JP2003503376A - Dust-free calcium formate - Google Patents

Abstract

  (57) [Summary] The dust-free calcium formate can be obtained by agglomeration, in particular by co-agglomeration, from microcrystalline calcium formate having a significant proportion of fine particles and dust during the addition of at least one auxiliary.

Description

Detailed Description of the Invention

The present invention is of the formula Ca (HCO), manufactured as dust-free.
O) ₂ calcium formate-comprising material, the method comprising the addition of at least one processing aid and, if appropriate, one or more other components, in the form of fine crystals (fin).
Ely crystalline) A method for aggregating calcium formate.
The invention further relates to the use of this substance as well as the available calcium formate, which is likewise produced dust-free.

Calcium formate is used for example in the following fields of the market:
ht) is a crystalline solid. -Additives in the field of animal nutrition (pig feed, livestock feed and turkey feed) -Use in the construction industry (improvement of hardening of cement, gypsum and cement compositions, and antifreeze of mortar) ) -Production of formic acid-Processing aids in the leather industry-Auxiliaries for the production of high-gloss papers-Treatment of scrubbing water for flue gas desulfurization-Aids for silylation Calcium formate can be processed in various ways, for example formic acid. With calcium hydroxide, or by reacting carbon monoxide with calcium hydroxide. This form of synthesis is described, for example, in Ullmann's Enzyklopae.
die der Technischen Chemie [Ullman's Encyclopaedia of Industrial Chemistr
y] (4th edition), vol. 7, pages 364 and 370, and Ullmann's.
Encyclopaedia of Industrial Chemistr
y] (5th edition), A12, p. 29.

The most important industrial production of calcium formate is carried out according to the methods known in the various literature for the production of polyols in which calcium formate is obtained as a by-product.
An example which may be mentioned here is the production of trimethylolpropane from n-butyraldehyde and formaldehyde using calcium hydroxide as base. In this method, calcium formate is coupled to the coupled product.
manufactured as ct).

Calcium formate may be crystallized, isolated and purified using suitable techniques known per se. Examples of crystallization techniques which are available in principle and which may be mentioned are evaporative crystallization, cooling crystallization and spray-drying of aqueous solutions, where appropriate containing organic components. Examples of isolation techniques which are suitable in principle and which may be mentioned are filtration or centrifugation. Possible purification operations which may be mentioned by way of example are redissolving, dispersing, washing and extracting with suitable solvents. Where appropriate, such operations or operating sequences are followed by one or more suitable drying steps, of which the methods which may be mentioned by way of example as generally suitable are hot air drying, contact drying. And vacuum drying.

All of these processes have in common the fact that they give polydisperse products which are distinguished by a characteristic particle size distribution which is more or less wide. In all known industrial processes for producing calcium formate, a fairly high proportion of total crystals, in particular of fine particles with a diameter of <0.2 mm.
It exists in the grained) range. However, various applications require that the product preferably has a low fines content and does not produce dust during processing. The reason for this is, for example, occupational hygiene (occu).
There is a certain need for a partial hygiene, which presents the problem of dealing with dusty calcium formate that can only be eliminated by using additional technical means. Another reason is due to the physical behavior of fine-grained calcium formate, which contains a significant amount of dust. For example, some commercially available coarse-grained (coa) calcium formates with high fines or dust content.
rse-grained structure or shape (sha)
ped) when incorporated into animal or green feed ingredients, this is often associated with considerable mixing problems and unwanted separation problems during further handling of the finished mixture. These effects limit the use of calcium formate, which is itself advantageous in many fields of application. For example, it is possible to separate the coarsely-grained parts using suitable techniques of classification, screening and sieving, but firstly this is more expensive and secondly the remaining fines Part of the particulates or dust can only be provided for further use, for example with the additional additional expense of re-dissolving them, crystallizing, isolating and drying, and then feeding them back into the fractionation process. Is.

In the process in which calcium formate is obtained solely as a by-product, precisely the preferred and preferred main product is such that calcium formate is produced in the coarsest possible granulated or dust-free fraction. Modifying the isolation is often not technically or economically convenient. Finely divided or powdered
For the conversion of solids into coarsely granulated substances, in principle various agglomeration techniques are available whose application can be largely referred to in the case of crystalline calcium formate. For the reasons of the process in this case, it is often desirable to maintain the inherent good flowability of calcium formate. Calcium formate is added to the agglomeration of fine particles (cohesi).
On the other hand, attempts to moisten such as by adding a small amount of water, resulting in larger crystallographic associations, are generally due to the hygroscopic nature of the dry calcium formate, which is generally a constituent of the fine-particles unchanged. In addition, it results in the formation of a heterogeneous material with undefined relatively coarse components.

German Offenlegungschrifft German patent (DE-
OS) No. 1 518 686 describes granules having a diameter of 2 to 5 mm.
high content of les (55 to 65% based on the amount of the resulting granules)
Discloses a method for granulating calcium formate to obtain
In this method magnesium oxide must be added to calcium formate to be granulated and the mixture must be sprayed with an aqueous magnesium chloride solution. This results in the material containing 2.2 to 23.4% by weight of the magnesium compound, calculated as magnesium oxide. It is not possible to obtain magnesium-free substances by this method. No mention is made of the behavior of the particulate dust formation.

Therefore, especially for the production of animal feed products and the most versatile forms of ensiling aids, on the basis of calcium formate, a dust-free and further processing is possible, and The aim is to produce substances which have good flowability and have as low a fines content as possible. An industrially feasible and economical route for producing such products should be found. This object is achieved by the method of the invention.

At least 50% by weight of polydisperse calcium formate having a high fines or dust content, ie particles having a mean particle size of less than 0.2 mm, preferably less than 0.1 mm.
Calcium formate, preferably containing at least 60% by weight, together with suitable flocculation-promoting processing aids and, where appropriate, other components which do not affect the flocculation or only insignificant amounts, The small calcium formate particles that cause the formation of a large amount of calcium formate bound to form larger calcium formate particles (bound)
A) as a result of the aids used in the present invention and / or jointly with the process aids to agglomerate to produce larger particles. In contrast to experimental agglomeration, where high particle settling rates lead to avoidance of unwanted dust, dust-free ones are admitted during the further process. It has been surprisingly found that a calcium formate is obtained which remains and has satisfactory applicability. Calcium formate with a high fines or dust content, ie calcium formate containing at least 50% by weight of particles having a mean particle size of less than 0.2 mm, is produced, for example, as a by-product of the process for polyol production.

The invention therefore relates to a process for the production of dust-free substances containing calcium formate, which comprises at least 50% by weight of particles having a mean particle size of less than 0.2 mm, preferably less than 0.1 mm. %, Preferably at least 60% by weight, of finely divided calcium formate, together with the addition of at least one processing aid. Furthermore, the present invention relates to the use of this substance as an additive in the field of animal nutrition, as well as containing less than 20% by weight of particles produced as dust-free and having a maximum particle size of 0.05 mm, and according to the method of the invention. It also relates to the obtainable calcium formate.

The method of the present invention provides a calcium formate-containing substance which is industrially easy to carry out and which can be handled dust-free and which exhibits good flow behavior.

According to the invention, agglomeration is in principle all known and possible deposits (b
Depending on the method of oil-up agglomeration, for example mixer agglomeration, disc
) Agglomeration, rotor agglomeration, fluid bed agglomeration and steam jet
) It can be obtained by aggregation.

The calcium formate of the present invention produced as dust-free is preferably produced by the mixer agglomeration method. In this case, the calcium formate used as starting material is mixed with a suitable processing aid. Mixer agglomeration can be performed using solids mixers with a stirring working part. In this case, mixers with high mechanical input are generally suitable. This form of mixer is also a termed high intensity mixer.
The flowability of the agglomerated product increases with increasing mechanical input.

The agglomeration of the calcium formate of the invention can in principle be carried out either continuously or batchwise. The equipment is known to those skilled in the art, preferably using what is available in the specialist trade. For suitable mixer agglomeration, a continuous mode of operation of the mixer with an annular layer is preferred.

The calcium formate used is any calcium formate having a considerable fines or dust content, ie at least 50% by weight of particles having a mean particle size of less than 0.2 mm, preferably less than 0.1 mm, It may suitably contain at least 60% by weight. It is preferred to use this method of calcium formate, which is typically produced after isolation and purification, as a by-product of the method for the production of polyols such as trimethylolethane, trimethylolpropane, or pentaerythritol. .

The calcium formate to be agglomerated can be introduced into the agglomerator, in principle using all transport unit equipment known to the person skilled in the art, together with the addition of other processing aids and / or components where appropriate. These which may be mentioned by way of example are conveyor belts, screws and oscillating channels.

The processing aids used according to the invention can be introduced into the mixer in liquid form or in solid form, for example in powder form. In this case, introduction in liquid form is preferred. Processing aids which are solid at room temperature can be melted where appropriate and can be fed to the agglomeration process in the form of a melt.

The finely divided calcium formate, the processing aids and, if appropriate, the other components can each be introduced separately or in the form of any mixture in the agglomerator. Introductory sequence (se
(q) is not important. Preferably, the finely crystalline calcium formate is initially charged, and then the processing aids and, where appropriate, other ingredients are added.

The agglomeration of the present invention is carried out, for example, in the temperature range of −70 ° C. and 150 ° C., preferably −20 ° C.
And 110 ° C., particularly preferably 0 ° C. and 75 ° C.

The content of processing aids in the substances produced according to the invention is generally in the range of 0.1 and 20% by weight, preferably 0.3 and 15% by weight, based on the substances produced. In the range of 0.5 and 8% by weight is particularly preferred. Depending on the processing aid used, it may be advantageous to use a minimum of 6% by weight processing aid.

The processing aids used in the present invention are, for example, compacting aids.
Liquids or solids processing aids known to the person skilled in the art as ids) and production aids. Processing aids in this form which may be mentioned by way of example are, for example, water, mineral acids or mineral acids diluted with water, monohydric, dihydric, trihydric and polyhydric alcohols, for example ethylene glycol, propane-1,2- Diols or glycerol, carboxylic acids, carboxylic acid esters, carboxamides, sulfoxides, fats, especially hardened fats, fatty acids, especially Isomerginic acid, fatty alcohols, waxes, tallows and oils of synthetic or natural (animal or plant) origin. is there. further,
Possible processing aids which may be mentioned are monosaccharides, disaccharides, oligosaccharides and polysaccharides such as glucose, sucrose, lactose, dextrins, starches, celluloses, cellulose derivatives or technical grade molasses.
In addition, it is also possible to use mixtures of these processing aids.

Suitable processing aids are ethylene glycol, propane-1,2-diol, glycerol, fats, isomeric acids and / or waxes, tallow and oils of synthetic or natural (animal or plant) origin.

Particularly suitable are ethylene glycol, propane-1,2-diol, glycerol, fat and / or isomeric acid.

If appropriate, after the agglomeration has taken place, uncontrolled solidification
It is expedient to specially cool the resulting material in order to remove the clumping during further treatment after cation and storage or packing.

In principle, in the present production of calcium formate produced as dust-free,
In addition to the processing aids, it is also possible to add one or more other substances which, if appropriate, do not or only slightly affect the flocculation process, but which still bring about the desired effect of application, and thus It is likewise a subject matter of the present invention. Examples of further uses of substances and / or the calcium formate piece-forms of the present invention, which may possibly have a beneficial effect on applicability, are perfumes, flavors, carbon, such as activated or medicinal carbon, preservatives. Agents and a wide variety of inorganic and organic salts of natural and synthetic origin. Examples which may be mentioned are sodium salts, potassium salts, ammonium salts, magnesium salts, calcium salts and iron salts and also chlorides, sulfates, phosphates, silicates, carbonates, hydrogen carbonates, acetates, benzoates. Acid salts and citrates with one or more counterions.

Other further partners which have a beneficial effect on the use of the products according to the invention can be growth-promoting and / or nutritionally active substances, for example, especially in the field of animal nutrition. Examples which may be mentioned are, in their broadest sense, certain feed ingredients, vitamins and pharmaceuticals.

[0027]   It is also possible to add mixtures of different additives.

Calcium formate with a high fines or dust content, ie calcium formate comprising at least 50% by weight, preferably at least 60% by weight of particles having an average particle size of less than 0.2 mm, preferably less than 0.1 mm. Can be mixed with the other substances, for example during agglomeration, preferably mixer agglomeration. In principle, it is also possible to premix in any desired mixing unit device, after which the premixed substances are fed to the actual flocculation stage. This can be done in virtually any manner suitable for that purpose and known to the person skilled in the art. For example, the premixing may be a mixer using a screw with an agitating mixing operating part, ie a free hole
In an e-fall) mixer, by air mixing (air vortexing), by milling in all mill forms suitable therefor, by mixing screening,
This can be done by uniform wetting or by wet precoagulation. In principle, a plurality of said substances may also be mixed with the calcium formate used according to the invention, subsequently fed to the flocculation and converted into a substance containing the calcium formate of the invention produced as dust-free. Good.

The substances used as starting material and calcium formate may in principle be mixed with one another in any proportion, although subject to restrictions from the physical consistency of the resulting mixture, and they are prepared. After it has been carried out, it should be a product which eventually becomes a solid but is sufficiently flowable.

Within the scope of calcium formate produced according to the invention as dust-free, the content of pure calcium formate is generally 5 if one or more mixtures are mixed during its production according to the invention. And 99.9% by weight, preferably 25 and 99.7% by weight, particularly preferably 50 and 99.6% by weight, and particularly preferably 75 and 99.5% by weight.
Is the range.

Calcium formate produced, for example, by the method of the present invention as being dust-free,
Processing aids in the range of 0.1 and 20% by weight, preferably 0.1 and 15% by weight, particularly preferably 0.1 and 10% by weight, and less than 20% by weight, preferably less than 18% by weight Of particles having a maximum particle size of 0.05 mm.

The method of the present invention is further illustrated by the following examples, but the present invention is in no way limited by these examples.

[0033]

【Example】

Example 1 4.5 kg of calcium formate (bonded product) from the production of trimethylolpropane (composition product) containing at least 50% by weight of particles having an average particle size of less than 0.2 mm are mixed with an EIICH high intensity mixer (type R02, normal volume). 5 L). The vortexer was operated at a rotation speed of 3000 rpm. This rotation speed corresponds to the Froude number Fr = 700, which is defined as follows.

Fr = ω ² · R / g where ω = 2 · π · n [S ⁻² ] is the angular frequency n [S ⁻¹ ] is the rotational speed R [m] of the mixer operating part. , Radius of rotary mixer operating part g [m / s ² ] is accelerated by gravity Different processing aids (see Table 1) are added as single components (single com
sprayed in liquid form using a nozzle or introduced into the mixer in the form of a jet. It was confirmed in each preliminary experiment that the method of adding the processing aid had no effect. Solid process which is the aid at room temperature ^(Witocan (R) HS
Form and Witocan ^(R) 42/44 form of hard fat (hard fat) (fatty acid glycerides), vegetable fats, Isomeruginin acid and Dynasan ^(R) 60 form of hard fat (fatty acid glycerides)) is about 20K than the respective melting points It was liquefied by heating to a high temperature.

In addition to different processing aids, different aggregation times were chosen (see Table 1). The content of the processing aid specified in Table 1 indicates a mass fraction (mass of processing aid / mass of calcium formate).

The dust freeness of the resulting product was assessed visually by transfer from one container to another. The bulk density was determined by introducing the product without further compression in a container with a volume of 1.0 liter.

The flow behavior of the product was evaluated by a funnel outlet experiment. Funnels with different outlet diameters (volume about 200 ml) were used. The product was loaded into each funnel without compression, closing the exit orifice of the funnel. The exit orifice was then released and it was observed whether the product flowed freely or formed a bridge or a shaft on the exit orifice. Table 1 shows the minimum funnel exit orifice required to exit fault-free. Hard fat Witocan ^(R) HS-shaped, resulting in the best flow behavior.

The sample treated with the processing aid had a reduced bulk density and no longer showed dust formation.

If different processing aids are used, different minimum binder contents are advantageous in order to ensure that they are completely dust-free. When 1,2-propanediol and water is used, the minimum content of 0.5 wt% and 0.6 wt% is preferred, Witocnan ^(R) 42/44 forms and Dynasan ^(R) 60 If hard fats in the form are used, they are advantageously 6.0% by weight.

[0040]

[Table 1]

Example 2 Calcium formate (bond product) 3.0 k obtained from the preparation of trimethylolpropane, containing at least 50% by weight of particles having an average particle size of less than 0.2 mm.
g to the LOEDIGE plowshare mixer (5
MR type, volume 5L) was introduced. The ploughshare was operated at a rotational speed of 274 rpm. This rotation speed corresponds to the Froude number of FR = 8.

The different processing aids (see Table 2) were atomized in liquid form using a single-component nozzle or introduced into the mixer in the form of jets. It was confirmed in preliminary experiments that the method of adding the processing aid had no effect. Processing aids that are solid at room temperature ⁽ Witocan® HS form hard fat (fatty acid glycerides) and isomerate) were liquefied by heating to about 20 K above their respective melting points.

In addition to different processing aids, different flocculation times were selected (see Table 2).
. The content of processing aids reported in Table 2 indicates the mass fraction (weight of binder / weight of calcium formate). Avoidance of the resulting product from dust was assessed visually by transfer from one container to another. The bulk density was determined by introducing the product without further compression in a container with a volume of 1.0 liter.

The flow behavior of the product was evaluated by a funnel outlet experiment. Funnels with different outlet diameters (
A volume of about 200 ml) was used. The product was loaded into each funnel without compression, closing the exit orifice of the funnel. The exit orifice is then released,
It was observed whether the product flowed freely or formed a bridge or shaft on the exit orifice. Table 2 shows the minimum funnel outlet orifices required to exit without catching.

For all treatment aids, a higher content of treatment aid was required to ensure avoidance from dust, as compared to the experiment on the EIRIC high intensity mixer (Experiment 1).

[0046]

[Table 2]

Example 3 Calcium formate obtained from the preparation of trimethylolpropane (bonding product) containing at least 50% by weight of particles having an average particle size of less than 0.2 mm and W
molten hard fat of ITOCAN ^(R) HS type (molten fat temperature: 50-60 ° C)
Fatty acid glyceride) is a LOEDIGE continuous annular layer.
er) mixer (CB30P type, diameter 300 mm, length: 1250 mm, mixer operating part: pin and paddle). Calcium formate is continuously fed by a metering screw and molten hard fat is peristaltic (per).
It was fed to the annular bed mixer via an istaltic pump.

The experiments were carried out at different treatment aid contents (treatment aid weight / calcium formate weight), different rotation speeds and different flow rates (see Table 3).

Aggregation at low rotation speeds of 850 rpm resulted in products with poorer flowability than that at aggregation at high rotation speeds (1500 rpm and 2000 rpm). The minimum content of hard fat advantageous Witocan ^(R) HS form for dedusting could reduced to 0.7 wt%. This reduction in hard fat content results in improved flowability of the product.

[0050]

[Table 3]

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, C H, CN, CR, CU, CZ, DE, DK, DM, DZ , EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, K G, KP, KR, KZ, LC, LK, LR, LS, LT , LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, RU, S D, SE, SG, SI, SK, SL, TJ, TM, TR , TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Syutorshiyu, Jurgen             GERMAN DAY-41542 DORMAGEN AM             Klausberg 15 (72) Inventor Clausener, Alexander             German Day-50259 Pulheim Schiffge             Sbak 18 (72) Inventor Jiule, Melanie             German Day-51381 Lef Elkuse             N'Holster Bake 37 F term (reference) 2B150 AA01 AA03 AA05 AB03 DH04                 4H006 AA02 AD15 AD40 BC51 BS10                       BS70

Claims (13)

[Claims] 1. A method of producing a substance containing calcium formate produced dust-free, comprising at least one fine crystalline calcium formate containing at least 50% by weight of particles having an average particle size of less than 0.2 mm. A method comprising the step of aggregating with the addition of a processing aid. 2. A method according to claim 1, characterized in that the resulting material is cooled immediately after agglomeration has taken place. 3. At least one of claims 1 or 2, characterized in that the agglomeration is carried out in one or more stages by mixer agglomeration, disk agglomeration, rotor agglomeration, fluid bed agglomeration or steam-jet agglomeration. The method described in. 4. Method according to at least one of claims 1 to 3, characterized in that the agglomeration is carried out by mixer agglomeration. 5. Process according to at least one of claims 1 to 4, characterized in that the processing aid is present in a content of 0.1 to 20% by weight, based on the resulting manufactured material. the method of. 6. The method according to claim 1, wherein the processing aid is a solid or liquid binder, a compression aid or a production aid. 7. The solid or liquid binder, the compression aid or the production aid is water, a mineral acid, or a mineral acid diluted with water, monohydric, dihydric, trihydric and polyhydric alcohols, carboxylic acids, carboxylic acids. Characterized by esters, carboxamides, sulfoxides, fats, fatty acids, fatty alcohols, waxes, tallow and oils of synthetic or natural (animal or plant) origin, monosaccharides, disaccharides, oligosaccharides and polysaccharides or sugars of industrial grade The method according to at least one of claims 1 to 6. 8. At least 50 particles having an average particle size of less than 0.2 mm.
8. Process according to at least one of the claims 1 to 7, characterized in that finely divided calcium formate, which comprises by weight, is obtained as a by-product of the industrial production of polyols. 9. Method according to at least one of claims 1 to 8, characterized in that one or more other components are added in the agglomeration. 10. Process according to claim 9, characterized in that the other ingredients added are fragrances, flavors, carbon, preservatives, inorganic salts and / or organic salts. 11. Method according to at least one of claims 9 to 10, characterized in that the other ingredient is a growth-promoting and / or nutritionally active substance, a vitamin and / or a drug. 12. Manufactured dust-free, containing from 0.1 to 2 processing aids according to claim 6.
Calcium formate containing between 0% by weight and less than 20% by weight of particles with a maximum particle size of 0.05 mm. 13. Use of a substance according to at least one of claims 1 to 12 as an additive in the field of animal nutrition.