achim Noack
Hanspeter Baumgartner
Jürgen STRUSCH
Alexander Klausener
Mélanie JURET
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.)
Bayer Chemicals AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP1196368A1 publication Critical patent/EP1196368A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • 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
    • A23K20/10—Organic substances
    • A23K20/105—Aliphatic or alicyclic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K30/00—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs
    • A23K30/10—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs of green fodder
    • A23K30/15—Processes specially adapted for preservation of materials in order to produce animal feeding-stuffs of green fodder using chemicals or microorganisms for ensilaging
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to a process for the production of a material which contains dust-free assembled calcium formate of the formula Ca (HCOO) 2 , wherein finely crystalline calcium formate is subjected to agglomeration with the addition of at least one auxiliary and optionally one or more further components. Furthermore, the invention relates to the use of this material and correspondingly available dust-free assembled calcium formate.
  • Calcium formate is a light, crystalline solid that is used commercially, for example, in the following areas:
  • Calcium formate is obtained in various ways, for example by reacting formic acid with calcium hydroxide or by the action of carbon monoxide on calcium hydroxide. Such syntheses are described for example in Ullmann's Encyclopedia of Industrial Chemistry (4th edition), Vol. 7, pp 364 and 370, and in Ullmann's Encyclopedia of Industrial Chemistry (5th edition) Vol. A 12, page 29.
  • Calcium formate can be crystallized, isolated and purified using suitable techniques known per se. Evaporation crystallization of aqueous solutions which may contain organic components, cooling crystallization and spray drying may be mentioned as examples of crystallization techniques which can be used in principle. Filtration or centrifugation may be mentioned as examples of basically suitable isolation techniques. Possible cleaning operations include redissolution, dispersion, washing and extraction with suitable solvents. Where appropriate, such operations or operation sequences are followed by another suitable drying step, of which hot air drying, contact drying and vacuum drying are mentioned as examples of basically suitable methods.
  • Calcium formate containing dust If calcium formate, for example, is introduced into certain commercially available coarse-grained, structured or shaped animal feed or silage components that contains high levels of fine grains or dust, this is often associated with considerable mixing problems and undesirable segregation in the further handling of the finished mixture. These effects can limit the advantageous use of calcium formate in many areas of application. Although it is possible to separate coarse-grained fractions with the help of suitable techniques such as classifying, screening and sifting, on the one hand additional costs are incurred, on the other hand the remaining fine-grained or dust-like fractions can only be used with considerable additional effort by for example, they are redissolved, crystallized, isolated, dried and then returned to the fractionation process. Especially in processes in which calcium formate is only obtained as a by-product, it is often not technically and economically sensible to isolate what is preferred
  • Crystal dressings arise due to the hygroscopic properties of Dry calcium formate in general for the formation of inhomogeneous material, which contains undefined coarser components in addition to unchanged fine-grained components.
  • DE-OS-1 518 686 discloses a process for granulating calcium formate, according to which a high proportion (55 to 65% based on the amount of granules obtained) of granules with a diameter of 2 to 5 mm is obtained.
  • Magnesium oxide must be added to the calcium formate to be granulated and the mixture sprayed with aqueous magnesium chloride solution. The result is a material which contains 2.2 to 23.4% by weight of magnesium compound, calculated as magnesium oxide. It is not possible to obtain magnesium-free material by this method. None is said about the dust behavior of the granules.
  • Contains 0.2 mm is a by-product of a process for the production of polyols.
  • the invention accordingly relates to a process for the production of material which contains dust-free calcium formate and is characterized in that finely crystalline calcium formate which contains at least 50% by weight, preferably at least 60% by weight, of particles with an average particle size below 0 , 2 mm, preferably less than 0.1 mm, is subjected to agglomeration with the addition of at least one auxiliary substance. Furthermore, the invention relates to the use of this material as an additive in the field of animal nutrition and dust-free assembled calcium formate which contains less than 20% by weight of particles with a maximum grain size of 0.05 mm and can be obtained by the process according to the invention.
  • the inventive method leads in a technically easy to implement and
  • the agglomeration can in principle be obtained by all known and conceivable methods of structural agglomeration, for example by
  • the calcium formate which is made up dust-free according to the invention, is preferably produced by mixed agglomeration.
  • the calcium format used as the starting material is mixed with a suitable auxiliary.
  • the mixing agglomeration can be carried out using a solid mixer with moving tools. Mixers with high mechanical power input are generally preferred. Such mixers are also referred to as intensive mixers. The greater the mechanical power input, the better the flowability of the agglomerated product.
  • the agglomeration of calcium formate according to the invention can in principle be carried out either continuously or batchwise. It is carried out with the aid of devices known to the person skilled in the art, preferably those which are available from specialist dealers.
  • the continuous agglomeration the continuous agglomeration of calcium formate according to the invention.
  • Any calcium formate can be used as calcium formate that contains significant fine grain or dust, i.e. contains at least 50% by weight, preferably at least 60% by weight, of particles with an average grain size below 0.2 mm, preferably below 0.1 mm.
  • Calcium formate is preferably used, as is typically obtained after isolation and purification as a by-product of a process for the production of polyols such as trimethylolethane, trimethylolpropane or pentaerythritol.
  • the calcium formate to be subjected to the agglomeration can in principle be introduced into the agglomeration device, optionally with the addition of further auxiliaries and / or components, with the aid of all conveying units known to the person skilled in the art. Conveyor belts, screws and vibrating troughs may be mentioned as examples.
  • the auxiliary material used according to the invention can be introduced into the mixer in liquid or solid, approximately powdered form.
  • the introduction in liquid form is preferred.
  • Auxiliaries that are solid at room temperature can optionally be melted and fed to the agglomeration process in the form of a melt. - 1 -
  • the finely crystalline calcium formate, the auxiliaries and, if appropriate, the further components can each be introduced into the agglomeration apparatus individually or in any mixture.
  • the order of introduction is irrelevant.
  • the finely crystalline calcium formate is preferably introduced and then the auxiliaries and optionally the further components are added.
  • the agglomeration according to the invention can take place, for example, in a temperature range between -70 and 150 ° C., preferably in the temperature range between -20 and 110 ° C., particularly preferably in the temperature range between 0 and 75 ° C.
  • the auxiliary substance contents in the material produced according to the invention are generally in the range between 0.1 and 20% by weight, preferably in the range between 0.3 and 15% by weight, particularly preferably between 0.5 and 8% by weight on the resulting ready-made material.
  • the auxiliary substance contents in the material produced according to the invention are generally in the range between 0.1 and 20% by weight, preferably in the range between 0.3 and 15% by weight, particularly preferably between 0.5 and 8% by weight on the resulting ready-made material.
  • the auxiliary substance contents in the material produced according to the invention are generally in the range between 0.1 and 20% by weight, preferably in the range between 0.3 and 15% by weight, particularly preferably between 0.5 and 8% by weight on the resulting ready-made material.
  • the auxiliary substance contents in the material produced according to the invention are generally in the range between 0.1 and 20% by weight, preferably in the range between 0.3 and 15% by weight, particularly preferably between 0.5 and 8% by weight on the resulting ready-made material.
  • auxiliaries used according to the invention can be, for example, liquid or solid auxiliaries which are known to the person skilled in the art as compacting and formulation auxiliaries.
  • auxiliaries are water, optionally aqueous mineral acids, mono-, di-, tri- and polyhydric alcohols such as ethylene glycol, propane-1,2-diol or glycerol, carboxylic acids, carboxylic esters, carboxamides, sulfoxides, fats, especially hard fats, Fatty acids, in particular isomergic acid, fatty alcohols, waxes, tallows and oils of synthetic or natural (animal or vegetable) origin. Be further as possible
  • auxiliaries called mono-, di-, oligo- and polysaccharides such as glucose, sucrose, lactose, dextrins, starch, cellulose, cellulose derivatives or technical molasses. It is also possible to use mixtures of the auxiliaries mentioned.
  • Preferred auxiliaries are ethylene glycol, propane-1,2-diol, glycerol, fats, isomergic acid and / or waxes, tallow and oils of synthetic or natural (animal or vegetable) origin.
  • Ethylene glycol propane-1,2-diol, glycerol, fats and / or are particularly preferred
  • Substances which can possibly have a positive influence on the application properties and / or the further use of the lumpy calcium formate according to the invention are, for example, fragrances, flavorings, carbon such as activated or medicinal carbon, preservatives, and various inorganic or organic salts of natural or synthetic origin.
  • fragrances for example, fragrances, flavorings, carbon such as activated or medicinal carbon, preservatives, and various inorganic or organic salts of natural or synthetic origin.
  • Sodium, potassium, ammonium, magnesium, calcium and iron salts and chlorides, sulfates, phosphates, silicates, carbonates, bicarbonates, acetates, benzoates and citrates with any counterion or counterions may be mentioned by way of example.
  • mixing partners that have a positive influence on the use of the product according to the invention can, for example, in particular in the field of animal nutrition, be performance-promoting and / or nutritionally active substances.
  • examples include special feed ingredients, vitamins and pharmaceuticals in the broadest sense. It is also possible to add mixtures of different additives.
  • % By weight of particles with an average grain size of less than 0.2 mm, preferably less than 0.1 mm, with the other substances mentioned can take place, for example, in the course of agglomeration, preferably mixed agglomeration.
  • premixing is also possible in any mixing unit, after which the premixed material is fed to the actual agglomeration step. This can be done in practically all suitable ways known to those skilled in the art. For example, pre-mixing in mixers with moving mixing tools, in free-fall mixers, with the aid of screws, by pneumatic mixing (pneumatic swirling), by grinding in all suitable mill types, by mixing screening, by uniform wetting or by wetting pre-agglomeration.
  • several of the substances mentioned can also be mixed with the calcium formate used according to the invention and fed to the subsequent agglomeration and transfer into the material containing calcium-free iate which is made up according to the invention without dust.
  • the substances mentioned and the calcium formate used as the starting material can in principle be mixed with one another in any proportions, although there are only restrictions due to the physical consistency of the mixtures obtained - they must ultimately lead to solid, sufficiently free-flowing products after assembly.
  • the proportion of pure calcium formate is generally between 5 and 99.9% by weight, preferably between 25 and 99.7 % By weight, particularly preferably between 50 and 99.6% by weight and particularly preferably between 75 and 99.5% by weight.
  • dust-free assembled calcium formate which is between 0.1 and 20% by weight, preferably between 0.1 and 15% by weight, particularly preferably between 0.1 and 10% by weight an auxiliary and contains less than 20 wt .-%, preferably less than 18 wt .-% of particles with a maximum grain size of 0.05 mm.
  • auxiliaries see Table 1
  • auxiliary substances solid at room temperature (hard fat (fatty acid glyceride) of
  • Types Witocan ® HS and Witocan ® 42/44, vegetable fat, isomergic acid and hard fat (fatty acid glyceride) of the Dynasan ® 60 type) were liquefied by heating to a temperature which was about 20 K above the respective melting point.
  • the dust-free nature of the products obtained was assessed visually by spilling from one container into another.
  • the bulk density was measured in a vessel the volume of 1.0 liter, into which the product was poured without further compression.
  • the flow behavior of the products was assessed by funnel outlet tests. Funnels (volume approx. 200 ml) with different funnel outlet diameters were used. The product was filled into the respective funnel without being sealed while the outlet was closed. The outlet opening was then opened and it was observed whether the product flows out freely or whether a bridge or a shaft forms above the outlet opening. Table 1 shows the minimum funnel outlet openings required for trouble-free flow. It was shown that the Witocan ® HS hard grease leads to the most favorable flow behavior.
  • Dynasan ® 60 is 6.0% by weight.
  • auxiliaries which are solid at room temperature (hard fat (fatty acid glyceride) of the Witocan ® HS type and isomergic acid) were liquefied by heating to a temperature which was about 20 K above the respective melting point.
  • Mass fractions (mass binder / mass calcium formate). The freedom from dust the products obtained were assessed visually by spilling from one container into another. The bulk density was determined in a 1.0 liter volume into which the product was filled without further compression.
  • Calcium formate from the production of trimefhylolpropane (by-product)) containing at least 50% by weight of calcium formate was produced in a continuously operating ring layer mixer from L ⁇ DIGE (type CB 30 P, diameter 300 mm, length: 1250 mm, mixing tools: pens and paddles) Contains particles with an average grain size of less than 0.2 mm, and melted hard fat (fatty acid glyceride) of type Witocan HS (temperature of the melted fat: 50 ° C - 60 ° C) mixed.
  • the calcium formate was fed continuously to the annular layer mixer by means of a metering screw and the molten hard fat by means of a peristaltic pump.
  • Tests were carried out at different levels of the auxiliary (mass of auxiliary / mass of calcium formate), at different speeds and at different flow rates (see Table 3).
  • the agglomeration at the low speed of 850 min “1 leads to a product with poorer flow properties than at higher speeds (1500 min " 1 and 2000 min “1 ).
  • the minimum level of hard fat of the type Witocan HS, which is advantageous for dedusting, can be reduced to 0.7 This reduction in hard fat content results in better flowability of the product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Fodder In General (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Selon l'invention, du formiate de calcium exempt de poussière est obtenu par agglomération, notamment par agglomération mixte, à partir de formiate de calcium en fins cristaux comportant une part significative de grains fins et de poussières, par adjonction d'au moins un auxiliaire.
EP00942057A 1999-06-26 2000-06-13 Formiate de calcium exempt de poussiere Withdrawn EP1196368A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19929346A DE19929346A1 (de) 1999-06-26 1999-06-26 Staubfreies Calciumformiat
DE19929346 1999-06-26
PCT/EP2000/005415 WO2001000556A1 (fr) 1999-06-26 2000-06-13 Formiate de calcium exempt de poussiere

Publications (1)

Publication Number Publication Date
EP1196368A1 true EP1196368A1 (fr) 2002-04-17

Family

ID=7912664

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00942057A Withdrawn EP1196368A1 (fr) 1999-06-26 2000-06-13 Formiate de calcium exempt de poussiere

Country Status (8)

Country Link
EP (1) EP1196368A1 (fr)
JP (1) JP2003503376A (fr)
CN (1) CN1358166A (fr)
AU (1) AU5681000A (fr)
DE (1) DE19929346A1 (fr)
HK (1) HK1046130A1 (fr)
NO (1) NO20016244L (fr)
WO (1) WO2001000556A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104016850B (zh) * 2014-06-16 2016-08-24 聊城市鲁西化工工程设计有限责任公司 一种甲酸钙的生产方法
CN104674350B (zh) * 2015-03-09 2017-12-12 王军柳 一种多铁性甲酸盐类LiCo(COOH)3单晶材料及其制备方法
CN104674351B (zh) * 2015-03-09 2018-03-20 张香丽 一种甲酸盐类LiCa(COOH)3单晶光学材料及其制备方法
CN104651942B (zh) * 2015-03-09 2018-03-20 王军柳 一种多铁性甲酸盐类LiMn(COOH)3单晶材料及其制备方法
CN104726937B (zh) * 2015-03-09 2017-05-03 孙王淇 一种甲酸钙单晶光学材料及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1518686A1 (de) * 1965-12-07 1969-04-10 Kalk Chemische Fabrik Gmbh Verfahren zur Granulierung von Calciumformiat
DE19807996A1 (de) * 1998-02-26 1999-09-02 Bayer Ag Stückiges Calciumformiat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0100556A1 *

Also Published As

Publication number Publication date
WO2001000556A1 (fr) 2001-01-04
JP2003503376A (ja) 2003-01-28
DE19929346A1 (de) 2000-12-28
NO20016244D0 (no) 2001-12-19
CN1358166A (zh) 2002-07-10
AU5681000A (en) 2001-01-31
NO20016244L (no) 2002-02-13
HK1046130A1 (zh) 2002-12-27

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